CN106637467A - A boron-containing nanometer zinc oxide/polyvinyl alcohol composite fiber and a preparing method thereof - Google Patents
A boron-containing nanometer zinc oxide/polyvinyl alcohol composite fiber and a preparing method thereof Download PDFInfo
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- CN106637467A CN106637467A CN201610986204.6A CN201610986204A CN106637467A CN 106637467 A CN106637467 A CN 106637467A CN 201610986204 A CN201610986204 A CN 201610986204A CN 106637467 A CN106637467 A CN 106637467A
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- Prior art keywords
- polyvinyl alcohol
- zine oxide
- nano zine
- composite fiber
- acid
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
A boron-containing nanometer zinc oxide/polyvinyl alcohol composite fiber and a preparing method thereof are provided. The method includes 1) a step of dissolving polyvinyl alcohol into water, heating the mixture to raise the temperature of the mixture, adding boric acid into the mixture, fully mixing the mixture, then adding nanometer zinc oxide, fully mixing the mixture, adjusting the pH value of the system, and performing filtration and deaeration to obtain a spinning solution; and 2) a step of subjecting the spinning solution in the step 1) to boron-containing alkaline wet spinning treatment, then performing neutralization, wet drafting, water washing and thermal treatment to obtain a semi-finished fiber product, washing the semi-finished fiber product with water and drying the product. The prepared composite fiber has excellent mechanical properties and antibacterial properties. The preparing method is simple in process, low in cost and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of boracic nano zine oxide/polyvinyl alcohol composite fiber and preparation method thereof, belongs to polyethylene
Alcohol composite fibre technology field.
Background technology
Nano zine oxide is nontoxic, tasteless, there is preferable biocompatibility to skin, and heat endurance is good, originally as white,
Can simply be coloured when product is fabricated to, therefore, the external used medicine of skin is often used as, there is convergence to skin, disappear
The functions such as inflammation, anti-corrosion, wrinkle resistant and protection.Nano zine oxide sunlight irradiation under can produce very active hydroxyl radical free radical,
Peroxide free radical and O2H free radicals, can destroy the multiplication capacity of microbial cell, reach suppression or kill bacterium
Effect.Nano zine oxide as antiseptic, have the advantages that it is nontoxic, long-acting, do not develop immunity to drugs, higher heat resistance, because
And good anti-microbial property is all shown in plastics, coating, fiber.Additionally, nano zine oxide acts not only as antiseptic,
Ultraviolet light screener is also used as, in being commonly used for cosmetics and fibrous material, so that material obtains anti-ultraviolet performance.
Nano zine oxide has wide market and tempting as a kind of new inorganic functional material in daily life and scientific research field
Application prospect.
Composite fibre is the physical modification fiber that the sixties in 20th century grows up, and belongs to one kind of multicomponent fibre, main
It is used for woollen blanket, knitting wool, wool fabric, warming wadding suede filler, silk fabric, non-weaving cloth, medical and hygiene article and special work
Take.At present the conventional preparation method of composite fibre has dry method melt spinning and electrostatic spinning, and preparation technology is more complicated, and
The composite fibre mechanical property of production is poor.Patent publication No discloses a kind of anti-for the Chinese invention patent of CN103388190A
The preparation method of the degradable polyvinyl of bacterium, including by the complexing nano copper dissolution of polyvinyl alcohol, boric acid and 8～12% solid contents 80
In～90 DEG C of hot water, plasticity chelant thing is generated as spinning solution, the spinning solution is extruded by spinneret, and make ejection
Spinning solidifies in the alkaline coagulating bath that sodium sulphate and NaOH are formed, and obtains polyvinyl silk, and fiber prepared by the method has
Good degradable and anti-microbial property, but it is relatively costly, and the mechanical property for generating fiber is poor.Therefore it provides a kind of technique letter
The preparation method of the good composite fibre of single, with low cost, mechanical property is extremely urgent.
