CN102677211B - Method for producing anti-ultraviolet functional polyvinyl chloride fiber - Google Patents
Method for producing anti-ultraviolet functional polyvinyl chloride fiber Download PDFInfo
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Abstract
The invention relates to a method for producing an anti-ultraviolet functional polyvinyl chloride fiber. Zn-Ni composite anti-ultraviolet powder is prepared by adopting transition metal nickel with excellent lightfastness and heat resistance to dope zinc oxide; an anti-ultraviolet polyvinyl chloride composite material is prepared by using in-situ polymerization of powder microemulsion and vinyl chloride, and the anti-ultraviolet functional polyvinyl chloride fiber is prepared by melt spinning. According to the method disclosed by the invention, the anti-ultraviolet functional polyvinyl chloride fiber produced by ultrahigh pressure melt spinning is utilized; the transition metal nickel is utilized to dope the zinc oxide; a PH regulator is added to control a reaction system into alkalinity, and the nickel dosage is increased, so the anti-ultraviolet ability of polrvinyl chloride is improved and the dispersibility of inorganic nano particles in a PVC (polyvinyl chloride) matrix is also improved.
Description
Technical field
The present invention relates to a kind of production method of anti-ultraviolet functional polyvinyl chloride fiber.
Background technology
Polyvinyl chloride have fire-retardant (fire-retardant value is more than 40), chemical proofing high (resistance to concentrated hydrochloric acid, concentration be 90% sulfuric acid, concentration be the nitric acid of 60% and the NaOH of concentration 20%), mechanical strength and the good advantage of electrical insulating property be widely used.Polyvinyl chloride fiber is also often selected because of these advantages is the raw material of artificial hair.But in recent years, because forest cover is destroyed serious, in addition a large amount of uses of the frequent and freon refrigerant of Sunspot Activities, the ultraviolet radiation mankind being faced with day by day strengthen, easily make skin pitch-dark, there is erythema, inflammation, skin aging, even cause cutaneum carcinoma.As can be seen here, research and development have the polyvinyl chloride composite materials of anti-ultraviolet functional, and not only can improve health and the comfortableness of hair products, and can increase the anti-ultraviolet functional of polyvinyl chloride product, increase the service life, benefit is a lot of.
Ultraviolet light material commercially available at present is mainly divided into inorganic matter ultraviolet light screener and organic matter ultraviolet light screener, because inorganic matter ultraviolet light screener has chemical inertness, use safety, all higher than organic matter ultraviolet light screener in heat endurance and solvent resistance, so exploitation low toxicity, efficiently inorganic matter ultraviolet light screener receive more concern.Nano zine oxide (ZnO) has absorption, scatters ultraviolet and photo-catalysis capability etc., is often used as anti-ultraviolet material.Patent of invention CN101429348 discloses a kind of preparation method of titanium dioxide-zinc oxide composite powder material, by the decomposition of subcarbonate on titanium dioxide granule surface of zinc, stop the sintering between particle, but the photostability of this composite need to improve.Patent of invention CN 1246443 discloses a kind of nanometer Zinc oxide powder and preparation method's bag of particles cladded by metallic compound on surface, this material has excellent UV Absorption characteristic, but low for the transmitance of visible ray, and not easily dispersed in lipophile matrix.Patent of invention CN 101898747 discloses a kind of preparation method of shielding ultraviolet rays zinc/cerium composite powder nano material, propose the composite anti-ultraviolet powder adopting hydrothermal deposition legal system for cerium dopping zinc oxide, but the method effectively can not solve inorganic uvioresistant powder dispersion problem in the base.Patent of invention CN 1224640C discloses a kind of method that nano titanium oxide original position prepares anti-ultraviolet radiation poly ester, nano titanium oxide is selected to be anti-ultraviolet functional additive, inorganic/organic complex surface modification is carried out to it, last polyester monocase in-situ copolymerization obtains anti-ultraviolet functional polyester composite, though the method solves nano titanium oxide dispersion problem in the polyester, but uvioresistant shielding index fails to reach very satisfied effect.Patent of invention CN101618850 and CN101898747 discloses the preparation method of a kind of ultraviolet light zinc zirconium nano composite material and zinc cerium nano composite material, though the anti-ultraviolet composite material prepared of the method can effective shielding ultraviolet rays, uvioresistant shielding also fails to reach more satisfied effect.
