CN103572585B - A kind of titania modified silk and preparation method thereof - Google Patents
A kind of titania modified silk and preparation method thereof Download PDFInfo
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- CN103572585B CN103572585B CN201310476005.7A CN201310476005A CN103572585B CN 103572585 B CN103572585 B CN 103572585B CN 201310476005 A CN201310476005 A CN 201310476005A CN 103572585 B CN103572585 B CN 103572585B
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Abstract
The present invention relates to a kind of titania modified silk and preparation method thereof, is that reactant and benzinum are covered in silk surface for solvent generates fine and close hydrated titanium dioxide under original position room temperature with titanate esters, can adopt direct impregnation and continuous impregnating legal system standby.Its fracture strength is 300 ~ 680MPa, and energy to failure is 30 ~ 100MJ/m
3, thermal degradation temperature reaches more than 288.7 DEG C, and glass transition temperature reaches more than 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is greater than 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 100 ~ 500nm at the thickness of fiber surface.Preparation process of the present invention is simple, and cost is low.Silk fiber through the method modification is not only provided with the mechanical property surmounting natural silk, and in antibacterial, uvioresistant and hot property all comparatively natural silk increase.
Description
Technical field
The present invention relates to a kind of titania modified silk and preparation method thereof, particularly relate to a kind of titania modified silk adopting titanate esters/petroleum ether solution and preparation method thereof.
Background technology
Secrete the continuous fiber that silk liquid solidifies formation when matured silkworm cocoons and be called silk, be also referred to as " natural silk ".It is one of animal fiber of utilizing the earliest of the mankind.Silk has very unique various performances, and except the such as comfort known by masses is good, beyond glossiness is high, fibroin fiber also has certain uvioresistant and antibiotic effect.Silk or a kind of novel bio-medical material, have special performance and application prospect that other fiber and processed goods can not be substituted.
Although silk has many advantages and characteristic, make to utilize in process or finding some shortcomings part.Silk is hemicrystalline macromolecular material, although its fracture strength about has 500MPa, its toughness is poor, and energy to failure only has 69MJ/m
3.Although silk self has certain uvioresistant, the feature such as antibacterial, very not remarkable.As undressed natural silk only has certain anti-microbial property, there is not obvious inhibition zone in its surface in testing.Therefore be necessary, on the basis keeping the primary characteristic of silk own, to improve the toughness of fiber, uvioresistant and antibiotic property.Patent " a kind of butyl titanate that adopts carries out the method for modification to real silk fabric " (application number 201110169433.6) employing tetrabutyl titanate is reactant, water is solvent, is impregnated into by real silk fabric in solution to be placed in high temperature and high pressure kettle again and to react.Because tetrabutyl titanate is very active, meet water immediate response.Be dipped in wherein by fabric again, product is deposited on fabric face.In addition, silk, as protein, has the weakness of non-refractory, silk is placed in high temperature and high pressure kettle and can destroys protein structure unavoidably, reduce its mechanical property, even make protein degradation.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of titania modified silk and preparation method thereof, is a kind of method improving regenerated silk fracture strength and toughness.The method is simple to operation, and cost is low; Gained silk has good mechanical property, and its fracture strength is 300 ~ 680MPa, and energy to failure is 30 ~ 100MJ/m
3; The hot property of modified silk, uvioresistant performance and anti-microbial property increase all more before modified.The present invention adopts benzinum to be solvent, slow down the reaction speed of titanate esters, within titanate esters inwardly can penetrate into the silk surface or surface crossed through boiling water boiling from benzinum, because chemical reaction at room temperature carries out, the water on titanate esters and silk surface reacts the hydrated titanium dioxide generated containing great amount of hydroxy group, this hydrated titanium dioxide and protein bound, also likely titanate esters reacts with protein within penetrating into silk surface, form firmly chemical bond or metal-protein chelates key, thus the fracture strength of silk is improved, toughness increases.The titanate esters of not infiltrating, along with the volatilization of benzinum, is reacted with the water in air and is formed hydrated titanium dioxide and be attached to silk surface, form the titanium dioxide film of one deck densification.
