CN105821523B - A kind of sodium alginate fire resistance fibre of loaded metal ion and preparation method thereof - Google Patents

A kind of sodium alginate fire resistance fibre of loaded metal ion and preparation method thereof Download PDF

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CN105821523B
CN105821523B CN201610277990.2A CN201610277990A CN105821523B CN 105821523 B CN105821523 B CN 105821523B CN 201610277990 A CN201610277990 A CN 201610277990A CN 105821523 B CN105821523 B CN 105821523B
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sodium alginate
metal ion
hybrid material
aqueous solution
fire resistance
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CN105821523A (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
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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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a kind of sodium alginate fire resistance fibre of loaded metal ion and preparation method thereof.The sodium alginate fire resistance fibre by the sodium alginate hybrid material of water soluble negative carrying metal ion is dissolved in water and prepares spinning solution to be made through wet spinning technology；The sodium alginate hybrid material of the water soluble negative carrying metal ion is made of sodium alginate, the metal ion stablized agent molecule and have flame retardant effect.The fiber produced using the method for the present invention has the characteristics that fire-retardant and fracture strength is high.The fiber limited oxygen index can reach more than 34%, and the tensile strength of fiber is more than 3.5cN/tex, and line 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 the present invention relates to a kind of loaded metal ion and preparation method thereof, it is more particularly to a kind of Using the sodium alginate hybrid material of loaded metal ion as spinning material, the sodium alginate prepared by wet spinning process Prospect for Flame Retardant Fiber Materials.
Background technology
In work clothes, firefighter's garment, cloth system, system interior trim, system and commercial carpets, transport, military clothing With bedding etc., Fire-proof Finishing Agents for Textile performance requirement is all higher.Research to the fire resistance of Textile material It is constantly subjected to the concern of people.But environmental regulation limits the selection of some halogen system fire proofings, while to discarding fire-retardant material The recycling of material products is even more very urgent.The fire proofing used from now on, it is necessary to while meet the requirement of these two aspects. The environmental requirement to fire proofing has been imperative at present.At the same time, stringenter flame retardant regulation also requires to use one The high efficiency flame retardant material that a little heat endurances are high, heat release rate is low, raw smoke is small and less toxic.Have now been found that the biology based on plant Matter resource-native cellulose and biomass resource-alginic acid based on marine organisms, have rich reserves, it is renewable and The advantages that non-secondary pollution, be the preferable living resources of human future.And biomass resource-sea based on marine organisms Alginic acid is of increased attention with its excellent fire resistance.
And stoste spin processes traditional at present are that nano metal is placed in spinning solution in spinning, flame-retardant textile is made, The great advantage of the method is that nano metal may be homogenously dispersed in fibrous inside, and durability is good, and uses peace because stripping quantity is few Entirely.But nano metal surface energy is very big, it is easy to assemble, spinneret orifice is easily blocked in spinning process, continuous production is relatively difficult. Often exist in addition, being directly added into metal material fibrous inside is unstable the problem of, influence the use of fire resistance fibre.Therefore Dispersiveness and stability of the metal nanoparticle in sodium alginate fibrous matrix is solved to be a problem to be solved.
The content of the invention
The purpose of the present invention is to solve in existing sodium alginate fire resistance fibre, metal nanoparticle bad dispersibility and stabilization A kind of the problem of property is poor, there is provided sodium alginate fire resistance fibre of loaded metal ion and preparation method thereof.The present invention is using water-soluble The sodium alginate hybrid material of property loaded metal ion has good water as the raw material for preparing fire resistance fibre, the hybrid material Dissolubility, i.e., what the hybrid material can be stablized is dispersed in water, its aqueous solution is that no obvious particulate matter suspends or precipitates saturating Phaneroplasm system.In the preparation process of the hybrid material, by the pH value of regulation system, formation metal ion is with sodium alginate and surely Carrier sodium alginate can be supported in the form of ionic state always by determining the ionic bond between agent molecule and coordinate bond bonding, metal ion On class material, and it is scattered in aqueous, metal ion during without adding stabilizer molecular species stabilizer in aqueous solution Easily it is reduced.The hybrid material raw material is finally prepared into by sodium alginate fire resistance fibre using wet spinning technology so that this hair The sodium alginate fire resistance fibre of the loaded metal ion of bright preparation is excellent with inherent flame retardant, fracture strength height and biodegradable etc. Point.
To achieve the above object, the present invention is achieved by the following technical programs：
A kind of sodium alginate fire resistance fibre of loaded metal ion of the present invention, it passes through water soluble negative carrying metal ion Sodium alginate hybrid material is dissolved in water and prepares spinning solution to be made through wet spinning technology；The water soluble negative carrying metal ion Sodium alginate hybrid material is made of sodium alginate, the metal ion stablized agent molecule and have flame retardant effect；The water solubility In the sodium alginate hybrid material of loaded metal ion, the carboxyl of sodium alginate, stablize the amino of agent molecule and have fire-retardant effect It is bonded by ionic bond and coordinate bond between the metal ion of fruit；
In the sodium alginate and the stable agent molecule, the sum of carboxyl-content, amino content and hydroxy radical content are more than etc. In the 160% of the sum of the mole of the sodium alginate and the stable agent molecule；In sodium alginate, stabilizer molecular complex Carboxyl, amino and hydroxyl hydrophilic group be ensure the water miscible principal element of Compound complex, 160% this numerical value be protect Card Compound complex can have water miscible minimum numerical value；
The carboxyl bonded by ionic bond and coordinate bond and the amino bonded by ionic bond and coordinate bond contain 30% of the sum of amount more than or equal to the sum of carboxyl in the sodium alginate and the stable agent molecule and amino mole；
Relative molecular weight >=10000 of the sodium alginate；
Relative molecular weight≤5000 of the stable agent molecule, alkyl streptamine, the polyetheramine of 6 carbon are less than for chain length D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fat Fat amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, fatty amine One kind in polyoxyethylene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；Institute The alkyl streptamine that chain length is stated less than 6 carbon is n-propylamine, n-butylamine, n-amylamine or n-hexylamine；
The general structure of the sodium alginate hybrid material of the water soluble negative carrying metal ion is：
Wherein, strand repetitive unit number n>0；
Wherein, R is one kind in following functional group：Cation group, anionic group or polar nonionic group；It is described Cation group is tertiary amine base or quaternary ammonium group；The anionic group is carboxylic acid group；The polar nonionic group is hydroxyl, ether Base, amino, amide groups, sulfydryl or halogen；
Mx+For the metal ion with flame retardant effect, the value of valence state x is 1~3, is：Ag+、Fe2+、Fe3+、Zn2+Or Cu2+。
The mechanism that the triangle bonding scheme stablized in general structure schematic diagram is formed is as follows：Sodium alginate and stabilizer point - COO in son-With-NH3 +Because the attraction of positive and negative charge, electrostatic attraction is produced, that is, forms ionic bond；-COO-In hydroxyl oxygen On have a lone pair electrons, therefore lone pair electrons enter the unoccupied orbital of metal ion and metal ion occurs covalent coordinate and combined, formation Coordinate bond；-NH3 +In N atoms there is also lone pair electrons, be equally capable of providing lone pair electrons and form coordination bond with metal ion Close.Therefore the triangle bonding scheme of the stabilization in general structure schematic diagram is formd.