The content of the invention
It is an object of the invention to provide a kind of preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber, the party
Composite fibre obtained in method can take into account excellent anti-microbial property and mechanical property.
Second object of the present invention is to provide boracic nano zine oxide/polyvinyl alcohol obtained in a kind of said method and is combined
Fiber.
In order to realize object above, a kind of preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber of the invention
Comprise the following steps：
1) 94～99 parts of polyvinyl alcohol are dissolved in 400～900 parts of water, after being heated to 95～100 DEG C, add 0.1
～1 part of boric acid, being well mixed is completely dissolved boric acid, obtains poly-vinyl alcohol solution, adds 1～5 part of nano zine oxide, and mixing is equal
Even rear regulation system pH value is 3～6, Jing after filtration, deaeration, spinning solution is obtained；
2) by step 1) gained spinning solution carry out wet spinning process, neutralized afterwards, wet drawing-off, washing, heat treatment
Semifinished fibre is obtained, then Jing is washed, is drying to obtain.
Above-mentioned steps 1) in water used be 40～60 DEG C of warm water.
The nano zine oxide average grain diameter is 30～100nm.
The degree of polymerization of the polyvinyl alcohol is 1700～1800, alcoholysis degree >=99%.
The step 1) in adjust pH value used by acid be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, acrylic acid, first
Any one in base acrylic acid, polyacrylic acid, polymethylacrylic acid, ascorbic acid or any combination；Alkali used is hydrogen-oxygen
Change sodium, potassium hydroxide, diethanol amine, triethanolamine, ethanol sodium sulfonate, in disodium ethylene diamine tetraacetate any one or arbitrarily
Combination.
The step 1) mode being well mixed after nano zine oxide is added to stir and evenly mix, mixing time is 2～4h.
The step 1) in gained spinning solution polyvinyl alcohol and nano zine oxide mass concentration sum be 10～20%.
The step 2) in wet spinning process when adopt saltcake coagulating bath, wherein the mass concentration of sodium sulphate be 340～
420g/L。
The temperature of the saltcake coagulating bath is 40～50 DEG C, and pH value is 8～12.
The step 2) in wet drawing-off be 1.5～2 times of drawing-off in 88～92 DEG C of saltcake coagulating baths, wherein, sodium sulphate
Mass concentration is 350～390g/L.
The step 2) in heat treatment be under the conditions of xeothermic 210～220 DEG C, stretch 1.5～2 times.
The step 2) in gained boracic nano zine oxide/polyvinyl alcohol composite fiber carry out oiling treatment or cut-off part
Reason carries out cut-off part reason after oiling treatment.
The technical scheme of the boracic nano zine oxide/polyvinyl alcohol composite fiber of the present invention is as follows：
A kind of boracic nano zine oxide/polyvinyl alcohol composite fiber, is obtained using said method.
Of the present invention boracic nano zine oxide/polyvinyl alcohol composite fiber preparation process is raw materials used is convenient source, comes
Source is extensive, cheap, and technological process is simple, and equipment investment is little, and cost low yield is big, it is easy to accomplish industrialized production.
