CN102965748A - Nano-bubble-containing fiber and method for producing same - Google Patents
Nano-bubble-containing fiber and method for producing same Download PDFInfo
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- CN102965748A CN102965748A CN2011103034843A CN201110303484A CN102965748A CN 102965748 A CN102965748 A CN 102965748A CN 2011103034843 A CN2011103034843 A CN 2011103034843A CN 201110303484 A CN201110303484 A CN 201110303484A CN 102965748 A CN102965748 A CN 102965748A
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- 150000001875 compounds Chemical class 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 51
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
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- 239000001301 oxygen Substances 0.000 claims description 9
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
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- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004698 Polyethylene Substances 0.000 claims description 4
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- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
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- 229920000052 poly(p-xylylene) Polymers 0.000 claims description 4
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- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 4
- 235000021286 stilbenes Nutrition 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 claims description 3
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- 229920001577 copolymer Polymers 0.000 claims description 3
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- 239000002657 fibrous material Substances 0.000 claims description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims 2
- CSPTZWQFHBVOLO-UHFFFAOYSA-N 4-phenyldiazenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N=NC1=CC=CC=C1 CSPTZWQFHBVOLO-UHFFFAOYSA-N 0.000 claims 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims 2
- OCJGAAJDXODLCX-UHFFFAOYSA-N n,n-dimethyl-2-phenyldiazenylaniline Chemical class CN(C)C1=CC=CC=C1N=NC1=CC=CC=C1 OCJGAAJDXODLCX-UHFFFAOYSA-N 0.000 claims 2
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
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- CSYSRRCOBYEGPI-UHFFFAOYSA-N diazo(sulfonyl)methane Chemical class [N-]=[N+]=C=S(=O)=O CSYSRRCOBYEGPI-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a fiber containing nano bubbles and a preparation method thereof, the method comprises the steps of mixing a polymer material and a photosensitive compound to form a mixture, carrying out a spinning manufacturing method on the mixture to form the fiber, and after the fiber is solidified, carrying out light irradiation or heating treatment on the fiber to enable the photosensitive compound to generate gas, wherein the gas forms a plurality of closed nano bubbles in the fiber, and the size of the nano bubbles is between 300nm and 800 nm.
Description
Technical field
The present invention relates to a kind of manufacture method of fiber, particularly a kind of manufacture method that forms the nano bubble of sealing at fibrous inside.
Background technology
Usually the method that produces hole in fiber is to utilize foaming technique (foam technology), under fibrous material is in molten condition, uses blowing agent to form open hole in fiber, reaches the purpose that makes the fiber lighting.In addition, in the manufacture process of fiber, may form the space of a little in fiber, the distribution in these spaces and size can't be controlled, so these space meetings become a kind of defective of fiber so that the characteristic of fiber is adversely affected.
Light-sensitive compound (photoactive compounds) is applied in the photoresist usually, by the sensitiveness of light-sensitive compound to light, allow photoresist be subject to the part of light irradiation and produce different solubility from illumination part not for developer, and then so that photoresist can be patterned, therefore existing light-sensitive compound all is applied on the semiconductor making method usually.
The formation of present existing nano bubble (nanobubble) is to utilize the electrolysis manufacture method to produce, and nano bubble is formed in the electrolytic aqueous solution, and these nano bubbles can be adsorbed on the surface of polymeric material.
Yet above-mentioned prior art all can't form in the inside of fiber size and the enclosed type nano bubble that distributes and be controlled.
Summary of the invention
Embodiments of the invention provide the manufacture method of the fiber that contains nano bubble, comprise: polymeric material is provided, with light-sensitive compound and polymeric material mixed-shaped resulting mixture, mixture is carried out the spinning manufacture method form fiber, after fiber solidifies, fiber is carried out photo-irradiation treatment or heat treated, so that intrastitial photosensitive compound deposits yields gas, this gas forms the nano bubble of a plurality of sealings at fibrous inside, and the size of these nano bubbles is between between the 300nm to 800nm.