In the process, the pH value of reaction system is to-COO in system-、-NH3 +And Mx+The formation of bonding structure has very big Influence.- NH in sodium alginate2In pH value<In the case of 7 ,-NH can be combined to form with H protons excessive in solution3 +；With The rise of pH value, to neutral or alkaline condition, the H protons to dissociate in solution are reduced, it is impossible to re-form-NH3 +Structure.For Sodium alginate and for stablizing-COOH in agent molecule, in strong acid condition pH value<When 2, the dissociation of-COOH is suppressed, system In-COO-Content it is less, therefore the complexing power of metal ion is weakened significantly；As pH value increases, with metal ion Complexing power gradually increases, when solution ph reaches 5~7 ,-COO-Tend to be maximum with metal ion combination degree；But work as When the pH value of system improves again, and-NH can be destroyed3 +Structure, so as to destroy the three-legged structure relation for making stable system.Therefore, In order to form the triangle bonding scheme of the stable stabilization as shown in schematic diagram, so the pH of necessary effective adjustment and control system Value, and ensure pH value scope be 4~6.
As preferable technical solution：
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the stable agent molecule also include hydroxyl Or carboxyl.
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the carboxyl are located at molecular backbone or branch Chain；The amino is located at molecular backbone or side chain.
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the stabilizer molecular backbone further include Common element O, N or S in organic matter.
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the water soluble negative carrying metal ion The load capacity of the metal ion with flame retardant effect is 10~825mg/g in sodium alginate hybrid material；The carried metal from The sodium alginate fire resistance fibre limited oxygen index of son reaches more than 34%, and the tensile strength of fiber is more than 3.5cN/tex, line density For 2.2~3.5dtex.
Present invention also offers a kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion, by sodium alginate Aqueous solution is mixed with containing the aqueous solution for stablizing agent molecule, is adjusted the pH value of reaction system to 4~6, is then added dropwise into mixed liquor Metal ion salt solution, is stirred after being added dropwise, and obtains the hybrid material aqueous solution of the sodium alginate of loaded metal ion, is continued Stir and add precipitating reagent, sediment is collected by filtration, the alginic acid of water soluble negative carrying metal ion is obtained after drying precipitate Sodium hybrid material；The sodium alginate hybrid material of water soluble negative carrying metal ion is dissolved into deionized water, stirs evenly, matches somebody with somebody Into wet spinning solution, using wet spinning technology, the sodium alginate fire resistance fibre of loaded metal ion is obtained.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion as described above, by the water of sodium alginate Solution is mixed with containing the aqueous solution for stablizing agent molecule, is under the conditions of 20~60 DEG C；Stirring is accompanied by during mixing；Adjust reaction system PH value use 0.1~0.3mol/L HCl solution, the H of 0.05~0.15mol/L2SO4Solution or 0.1~0.3mol/L's HNO3Solution is adjusted；Metal ion salt solution stirs after being added dropwise, and the duration is 1~2h；Drying precipitate uses vacuum Oven drying.
A kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion as described above, the metal cation salt Solution is AgNO3、FeCl2、FeCl3、ZnCl2Or CuSO4Aqueous solution；The precipitating reagent is ethanol or acetone.
A kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion as described above, the sodium alginate When aqueous solution is mixed with containing the aqueous solution for stablizing agent molecule, sodium alginate and the molar ratio for stablizing agent molecule are 1:0.3~1；
The mass percent concentration of the sodium alginate aqueous solution is 0.5%~3%；
The mass percent concentration containing the aqueous solution for stablizing agent molecule is 3%~10%；
The concentration of the metal ion salt solution is 0.005~2g/mL；
The molar ratio of the metal cation salt and sodium alginate is 0.1~10:1；
The mass percent concentration of the hybrid material aqueous solution of the sodium alginate of the loaded metal ion for 0.5%~ 10.5%；
The volume ratio of the precipitating reagent and the aqueous solution of the sodium alginate hybrid material of load factor metal ion is 2~4: 1；
The temperature of the drying precipitate is 25~30 DEG C, and vacuum is 0.09~-0.1MPa.
A kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion as described above, the wet spinning work Skill is：The mass concentration percentage of the sodium alginate hybrid material of loaded metal ion is 1~10% in spinning solution, spinning temperature Spend for 10~60 DEG C, coagulating bath is the calcium chloride solution that mass percent concentration is 1%~15% or mass percent concentration is 1%~15% calcium chloride and zinc chloride mixed solution, calcium chloride and the matter of calcium chloride and zinc chloride in zinc chloride mixed solution Measure ratio 1~3:1, coagulation bath temperature is 10~50 DEG C, and draw ratio is 120%~300%.
Beneficial effect：
The sodium alginate fire resistance fibre of the loaded metal ion prepared using the present invention has inherent flame retardant, fracture strength height And the advantages that biodegradable, using natural sea mosanom fiber as carrier, helped with stablizing supplemented by agent molecule, metal ion is stablized Be dispersed on sodium alginate matrix.Less input for the instrument and equipment that preparation process uses, and operating process is simply easy to implement, instead The raw material used during answering are environmental-friendly and pollution-free, and impurity in products is few, is easy to post-process, and whole reaction process is conducive to Industrial amplification production.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed scope.
The sea that a kind of sodium alginate fire resistance fibre of loaded metal ion of the present invention passes through water soluble negative carrying metal ion Mosanom hybrid material is dissolved in water and prepares spinning solution to be made through wet spinning technology；The sea of the water soluble negative carrying metal ion Mosanom hybrid material is made of sodium alginate, the metal ion stablized agent molecule and have flame retardant effect；The water soluble negative In the sodium alginate hybrid material of carrying metal ion, the carboxyl of sodium alginate, stablize the amino of agent molecule and have flame retardant effect Metal ion between it is bonded by ionic bond and coordinate bond；
In the sodium alginate and the stable agent molecule, the sum of carboxyl-content, amino content and hydroxy radical content are more than etc. In the 160% of the sum of the mole of the sodium alginate and the stable agent molecule；
The carboxyl bonded by ionic bond and coordinate bond and the amino bonded by ionic bond and coordinate bond contain 30% of the sum of amount more than or equal to the sum of carboxyl in the sodium alginate and the stable agent molecule and amino mole；
Relative molecular weight >=10000 of the sodium alginate；
Relative molecular weight≤5000 of the stable agent molecule, alkyl streptamine, the polyetheramine of 6 carbon are less than for chain length D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fat Fat amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, fatty amine One kind in polyoxyethylene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；Institute The alkyl streptamine that chain length is stated less than 6 carbon is n-propylamine, n-butylamine, n-amylamine or n-hexylamine；
The general structure of the sodium alginate hybrid material of the water soluble negative carrying metal ion is：
Wherein, strand repetitive unit number n>0；
Wherein, R is one kind in following functional group：Cation group, anionic group or polar nonionic group；It is described Cation group is tertiary amine base or quaternary ammonium group；The anionic group is carboxylic acid group；The polar nonionic group is hydroxyl, ether Base, amino, amide groups, sulfydryl or halogen；
Mx+For the metal ion with flame retardant effect, the value of valence state x is 1~3, is：Ag+、Fe2+、Fe3+、Zn2+Or Cu2+。
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the stable agent molecule also include hydroxyl Or carboxyl.