Boracic nano zine oxide/polyvinyl alcohol composite fiber preparation process of the present invention has used nano zine oxide, nano oxygen
Change zinc nontoxic, tasteless, there is preferable biocompatibility to skin, with the effect for suppressing or killing bacterium.In addition, using this
The compound fibre of boracic nano zine oxide/polyvinyl alcohol that bright boracic nano zine oxide/polyvinyl alcohol composite fiber preparation method is obtained
The mechanical property that dimension has had：Fiber number does fracture strength for 6.50～8.50cN/dtex, introductory die in 1.42～1.55dtex
Amount reaches 130～150cN/dtex.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1 part of nano zine oxide, 99 parts of polyvinyl alcohol, wherein 0.6 part of boric acid, nano zine oxide average grain diameter are 35nm, polyvinyl alcohol
The degree of polymerization is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 50 DEG C of water, after being heated to 95 DEG C, to keep system temperature 99 parts of polyvinyl alcohol to be dissolved in into 900 parts of temperature
Degree is constant, adds 0.6 part of boric acid while stirring afterwards, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 1 part of nano oxygen
Change zinc, be sufficiently stirred for 2h, after being well mixed, add hydrochloric acid regulation system pH value to be 4, Jing after filtration, standing and defoaming 6h, be obtained poly-
Vinyl alcohol and the spinning solution that nano zine oxide mass concentration sum is 10%；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 380g/L) temperature is 44 DEG C, and pH value is 10；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.5 times of the drawing-off in 90 DEG C of metabisulfite solution (mass concentration is 370g/L), heat treatment
It is at xeothermic 210 DEG C, to stretch 1.5 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 2
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1.5 parts of nano zine oxide, 99 parts of polyvinyl alcohol, 0.6 part of boric acid, wherein nano zine oxide average grain diameter be 35nm, polyvinyl alcohol
The degree of polymerization be 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 50 DEG C of water, after being heated to 95 DEG C, to keep system temperature 99 parts of polyvinyl alcohol to be dissolved in into 900 parts of temperature
Degree is constant, adds 0.6 part of boric acid while stirring afterwards, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 1.5 parts of nanometers
Zinc oxide, is sufficiently stirred for 3h, after being well mixed, adds formic acid regulation system pH value to be 4, Jing after filtration, standing and defoaming 6h, is obtained
Polyvinyl alcohol and the spinning solution that nano zine oxide mass concentration sum is 10%；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 340g/L) temperature is 44 DEG C, and pH value is 10；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.5 times of the drawing-off in 90 DEG C of metabisulfite solution (mass concentration is 350g/L), heat treatment
It is at xeothermic 210 DEG C, to stretch 1.5 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 3
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1 part of nano zine oxide, 99 parts of polyvinyl alcohol, wherein 0.6 part of boric acid, nano zine oxide average grain diameter are 48nm, polyvinyl alcohol
The degree of polymerization is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 50 DEG C of water, after being heated to 95 DEG C, to keep system temperature 99 parts of polyvinyl alcohol to be dissolved in into 900 parts of temperature
Degree is constant, adds 0.6 part of boric acid while stirring afterwards, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 1 part of nano oxygen
Change zinc, be sufficiently stirred for 4h, after being well mixed, add ascorbic acid regulation system pH value to be 4, Jing after filtration, standing and defoaming 6h, system
Polyvinyl alcohol and spinning solution that nano zine oxide mass concentration sum is 10%；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 420g/L) temperature is 44 DEG C, and pH value is 10；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.5 times of the drawing-off in 90 DEG C of metabisulfite solution (mass concentration is 390g/L), heat treatment
It is at xeothermic 210 DEG C, to stretch 1.5 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 4
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1.5 parts of nano zine oxide, 99 parts of polyvinyl alcohol, 0.6 part of boric acid, wherein nano zine oxide average grain diameter be 48nm, polyvinyl alcohol
The degree of polymerization be 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 50 DEG C of water, after being heated to 95 DEG C, to keep system temperature 99 parts of polyvinyl alcohol to be dissolved in into 900 parts of temperature
Degree is constant, adds 0.6 part of boric acid while stirring afterwards, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 1.5 parts of nanometers