Summary of the invention
The object of this invention is to provide a kind of production method of anti-ultraviolet functional polyvinyl chloride fiber, employing nickel doping zinc-oxide prepares composite anti-ultraviolet material and situ aggregation method prepares PVC/ZnO anti-ultraviolet composite material, then with polychloroethylene blended spinning.In the method preparing nickel-zinc composite anti-ultraviolet material, adopt and add PH conditioning agent, to make reaction system meta-alkalescence, meanwhile, increase the consumption of nickel, to reach supersaturation.The advantage of the method is to use magnesium-yttrium-transition metal nickel doping zinc-oxide, not only because nickel has excellent fast light heat resistance, and the defect of zinc oxide lattice can be increased, increase the crystal face of uv reflectance, add PH conditioning agent, the pH value of reaction system is increased, and pH value is larger, the actual Ni ion concentration entering lattice is higher, and the lattice defect caused is just more; Increase the consumption of Ni, more Ni enters lattice, make distortion of lattice obvious, and along with the doping of Ni is close to saturation state, excessive Ni generate the NiO of cube hexahedron structure, the crystal boundary formed between itself and the ZnO of hexagonal crystallographic texture, can more multiple reflection ultraviolet light, thus strengthen the ability of shielding ultraviolet rays, secondly, use in-situ polymerization to prepare the method for uvioresistant PVC, zinc oxide particles can be solved dispersed not good and affect the defect of properties of product in matrix PVC.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber of the present invention, concrete steps are as follows:
Be uvioresistant poly vinyl chloride 100 weight portion of 750 ~ 1000, the non-sulphur organic system heat stabilizer of 0.05 ~ 2 weight portion, the lubricant polyethylene wax of 0.01 ~ 1 weight portion and the antioxidant of 0.01 ~ 1 weight portion by the degree of polymerization, fully mix 0.5 ~ 1h in 60 ~ 70 DEG C and form mixture, extruder type spinning machine is injected after metering, super-pressure production anti-ultraviolet functional polyvinyl chloride fiber, spinning machine head pressure is 800 ~ 1000kg/cm
2effectively can improve the mobility of polyvinyl chloride, spinning temperature, at 160 ~ 170 DEG C, adds hot-stretch in an oven, draw ratio is 5 ~ 8 times, draft temperature is 70 ~ 160 DEG C, finally heat-treats and oiling treatment, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent to be main finish component, oiled before fiber densification, second adopts antistatic additive to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.15wt% ~ 0.25wt% of polyvinyl chloride fiber; Heat treatment temperature is 100 ~ 140 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber;
Described uvioresistant poly vinyl chloride is obtained by following steps:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:50 ~ 1, Zn (NO
3)
2with the mol ratio of hexadecyltrimethylammonium chloride be 100:1 ~ 0.01 wherein, hexadecyltrimethylammonium chloride uses as cationic surfactant, NiCl
26H
2the consumption of O is got greatly as far as possible, and a large amount of nickel, until it is saturated to reach nickel, can increase distortion of lattice; ;
(2) under the condition of 70 ~ 90 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 9 ~ 12 blunting of attention to drip, within one second to two seconds, drip one, note observing PH change, pH value increases, and is conducive to the generation of lattice defect equally;
(3) then the NaOH solution that mass fraction is described mixed liquor 0.5 ~ 10% is slowly dripped, precipitated oxide while NaOH solution drips, therefore the rate of addition of NaOH solution must be slow, is generally one to two seconds and drips one, half an hour drips off, reaction 0.5 ~ 4h;
(4) continue reaction 0.5 ~ 4h by after the slurry high speed dispersion of reaction gained in 100 ~ 150 DEG C, make to react completely, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) subsequently, in order to complete in-situ polymerization, first Zn-Ni anti-ultraviolet composite material and cationic surfactant being made microemulsion, better disperseing to make anti-ultraviolet composite material.By the volume ratio of 5:95 ~ 20:80, quaternary ammonium salt cationic surfactant is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 0.5 ~ 10% of the quaternary ammonium salt cationic surfactant aqueous solution, ultrasonic disperse 20 ~ 30min, under the temperature conditions of 70 ~ 80 DEG C, adopt high pressure homogenizer shear agitation 1 ~ 2h subsequently, obtain the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 1 ~ 15 weight portion and two carbonic acid ester peroxide initiators of 0.05 ~ 1 weight portion, control reaction temperature very important, general temperature can control at 60 DEG C ± 0.2 DEG C, adopt the mode of chuck cooling, polymerization obtains uvioresistant functional polrvinyl chloride.