A kind of titania modified silk of the present invention, for the densification of surface coverage one deck take titanate esters as the hydrated titanium dioxide that reactant and benzinum generate under original position room temperature for solvent, and its fracture strength is 300 ~ 680MPa, and energy to failure is 30 ~ 100MJ/m
3, thermal degradation temperature reaches more than 288.7 DEG C, and glass transition temperature reaches more than 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is greater than 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 100 ~ 500nm at the thickness of fiber surface.
As preferred technical scheme:
A kind of titania modified silk as above, described silk is the natural mulberry silk or tussah silk that come unstuck, or the fibroin fiber of regeneration.
A kind of titania modified silk as above, the fibroin fiber of described regeneration is regenerated fibroin fiber prepared by wet method or dry spinning.
A kind of titania modified silk as above, described titanate esters is the one in tetraethyl titanate, tetrabutyl titanate or isopropyl titanate.
Present invention also offers a kind of preparation method of titania modified silk, silk direct impregnation being taken out after 15 ~ 30s in titanate esters/petroleum ether solution and being placed on relative humidity is that in the humid air of more than 50%, 48 ~ 72h obtains modified silk, fracture strength is 300 ~ 550MPa, and energy to failure is 30 ~ 60MJ/m
3;
Described titanate esters/petroleum ether solution is volume ratio is the titanate esters of 0.5 ~ 10:99.5 ~ 90 and the mixed solution of benzinum.
Invention further provides a kind of preparation method of titania modified silk, comprise the following steps:
(1) titanate esters and benzinum are prepared titanate esters/petroleum ether solution in 0.5 ~ 10:99.5 ~ 90 by volume;
(2) by silk continuous impregnating by described titanate esters/petroleum ether solution;
(3) then silk is placed in humid air 48 ~ 72h that relative humidity is more than 50%;
Namely obtained titania modified silk, fracture strength is 450 ~ 680MPa, and energy to failure is 50 ~ 100MJ/m
3.
The preparation method of a kind of titania modified silk as above, in described (2) step, described continuous impregnating is by referring to described silk process from described titanate esters/petroleum ether solution, and dip time at least 15s.
The preparation method of a kind of titania modified silk as above, in described (3) step, silk is placed in the closed container that relative humidity is more than 50%, temperature is 10 ~ 100 DEG C.
The preparation method of a kind of titania modified silk as above, in described (2) step, described continuous impregnating is by adopting continuous modification device, above the longitudinal both sides of solution tank having titanate esters/petroleum ether solution, feeding roller and godet roller are set respectively, feeding roller front arranges precursor roller, and godet roller rear arranges receipts roll dies; In solution tank, just a guiding roller and slewing rollers are respectively installed to the below of feeding roller and godet roller; Unmodified silk is wound on precursor roller, completes whole continuous impregnating and passes through process successively through feeding roller, guiding roller, slewing rollers, godet roller and receipts roll dies.
The preparation method of a kind of titania modified silk as above, described receipts roll dies is driven by motor.
After deliberation, at high temperature, water can destroy the Van der Waals force key of spider silk fibroin, makes protein chain separately, makes Small molecular to enter into fibrous inside; They will enter isopropyl titanate and penetrate into spider silk inside, find that isopropyl titanate can react with spider silk fibroin, form chemical bond, thus greatly improve fracture strength and the toughness of fiber.In the present invention, through the poach of two hours after natural silk degumming, under the effect of water, a part of protein chain in silk surface separately.Wrapped up in one deck titanate esters/petroleum ether solution by Tu subsequently, benzinum fully can delay the reaction of titanate esters, and the titanate esters in solution just can enter into silk inside between the protein chain separated, with fibroin or the water generation chemical reaction first advanced into.Titanate esters and protein directly react, and form chemical bond, be cross-linked with chemical bond by protein, this is conducive to the raising of silk mechanical property; Titanate esters is reacted with the water first advanced into, and generate the hydrated titanium dioxide containing hydroxyl, the hydroxyl on hydrated titanium dioxide can interact with hydrogen bond formation or between chelated forms and albumen, is also conducive to the raising of silk mechanical property.Major part titanate esters solution covers silk surface, along with the volatilization of benzinum, reacts with the water in air, generates fine and close titanium dioxide Tu and wraps up in and silk surface, can improve the uvioresistant of silk, antibacterial and hot property.