Zinc oxide, is sufficiently stirred for 2.5h, after being well mixed, adds polyacrylic acid regulation system pH value to be 4, Jing filtrations, standing and defoaming 6h
Afterwards, polyvinyl alcohol and spinning solution that nano zine oxide mass concentration sum is 10% is obtained；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 390g/L) temperature is 44 DEG C, and pH value is 10；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.5 times of the drawing-off in 90 DEG C of metabisulfite solution (mass concentration is 360g/L), heat treatment
It is at xeothermic 210 DEG C, to stretch 1.5 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 5
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1 part of nano zine oxide, 99 parts of polyvinyl alcohol, wherein 0.1 part of boric acid, nano zine oxide average grain diameter are 60nm, polyvinyl alcohol
The degree of polymerization is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 40 DEG C of water, after being heated to 96 DEG C, to keep system temperature 99 parts of polyvinyl alcohol to be dissolved in into 400 parts of temperature
Degree is constant, adds 0.1 part of boric acid while stirring afterwards, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 1 part of nano oxygen
Change zinc, be sufficiently stirred for 3h, after being well mixed, add sulfuric acid regulation system pH value to be 3, Jing after filtration, standing and defoaming 6h, be obtained poly-
Vinyl alcohol and the spinning solution that nano zine oxide mass concentration sum is 20%；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 350g/L) temperature is 40 DEG C, and pH value is 8；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 2 times of the drawing-off in 88 DEG C of metabisulfite solution (mass concentration is 380g/L), and heat treatment is
At xeothermic 213 DEG C, 1.8 times are stretched；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 6
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1.5 parts of nano zine oxide, 98.5 parts of polyvinyl alcohol, 0.3 part of boric acid, wherein nano zine oxide average grain diameter be 60nm, polyethylene
The degree of polymerization of alcohol is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 47 DEG C of water, after being heated to 97 DEG C, to keep system 98.5 parts of polyvinyl alcohol to be dissolved in into 426 parts of temperature
Temperature constant, adds while stirring afterwards 0.3 part of boric acid, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 1.5 parts and receives
Rice zinc oxide, is sufficiently stirred for 4h, and after being well mixed, addition methacrylic acid regulation system pH value is filtered for 3.5, Jing, standing is de-
After bubble 6h, polyvinyl alcohol and spinning solution that nano zine oxide mass concentration sum is 19% is obtained；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 360g/L) temperature is 41 DEG C, and pH value is 11；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.7 times of the drawing-off in 92 DEG C of metabisulfite solution (mass concentration is 355g/L), heat treatment
It is at xeothermic 220 DEG C, to stretch 1.9 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 7
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
2 parts of nano zine oxide, 98 parts of polyvinyl alcohol, wherein 0.4 part of boric acid, nano zine oxide average grain diameter are 60nm, polyvinyl alcohol
The degree of polymerization is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 49 DEG C of water, after being heated to 98 DEG C, to keep system temperature 98 parts of polyvinyl alcohol to be dissolved in into 482 parts of temperature
Degree is constant, adds 0.4 part of boric acid while stirring afterwards, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 2 parts of nano oxygens
Change zinc, be sufficiently stirred for 3h, after being well mixed, add acrylic acid regulation system pH value to be 4.5, Jing after filtration, standing and defoaming 6h, system
Polyvinyl alcohol and spinning solution that nano zine oxide mass concentration sum is 17%；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 370g/L) temperature is 42 DEG C, and pH value is 9；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.8 times of the drawing-off in 89 DEG C of metabisulfite solution (mass concentration is 365g/L), heat treatment
It is at xeothermic 215 DEG C, to stretch 2 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 8
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1 part of nano zine oxide, 98.5 parts of polyvinyl alcohol, 0.7 part of boric acid, wherein nano zine oxide average grain diameter be 100nm, polyvinyl alcohol
The degree of polymerization be 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 55 DEG C of water, after being heated to 99 DEG C, to keep system 98.5 parts of polyvinyl alcohol to be dissolved in into 567 parts of temperature