Embodiments of the invention also provide the fiber that contains nano bubble, comprise: fibrous body, the nano bubble of a plurality of sealings is arranged in the fibrous body, the size of these nano bubbles is between between the 300nm to 800nm, and the residue of light-sensitive compound is mixed in the fibrous body, and the residue of light-sensitive compound is the residue after light-sensitive compound discharges gas.
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, below cooperate embodiment, elaborate.
Description of drawings
Figure 1A shows the optical microscope photograph of the PAN film that does not add light-sensitive compound;
Figure 1B shows the optical microscope photograph that adds the 5wt% light-sensitive compound and do not pass through the PAN-DNQ film of photo-irradiation treatment;
Fig. 1 C show to add the 5wt% light-sensitive compound and through the optical microscope photograph of the PAN-DNQ film after 5 minutes dryings and the photo-irradiation treatment;
Fig. 1 D show to add the 5wt% light-sensitive compound and through the optical microscope photograph of the PAN-DNQ film after 24 hours dryings and the photo-irradiation treatment;
Fig. 2 A and 2B show respectively the surface of the PAN film that does not add light-sensitive compound and the SEM photo of section;
Fig. 2 C and 2D show respectively the surface of the PAN-DNQ film that adds the 5wt% light-sensitive compound and do not pass through photo-irradiation treatment and the SEM photo of section;
Fig. 2 E, 2F show respectively the surface of the PAN-DNQ film after interpolation 5wt% light-sensitive compound and the process photo-irradiation treatment and the SEM photo of section;
Fig. 3 A shows the optical microscope photograph of the PLA fiber that does not add light-sensitive compound;
Fig. 3 B shows the optical microscope photograph that adds the 0.4wt% light-sensitive compound and do not pass through the PLA-DNQ fiber of photo-irradiation treatment; And
Fig. 3 C shows the optical microscope photograph of the PLA-DNQ fiber after interpolation 0.4wt% light-sensitive compound and process are processed according to UV light.
The specific embodiment
Embodiments of the invention use gas permeability coefficient is low and have the polymer of light transmission as the raw material of preparation fiber, for example is polyacrylonitrile (polyacrylonitrile; Be called for short PAN), polymethacrylonitrile (polymethacrylonitrile), polyacrylonitrile styrene (Lopac), polyvinylidene chloride (polyvinylidene chloride), acrylonitrile methyl meth acrylat copolymer (Barex), polyethylene terephthalate (polyethylene terephtalate), polyamide 6 (Nylon 6), polyvinyl chloride (polyvinyl chloride), polyethylene (polyethylene), Parylene (parylene), cellulose acetate (cellulose acetate), PLA (polylactic acid; Be called for short PLA) or aforesaid derivative, these polymeric materials have nitrogen infiltration coefficient≤0.2barrer behind dry solidification, oxygen permeability coefficient≤1barrer, and carbon dioxide infiltration coefficient≤3barrer, wherein barrer is the unit of gas permeability coefficient, equals 10
-10Cm
3(STP)-cm/ (s-cm
2-cmHg), referred to as P.
In above-mentioned polymeric material, the oxygen permeability coefficient of polyacrylonitrile (PAN) when 25 ℃ of temperature is 0.0003P, and the nitrogen infiltration coefficient is 0.00016P, and the carbon dioxide infiltration coefficient is 0.0018P; The oxygen permeability coefficient of PLA (PLA) when 25 ℃ of temperature is 0.83P, and the nitrogen infiltration coefficient is 0.18P, and the carbon dioxide infiltration coefficient is 2.59P.
Light-sensitive compound (the photoactive compounds that embodiments of the invention use; Abbreviation PAC) comprises diazonium compound (diazo compounds), azo-compound (azo compounds) or cationic photosensitive initiator (cationic photoinitiators), these light-sensitive compounds can produce gas when processing with illumination methods, the Photoactive compounds of part, also can be because thermal cracking produce gas when for example diazonium compound or azo-compound are processed with mode of heating, its cracking temperature (decomposition temperature) that discharges gas is higher than 120 ℃.Therefore, in an embodiment of the present invention, select the light-sensitive compound that can produce because of illumination and thermal cracking gas, process making it produce gas with illumination methods or mode of heating.In addition, the employed light-sensitive compound of the embodiment of the invention has heat endurance in the wet spinning manufacture method of fiber and melt spinning manufacture method.