Beneficial effect
A kind of titania modified silk of the present invention, fracture strength and toughness improve greatly, its fracture strength 300 ~ 680MPa, and energy to failure is 30 ~ 100MJ/m
3.The fracture strength of the silk wherein boiled silk direct impregnation obtained in titanate esters/petroleum ether solution is 300 ~ 550MPa, and energy to failure is 30 ~ 60MJ/m
3; Boiled silk being continued through the silk fracture strength that titanate esters/petroleum ether solution obtains is 450 ~ 680MPa, and energy to failure is 50 ~ 100kJ/m
3.
Preparation process of the present invention is simple, and cost is low.Silk fiber through the method modification is not only provided with the mechanical property surmounting natural silk, and in antibacterial, uvioresistant and hot property all comparatively natural silk increase.
Accompanying drawing explanation
Fig. 1 is the continuous modification device that the present invention adopts;
Fig. 2 is the load-deformation curve of titania modified silk prepared by the present invention;
Fig. 3 is the SEM picture of titania modified silk prepared by the present invention.
Wherein 1 be precursor roller 2 are feeding rollers 3 are guiding rollers 4 is slewing rollers
5 is godet rollers 6 is receive roll dies
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 model that the application's appended claims limits equally after the content of having read the present invention's instruction
A kind of titania modified silk of the present invention, for the densification of surface coverage one deck take titanate esters as the hydrated titanium dioxide that reactant and benzinum generate under original position room temperature for solvent, and its fracture strength is 300 ~ 680MPa, and energy to failure is 30 ~ 100MJ/m
3, thermal degradation temperature reaches more than 288.7 DEG C, and glass transition temperature reaches more than 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is greater than 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 100 ~ 500nm at the thickness of fiber surface.
A kind of titania modified silk as above, the natural mulberry silk of described natural silk degumming or tussah silk, or the fibroin fiber of regeneration.
A kind of titania modified silk as above, the fibroin fiber of described regeneration is regenerated fibroin fiber prepared by wet method or dry spinning.
A kind of titania modified silk as above, described titanate esters is the one in tetraethyl titanate, tetrabutyl titanate or isopropyl titanate.
Embodiment 1
Be take out after 20s in the tetrabutyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 50%, 48h obtains modified silk in volume ratio by degummed mulberry silk direct impregnation, fracture strength is 500MPa, and energy to failure is 48MJ/m
3; Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.6mm to colibacillary inhibition zone, hydrated titanium dioxide is 200nm at the thickness of fiber surface.
Embodiment 2
Be take out after 20s in the tetrabutyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 50%, 48h obtains modified silk in volume ratio by tussah silk direct impregnation of coming unstuck, fracture strength is 550MPa, and energy to failure is 54MJ/m
3; Thermal degradation temperature reaches 290 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 200nm at the thickness of fiber surface.
Embodiment 3
Be take out after 20s in the tetrabutyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 50%, 48h obtains modified silk in volume ratio by Wet-spinning regenerated fibroin fiber direct impregnation, fracture strength is 400MPa, and energy to failure is 40MJ/m
3; Thermal degradation temperature reaches 288.7 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 200nm at the thickness of fiber surface.
Embodiment 4
Dry method being spun regenerated fibroin fiber direct impregnation is take out after 20s in the tetrabutyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 50%, 48h obtains modified silk in volume ratio, and fracture strength is 350MPa, and energy to failure is 32MJ/m
3; Thermal degradation temperature reaches 288.7 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.6mm to colibacillary inhibition zone, hydrated titanium dioxide is 200nm. at the thickness of fiber surface
Embodiment 5
Be take out after 15s in the tetrabutyl titanate/petroleum ether solution of 0.5:99.5 that to be placed on relative humidity be that in the humid air of 50%, 48h obtains modified silk in volume ratio by degummed mulberry silk direct impregnation, fracture strength is 450MPa, and energy to failure is 41MJ/m
3; Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.6mm to colibacillary inhibition zone, hydrated titanium dioxide is 100nm at the thickness of fiber surface.