Temperature constant, adds while stirring afterwards 0.7 part of boric acid, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 1 part of nanometer
Zinc oxide, is sufficiently stirred for 3.5h, after being well mixed, adds diethanol amine regulation system pH value to be 5, Jing filtrations, standing and defoaming 6h
Afterwards, polyvinyl alcohol and spinning solution that nano zine oxide mass concentration sum is 15% is obtained；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 400g/L) temperature is 43 DEG C, and pH value is 10；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.6 times of the drawing-off in 91 DEG C of metabisulfite solution (mass concentration is 375g/L), heat treatment
It is at xeothermic 217 DEG C, to stretch 2 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 9
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
1.5 parts of nano zine oxide, 98.5 parts of polyvinyl alcohol, 0.8 part of boric acid, wherein nano zine oxide average grain diameter be 100nm, polyethylene
The degree of polymerization of alcohol is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) 98.5 parts of polyvinyl alcohol are dissolved in into 669 parts of temperature is in 58 DEG C of water, after being heated to 100 DEG C, keeping body
It is temperature constant, adds 0.8 part of boric acid while stirring afterwards, stir to poly-vinyl alcohol solution is completely dissolved to obtain, adds 1.5 parts
Nano zine oxide, is sufficiently stirred for 2h, after being well mixed, adds disodium ethylene diamine tetraacetate regulation system pH value to be 4.8, passes through
Filter, after standing and defoaming 6h, polyvinyl alcohol is obtained and spinning solution that nano zine oxide mass concentration sum is 13%；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 410g/L) temperature is 45 DEG C, and pH value is 12；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.9 times of the drawing-off in 89 DEG C of metabisulfite solution (mass concentration is 385g/L), heat treatment
It is at xeothermic 219 DEG C, to stretch 2 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 10
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
3 parts of nano zine oxide, 94 parts of polyvinyl alcohol, wherein 0.9 part of boric acid, nano zine oxide average grain diameter are 30nm, polyvinyl alcohol
The degree of polymerization is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 60 DEG C of water, after being heated to 99 DEG C, to keep system temperature 94 parts of polyvinyl alcohol to be dissolved in into 733 parts of temperature
Degree is constant, adds 0.9 part of boric acid while stirring afterwards, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 3 parts of nano oxygens
Change zinc, be sufficiently stirred for 4h, after being well mixed, add NaOH regulation system pH value to be 4.3, Jing after filtration, standing and defoaming 6h,
Prepared polyvinyl alcohol and the spinning solution that nano zine oxide mass concentration sum is 12%；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 420g/L) temperature is 47 DEG C, and pH value is 11；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 2 times of the drawing-off in 92 DEG C of metabisulfite solution (mass concentration is 390g/L), and heat treatment is
At xeothermic 214 DEG C, 1.6 times are stretched；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Embodiment 11
The present embodiment boracic nano zine oxide/polyvinyl alcohol composite fiber is mainly made up of the component of following mass fraction：
5 parts of nano zine oxide, 96 parts of polyvinyl alcohol, wherein 1.0 parts of boric acid, nano zine oxide average grain diameter are 30nm, polyvinyl alcohol
The degree of polymerization is 1700～1800, alcoholysis degree >=99%.
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber is comprised the following steps：
1) it is in 53 DEG C of water, after being heated to 100 DEG C, to keep system 96 parts of polyvinyl alcohol to be dissolved in into 809 parts of temperature
Temperature constant, adds while stirring afterwards 1.0 parts of boric acid, stirs to poly-vinyl alcohol solution is completely dissolved to obtain, and adds 5 parts of nanometers
Zinc oxide, is sufficiently stirred for 4h, after being well mixed, adds ethanol sodium sulfonate regulation system pH value to be 3.7, Jing filtrations, standing and defoaming
After 6h, polyvinyl alcohol and spinning solution that nano zine oxide mass concentration sum is 11% is obtained；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 340g/L) temperature is 50 DEG C, and pH value is 8；Neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, wherein, wet drawing-off is 1.5 times of the drawing-off in 88 DEG C of metabisulfite solution (mass concentration is 350g/L), heat treatment
It is at xeothermic 220 DEG C, to stretch 1.7 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Comparative example
This comparative example polyvinyl alcohol composite fiber is mainly made up of 100kg polyvinyl alcohol.