As preferred technical scheme:
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described anti-ultraviolet functional polyvinyl chloride fiber is hair fiber, and fibre number is that 40 ~ 55dtex, UPF value reaches more than 100.Institute's fiber that spins is for artificial hair use, and except having excellent uvioresistant performance, also have feel like human hair, cans degree waits premium properties well.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described non-sulphur organic system heat stabilizer is non-sulphur organic system heat stabilizer, comprise non-sulphur organotin and non-sulphur antimony organic class, be specially one or more compounds in organic pressure phosphoric acid tin, methyl tin, laurate class, maleate class and Antimony Carboxylates.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described antioxidant is Hinered phenols antioxidant, comprise 2,6-tri-grades of butyl-4-methylphenols, two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether, one or more compounds in four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent to be main finish component, oiled before fiber densification, second adopts antistatic additive to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.15wt% ~ 0.25wt% of polyvinyl chloride fiber; Described smooth agent is esters surface active agent, comprises one or more in methylpropane ester, pentaerythritol ester, sorbitol ester of butyl/isobutyl group stearate, sebacate, three; Described antistatic additive is main finish component is quaternary ammonium salt surface active agent, comprises in alkyl quaternary ammonium salts, ester based quaternary ammonium salt a kind of.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described strong agitation refers to that speed of agitator reaches 2000 ~ 3000r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 0.5 ~ 2mol/L.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, the substance withdrawl syndrome of described NaOH solution is 1.5 ~ 5mol/L.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described high speed dispersion refers to and adopts homogenizer to control rotating speed at 2000 ~ 3000r/min; Described continuation reaction is reacted in hydrothermal reaction kettle.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described is separated into ultrasonic disperse, and jitter time is 20 ~ 30min; Described shear agitation is under the temperature conditions of 70 ~ 80 DEG C, adopt high pressure homogenizer shear agitation.
The production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber as above, described quaternary ammonium salt cationic surfactant is the one in Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride and dodecyl benzyl dimethyl ammonium chloride; Two described carbonic acid ester peroxide initiators comprise in benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester, di-isopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate one or more.
Beneficial effect:
(1) with magnesium-yttrium-transition metal nickel doping zinc-oxide, not only because nickel has excellent fast light heat resistance, and the defect of zinc oxide lattice can be increased, increase the crystal face of uv reflectance, add PH conditioning agent, the pH value of reaction system is increased, and pH value is larger, the actual Ni ion concentration entering lattice is higher, and the lattice defect caused is just more; Increase the consumption of Ni, more Ni enters lattice, make distortion of lattice obvious, and along with the doping of Ni is close to saturation state, excessive Ni generates the NiO of cube hexahedron structure, the crystal boundary formed between itself and the ZnO of hexagonal crystallographic texture, can more multiple reflection ultraviolet light, thus strengthens the ability of shielding ultraviolet rays;
(2) use in-situ polymerization to prepare the method for uvioresistant PVC, zinc oxide particles can be solved dispersed not good and affect the defect of properties of product in matrix PVC.Because nanometer Zinc oxide powder has higher specific surface energy, not easily disperse in matrix polyvinyl chloride, zinc oxide microemulsion is prepared in the present invention's employing and Vinyl Chloride Monomer in-situ polymerization prepares uvioresistant poly vinyl chloride resin, efficiently solve uvioresistant powder dispersion problem in the base, use dispersant can be saved, Simplified flowsheet simultaneously;
(3) apply super-pressure spinning process and prepare anti-ultraviolet functional polyvinyl chloride fiber, when using as artificial hair, by changing process conditions, there is make fiber for artificial hair except general hair advantage, also have anti-ultraviolet functional, improve health and the comfortableness of hair fiber.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
A production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:50, Zn (NO
3)
2be 100:1 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 70 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 9; Described strong agitation refers to that speed of agitator is 2000r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 0.5mol/L.