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the carboxyl are located at molecular backbone or branch Chain；The amino is located at molecular backbone or side chain.
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the stabilizer molecular backbone further include Common element O, N or S in organic matter.
A kind of sodium alginate fire resistance fibre of loaded metal ion as described above, the water soluble negative carrying metal ion The load capacity of the metal ion with flame retardant effect is 10~825mg/g in sodium alginate hybrid material；The carried metal from The sodium alginate fire resistance fibre limited oxygen index of son reaches more than 34%, and the tensile strength of fiber is more than 3.5cN/tex, line density For 2.2~3.5dtex.
Embodiment 1
A kind of loaded Ag+Sodium alginate fire resistance fibre preparation method, under the conditions of 20 DEG C, by mass percent concentration The aqueous solution for the n-amylamine that aqueous solution for 0.5% sodium alginate is 3% with mass percent concentration mixes, sodium alginate with The molar ratio of n-amylamine is 1:0.3, the relative molecular weight of sodium alginate and n-amylamine is respectively 25000 and 87.16, companion during mixing With stirring, the pH value of system is adjusted to 4 with the HCl solution of 0.1mol/L, it is 0.005g/ that concentration is then added dropwise into mixed liquor The AgNO of mL3Aqueous solution, AgNO3Molar ratio with sodium alginate is 0.1:1, stirred after being added dropwise, duration 1h, i.e., Obtain loaded Ag+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 0.5%, persistently stir and add Precipitating reagent ethanol, precipitating reagent ethanol and loaded Ag+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, filter and receive Collect sediment, rinse sediment repeatedly with ethanol 2 times, sediment is 25 DEG C in temperature, and vacuum is vacuum under the conditions of 0.09MPa Water soluble negative is obtained after oven drying and carries Ag+Sodium alginate hybrid material, there is in the hybrid material Ag of flame retardant effect+ Load capacity be 42mg/g.
By the water-soluble loaded Ag of preparation+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 1% wet spinning solution, using wet spinning technology, obtains loaded Ag+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 10 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 1% is molten Liquid, coagulation bath temperature are 10 DEG C, draw ratio 120%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.51cN/tex, line density 2.2dtex, limited oxygen index 34.1%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 2
One kind load Fe2+Sodium alginate fire resistance fibre preparation method, under the conditions of 60 DEG C, by mass percent concentration The aqueous solution for the n-butylamine that aqueous solution for 0.6% sodium alginate is 6% with mass percent concentration mixes, sodium alginate with The molar ratio of n-butylamine is 1:0.7, the relative molecular weight of sodium alginate and n-butylamine is respectively 250000 and 73.14, during mixing Stirring is accompanied by, is adjusted the pH value of system to 6 with the HCl solution of 0.15mol/L, concentration is then added dropwise into mixed liquor is The FeCl of 0.2g/mL2Aqueous solution, FeCl2Molar ratio with sodium alginate is 2.5:1, stirred after being added dropwise, the duration is 2h, that is, obtain load Fe2+Sodium alginate hybrid material aqueous solution, its mass percent concentration is 1.2%, and lasting stirring is simultaneously Add precipitating reagent acetone, precipitating reagent acetone and load Fe2+Sodium alginate hybrid material aqueous solution volume ratio be 4:1, take out Sediment is collected in filter, rinses sediment repeatedly with acetone 3 times, and sediment is 30 DEG C in temperature, under the conditions of vacuum is -0.1MPa Water soluble negative, which is obtained, after vacuum drying oven drying carries Fe2+Sodium alginate hybrid material, there is flame retardant effect in the hybrid material Fe2+Load capacity be 263mg/g.
By the water-soluble load Fe of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 2% wet spinning solution, using wet spinning technology, obtains load Fe2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 20 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 3% is molten Liquid, coagulation bath temperature are 15 DEG C, draw ratio 130%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.53cN/tex, line density 2.5dtex, limited oxygen index 35.3%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 3
One kind load Fe3+Sodium alginate fire resistance fibre preparation method, under the conditions of 25 DEG C, by mass percent concentration The aqueous solution for the polyetheramine D400 that aqueous solution for 1% sodium alginate is 4% with mass percent concentration mixes, sodium alginate Molar ratio with polyetheramine D400 is 1:0.5, the relative molecular weight of sodium alginate and polyetheramine D400 is respectively 10000 and 400, Stirring is accompanied by during mixing, the pH value of system is adjusted to 6 with the HCl solution of 0.2mol/L, concentration is then added dropwise into mixed liquor For the FeCl of 0.1g/mL3Aqueous solution, FeCl3Molar ratio with sodium alginate is 0.5:1, stirred after being added dropwise, the duration For 1.5h, that is, obtain load Fe3+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 1.5%, persistently stir Mix and add precipitating reagent acetone, precipitating reagent acetone and load Fe3+Sodium alginate hybrid material aqueous solution volume ratio be 3: 1, collected by suction sediment rinses sediment with acetone 2 times repeatedly, and sediment is 26 DEG C in temperature, and vacuum is 0.09MPa bars Water soluble negative is obtained after vacuum drying oven drying carry Fe under part3+Sodium alginate hybrid material, have in the hybrid material fire-retardant The Fe of effect3+Load capacity be 10mg/g.
By the water-soluble load Fe of preparation3+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 3% wet spinning solution, using wet spinning technology, obtains load Fe3+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 25 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 5% is molten Liquid, coagulation bath temperature are 20 DEG C, draw ratio 140%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.58cN/tex, line density 2.5dtex, limited oxygen index 36.1%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 4
One kind load Zn2+Sodium alginate fire resistance fibre preparation method, under the conditions of 30 DEG C, by mass percent concentration The aqueous solution for the polyetheramine D2000 that aqueous solution for 1% sodium alginate is 5% with mass percent concentration mixes, alginic acid The molar ratio of sodium and polyetheramine D2000 are 1:0.5, the relative molecular weight of sodium alginate and polyetheramine D2000 are respectively 30000 Hes 2000, when mixing, accompanies by stirring, is adjusted the pH value of system to 5 with the HCl solution of 0.25mol/L, is then dripped into mixed liquor Add the ZnCl that concentration is 1g/mL2Aqueous solution, ZnCl2Molar ratio with sodium alginate is 0.5:1, stir, continue after being added dropwise Time is 1h, that is, obtains load Zn2+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 2.9%, continue Stir and add precipitating reagent ethanol, precipitating reagent ethanol and load Zn2+The volume ratio of hybrid material aqueous solution of sodium alginate be 4:1, collected by suction sediment rinses sediment with ethanol 2 times repeatedly, and sediment is 27 DEG C in temperature, vacuum 0.09MPa Under the conditions of vacuum drying oven drying after i.e. obtain water soluble negative carry Zn2+Sodium alginate hybrid material, there is in the hybrid material resistance The Zn of fuel efficiency fruit2+Load capacity be 73mg/g.