The preparation method of the polyvinyl alcohol composite fiber is comprised the following steps：
1) 100kg polyvinyl alcohol is dissolved in the water that 700kg temperature is 50 DEG C, after being heated to 90 DEG C, is stirred to complete
CL obtains poly-vinyl alcohol solution, adds NaOH regulation system pH value to be 7.5, and it is 95 to continue to heat maintenance system temperature
DEG C, Jing after filtration, standing and defoaming 6h, the spinning solution that polyvinyl alcohol mass concentration is 18% is obtained；
2) by step 1) gained spinning solution carries out wet spinning process, and specific experiment parameter is control saltcake coagulating bath
(sodium sulfate quality concentration is 380g/L) temperature is 50 DEG C, and pH value is 6.5；Neutralized afterwards, wet drawing-off, wash, be heat-treated
Semifinished fibre, wherein, wet drawing-off is 1.5 times of the drawing-off in 90 DEG C of metabisulfite solution (mass concentration is 370g/L), at heat
Reason is at xeothermic 210 DEG C, to stretch 1.5 times；Again Jing is washed, is dried, oils, cutting off gained Semifinished fibre, is obtained final product.
Experimental example
This experimental example have detected the mechanical property of embodiment 1～11 and the composite fibre obtained by comparative example, gained experiment
As a result it is as shown in table 1.
The mechanical performance data table of the composite fibre obtained by the embodiment 1～11 of table 1 and comparative example
From table 1 it follows that the mechanical strength of the composite fibre obtained by the embodiment of the present invention 1～11 be substantially better than it is right
Ratio, illustrates the excellent in mechanical performance of boracic nano zine oxide/polyvinyl alcohol composite fiber obtained by technical solution of the present invention, energy
Enough meet industrial processes requirement.
Claims (10)
1. a kind of preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber, it is characterised in that comprise the following steps：
1) 94～99 parts of polyvinyl alcohol are dissolved in 400～900 parts of water, after being heated to 95～100 DEG C, add 0.1～1 part
Boric acid, being well mixed is completely dissolved boric acid, obtains poly-vinyl alcohol solution, 1～5 part of nano zine oxide is added, after being well mixed
Regulation system pH value is 3～6, Jing after filtration, deaeration, spinning solution is obtained；
2) by step 1) gained spinning solution carries out wet spinning process, neutralized afterwards, wet drawing-off, wash, be heat-treated half
Finished fiber, then Jing washing, be drying to obtain.
2. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 1, its feature exists
In the nano zine oxide average grain diameter is 30～100nm.
3. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 1, its feature exists
In the degree of polymerization of the polyvinyl alcohol is 1700～1800, alcoholysis degree >=99%.
4. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 1, its feature exists
In step 1) in adjust pH value used by acid be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, acrylic acid, methacrylic acid,
Any one in polyacrylic acid, polymethylacrylic acid, ascorbic acid or any combination；Alkali used is NaOH, hydrogen-oxygen
Change any one in potassium, diethanol amine, triethanolamine, ethanol sodium sulfonate, disodium ethylene diamine tetraacetate or any combination.
5. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 1, its feature exists
In step 1) mode being well mixed after nano zine oxide is added to stir and evenly mix, mixing time is 2～4h.
6. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 1, its feature exists
In step 2) in wet spinning process when adopt saltcake coagulating bath, wherein the mass concentration of sodium sulphate be 340～420g/L.
7. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 6, its feature exists
In：The temperature of the saltcake coagulating bath is 40～50 DEG C, and pH value is 8～12.
8. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 1, its feature exists
In step 2) in wet drawing-off be 1.5～2 times of drawing-off in 88～92 DEG C of saltcake coagulating baths, wherein, the mass concentration of sodium sulphate is
350～390g/L.
9. the preparation method of boracic nano zine oxide/polyvinyl alcohol composite fiber according to claim 1, its feature exists
In step 2) in heat treatment be under the conditions of xeothermic 210～220 DEG C, stretch 1.5～2 times.
10. a kind of boracic nano zine oxide/polyvinyl alcohol composite fiber, it is characterised in that using as claim 1～9 it is arbitrary
The preparation method of the boracic nano zine oxide/polyvinyl alcohol composite fiber described in is obtained.
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