(3) then the NaOH solution that mass fraction is described mixed liquor 0.5% is slowly dripped, reaction 0.5h; The substance withdrawl syndrome of described NaOH solution is 1.5mol/L;
(4) continue reaction 0.5h by after the slurry high speed dispersion of reaction gained in 100 DEG C, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 5:95, quaternary ammonium salt cationic surfactant Dodecyl trimethyl ammonium chloride is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 0.5% of the quaternary ammonium salt cationic surfactant aqueous solution, shear agitation 1h after dispersion, obtains the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 1 weight portion and two carbonic acid ester peroxide initiator benzoyl peroxides of 0.05 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
(7) by the degree of polymerization be 750 uvioresistant poly vinyl chloride 100 weight portion, heat stabilizer organic pressure phosphoric acid tin of 0.05 weight portion, the lubricant polyethylene wax of 0.01 weight portion and the antioxidant 2 of 0.01 weight portion, 6-tri-grades of butyl-4-methylphenols, fully mix 0.5h in 60 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 800kg/cm
2spinning temperature is at 160 DEG C, add hot-stretch in an oven, draw ratio is 5 times, and draft temperature is 70 DEG C, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent butyl stearate to be main finish component, oiled before fiber densification, second adopts antistatic additive alkyl quaternaries surfactant to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.15wt% of polyvinyl chloride fiber, and heat treatment temperature is 100 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 1
Table 1:
Embodiment 2
A production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:30, Zn (NO
3)
2be 100:0.05 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 80 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 9.5; Described strong agitation refers to that speed of agitator is 2500r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 1.2mol/L.
(3) then the NaOH solution that mass fraction is described mixed liquor 3% is slowly dripped, reaction 0.5h; The substance withdrawl syndrome of described NaOH solution is 1.5mol/L;
(4) continue reaction 1.5h by after the slurry high speed dispersion of reaction gained in 120 DEG C, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 10:90, quaternary ammonium salt cationic surfactant hexadecyltrimethylammonium chloride is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 4.5% of the quaternary ammonium salt cationic surfactant aqueous solution, shear agitation 1h after dispersion, obtains the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 5 weight portions and two carbonic acid ester peroxide initiator lauroyl peroxides of 0.55 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
(7) by the degree of polymerization be 850 uvioresistant poly vinyl chloride 100 weight portion, the heat stabilizer methyl tin of 0.1 weight portion, the lubricant polyethylene wax of 0.05 weight portion and 0.03 weight portion antioxidant two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether, fully mix 0.5h in 60 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 850kg/cm
2spinning temperature is at 165 DEG C, add hot-stretch in an oven, draw ratio is 6 times, and draft temperature is 80 DEG C, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent sebacate to be main finish component, oiled before fiber densification, second adopts antistatic additive quaternary ammonium alkyl salt surfactant to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.15wt% of polyvinyl chloride fiber, and heat treatment temperature is 110 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 2:
Table 2:
Embodiment 3
A production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:20, Zn (NO
3)
2be 100:0.03 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 80 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 10; Described strong agitation refers to that speed of agitator is 2500r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 1.5mol/L.
(3) then the NaOH solution that mass fraction is described mixed liquor 5% is slowly dripped, reaction 1.5h; The substance withdrawl syndrome of described NaOH solution is 2.5mol/L;
(4) continue reaction 2h by after the slurry high speed dispersion of reaction gained in 130 DEG C, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 10:90, quaternary ammonium salt cationic surfactant octadecyl trimethyl ammonium chloride is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 5.5% of the quaternary ammonium salt cationic surfactant aqueous solution, shear agitation 1.5h after dispersion, obtains the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 7.5 weight portions and two carbonic acid ester peroxide initiator isopropyl benzene hydroperoxides of 0.65 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
(7) by the degree of polymerization be 900 uvioresistant poly vinyl chloride 100 weight portion, the heat stabilizer laurate class of 0.12 weight portion, the lubricant polyethylene wax of 0.06 weight portion and 0.05 weight portion antioxidant four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester, fully mix 1h in 65 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 900kg/cm
2spinning temperature is at 165 DEG C, add hot-stretch in an oven, draw ratio is 7 times, and draft temperature is 100 DEG C, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent three to be main finish component through methylpropane ester, oiled before fiber densification, second adopts antistatic additive esterquat surfactant to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.18wt% of polyvinyl chloride fiber, and heat treatment temperature is 120 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 3:
Table 3:
Embodiment 4
A production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:15, Zn (NO
3)
2be 100:0.03 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 80 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 11; Described strong agitation refers to that speed of agitator is 2800r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 1.5mol/L.