By the water-soluble load Zn of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 2% wet spinning solution, using wet spinning technology, obtains load Zn2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 30 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 7% is molten Liquid, coagulation bath temperature are 25 DEG C, draw ratio 150%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.63cN/tex, line density 2.6dtex, limited oxygen index 35.3%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 5
A kind of loaded Cu2+Sodium alginate fire resistance fibre preparation method, under the conditions of 50 DEG C, by mass percent concentration The aqueous solution for the polyetheramine D4000 that aqueous solution for 1.5% sodium alginate is 8% with mass percent concentration mixes, seaweed The molar ratio of sour sodium and polyetheramine D4000 are 1:The relative molecular weight of 0.8 sodium alginate and polyetheramine D4000 are respectively 66000 With 4000, when mixing, accompanies by stirring, is adjusted the pH value of system to 4 with the HCl solution of 0.3mol/L, is then dripped into mixed liquor Add the CuSO that concentration is 0.5g/mL4Aqueous solution, CuSO4Molar ratio with sodium alginate is 5:1, stir, continue after being added dropwise Time is 2h, that is, obtains loaded Cu2+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 6.3%, continue Stir and add precipitating reagent acetone, precipitating reagent acetone and loaded Cu2+The volume ratio of hybrid material aqueous solution of sodium alginate be 3:1, collected by suction sediment rinses sediment with acetone 3 times repeatedly, and sediment is 28 DEG C in temperature, and vacuum is -0.1MPa Under the conditions of vacuum drying oven drying after i.e. obtain water soluble negative carry Cu2+Sodium alginate hybrid material, there is in the hybrid material resistance The Cu of fuel efficiency fruit2+Load capacity be 70mg/g.
By the water-soluble loaded Cu of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 4% wet spinning solution, using wet spinning technology, obtains loaded Cu2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 32 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 8% is molten Liquid, coagulation bath temperature are 25 DEG C, draw ratio 150%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.66cN/tex, line density 3.3dtex, limited oxygen index 35.5%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 6
A kind of loaded Ag+Sodium alginate fire resistance fibre preparation method, under the conditions of 60 DEG C, by mass percent concentration The aqueous solution for the polyetheramine T403 that aqueous solution for 2% sodium alginate is 6% with mass percent concentration mixes, sodium alginate Molar ratio with polyetheramine T403 is 1:0.8, the relative molecular weight of sodium alginate and polyetheramine T403 is respectively 30000 and 400, Stirring is accompanied by during mixing, with the H of 0.05mol/L2SO4Solution adjusts the pH value of system to 6, is then added dropwise into mixed liquor dense Spend the AgNO for 0.03g/mL3Aqueous solution, AgNO3Molar ratio with sodium alginate is 8:1, stirred after being added dropwise, the duration For 2h, that is, obtain loaded Ag+Sodium alginate hybrid material aqueous solution, its mass percent concentration is 2.0%, lasting stirring And precipitating reagent acetone is added, precipitating reagent acetone and loaded Ag+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, Collected by suction sediment, sediment is rinsed with acetone 3 times repeatedly, and sediment is 30 DEG C in temperature, and vacuum is 0.09MPa conditions Water soluble negative, which is obtained, after lower vacuum drying oven drying carries Ag+Sodium alginate hybrid material, there is fire-retardant effect in the hybrid material The Ag of fruit+Load capacity be 408mg/g.
By the water-soluble loaded Ag of preparation+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 5% wet spinning solution, using wet spinning technology, obtains loaded Ag+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 35 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 10% is molten Liquid, coagulation bath temperature are 35 DEG C, draw ratio 170%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.59cN/tex, line density 3.4dtex, limited oxygen index 36.3%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 7
One kind load Fe2+Sodium alginate fire resistance fibre preparation method, under the conditions of 28 DEG C, by mass percent concentration The aqueous solution for the polyetheramine T3000 that aqueous solution for 1.7% sodium alginate is 9% with mass percent concentration mixes, seaweed The molar ratio of sour sodium and polyetheramine T3000 are 1:0.7, the relative molecular weight of sodium alginate and polyetheramine T3000 are respectively 36000 With 3000, when mixing, accompanies by stirring, with the H of 0.07mol/L2SO4Solution adjusts the pH value of system to 6, then into mixed liquor The FeCl that concentration is 1.6g/mL is added dropwise2Aqueous solution, FeCl2Molar ratio with sodium alginate is 0.5:1, stirred after being added dropwise, Duration is 1h, that is, obtains load Fe2+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 5.5%, Persistently stir and add precipitating reagent ethanol, precipitating reagent ethanol and load Fe2+Sodium alginate hybrid material aqueous solution volume Than for 3:1, collected by suction sediment rinses sediment with ethanol 2 times repeatedly, sediment temperature be 30 DEG C, vacuum for- Water soluble negative is obtained after vacuum drying oven drying carry Fe under the conditions of 0.1MPa2+Sodium alginate hybrid material, in the hybrid material Fe with flame retardant effect2+Load capacity be 40mg/g.
By the water-soluble load Fe of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 6% wet spinning solution, using wet spinning technology, obtains load Fe2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 40 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 11% is molten Liquid, coagulation bath temperature are 40 DEG C, draw ratio 180%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.56cN/tex, line density 3.5dtex, limited oxygen index 36.2%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 8
One kind load Fe3+Sodium alginate fire resistance fibre preparation method, under the conditions of 40 DEG C, by mass percent concentration The aliphatic amine polyoxyethylene ether AC-1210's that aqueous solution for 1.5% sodium alginate is 7% with mass percent concentration is water-soluble Liquid mixes, and the molar ratio of sodium alginate and aliphatic amine polyoxyethylene ether AC-1210 are 1:0.6, sodium alginate and fatty amine polyoxy The relative molecular weight of vinethene AC-1210 is respectively 10000 and 1200, and when mixing accompanies by stirring, with the H of 0.1mol/L2SO4It is molten Liquid adjusts the pH value of system to 6, and the FeCl that concentration is 0.01g/mL is then added dropwise into mixed liquor3Aqueous solution, FeCl3With sea The molar ratio of mosanom is 3:1, stirred after being added dropwise, duration 2h, that is, obtain load Fe3+Sodium alginate hydridization Material aqueous solution, its mass percent concentration are 3.1%, persistently stir and add precipitating reagent acetone, precipitating reagent acetone and load Fe3+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, collected by suction sediment, precipitation is rinsed with acetone repeatedly Thing 2 times, sediment are 26 DEG C in temperature, obtain water soluble negative load under the conditions of vacuum is -0.1MPa after vacuum drying oven drying Fe3+Sodium alginate hybrid material, there is in the hybrid material Fe of flame retardant effect3+Load capacity be 180mg/g.
By the water-soluble load Fe of preparation3+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 7% wet spinning solution, using wet spinning technology, obtains load Fe3+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 45 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 12% is molten Liquid, coagulation bath temperature are 45 DEG C, draw ratio 190%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.68cN/tex, line density 3.5dtex, limited oxygen index 36.8%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 9
One kind load Zn2+Sodium alginate fire resistance fibre preparation method, under the conditions of 50 DEG C, by mass percent concentration The aliphatic amine polyoxyethylene ether AC-1810's that aqueous solution for 0.5% sodium alginate is 5% with mass percent concentration is water-soluble Liquid mixes, and the molar ratio of sodium alginate and aliphatic amine polyoxyethylene ether AC-1810 are 1:0.8, sodium alginate and fatty amine polyoxy The relative molecular weight of vinethene AC-1810 is respectively 80000 and 1800, and when mixing accompanies by stirring, with the H of 0.12mol/L2SO4It is molten Liquid adjusts the pH value of system to 6, and the ZnCl that concentration is 0.05g/mL is then added dropwise into mixed liquor2Aqueous solution, ZnCl2With sea The molar ratio of mosanom is 0.8:1, stirred after being added dropwise, duration 1h, that is, obtain load Zn2+Sodium alginate it is miscellaneous Change material aqueous solution, its mass percent concentration is 2.2%, persistently stirs and adds precipitating reagent ethanol, and precipitating reagent ethanol is with bearing Carry Zn2+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, collected by suction sediment, it is heavy to be rinsed repeatedly with ethanol Starch 3 times, sediment are 29 DEG C in temperature, and water soluble negative is obtained after vacuum drying oven drying under the conditions of vacuum is 0.05MPa Carry Zn2+Sodium alginate hybrid material, there is in the hybrid material Zn of flame retardant effect2+Load capacity be 27mg/g.