Embodiment 6
Be take out after 15s in the tetrabutyl titanate/petroleum ether solution of 10:90 that to be placed on relative humidity be that in the humid air of 50%, 72h obtains modified silk in volume ratio by degummed mulberry silk direct impregnation, fracture strength is 300MPa, and energy to failure is 30MJ/m
3; Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.6mm to colibacillary inhibition zone, hydrated titanium dioxide is 500nm at the thickness of fiber surface.
Embodiment 7
Be take out after 15s in the tetraethyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 54%, 48h obtains modified silk in volume ratio by degummed mulberry silk direct impregnation, fracture strength is 480MPa, and energy to failure is 44MJ/m
3; Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.6mm to colibacillary inhibition zone, hydrated titanium dioxide is 200nm at the thickness of fiber surface.
Embodiment 8
Be take out after 15s in the isopropyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 58%, 48h obtains modified silk in volume ratio by degummed mulberry silk direct impregnation, fracture strength is 530MPa, and energy to failure is 49MJ/m
3; Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 200nm at the thickness of fiber surface.
Embodiment 9
Be take out after 30s in the tetraethyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 55%, 60h obtains modified silk in volume ratio by degummed mulberry silk direct impregnation, fracture strength is 480MPa, and energy to failure is 44MJ/m
3; Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 400nm at the thickness of fiber surface.
Embodiment 10
Be take out after 20s in the tetraethyl titanate/petroleum ether solution of 1:99 that to be placed on relative humidity be that in the humid air of 55%, 72h obtains modified silk in volume ratio by degummed mulberry silk direct impregnation, fracture strength is 510MPa, and energy to failure is 47MJ/m
3; Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 380nm at the thickness of fiber surface.
Embodiment 11
By tetrabutyl titanate and benzinum by volume 1:99 prepare tetrabutyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described tetrabutyl titanate/petroleum ether solution, and dip time is 15s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having tetrabutyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 50%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 580MPa, and energy to failure is 78MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 385nm at the thickness of fiber surface.
Embodiment 12
By tetrabutyl titanate and benzinum by volume 1:99 prepare tetrabutyl titanate/petroleum ether solution; Adopted by tussah silk Fig. 1 device continuous impregnating by described tetrabutyl titanate/petroleum ether solution; And dip time is 20s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having tetrabutyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 50%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 630MPa, and energy to failure is 83MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 385nm at the thickness of fiber surface.
Embodiment 13
By tetrabutyl titanate and benzinum by volume 1:99 prepare tetrabutyl titanate/petroleum ether solution; Regeneration dry method being spun fibroin fiber adopts Fig. 1 device continuous impregnating by described tetrabutyl titanate/petroleum ether solution; And dip time is 20s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having tetrabutyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 50%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 450MPa, and energy to failure is 48MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 385nm at the thickness of fiber surface.
Embodiment 14
By tetrabutyl titanate and benzinum by volume 1:99 prepare tetrabutyl titanate/petroleum ether solution; Adopted by Wet-spinning regenerated fibroin fiber Fig. 1 device continuous impregnating by described tetrabutyl titanate/petroleum ether solution; And dip time is 20s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having tetrabutyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 60%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 500MPa, and energy to failure is 60MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 385nm at the thickness of fiber surface.
Embodiment 15
By tetrabutyl titanate and benzinum by volume 0.5:99.5 prepare tetrabutyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described tetrabutyl titanate/petroleum ether solution; And dip time is 15s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having tetrabutyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 60%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 540MPa, and energy to failure is 72MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 120nm at the thickness of fiber surface.