The polymeric material of this light-sensitive compound and above-mentioned preparation fiber has good compatibility, can dissolve in the solvent of dissolve polymer material, and can fully be distributed in the polymeric material of melting.Light-sensitive compound is under ultraviolet light (UV) irradiation or can discharge escaping gas under the solar radiation, for example nitrogen, oxygen or carbon dioxide.In the back segment high temperature drying manufacture method of spinning, the light-sensitive compound of complete reaction can not discharge escaping gas, for example nitrogen, oxygen or carbon dioxide yet under the heat treated that is higher than its cracking temperature that discharges gas in addition.
In an embodiment of the present invention, the diazonium compound as light-sensitive compound can be 1,2-diazido naphthoquinones-5-sulphonic acid ester (1,2-naphthoquinonediazide-5-sulfonate; Be called for short DNQ-5-sulfonate) or derivatives thereof, for example be 2,3,4-trihydroxybenzophenone 31,2-diazido naphthoquinones-5-sulphonic acid ester (2,3,4-Trihydroxybenzophenone tris (1,2-naphthoquinonediazide-5-sulfonate) or 1-naphthalene sulfonic aicd-6-diazonium-5,6-dihydro-5-oxo-4-(1-methyl isophthalic acid-phenethyl) phenyl ester (1-Naphthalenesulfonic acid, 6-diazo-5,6-dihydro-5-oxo-, 4-(1-methy-1-phenylethyl) phenyl ester).
The reaction equation that light-sensitive compound DNQ-5-sulfonate shines behind the UV light is as follows:
Behind UV light, the structure of DNQ-5-sulfonate changes accepted way of doing sth II by formula I, and discharges nitrogen.Then, the structure of formula II can be transformed into formula III rapidly, and then absorbs the structure that aqueous vapor changes accepted way of doing sth IV, and the structure of formula IV is that light-sensitive compound DNQ-5-sulfonate shines the residue after UV light discharges nitrogen.
R among the above-mentioned light-sensitive compound DNQ-5-sulfonate structural formula I-IV is for stablizing with functional group (ballast groups), Molecular Design by different R, can be so that light-sensitive compound DNQ-5-sulfonate have compatibility from different polymeric material, and then allow light-sensitive compound in polymeric material, disperse equably.In addition, utilize the Molecular Design of different R, can allow the light penetration of light-sensitive compound DNQ-5-sulfonate improve, and improve its heat resistance.
In an embodiment of the present invention, as the azo-compound of light-sensitive compound for example be 2-(4 '-hydroxy benzenes azoles) benzoic acid (2-(4 '-hydroxybenzeneazo) benzoic acid; Abbreviation HABA), α, β-two (phenylazo) stilbene mixture (α, β-bis (phenylazo) stilbene), 4-be amino-4 '-dimethylaminoazobenzene (4-amino-4 '-dimethylaminoazobenzene), the derivative of 4-phenylazo benzoic acid (4-(phenylazo) benzoic acid) or two (sulfonic group) diazomethane (bis (sulfonyl) diazomethanes).
In an embodiment of the present invention, cationic photosensitive initiator as light-sensitive compound for example is 3, the derivative of 5-dichloro-benzenes diazonium tetrafluoroborate (3,5-dichloro-phenyl diazonium tetrafluoroborate), 4-methoxybenzene diazonium tetrafluoroborate (4-methoxybenzene diazonium tetrafluoroborate) or benzophenone (benzophenone).
With above-mentioned light-sensitive compound and polymeric material mixed-shaped resulting mixture, the content of light-sensitive compound is that 0.1 percentage by weight (wt%) of polymeric material is between 5 percentage by weights (wt%), form fiber via wet spinning manufacture method or melt spinning manufacture method, in the wet spinning manufacture method, polymeric material is dissolved in the identical solvent with light-sensitive compound; In the melt spinning manufacture method, light-sensitive compound is dispersed in the polymeric material of melting.