By the water-soluble load Zn of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 8% wet spinning solution, using wet spinning technology, obtains load Zn2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 50 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 14% is molten Liquid, coagulation bath temperature are 50 DEG C, draw ratio 200%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.88cN/tex, line density 3.4dtex, limited oxygen index 36.1%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 10
A kind of loaded Cu2+Sodium alginate fire resistance fibre preparation method, under the conditions of 20 DEG C, by mass percent concentration The aliphatic amine polyoxyethylene ether AC-1812's that aqueous solution for 2.5% sodium alginate is 5% with mass percent concentration is water-soluble Liquid mixes, and the molar ratio of sodium alginate and aliphatic amine polyoxyethylene ether AC-1812 are 1:0.6, sodium alginate and fatty amine polyoxy The relative molecular weight of vinethene AC-1812 is respectively 10000 and 1900, and when mixing accompanies by stirring, with the H of 0.15mol/L2SO4It is molten Liquid adjusts the pH value of system to 4, and the CuSO that concentration is 0.16g/mL is then added dropwise into mixed liquor4Aqueous solution, CuSO4With sea The molar ratio of mosanom is 0.6:1, stirred after being added dropwise, duration 1.5h, that is, obtain loaded Cu2+Sodium alginate Hybrid material aqueous solution, its mass percent concentration be 4.2%, persistently stir and add precipitating reagent acetone, precipitating reagent acetone with Loaded Cu2+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, collected by suction sediment, is rinsed repeatedly with acetone Sediment 2 times, sediment are 30 DEG C in temperature, and water solubility is obtained after vacuum drying oven drying under the conditions of vacuum is 0.02MPa Loaded Cu2+Sodium alginate hybrid material, there is in the hybrid material Cu of flame retardant effect2+Load capacity be 23mg/g.
By the water-soluble loaded Cu of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 10% wet spinning solution, using wet spinning technology, obtains loaded Cu2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature is 55 DEG C, and coagulation bath composition is that the calcium chloride that mass percent concentration is 15% is molten Liquid, coagulation bath temperature are 10 DEG C, draw ratio 210%.Mechanical property and combustibility analysis are carried out to obtained alginate fibre, Test result is：Tensile strength is 3.77cN/tex, line density 3.5dtex, limited oxygen index 35.8%.Illustrate to pass through this Sodium alginate fiber prepared by inventive method has more excellent intensity and inherent flame retardancy.
Embodiment 11
A kind of loaded Ag+Sodium alginate fire resistance fibre preparation method, under the conditions of 40 DEG C, by mass percent concentration The aliphatic amine polyoxyethylene ether AC-1815's that aqueous solution for 2.8% sodium alginate is 6% with mass percent concentration is water-soluble Liquid mixes, and the molar ratio of sodium alginate and aliphatic amine polyoxyethylene ether AC-1815 are 1:0.8, sodium alginate and fatty amine polyoxy The relative molecular weight of vinethene AC-1815 is respectively 32000 and 900, and when mixing accompanies by stirring, with the HNO of 0.1mol/L3Solution The pH value of system is adjusted to 6, the AgNO that concentration is 0.18g/mL is then added dropwise into mixed liquor3Aqueous solution, AgNO3With seaweed The molar ratio of sour sodium is 3:1, stirred after being added dropwise, duration 2h, that is, obtain loaded Ag+Sodium alginate hydridization material Expect aqueous solution, its mass percent concentration is 3%, persistently stirs and adds precipitating reagent ethanol, precipitating reagent ethanol and loaded Ag+'s The volume ratio of the hybrid material aqueous solution of sodium alginate is 4:1, collected by suction sediment rinses sediment with ethanol 2 times repeatedly, Sediment is 26 DEG C in temperature, and obtaining water soluble negative after vacuum drying oven drying under the conditions of vacuum is 0.01MPa carries Ag+Sea Mosanom hybrid material, has the Ag of flame retardant effect in the hybrid material+Load capacity be 148mg/g.
By the water-soluble loaded Ag of preparation+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 10% wet spinning solution, using wet spinning technology, obtains loaded Ag+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 60 DEG C, coagulation bath composition be mass percent concentration be 1% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 1:1, coagulation bath temperature is 15 DEG C, draw ratio 220%.It is right Obtained alginate fibre carries out mechanical property and combustibility analysis, test result are：Tensile strength is 4.12cN/tex, and line is close Spend for 3.5dtex, limited oxygen index 34.9%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more excellent Good intensity and inherent flame retardancy.
Embodiment 12
One kind load Fe2+Sodium alginate fire resistance fibre preparation method, under the conditions of 30 DEG C, by mass percent concentration The aliphatic amine polyoxyethylene ether AC-1205's that aqueous solution for 0.9% sodium alginate is 8% with mass percent concentration is water-soluble Liquid mixes, and the molar ratio of sodium alginate and aliphatic amine polyoxyethylene ether AC-1205 are 1:1, sodium alginate and fatty amine polyoxy second The relative molecular weight of alkene ether AC-1205 is respectively 28000 and 1200, and when mixing accompanies by stirring, with the HNO of 0.15mol/L3Solution The pH value of system is adjusted to 5, the FeCl that concentration is 0.006g/mL is then added dropwise into mixed liquor2Aqueous solution, FeCl2With seaweed The molar ratio of sour sodium is 0.6:1, stirred after being added dropwise, duration 1h, that is, obtain load Fe2+Sodium alginate hydridization Material aqueous solution, its mass percent concentration are 2.8%, persistently stir and add precipitating reagent ethanol, precipitating reagent ethanol and load Fe2+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, collected by suction sediment, precipitation is rinsed with ethanol repeatedly Thing 3 times, sediment are 25 DEG C in temperature, obtain water soluble negative load under the conditions of vacuum is -0.09MPa after vacuum drying oven drying Fe2+Sodium alginate hybrid material, there is in the hybrid material Fe of flame retardant effect2+Load capacity be 34mg/g.
By the water-soluble load Fe of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 3% wet spinning solution, using wet spinning technology, obtains load Fe2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 10 DEG C, coagulation bath composition be mass percent concentration be 8% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 2.5:1, coagulation bath temperature is 22 DEG C, draw ratio 210%. Mechanical property is carried out to obtained alginate fibre and combustibility analysis, test result are：Tensile strength is 3.95cN/tex, line Density is 3.47dtex, limited oxygen index 34.5%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Add excellent intensity and inherent flame retardancy.