Embodiment 16
By tetrabutyl titanate and benzinum by volume 10:90 prepare tetrabutyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described tetrabutyl titanate/petroleum ether solution; And dip time is 15s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having tetrabutyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 60%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 510MPa, and energy to failure is 68MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 450nm at the thickness of fiber surface.
Embodiment 17
By tetraethyl titanate and benzinum by volume 1:99 prepare tetraethyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described tetraethyl titanate/petroleum ether solution; And dip time is 15s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having tetraethyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 50%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 560MPa, and energy to failure is 77MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 385nm at the thickness of fiber surface.
Embodiment 18
By isopropyl titanate and benzinum by volume 1:99 prepare isopropyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described isopropyl titanate/petroleum ether solution; And dip time is 20s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having isopropyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 50%, temperature is 40 DEG C.Namely obtained titania modified silk, fracture strength is 680MPa, and energy to failure is 100MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 250nm at the thickness of fiber surface.The load-deformation curve of modified silk is shown in Fig. 2.
Embodiment 19
By isopropyl titanate and benzinum by volume 1:99 prepare isopropyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described isopropyl titanate/petroleum ether solution; And dip time is 20s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having isopropyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 70%, temperature is 100 DEG C.Namely obtained titania modified silk, fracture strength is 610MPa, and energy to failure is 91MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 250nm at the thickness of fiber surface.The SEM of modified silk is shown in Fig. 3.
Embodiment 20
By isopropyl titanate and benzinum by volume 1:99 prepare isopropyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described isopropyl titanate/petroleum ether solution; And dip time is 30s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having isopropyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating successively pass through process through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 50%, temperature is 50 DEG C.Namely obtained titania modified silk, fracture strength is 580MPa, and energy to failure is 79MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 250nm at the thickness of fiber surface.
Embodiment 21
By isopropyl titanate and benzinum 1:99 by volume: prepare isopropyl titanate/petroleum ether solution; Adopted by mulberry silk Fig. 1 device continuous impregnating by described isopropyl titanate/petroleum ether solution; And dip time is 20s; Fig. 1 is that continuous impregnating passes through to adopt continuous modification device, and arrange feeding roller 2 and godet roller 5 respectively above the longitudinal both sides of solution tank having isopropyl titanate/petroleum ether solution, feeding roller 2 front arranges precursor roller 1, and godet roller 5 rear is arranged receives roll dies 6; In solution tank, just guiding roller 3 and slewing rollers 4 are respectively installed to the below of feeding roller 2 and godet roller 5; Unmodified silk is wound on precursor roller 1, completes whole continuous impregnating by process successively, wherein receive roll dies and driven by motor through feeding roller 2, guiding roller 3, slewing rollers 4, godet roller 5 and receipts roll dies 6.Then silk is placed in the closed container that relative humidity is 70%, temperature is 100 DEG C.Namely obtained titania modified silk, fracture strength is 610MPa, and energy to failure is 91MJ/m
3.Thermal degradation temperature reaches 289 DEG C, and glass transition temperature reaches 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is 13.7mm to colibacillary inhibition zone, hydrated titanium dioxide is 250nm at the thickness of fiber surface.
Claims (10)
1. a titania modified silk, it is characterized in that: described titania modified silk be the densification of surface coverage one deck take titanate esters as the silk of the hydrated titanium dioxide that reactant and benzinum generate under original position room temperature for solvent, be silk direct impregnation to take out after 15 ~ 30s in titanate esters/petroleum ether solution and be then placed in the silk of modification that obtains of humid air 48 ~ 72h that relative humidity is more than 50%, its fracture strength is 300 ~ 680MPa, and energy to failure is 30 ~ 100MJ/m
3, thermal degradation temperature reaches more than 288.7 DEG C, and glass transition temperature reaches more than 230 DEG C; Described titania modified silk is 1245 μ W/cm through light intensity
2and wavelength is that after the ultraviolet irradiation 3h of 390nm, fracture strength, without significantly sacrificing, is greater than 13.5mm to colibacillary inhibition zone, hydrated titanium dioxide is 100 ~ 500nm at the thickness of fiber surface.