Before fiber solidifies and/or after solidifying, can make light-sensitive compound discharge gas by photo-irradiation treatment.In addition, heat treated also can allow light-sensitive compound produce gas because of thermal cracking.In the experimental example of polyacrylonitrile, ultraviolet illumination process can be after fiber solidifies to the arbitrary manufacture method in centre stage enforcement that bone dry is rolled.Gas produces the nano bubble of a plurality of sealings at the fibrous inside that solidifies, and the size of these nano bubbles is between between the 300nm to 800nm.The size of nano bubble can be by the extent control of fiber curing, and the degree that fiber solidifies is higher, and the size of the nano bubble that then forms is less.In addition, gas can also form the micron bubble (microbubble) of size between 1 μ m to 3 μ m at the fibrous inside that solidifies.
In addition, because light-sensitive compound and polymeric material is compatible good, the gas that is therefore discharged by light-sensitive compound can be evenly dispersed in the polymeric material, that is the distributing position of intrastitial nano bubble depends on the distributed density of light-sensitive compound.
The gas that is discharged by light-sensitive compound forms the nano bubble that seals in the fiber that solidifies, these nano bubbles can produce internal stress (inner stress) in the fiber that solidifies, therefore can increase the mechanical strength of fiber, for example young's modulus (Young ' s modulus) and tensile stress (tensile stress).
Below enumerate the characteristic that the explanation of each embodiment and each comparative example prepares method, material and the fiber of the fiber that contains nano bubble:
[embodiment 1 and comparative example 1]
Polyacrylonitrile (PAN) the raw material grain that will contain 88 % by mole of acrylonitrile (acrylonitrile) and 12 % by mole of vinyl acetates (vinylacetate) is dissolved in DMA (N, N-dimethylacetamide; DMAc) in the solvent, form the solution A of concentration 20wt%, then take out a part of solution A, the light-sensitive compound 1 that in solution A, adds 0.4wt%, 2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate), stir until light-sensitive compound DNQ-5-sulfonate dissolves fully at temperature 70 C, form solution B.
Adopt the wet spinning manufacture method, via spinning mouth (spinneret) (pore quantity 300, hole diameter 10 μ m, gas is apart from (air gap) 0.5cm), spinning speed is 16.7m/min, solution A is made the PAN fiber of comparative example 1, solution B is made the PAN-DNQ fiber of embodiment 1, with the fiber of comparative example 1 and embodiment 1 through condensation water (3.6wt%CaCl
2Solution, 5 ℃) process, again through the second water bath processing of 60 ℃ the first water-bath and 98 ℃, 10 times stretchings, comparative example 1 and the fiber of embodiment 1 are solidified, form the cured fiber bundle of comparative example 1 and embodiment 1, at last with the oven of cured fiber bundle through 150 ℃, and then be collected on the scroll bar.
With the PAN-DNQ fibre bundle after the curing of embodiment 1 with UV light or solar radiation, perhaps process with 150 ℃ steam and the stretch ratio of 120-170%, so that the light-sensitive compound 1 in the PAN-DNQ fibre bundle after the curing of embodiment 1,2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate) activation discharges nitrogen, produce the nano bubble of nitrogen in the PAN-DNQ fibre bundle after curing, obtain the fiber that contains nano bubble of embodiment 1a and 1b.
The PAN fiber of comparative example 1 and the PAN-DNQ fiber that contains nano bubble of embodiment 1a and 1b are measured TENSILE STRENGTH (tensile strength) and modulus in tension (tensile modulus) with instron (INSTRON), and with the diameter of scanning type electron microscope (SEM) measurement fiber, result such as table 1 are listed.
The mechanical property of the fiber of table 1. embodiment 1a, 1b and comparative example 1
Result by table 1 can learn, PAN fiber than comparative example 1, the PAN-DNQ fiber that contains nano bubble of embodiment 1a and 1b has higher TENSILE STRENGTH and modulus in tension, increase approximately 40%, and the PAN-DNQ fibre diameter of embodiment 1a and 1b increases about 30% than the PAN fibre diameter of comparative example 1, this is illustrated in and adds light-sensitive compound 1 in the fibrous raw material, 2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate), and after solidifying, fiber carries out illumination or heat treated, so that produce nano bubble in the fiber, help to promote the mechanical strength of fiber, and increase fibre diameter.