(3) then the NaOH solution that mass fraction is described mixed liquor 8% is slowly dripped, reaction 2h; The substance withdrawl syndrome of described NaOH solution is 2.5mol/L;
(4) continue reaction 2h by after the slurry high speed dispersion of reaction gained in 140 DEG C, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 15:85, quaternary ammonium salt cationic surfactant octadecyl trimethyl ammonium chloride is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 6.5% of the quaternary ammonium salt cationic surfactant aqueous solution, shear agitation 1.5h after dispersion, obtains the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 8 weight portions and two carbonic acid ester peroxide initiator di-t-butyl peroxides of 0.65 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
(7) by the degree of polymerization be 950 uvioresistant poly vinyl chloride 100 weight portion, the heat stabilizer maleate class of 0.15 weight portion, the lubricant polyethylene wax of 0.07 weight portion and 0.06 weight portion antioxidant four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester and 2, the mixed liquor of 6-tri-grades of butyl-4-methylphenols 45:55 by volume, fully mix 1h in 65 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 950kg/cm
2spinning temperature is at 165 DEG C, add hot-stretch in an oven, draw ratio is 8 times, and draft temperature is 110 DEG C, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent pentaerythritol ester to be main finish component, oiled before fiber densification, second adopts antistatic additive esterquat surfactant to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.2wt% of polyvinyl chloride fiber, and heat treatment temperature is 130 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 4:
Table 4:
Embodiment 5
A production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:10, Zn (NO
3)
2be 100:0.02 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 85 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 11; Described strong agitation refers to that speed of agitator is 3000r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 1.5mol/L.
(3) then the NaOH solution that mass fraction is described mixed liquor 8% is slowly dripped, reaction 2.5h; The substance withdrawl syndrome of described NaOH solution is 3mol/L;
(4) adopted by the slurry of reaction gained homogenizer to control rotating speed and in hydrothermal reaction kettle, continue reaction 3h in 130 DEG C after 2600r/min high speed dispersion, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 15:85, quaternary ammonium salt cationic surfactant octadecyl trimethyl ammonium chloride is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 7.5% of the quaternary ammonium salt cationic surfactant aqueous solution, under the temperature conditions of 75 DEG C, adopt high pressure homogenizer shear agitation 2h after ultrasonic disperse 25min, obtain the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 9 weight portions and two carbonic acid ester peroxide initiator cumyl peroxides of 0.75 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
(7) by the degree of polymerization be 950 uvioresistant poly vinyl chloride 100 weight portion, the heat stabilizer maleate class of 1 weight portion, the lubricant polyethylene wax of 0.08 weight portion and 0.08 weight portion antioxidant four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester and 2, the mixed liquor of 6-tri-grades of butyl-4-methylphenols 30:70 by volume, fully mix 1h in 65 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 950kg/cm
2spinning temperature is at 165 DEG C, add hot-stretch in an oven, draw ratio is 8 times, and draft temperature is 130 DEG C, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent sorbitol ester to be main finish component, oiled before fiber densification, second adopts antistatic additive esterquat surfactant to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.2wt% of polyvinyl chloride fiber, and heat treatment temperature is 135 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 5:
Table 5:
Embodiment 6
A production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:5, Zn (NO
3)
2be 100:0.02 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 85 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 11.5; Described strong agitation refers to that speed of agitator is 3000r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 1.5mol/L.
(3) then the NaOH solution that mass fraction is described mixed liquor 9% is slowly dripped, reaction 3.5h; The substance withdrawl syndrome of described NaOH solution is 3.8mol/L;
(4) adopted by the slurry of reaction gained homogenizer to control rotating speed and in hydrothermal reaction kettle, continue reaction 2h in 145 DEG C after 3000r/min high speed dispersion, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 15:85, quaternary ammonium salt cationic surfactant octadecyl trimethyl ammonium chloride is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 8.5% of the quaternary ammonium salt cationic surfactant aqueous solution, under the temperature conditions of 70 DEG C, adopt high pressure homogenizer shear agitation 2h after ultrasonic disperse 30min, obtain the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 10 weight portions and two carbonic acid ester peroxide initiator peroxidized t-butyl perbenzoates of 0.85 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
(7) by the degree of polymerization be 1000 uvioresistant poly vinyl chloride 100 weight portion, the heat stabilizer Antimony Carboxylates of 1.5 weight portions, the lubricant polyethylene wax of 0.09 weight portion and 0.09 weight portion antioxidant four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester and 2, the mixed liquor of 6-tri-grades of butyl-4-methylphenols 55:45 by volume, fully mix 1h in 65 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 980kg/cm
2spinning temperature is at 165 DEG C, add hot-stretch in an oven, draw ratio is 8 times, and draft temperature is 150 DEG C, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent sorbitol ester and isobutyl group stearate to be the finish component led by weight the mixture of 50:50, oiled before fiber densification, second adopts antistatic additive esterquat surfactant to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.25wt% of polyvinyl chloride fiber, and heat treatment temperature is 135 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 6:
Table 6:
Embodiment 7
A production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:1, Zn (NO
3)
2be 100:0.01 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 90 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 12; Described strong agitation refers to that speed of agitator is 3000r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 2mol/L.