2. a kind of titania modified silk according to claim 1, is characterized in that, described silk is the natural mulberry silk or tussah silk that come unstuck, or the fibroin fiber of regeneration.
3. a kind of titania modified silk according to claim 2, is characterized in that, the fibroin fiber of described regeneration is regenerated fibroin fiber prepared by wet method or dry spinning.
4. a kind of titania modified silk according to claim 1, is characterized in that, described titanate esters is the one in tetraethyl titanate, tetrabutyl titanate or isopropyl titanate.
5. the preparation method of a kind of titania modified silk according to any one of Claims 1 to 4, it is characterized in that: silk direct impregnation being taken out after 15 ~ 30s in titanate esters/petroleum ether solution and being placed on relative humidity is that in the humid air of more than 50%, 48 ~ 72h obtains modified silk, fracture strength is 300 ~ 550MPa, and energy to failure is 30 ~ 60MJ/m
3;
Described titanate esters/petroleum ether solution is volume ratio is the titanate esters of 0.5 ~ 10:99.5 ~ 90 and the mixed solution of benzinum.
6. the preparation method of a kind of titania modified silk according to any one of Claims 1 to 4, is characterized in that comprising the following steps:
(1) titanate esters and benzinum are prepared titanate esters/petroleum ether solution in 0.5 ~ 10:99.5 ~ 90 by volume;
(2) by silk continuous impregnating by described titanate esters/petroleum ether solution;
(3) then silk is placed in humid air 48 ~ 72h that relative humidity is more than 50%;
Namely obtained titania modified silk, fracture strength is 450 ~ 680MPa, and energy to failure is 50 ~ 100MJ/m
3.
7. the preparation method of a kind of titania modified silk according to claim 6, it is characterized in that, in described (2) step, described continuous impregnating is by referring to described silk process from described titanate esters/petroleum ether solution, and dip time 15 ~ 30s.
8. the preparation method of a kind of titania modified silk according to claim 6, is characterized in that, in described (3) step, silk is placed in the closed container that relative humidity is more than 50%, temperature is 10 ~ 100 DEG C.
9. the preparation method of a kind of titania modified silk according to claim 6, it is characterized in that, in described (2) step, described continuous impregnating is by adopting continuous modification device, above the longitudinal both sides of solution tank having titanate esters/petroleum ether solution, feeding roller and godet roller are set respectively, feeding roller front arranges precursor roller, and godet roller rear arranges receipts roll dies; In solution tank, just a guiding roller and slewing rollers are respectively installed to the below of feeding roller and godet roller; Unmodified silk is wound on precursor roller, completes whole continuous impregnating and passes through process successively through feeding roller, guiding roller, slewing rollers, godet roller and receipts roll dies.
10. the preparation method of a kind of titania modified silk according to claim 9, is characterized in that, described receipts roll dies is driven by motor.
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| CN109338482A (en) * | 2018-09-21 | 2019-02-15 | 苏州经贸职业技术学院 | A kind of preparation method of nanocomposite degumming and refining agent |
| CN109554915B (en) * | 2018-12-04 | 2021-04-13 | 河南民兴生物科技股份有限公司 | Tussah silk functional treatment agent and treatment method |
| CN109505118B (en) * | 2018-12-04 | 2021-04-13 | 河南民兴生物科技股份有限公司 | Mulberry silk refining agent and processing method of mulberry silk |
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| CN101250811A (en) * | 2008-04-10 | 2008-08-27 | 上海交通大学 | Method for manufacturing carbon fiber surface titanium dioxide coating |
| CN102020312B (en) * | 2011-01-20 | 2012-06-27 | 苏州苏纳特科技有限公司 | Method for preparing nano TiO2 powder |
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Effective date of registration: 20210429 Address after: No. 1487 Shanghai-Hangzhou Highway, Fengxian District, Shanghai, 201400 Patentee after: SHANGHAI SHUIXING HOME TEXTILE Co.,Ltd. Address before: 201620 Shanghai, Songjiang new town, North Road, No. 2999 people Patentee before: DONGHUA University |