For the convenient distribution scenario of nano bubble in the PAN polymeric material of observing, with PAN polymeric material and interpolation 5wt% light-sensitive compound 1, the PAN polymeric material of 2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate) is made respectively PAN film and PAN-DNQ film.The PAN-DNQ film via after processing 5 minutes different drying times and 24 hours, is carried out daylight or UV photo-irradiation treatment again, utilize observation by light microscope PAN film and PAN-DNQ film, the result is shown in Figure 1A-1D.
Figure 1A shows the PAN film that does not add light-sensitive compound, and wherein being presented at does not have nano bubble to produce in the PAN film; Figure 1B shows interpolation 5wt% light-sensitive compound and does not pass through the PAN-DNQ film of photo-irradiation treatment that wherein being presented at does not have nano bubble to produce in the PAN-DNQ film; Fig. 1 C shows the state after the PAN-DNQ film is through 5 minutes dryings and photo-irradiation treatment, wherein is presented at the bubble size that produces in the PAN-DNQ film and is about 3-6 μ m; Fig. 1 D shows the state after the PAN-DNQ film is through 24 hours dryings and photo-irradiation treatment, wherein is presented at the bubble size that produces in the PAN-DNQ film and is about 200-500nm.Can be learnt by Figure 1A-1D, in the PAN polymeric material, after interpolation light-sensitive compound and the drying processing and photo-irradiation treatment through the long period, can in the PAN polymeric material, produce nano level bubble.
Then, surface and the profile morphology of the PAN-DNQ film of the PAN film of the above-mentioned Figure 1A of use scanning type electron microscope (SEM) observation, the PAN-DNQ film of Figure 1B and Fig. 1 D, the result is shown in Fig. 2 A-2F.Fig. 2 A, 2B show respectively the surface of the PAN film that does not add light-sensitive compound and the SEM photo of section, Fig. 2 C, 2D show respectively the surface of the PAN-DNQ film that adds the 5wt% light-sensitive compound and do not pass through photo-irradiation treatment and the SEM photo of section, and Fig. 2 E, 2F show respectively interpolation 5wt% light-sensitive compound and the surface of the PAN-DNQ film after super-dry and photo-irradiation treatment and the SEM photo of section.
Comparison by Fig. 2 A, 2C and 2E can learn, PAN film and add light-sensitive compound and the configuration of surface difference of the PAN-DNQ film after illumination and the photo-irradiation treatment is not little; Comparison by Fig. 2 B, 2D and 2F can be learnt, the section of PAN film is level and smooth, add light-sensitive compound and do not become coarse through the section of the PAN-DNQ film of photo-irradiation treatment, the section of the PAN-DNQ film after interpolation light-sensitive compound and the process photo-irradiation treatment then has bag shaped structure, and this expression light-sensitive compound is through producing nano bubble in the PAN polymer after photo-irradiation treatment.
In addition, with differential scanning calorimeter (Differential Scanning Calorimeter; Abbreviation DSC) light-sensitive compound 1 of measurement PAN polymer (concentration that is dissolved among the solvent DMAc is 15%), interpolation 1wt%, PAN-DNQ polymer (concentration that is dissolved among the solvent DMAc is 15%) after the PAN-DNQ polymer of 2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate) and the process UV photo-irradiation treatment, result such as table 2 are listed.
Table 2.PAN polymer, illumination and the dsc analysis result of the PAN-DNQ polymer of illumination not
Can be learnt by table 2, add light-sensitive compound 1,2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate) and photograph UV light can be so that the oxidizing temperature of PAN polymer reduce by 5 ℃ by 320 ℃.In addition, than the PAN polymer, light-sensitive compound in the PAN-DNQ polymer is not according to before the UV light, it is put, and enthalpy amount (Δ H) increases and the conversion initial temperature reduces, this expression light-sensitive compound DNQ-5-sulfonate can be in the oxidizing process of PAN polymer storage power, it helps to reduce oxidizing temperature in the oxidation of PAN fiber precursor becomes the oxidation manufacture method of oxidized fibre.