(3) then the NaOH solution that mass fraction is described mixed liquor 10% is slowly dripped, reaction 4h; The substance withdrawl syndrome of described NaOH solution is 5mol/L;
(4) adopted by the slurry of reaction gained homogenizer to control rotating speed and in hydrothermal reaction kettle, continue reaction 4h in 150 DEG C after 2000r/min high speed dispersion, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 20:80, quaternary ammonium salt cationic surfactant dodecyl benzyl dimethyl ammonium chloride is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 10% of the quaternary ammonium salt cationic surfactant aqueous solution, under the temperature conditions of 70 DEG C, adopt high pressure homogenizer shear agitation 2h after ultrasonic disperse 20min, obtain the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 15 weight portions and two carbonic acid ester peroxide initiator peroxidating trimethylacetic acid tertiary butyl ester of 1 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
(7) be uvioresistant poly vinyl chloride 100 weight portion of 1000, the heat stabilizer Antimony Carboxylates of 2 weight portions and organic pressure phosphoric acid tin by the degree of polymerization with antioxidant four (β-(3 of the lubricant polyethylene wax of the mixed liquor of volume ratio 30:70,1 weight portion and 1 weight portion, 5-tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester and 2, the mixed liquor of 6-tri-grades of butyl-4-methylphenols 55:45 by volume, fully mix 1h in 70 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 1000kg/cm
2spinning temperature is at 170 DEG C, add hot-stretch in an oven, draw ratio is 8 times, and draft temperature is 160 DEG C, and oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent sorbitol ester and isobutyl group stearate to be the finish component led by weight the mixture of 30:70, oiled before fiber densification, second adopts antistatic additive esterquat surfactant to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.25wt% of polyvinyl chloride fiber, and heat treatment temperature is 140 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 7:
Table 7:
Embodiment 8
Except initator in (6) is except di-isopropyl peroxydicarbonate, all the other are with embodiment 3.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 8:
Table 8:
Embodiment 9
Except initator in (6) is except di-cyclohexylperoxy di-carbonate, all the other are with embodiment 3.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 9:
Table 9:
Embodiment 10
Except the combination that initator in (6) is di-cyclohexylperoxy di-carbonate and lauroyl peroxide 45:55 by volume, all the other are with embodiment 3.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 10:
Table 10:
Embodiment 11
Except the combination that initator in (6) is isopropyl benzene hydroperoxide and peroxidized t-butyl perbenzoate 40:60 by volume, all the other are with embodiment 3.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 11:
Table 11:
Embodiment 12
Except the combination that initator in (6) is benzoyl peroxide, isopropyl benzene hydroperoxide and peroxidized t-butyl perbenzoate 30:20:50 by volume, all the other are with embodiment 3.After tested, the uvioresistant performance of anti-ultraviolet functional polyvinyl chloride fibers for hair is as following table 12:
Table 12:
Claims (10)
1. a production method for anti-ultraviolet functional polyvinyl chloride fiber, is characterized in that concrete steps are as follows:
Be uvioresistant poly vinyl chloride 100 weight portion of 750 ~ 1000, the non-sulphur organic system heat stabilizer of 0.05 ~ 2 weight portion, the lubricant polyethylene wax of 0.01 ~ 1 weight portion and the antioxidant of 0.01 ~ 1 weight portion by the degree of polymerization, fully mix 0.5 ~ 1h in 60 ~ 70 DEG C and form mixture, inject extruder type spinning machine after metering, spinning machine head pressure is 800 ~ 1000kg/cm
2spinning temperature is at 160 ~ 170 DEG C, add hot-stretch in an oven, draw ratio is 5 ~ 8 times, draft temperature is 70 ~ 160 DEG C, finally heat-treats and oiling treatment, and finish adhesion amount is the 0.05wt% ~ 0.25wt% of polyvinyl chloride fibre, heat treatment temperature is 100 ~ 140 DEG C, obtains anti-ultraviolet functional polyvinyl chloride fiber;
Described uvioresistant poly vinyl chloride is obtained by following steps:
(1) Zn (NO is configured
3)
2, NiCl
26H
2o and hexadecyltrimethylammonium chloride mixed liquor, Zn (NO
3)
2with NiCl
26H
2the mol ratio of O is 100:50 ~ 1, Zn (NO
3)