Embodiment 13
One kind load Fe3+Sodium alginate fire resistance fibre preparation method, under the conditions of 60 DEG C, by mass percent concentration The aqueous solution for the polyetheramine T5000 that aqueous solution for 3% sodium alginate is 10% with mass percent concentration mixes, alginic acid The molar ratio of sodium and polyetheramine T5000 are 1:1, the relative molecular weight of sodium alginate and polyetheramine T5000 are respectively 36000 Hes 5000, when mixing, accompanies by stirring, with the HNO of 0.2mol/L3Solution adjusts the pH value of system to 4, is then dripped into mixed liquor Add the FeCl that concentration is 2g/mL3Aqueous solution, FeCl3Molar ratio with sodium alginate is 10:1, stirred after being added dropwise, when continuing Between be 2h, that is, obtain load Fe3+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 8.3%, persistently stir Mix and add precipitating reagent ethanol, precipitating reagent ethanol and load Fe3+Sodium alginate hybrid material aqueous solution volume ratio be 2: 1, collected by suction sediment rinses sediment with ethanol 3 times repeatedly, and sediment is 30 DEG C in temperature, and vacuum is 0.09MPa bars Water soluble negative is obtained after vacuum drying oven drying carry Fe under part3+Sodium alginate hybrid material, have in the hybrid material fire-retardant The Fe of effect3+Load capacity be 49mg/g.
By the water-soluble load Fe of preparation3+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 1% wet spinning solution, using wet spinning technology, obtains load Fe3+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 15 DEG C, coagulation bath composition be mass percent concentration be 3% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 1.5:1, coagulation bath temperature is 25 DEG C, draw ratio 240%. Mechanical property is carried out to obtained alginate fibre and combustibility analysis, test result are：Tensile strength is 4.56cN/tex, line Density is 3.17dtex, limited oxygen index 36.2%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Add excellent intensity and inherent flame retardancy.
Embodiment 14
One kind load Zn2+Sodium alginate fire resistance fibre preparation method, under the conditions of 40 DEG C, by mass percent concentration The aliphatic amine polyoxyethylene ether AC-1215's that aqueous solution for 1.2% sodium alginate is 3% with mass percent concentration is water-soluble Liquid mixes, and the molar ratio of sodium alginate and aliphatic amine polyoxyethylene ether AC-1215 are 1:0.5, sodium alginate and fatty amine polyoxy The relative molecular weight of vinethene AC-1215 is respectively 53000 and 800, and when mixing accompanies by stirring, with the HNO of 0.25mol/L3It is molten Liquid adjusts the pH value of system to 5, and the ZnCl that concentration is 0.12g/mL is then added dropwise into mixed liquor2Aqueous solution, ZnCl2With sea The molar ratio of mosanom is 2:1, stirred after being added dropwise, duration 1h, that is, obtain load Zn2+Sodium alginate hydridization Material aqueous solution, its mass percent concentration are 2.9%, persistently stir and add precipitating reagent acetone, precipitating reagent acetone and load Zn2+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, collected by suction sediment, precipitation is rinsed with acetone repeatedly Thing 2 times, sediment are 26 DEG C in temperature, obtain water soluble negative load under the conditions of vacuum is -0.1MPa after vacuum drying oven drying Zn2+Sodium alginate hybrid material, there is in the hybrid material Zn of flame retardant effect2+Load capacity be 215mg/g.
By the water-soluble load Zn of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 2% wet spinning solution, using wet spinning technology, obtains load Zn2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 20 DEG C, coagulation bath composition be mass percent concentration be 3% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 1.8:1, coagulation bath temperature is 28 DEG C, draw ratio 250%. Mechanical property is carried out to obtained alginate fibre and combustibility analysis, test result are：Tensile strength is 3.56cN/tex, line Density is 3.22dtex, limited oxygen index 35.9%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Add excellent intensity and inherent flame retardancy.
Embodiment 15
A kind of loaded Cu2+Sodium alginate fire resistance fibre preparation method, under the conditions of 30 DEG C, by mass percent concentration The aqueous solution for the n-butylamine that aqueous solution for 1.6% sodium alginate is 7% with mass percent concentration mixes, sodium alginate with The molar ratio of n-butylamine is 1:0.9, the relative molecular weight of sodium alginate and n-butylamine is respectively 80000 and 73.14, companion during mixing With stirring, with the HNO of 0.3mol/L3Solution adjusts the pH value of system to 5, and it is 0.8g/ that concentration is then added dropwise into mixed liquor The CuSO of mL4Aqueous solution, CuSO4Molar ratio with sodium alginate is 6:1, stirred after being added dropwise, duration 1h, to obtain the final product To loaded Cu2+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 10.5%, persistently stir and add it is heavy Shallow lake agent ethanol, precipitating reagent ethanol and loaded Cu2+Sodium alginate hybrid material aqueous solution volume ratio be 3:1, collected by suction Sediment, sediment is rinsed with ethanol 3 times repeatedly, and sediment is 28 DEG C in temperature, and vacuum is dried under the conditions of vacuum is 0.09MPa Water soluble negative, which is obtained, after case drying carries Cu2+Sodium alginate hybrid material, there is in the hybrid material Cu of flame retardant effect2+ Load capacity be 825mg/g.
By the water-soluble loaded Cu of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 5% wet spinning solution, using wet spinning technology, obtains loaded Cu2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 30 DEG C, coagulation bath composition be mass percent concentration be 5% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 2:1, coagulation bath temperature is 30 DEG C, draw ratio 260%.It is right Obtained alginate fibre carries out mechanical property and combustibility analysis, test result are：Tensile strength is 3.99cN/tex, and line is close Spend for 3.22dtex, limited oxygen index 35.7%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Excellent intensity and inherent flame retardancy.
Embodiment 16
A kind of loaded Ag+Sodium alginate fire resistance fibre preparation method, under the conditions of 20 DEG C, by mass percent concentration The aqueous solution for the n-amylamine that aqueous solution for 2.4% sodium alginate is 6% with mass percent concentration mixes, sodium alginate with The molar ratio of n-amylamine is 1:0.4, the relative molecular weight of sodium alginate and n-amylamine is respectively 80000 and 87.16, companion during mixing With stirring, the pH value of system is adjusted to 6 with the HCl solution of 0.1mol/L, it is 0.06g/ that concentration is then added dropwise into mixed liquor The AgNO of mL3Aqueous solution, AgNO3Molar ratio with sodium alginate is 0.8:1, stirred after being added dropwise, duration 2h, i.e., Obtain loaded Ag+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 2.5%, persistently stir and add Precipitating reagent acetone, precipitating reagent acetone and loaded Ag+Sodium alginate hybrid material aqueous solution volume ratio be 3:1, filter and receive Collect sediment, rinse sediment repeatedly with acetone 2 times, sediment is 29 DEG C in temperature, and vacuum is vacuum under the conditions of 0.09MPa Water soluble negative is obtained after oven drying and carries Ag+Sodium alginate hybrid material, there is in the hybrid material Ag of flame retardant effect+ Load capacity be 119mg/g.
By the water-soluble loaded Ag of preparation+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 6% wet spinning solution, using wet spinning technology, obtains loaded Ag+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 40 DEG C, coagulation bath composition be mass percent concentration be 9% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 1:1, coagulation bath temperature is 34 DEG C, draw ratio 270%.It is right Obtained alginate fibre carries out mechanical property and combustibility analysis, test result are：Tensile strength is 4.26cN/tex, and line is close Spend for 3.5dtex, limited oxygen index 35.1%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more excellent Good intensity and inherent flame retardancy.