In addition, light-sensitive compound 1 to PAN fiber, interpolation 0.4wt%, the PAN-DNQ fiber of the PAN-DNQ fiber of 2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate), process UV photo-irradiation treatment and/or 150 ℃ of steam treatment carries out density analysis, and result such as table 3 are listed.
The density analysis result of table 3.PAN fiber, PAN-DNQ fiber
Can be learnt by table 3, add light-sensitive compound DNQ-5-sulfonate and through according to UV light and/or steam treatment in the PAN polymer, it is about 1.15% to reduce the density of PAN polymer, therefore helps the lighting of PAN fiber.
[embodiment 2 and comparative example 2]
With PLA (PLA) raw material grain and interpolation 0.4wt% light-sensitive compound 1, PLA (PLA) the raw material grain of 2-diazido naphthoquinones-5-sulphonic acid ester (DNQ-5-sulfonate) is filled in respectively in the twin-screw extrusion spinning machine (Twin screw extruder spinning machine), carry out the melt spinning manufacture method with 150-160 ℃, and solidify via 10 ℃ cold bath, form the PLA fiber of comparative example 2 and the PLA-DNQ fiber of comparative example 2a, the fibre diameter of comparative example 2 and comparative example 2a is between 70-90 μ m.
The PLA-DNQ fiber of comparative example 2a through the processing according to UV light of 500W, 40-60 ℃ and 1 hour, is formed the PLA-DNQ fiber of embodiment 2.
With the fiber of observation by light microscope comparative example 2, comparative example 2a and embodiment 2, the result is shown in Fig. 3 A-3C.Fig. 3 A shows the PLA fiber of comparative example 2, and it has smooth structure, does not have nano bubble to produce in the PLA of comparative example 2 fiber.Fig. 3 B shows interpolation 0.4wt% light-sensitive compound DNQ-5-sulfonate and does not pass through the PLA-DNQ fiber of photo-irradiation treatment, the dark particle that wherein shows is the crystallization of undissolved light-sensitive compound DNQ-5-sulfonate, does not have nano bubble to produce in the PLA-DNQ of comparative example 2a fiber.Fig. 3 C shows through the PLA-DNQ fiber after processing according to UV light, in the PLA-DNQ of embodiment 2 fiber, parallel pore appears near dark particle, its diameter is between 0.8-1.2 μ m, and this expression light-sensitive compound DNQ-5-sulfonate produces nano bubble in the PLA-DNQ fiber after processing according to UV light.
With dynamic mechanical analysis (dynamic mechanical analysis; Abbreviation DMA) method is measured the young's modulus of the fiber of comparative example 2, comparative example 2a and embodiment 2, and result such as table 4 are listed.
The characteristic of the fiber of table 4. comparative example 2, comparative example 2a and embodiment 2
Can be learnt by table 4, than the PLA fiber, add light-sensitive compound DNQ-5-sulfonate and can increase about 8 times through the young's modulus according to the PLA-DNQ fiber after the processing of UV light.In addition, but adding light-sensitive compound DNQ-5-sulfonate do not reduce through the young's modulus of the PLA-DNQ fiber processed according to UV light is because the light-sensitive compound DNQ-5-sulfonate of illumination does not produce crystallization and causes in fiber.
In sum, embodiments of the invention use light-sensitive compound to be added in the low polymeric material of printing opacity and gas permeability coefficient, after the fiber that polymeric material is made solidifies, via after the illumination or heat treated make light-sensitive compound discharge gas, in fiber, produce thus size between the enclosed type nano bubble between the 300nm to 800nm, these mechanical strengths that can increase fiber at intrastitial nano bubble are modulus in tension and TENSILE STRENGTH for example, the strength and toughness of reinforcing fiber, and can make the fiber lighting.