2be 100:1 ~ 0.01 with the mol ratio of hexadecyltrimethylammonium chloride;
(2) under the condition of 70 ~ 90 DEG C of strong agitation mixed liquors, add the pH adjusting agent sodium hydrogen phosphate aqueous solution, make the pH value of mixed liquor reach 9 ~ 12;
(3) then the NaOH solution that mass fraction is described mixed liquor 0.5 ~ 10% is slowly dripped, reaction 0.5 ~ 4h;
(4) continue reaction 0.5 ~ 4h by after the slurry high speed dispersion of reaction gained in 100 ~ 150 DEG C, products therefrom is purified, filter and drying process, obtained Zn-Ni anti-ultraviolet composite material;
(5) by the volume ratio of 5:95 ~ 20:80, quaternary ammonium salt cationic surfactant is dissolved in deionized water, add the described Zn-Ni anti-ultraviolet composite material that mass fraction is 0.5 ~ 10% of the quaternary ammonium salt cationic surfactant aqueous solution, shear agitation 1 ~ 2h after dispersion, obtains the Zn-Ni composite anti-ultraviolet microemulsion of below average grain diameter 50nm;
(6) in polymerization reaction kettle, add the Vinyl Chloride Monomer of 100 weight portions, the described Zn-Ni composite anti-ultraviolet microemulsion of 1 ~ 15 weight portion and two carbonic acid ester peroxide initiators of 0.05 ~ 1 weight portion, polymerization obtains uvioresistant functional polrvinyl chloride.
2. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, is characterized in that, described anti-ultraviolet functional polyvinyl chloride fiber is hair fiber, and fibre number is that 40 ~ 55dtex, UPF value reaches more than 100.
3. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, it is characterized in that, described non-sulphur organic system heat stabilizer is non-sulphur organic system heat stabilizer, comprise non-sulphur organotin and non-sulphur antimony organic class, be specially one or more compounds in methyl tin, laurate class, maleate class and Antimony Carboxylates.
4. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, it is characterized in that, described antioxidant is Hinered phenols antioxidant, comprise 2,6-tri-grades of butyl-4-methylphenols, two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether, one or more compounds in four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester.
5. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, it is characterized in that, described oiling treatment adopts twice oiling method, namely first oils and adopts smooth agent to be main finish component, oiled before fiber densification, second adopts antistatic additive to be main finish component, oils after fiber densification; The adhesion amount of described finish is the 0.15wt% ~ 0.25wt% of polyvinyl chloride fiber; Described smooth agent is main finish component is esters surface active agent, comprises one or more in butyl/isobutyl group stearate, sebacate, pentaerythritol ester, sorbitol ester; Described antistatic additive is main finish component is quaternary ammonium salt surface active agent, is alkyl quaternary ammonium salts or ester based quaternary ammonium salt.
6. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, is characterized in that, described strong agitation refers to that speed of agitator reaches 2000 ~ 3000r/min; The substance withdrawl syndrome of the described sodium hydrogen phosphate aqueous solution is 0.5 ~ 2mol/L.
7. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, is characterized in that, the substance withdrawl syndrome of described NaOH solution is 1.5 ~ 5mol/L.
8. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, is characterized in that, described high speed dispersion refers to and adopts homogenizer to control rotating speed at 2000 ~ 3000r/min; Described continuation reaction is reacted in hydrothermal reaction kettle.
9. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, is characterized in that, described is separated into ultrasonic disperse, and jitter time is 20 ~ 30min; Described shear agitation is under the temperature conditions of 70 ~ 80 DEG C, adopt high pressure homogenizer shear agitation.
10. the production method of a kind of anti-ultraviolet functional polyvinyl chloride fiber according to claim 1, it is characterized in that, described quaternary ammonium salt cationic surfactant is the one in Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride and dodecyl benzyl dimethyl ammonium chloride; Two described carbonic acid ester peroxide initiators comprise in di-isopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate one or both.
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