Embodiment 17
One kind load Fe2+Sodium alginate fire resistance fibre preparation method, under the conditions of 25 DEG C, by mass percent concentration The aqueous solution for the n-hexylamine that aqueous solution for 0.8% sodium alginate is 5% with mass percent concentration mixes, sodium alginate with The molar ratio of n-hexylamine is 1:0.7, the relative molecular weight of sodium alginate and n-hexylamine is respectively 21000 and 101.19, during mixing Stirring is accompanied by, is adjusted the pH value of system to 4 with the HCl solution of 0.3mol/L, concentration is then added dropwise into mixed liquor is The FeCl of 0.08g/mL2Aqueous solution, FeCl2Molar ratio with sodium alginate is 3.5:1, stirred after being added dropwise, the duration is 2h, that is, obtain load Fe2+Sodium alginate hybrid material aqueous solution, its mass percent concentration is 0.5%, and lasting stirring is simultaneously Add precipitating reagent acetone, precipitating reagent acetone and load Fe2+Sodium alginate hybrid material aqueous solution volume ratio be 3:1, take out Sediment is collected in filter, rinses sediment repeatedly with acetone 3 times, and sediment is 29 DEG C in temperature, under the conditions of vacuum is -0.1MPa Water soluble negative, which is obtained, after vacuum drying oven drying carries Fe2+Sodium alginate hybrid material, there is flame retardant effect in the hybrid material Fe2+Load capacity be 795mg/g.
By the water-soluble load Fe of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 8% wet spinning solution, using wet spinning technology, obtains load Fe2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 45 DEG C, coagulation bath composition be mass percent concentration be 10% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 3:1, coagulation bath temperature is 35 DEG C, draw ratio 280%.It is right Obtained alginate fibre carries out mechanical property and combustibility analysis, test result are：Tensile strength is 3.86cN/tex, and line is close Spend for 2.77dtex, limited oxygen index 34.9%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Excellent intensity and inherent flame retardancy.
Embodiment 18
One kind load Fe3+Sodium alginate fire resistance fibre preparation method, under the conditions of 50 DEG C, by mass percent concentration The aqueous solution for the n-hexylamine that aqueous solution for 2.6% sodium alginate is 5% with mass percent concentration mixes, sodium alginate with The molar ratio of n-hexylamine is 1:0.5, the relative molecular weight of sodium alginate and n-hexylamine is respectively 40000 and 101.19, during mixing Stirring is accompanied by, with the H of 0.05mol/L2SO4Solution adjusts the pH value of system to 6, and concentration is then added dropwise into mixed liquor is The FeCl of 0.5g/mL3Aqueous solution, FeCl3Molar ratio with sodium alginate is 5:1, stirred after being added dropwise, duration 1h, Obtain load Fe3+Sodium alginate hybrid material aqueous solution, its mass percent concentration is 7.3%, it is lasting stir simultaneously plus Enter precipitating reagent ethanol, precipitating reagent ethanol and load Fe3+Sodium alginate hybrid material aqueous solution volume ratio be 2:1, filter Sediment is collected, rinses sediment repeatedly with ethanol 2 times, sediment is 27 DEG C in temperature, under the conditions of vacuum is -0.09MPa Water soluble negative, which is obtained, after vacuum drying oven drying carries Fe3+Sodium alginate hybrid material, there is flame retardant effect in the hybrid material Fe3+Load capacity be 669mg/g.
By the water-soluble load Fe of preparation3+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 9% wet spinning solution, using wet spinning technology, obtains load Fe3+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 50 DEG C, coagulation bath composition be mass percent concentration be 11% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 3:1, coagulation bath temperature is 38 DEG C, draw ratio 285%.It is right Obtained alginate fibre carries out mechanical property and combustibility analysis, test result are：Tensile strength is 4.11cN/tex, and line is close Spend for 3.12dtex, limited oxygen index 34.7%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Excellent intensity and inherent flame retardancy.
Embodiment 19
One kind load Zn2+Sodium alginate fire resistance fibre preparation method, under the conditions of 60 DEG C, by mass percent concentration The aqueous solution for the n-propylamine that aqueous solution for 1.4% sodium alginate is 3% with mass percent concentration mixes, sodium alginate with The molar ratio of n-propylamine is 1:0.3, the relative molecular weight of sodium alginate and n-propylamine is respectively 23800 and 59.11, companion during mixing With stirring, with the H of 0.15mol/L2SO4Solution adjusts the pH value of system to 5, and concentration is then added dropwise into mixed liquor is The ZnCl of 0.15g/mL2Aqueous solution, ZnCl2The molar ratio of aqueous solution and sodium alginate is 0.6:1, stir, continue after being added dropwise Time is 1h, that is, obtains load Zn2+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 2.1%, continue Stir and add precipitating reagent ethanol, precipitating reagent ethanol and load Zn2+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction sediment rinses sediment with ethanol 3 times repeatedly, and sediment is 26 DEG C in temperature, vacuum 0.09MPa Under the conditions of vacuum drying oven drying after i.e. obtain water soluble negative carry Zn2+Sodium alginate hybrid material, there is in the hybrid material resistance The Zn of fuel efficiency fruit2+Load capacity be 246mg/g.
By the water-soluble load Zn of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 10% wet spinning solution, using wet spinning technology, obtains load Zn2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 60 DEG C, coagulation bath composition be mass percent concentration be 12% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 1:1, coagulation bath temperature is 40 DEG C, draw ratio 290%.It is right Obtained alginate fibre carries out mechanical property and combustibility analysis, test result are：Tensile strength is 3.57cN/tex, and line is close Spend for 3.27dtex, limited oxygen index 35.1%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Excellent intensity and inherent flame retardancy.
Embodiment 20
A kind of loaded Cu2+Sodium alginate fire resistance fibre preparation method, under the conditions of 20 DEG C, by mass percent concentration The aqueous solution for the polyetheramine D230 that aqueous solution for 2.9% sodium alginate is 4% with mass percent concentration mixes, alginic acid The molar ratio of sodium and polyetheramine D230 are 1:0.6, the relative molecular weight of sodium alginate and polyetheramine D230 are respectively 45000 Hes 230, when mixing, accompanies by stirring, with the HNO of 0.3mol/L3Solution adjusts the pH value of system to 6, is then added dropwise into mixed liquor Concentration is the CuSO of 0.5g/mL4Aqueous solution, CuSO4Molar ratio with sodium alginate is 3:1, stirred after being added dropwise, when continuing Between be 2h, that is, obtain loaded Cu2+Sodium alginate hybrid material aqueous solution, its mass percent concentration be 10.5%, continue Stir and add precipitating reagent ethanol, precipitating reagent ethanol and loaded Cu2+The volume ratio of hybrid material aqueous solution of sodium alginate be 4:1, collected by suction sediment rinses sediment with ethanol 3 times repeatedly, and sediment is 25 DEG C in temperature, and vacuum is -0.1MPa Under the conditions of vacuum drying oven drying after i.e. obtain water soluble negative carry Cu2+Sodium alginate hybrid material, there is in the hybrid material resistance The Cu of fuel efficiency fruit2+Load capacity be 544mg/g.