Although the present invention has disclosed above preferred embodiment; yet it is not to limit the present invention; any those skilled in the art; within not breaking away from theme of the present invention and scope; change arbitrarily and modify when doing, so protection scope of the present invention should be as the criterion with the scope that claim was defined.
Claims (21)
1. manufacture method that contains the fiber of nano bubble comprises:
One polymeric material is provided;
One light-sensitive compound is mixed with this polymeric material, form a mixture;
This mixture is carried out a spinning manufacture method, form a fiber; And
After this fiber solidifies, this fiber is carried out a photo-irradiation treatment or a heat treated, so that this intrastitial this photosensitive compound deposits yields one gas, wherein this gas forms the nano bubble of a plurality of sealings at this fibrous inside, and the size of described nano bubble is between between the 300nm to 800nm.
2. the manufacture method that contains the fiber of nano bubble according to claim 1, wherein this polymeric material has nitrogen infiltration coefficient≤0.2barrer, oxygen permeability coefficient≤1barrer, and carbon dioxide infiltration coefficient≤3barrer.
3. the manufacture method that contains the fiber of nano bubble according to claim 1, wherein this polymer is selected from polyacrylonitrile, polymethacrylonitrile, polyacrylonitrile styrene, polyvinylidene chloride, acrylonitrile methyl meth acrylat copolymer, polyethylene terephthalate, polyamide 6, polyvinyl chloride, polyethylene, Parylene, cellulose acetate, PLA and aforesaid derivative.
4. the manufacture method that contains the fiber of nano bubble according to claim 1, wherein this light-sensitive compound comprises diazonium compound, azo-compound or cationic photosensitive initiator.
5. the manufacture method that contains the fiber of nano bubble according to claim 4, wherein this diazonium compound comprises 1,2-diazido naphthoquinones-5-sulphonic acid ester, 2,3,4-trihydroxybenzophenone 1,2-diazido naphthoquinones-5-sulphonic acid ester or 1-naphthalene sulfonic aicd, 6-diazonium-5,6-dihydro-5-oxo, 4-cumenyl phenyl chloroformate.
6. the manufacture method that contains the fiber of nano bubble according to claim 4, wherein this azo-compound comprises 2-(4 '-hydroxy benzenes azoles) benzoic acid, α, β-two (phenylazo) stilbene mixture, 4-be amino-4 '-derivative of dimethylaminoazobenzene, 4-phenylazo benzoic acid or two (sulfonic group) diazomethane.
7. the manufacture method that contains the fiber of nano bubble according to claim 4, wherein this cationic photosensitive initiator comprises the derivative of 3,5-dichloro-benzenes diazonium tetrafluoroborate, 4-methoxybenzene diazonium tetrafluoroborate or benzophenone.
8. the manufacture method that contains the fiber of nano bubble according to claim 1, wherein this photo-irradiation treatment comprises according to ultraviolet light or according to daylight, the temperature of this heat treated between 120 ℃ between the fusing point of Fiber Materials, and the gas of this photosensitive compound deposits yields is escaping gas, comprises nitrogen, oxygen or carbon dioxide.
9. the manufacture method that contains the fiber of nano bubble according to claim 1, wherein the content of this light-sensitive compound is 0.1 percentage by weight to 5 percentage by weight of this polymeric material.
10. the manufacture method that contains the fiber of nano bubble according to claim 1, wherein this spinning manufacture method comprises a wet spinning manufacture method or a melt spinning manufacture method.
11. the manufacture method that contains the fiber of nano bubble according to claim 1, wherein this gas more comprises the micron bubble that forms a plurality of sealings at this fibrous inside, and the size of described micron bubble is between 1 μ m to 3 μ m.
12. a fiber that contains nano bubble comprises:
One fibrous body;
The nano bubble of a plurality of sealings is arranged in this fibrous body, and the size of wherein said nano bubble is between between the 300nm to 800nm; And
The residue of one light-sensitive compound is mixed in this fibrous body, and wherein the residue of this light-sensitive compound is the residue after a light-sensitive compound discharges a gas.
13. the fiber that contains nano bubble according to claim 12, wherein this fibrous body has nitrogen infiltration coefficient≤0.2barrer, oxygen permeability coefficient≤1barrer, and carbon dioxide infiltration coefficient≤3barrer.
14. the fiber that contains nano bubble according to claim 12, wherein the material of this fibrous body is selected from polyacrylonitrile, polymethacrylonitrile, polyacrylonitrile styrene, polyvinylidene chloride, acrylonitrile methyl meth acrylat copolymer, polyethylene terephthalate, polyamide 6, polyvinyl chloride, polyethylene, Parylene, cellulose acetate, PLA and aforesaid derivative.
15. the fiber that contains nano bubble according to claim 12, wherein this gas of this light-sensitive compound release is escaping gas, comprises nitrogen, oxygen or carbon dioxide.
16. the fiber that contains nano bubble according to claim 12, wherein this light-sensitive compound comprises diazonium compound, azo-compound or cationic photosensitive initiator.
17. the fiber that contains nano bubble according to claim 16, wherein this diazonium compound comprises 1,2-diazido naphthoquinones-5-sulphonic acid ester, 2,3,4-trihydroxybenzophenone 1,2-diazido naphthoquinones-5-sulphonic acid ester or 1-naphthalene sulfonic aicd, 6-diazonium-5,6-dihydro-5-oxo, 4-cumenyl phenyl chloroformate.
18. the fiber that contains nano bubble according to claim 16, wherein this azo-compound comprises 2-(4 '-hydroxy benzenes azoles) benzoic acid, α, β-two (phenylazo) stilbene mixture, 4-be amino-4 '-derivative of dimethylaminoazobenzene, 4-phenylazo benzoic acid or two (sulfonic group) diazomethane.
19. the fiber that contains nano bubble according to claim 16, wherein this cationic photosensitive initiator comprises the derivative of 3,5-dichloro-benzenes diazonium tetrafluoroborate, 4-methoxybenzene diazonium tetrafluoroborate or benzophenone.
20. the fiber that contains nano bubble according to claim 12, wherein the content of the residue of this light-sensitive compound in this fibrous body is between 0.1 percentage by weight to 5 percentage by weight.
21. the fiber that contains nano bubble according to claim 12 comprises that more the micron bubble of a plurality of sealings is arranged in this fibrous body, the size of wherein said micron bubble is between 1 μ m to 3 μ m.
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|---|---|---|---|---|
| CN104831448A (en) * | 2015-03-26 | 2015-08-12 | 苏州威尔德工贸有限公司 | Color-variable fabric |
| WO2022156215A1 (en) * | 2021-01-20 | 2022-07-28 | 东华大学 | Spinning stock solution, and heat-resistant creep-resistant fiber and preparation method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010045547A1 (en) * | 2000-02-24 | 2001-11-29 | Kris Senecal | Conductive (electrical, ionic and photoelectric) membrane articlers, and method for producing same |
| WO2008135276A2 (en) * | 2007-05-07 | 2008-11-13 | Universität Duisburg-Essen | Assembly and method for the three-dimensional distribution of light in a liquid medium |
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| TW200717179A (en) * | 2005-10-19 | 2007-05-01 | Ind Tech Res Inst | Nanofiber-based substrate with surface patterns and method for fabricating the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010045547A1 (en) * | 2000-02-24 | 2001-11-29 | Kris Senecal | Conductive (electrical, ionic and photoelectric) membrane articlers, and method for producing same |
| WO2008135276A2 (en) * | 2007-05-07 | 2008-11-13 | Universität Duisburg-Essen | Assembly and method for the three-dimensional distribution of light in a liquid medium |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104831448A (en) * | 2015-03-26 | 2015-08-12 | 苏州威尔德工贸有限公司 | Color-variable fabric |
| WO2022156215A1 (en) * | 2021-01-20 | 2022-07-28 | 东华大学 | Spinning stock solution, and heat-resistant creep-resistant fiber and preparation method therefor |
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| CN102965748B (en) | 2015-04-22 |
| TW201311953A (en) | 2013-03-16 |
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