By the water-soluble loaded Cu of preparation2+Sodium alginate hybrid material be dissolved into deionized water, stir evenly, be made into Mass percent concentration is 5% wet spinning solution, using wet spinning technology, obtains loaded Cu2+Sodium alginate it is fire-retardant Fiber, spinning process condition are：Spinning temperature be 10 DEG C, coagulation bath composition be mass percent concentration be 15% calcium chloride with The mass ratio of zinc chloride mixed solution, calcium chloride and zinc chloride is 3:1, coagulation bath temperature is 50 DEG C, draw ratio 300%.It is right Obtained alginate fibre carries out mechanical property and combustibility analysis, test result are：Tensile strength is 3.83cN/tex, and line is close Spend for 3.22dtex, limited oxygen index 35.4%.The sodium alginate fiber for illustrating to be prepared by the method for the present invention has more Excellent intensity and inherent flame retardancy.

Claims (10)

1. a kind of sodium alginate fire resistance fibre of loaded metal ion, it is characterized in that：Pass through the sea of water soluble negative carrying metal ion Mosanom hybrid material is dissolved in water and prepares spinning solution to be made through wet spinning technology；The sea of the water soluble negative carrying metal ion Mosanom hybrid material is made of sodium alginate, the metal ion stablized agent molecule and have flame retardant effect；The water soluble negative In the sodium alginate hybrid material of carrying metal ion, the carboxyl of sodium alginate, stablize the amino of agent molecule and have flame retardant effect Metal ion between it is bonded by ionic bond and coordinate bond；
In the sodium alginate and the stable agent molecule, the sum of carboxyl-content, amino content and hydroxy radical content are more than or equal to institute State the 160% of the sum of the mole of sodium alginate and the stable agent molecule；
The carboxyl bonded by ionic bond and coordinate bond and the amino content bonded by ionic bond and coordinate bond it With 30% more than or equal to the sum of carboxyl in the sodium alginate and the stable agent molecule and amino mole；
Relative molecular weight >=10000 of the sodium alginate；
Relative molecular weight≤5000 of the stable agent molecule, are less than the alkyl streptamine of 6 carbon, polyetheramine D230, poly- for chain length Ether amines D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, fatty amine gather Ethylene oxide ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, fatty amine polyoxy second One kind in alkene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；The chain length Alkyl streptamine less than 6 carbon is n-propylamine, n-butylamine or n-amylamine；
The general structure of the sodium alginate hybrid material of the water soluble negative carrying metal ion is：
Wherein, strand repetitive unit number n>0；
Wherein, R is one kind in following functional group：Cation group, anionic group or polar nonionic group；It is described sun from Subbase group is tertiary amine base or quaternary ammonium group；The anionic group is carboxylic acid group；The polar nonionic group for hydroxyl, ether, Amino, amide groups, sulfydryl or halogen；
Mx+For the metal ion with flame retardant effect, the value of valence state x is 1~3, and the metal ion with flame retardant effect is： Ag+、Fe2+、Fe3+、Zn2+Or Cu2+。
2. the sodium alginate fire resistance fibre of a kind of loaded metal ion according to claim 1, it is characterised in that described steady Determine agent molecule and also include hydroxyl or carboxyl.
A kind of 3. sodium alginate fire resistance fibre of loaded metal ion according to claim 1, it is characterised in that the carboxylic Base is located at molecular backbone or side chain；The amino is located at molecular backbone or side chain.
4. the sodium alginate fire resistance fibre of a kind of loaded metal ion according to claim 1, it is characterised in that described steady Determine agent molecule main chain and further include element O, N or S.
A kind of 5. sodium alginate fire resistance fibre of loaded metal ion according to claim 1, it is characterised in that the water In the sodium alginate hybrid material of dissolubility loaded metal ion the load capacity of the metal ion with flame retardant effect for 10~ 825mg/g；The sodium alginate fire resistance fibre limited oxygen index of the loaded metal ion reaches more than 34%, and the stretching of fiber is strong Degree is more than 3.5cN/tex, and line density is 2.2~3.5dtex.
6. the preparation side of the sodium alginate fire resistance fibre such as a kind of loaded metal ion according to any one of claims 1 to 5 Method, it is characterized in that：Sodium alginate aqueous solution is mixed with containing the aqueous solution for stablizing agent molecule, adjusts the pH value of reaction system to 4 ~6, metal ion salt solution is then added dropwise into mixed liquor, is stirred after being added dropwise, obtains the alginic acid of loaded metal ion The hybrid material aqueous solution of sodium, persistently stirs and adds precipitating reagent, and sediment is collected by filtration, is obtained after drying precipitate water-soluble The sodium alginate hybrid material of property loaded metal ion；The sodium alginate hybrid material of water soluble negative carrying metal ion is dissolved into In deionized water, stir evenly, be made into wet spinning solution, using wet spinning technology, obtain the seaweed of loaded metal ion Sour sodium fire resistance fibre.
7. a kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion according to claim 6, its feature It is, the aqueous solution of sodium alginate is mixed with containing the aqueous solution for stablizing agent molecule, is under the conditions of 20~60 DEG C；Companion during mixing With stirring；The pH value for adjusting reaction system uses HCl solution, the H of 0.05~0.15mol/L of 0.1~0.3mol/L2SO4Solution Or the HNO of 0.1~0.3mol/L3Solution is adjusted；Metal ion salt solution stirs after being added dropwise, and the duration is 1~2h；It is heavy Starch drying is dried using vacuum drying oven.
8. a kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion according to claim 6, its feature It is, the metal ion salt solution is AgNO3、FeCl2、FeCl3、ZnCl2Or CuSO4Aqueous solution；The precipitating reagent is ethanol Or acetone.
9. a kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion according to claim 6, its feature It is, when the aqueous solution of the sodium alginate is mixed with containing the aqueous solution for stablizing agent molecule, sodium alginate is with stablizing agent molecule Molar ratio is 1:0.3~1；
The mass percent concentration of the sodium alginate aqueous solution is 0.5%~3%；
The mass percent concentration containing the aqueous solution for stablizing agent molecule is 3%~10%；
The concentration of the metal ion salt solution is 0.005~2g/mL；
The molar ratio of the metal cation salt and sodium alginate is 0.1~10:1；
The mass percent concentration of the hybrid material aqueous solution of the sodium alginate of the loaded metal ion for 0.5%~ 10.5%；
The volume ratio of the aqueous solution of the sodium alginate hybrid material of the precipitating reagent and loaded metal ion is 2~4:1；
The temperature of the drying precipitate is 25~30 DEG C, and vacuum is 0.09~-0.1MPa.
10. a kind of preparation method of the sodium alginate fire resistance fibre of loaded metal ion according to claim 6, its feature It is, the wet spinning technology is：In spinning solution, the mass percent of the sodium alginate hybrid material of loaded metal ion Concentration is 1~10%, and spinning temperature is 10~60 DEG C, and coagulating bath is that the calcium chloride that mass percent concentration is 1%~15% is molten Liquid or calcium chloride and zinc chloride mixed solution, calcium chloride and zinc chloride mixed solution that mass percent concentration is 1%~15% The mass ratio 1~3 of middle calcium chloride and zinc chloride:1, coagulation bath temperature is 10~50 DEG C, and draw ratio is 120%~300%.
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