CN105220453A - A kind of preparation method of uvioresistant polypropylene - Google Patents
A kind of preparation method of uvioresistant polypropylene Download PDFInfo
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- CN105220453A CN105220453A CN201510800159.6A CN201510800159A CN105220453A CN 105220453 A CN105220453 A CN 105220453A CN 201510800159 A CN201510800159 A CN 201510800159A CN 105220453 A CN105220453 A CN 105220453A
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Abstract
The invention discloses a kind of preparation method of uvioresistant polypropylene.The present invention take polypropylene fibre as raw material, and dopamine-Tris mixed solution is modifier.By polypropylene fibre is soaked in dopamine-Tris solution, make it in polypropylene fibre surface autohemagglutination deposition, form poly-DOPA amine layer; By chelation, titanium dioxide is grafted to fiber surface again, makes it have uvioresistant characteristic.The simple environmental protection of abundant raw material source of the present invention, preparation method, fabric aspect will have broad application prospects out of doors.
Description
[technical field]: the invention belongs to fibre technology field, is specifically related to a kind of preparation method of uvioresistant polypropylene.
[background technology]: polypropylene fibre (PP) is the synthetic fiber that the isotactic polypropylene obtained with propylene polymerization spins for raw material.Density is 0.90 ~ 0.92g/cm
3, fusing point is 165 DEG C ~ 173 DEG C.Polypropylene fibre has good mechanical property, and initial modulus is high, and ABRASION RESISTANCE is good, good corrosion resistance, nontoxic, cost is low and the shaping advantage such as simply.Within 2014, China's polypropylene fibre output is 26.76 ten thousand tons/year, though decline to some extent than in other years, but still is one of fiber that utilization rate is the highest.Polypropylene fibre be in spin, clothes, construction material, textile for automobile, health care, packaging bag field be all widely used.But because polypropylene contains methyl chains, easily there is oxidation reaction by ultraviolet irradiation, make polypropylene fibre very easily aging.This characteristic makes the application of polypropylene fibre be very limited, and therefore, carries out uvioresistant modification be significant to polypropylene fibre.
At present, it is modifies with this that the uvioresistant method of modifying of Chinese scholars to polypropylene fibre mainly comprises surface modification, and following emphasis is set forth around these two kinds of method of modifying:
1. modifies
This is modifies is add a certain amount of ultraviolet-resistant aid to spinning process, fiber is made to have uvioresistant performance, titanium dioxide under this method of modifying and polypropylene belong to physical blending, there is not chemical bond and link, there is the shortcomings such as easy migration, effect are not lasting.And the interpolation of titanium dioxide also can affect spinning properties and final fibre property.
2. surface modification
2.1 sol-gel process
Sol-gel process refers to that the compound containing high chemical active ingredient is hydrolyzed in the solution, condensation reaction, obtain the sol system of stable transparent, the method gel being generated gel again by ageing process can prepare required material again through heat treatment and drying, TiO 2 sol is evenly attached to fiberglass surfacing by Wiener etc., find with after ultraviolet radiation 3h, intensity and the percentage elongation of unprocessed glass fiber sample significantly reduce, and the glass fibre after process is without significant change.But these class methods affect feel, the inadequate dense uniform of coating, easily come off, fastness to washing is poor.
2.2 electroless plating method
Chemical plating refer to controllable redox reaction by the catalytic action of metal metallic deposition process.Liu Zhi ability etc. carries out surface chemistry plating to polyamide 6 fabric, and make the uniform silver layer of its surface attachment, after process, the UPF value of fabric reaches 142.7.This mainly makes the optical absorption of material significantly strengthen due to the nano-Ag particles that fabric face particle diameter and optical wavelength are quite even less, therefore Absorbable rod some ultra violet rays.But this method can produce the discard solution containing heavy metal ion, contaminated environment.
2.3 magnetron sputtering method
Magnetron sputtering technology refers to that electronics collides with ar atmo under the effect of electric field, ionizes out Ar+ subsequently, and Ar+ bombards target, and a large amount of target atom is sputtered out and in deposition on substrate film forming.Xu Yang etc., technique of magnetron reactive sputtering is adopted to form titanium deoxid film on terylene non-weaving cloth surface at ambient temperature, find that the fabric after process has better uvioresistant performance, and within the specific limits, the chemical constitution impact of sputtering power on deposit film is little, but it is larger to the appearance effects of sputtering yield and film, the compactness of film, uniformity, sputtering yield all increases along with the increase of sputtering power, but the too high meeting of sputtering power makes matrix overheated, film deposition rate is not only made to reduce, uniformity declines, and easy damaged matrix, shortcoming be in this way that cost is high, and the mechanical property of fiber can be damaged.
And the present invention proposes a kind of preparation method of uvioresistant polypropylene, be soaked in dopamine-Tris solution by polypropylene fibre, dopamine can be oxidized autohemagglutination, is firmly adsorbed on polypropylene fiber surface, then will gather dopamine as secondary function layer, grafting titanium dioxide.The Novel modifier that dopamine gets up as development in recent years, it inspires by marine mussel, can be oxidized autohemagglutination under weak basic condition, firmly sticks to the green bionical material of one of almost various (organic and inorganic) material surface.And there is catechol, amido and imino group in poly-dopamine, so poly-DOPA amine layer again can as secondary function layer.
Catechol group on poly-dopamine is hydrolyzed the titanium dioxide generation chelation of generation in BAS with ammonium titanium fluoride, thus titanium dioxide is fixed on fiber surface with the link of chemical bond form, and titanium dioxide is ultraviolet light screener, can effective shielding ultraviolet rays, thus improve the ultraviolet-resistent property of polypropylene fibre.Polypropylene fiber prepared by this method: first, because poly-dopamine is coated on fiber surface, can protect fibrous inner structure not change as layer protective layer, so substantially remain unchanged through the mechanical property of modified fiber; Secondly, titanium dioxide is fixed on fiber surface with the form of covalent bond, and such adhesion can be stronger, difficult drop-off; Finally, the medicine of above-mentioned use is water-soluble substances, and equipment is simple and easy to get, easy and simple to handle.
[summary of the invention]: for the deficiencies in the prior art, this patent adopts a kind of method of simple to operate, green non-pollution, and object is the oxidation autohemagglutination by dopamine, adheres to fiber surface, again titanium dioxide is fixed in poly-DOPA amine layer with chemical bond form, improves the ultraviolet-resistent property of polypropylene fibre.
First dopamine is sticked to polypropylene fibre surface as secondary function layer by the present invention, simultaneously ammonium titanium fluoride be hydrolyzed in BAS generation titanium dioxide can on the catechol group of poly-dopamine growth in situ, link with chemical bond form and be fixed on fiber surface, thus improve the ultraviolet-resistent property of polypropylene fibre.The method has bonding force compared to traditional blending and modifying and drops by force, not easily, and can not change the advantage of the original mechanical property of fiber.
For reaching this object, the technology path that the present invention adopts is:
1) preliminary treatment of polypropylene fiber:
The polypropylene fibre commercially bought is soaked a period of time in ethanol, removes organic solvent residual on polypropylene fibre, then take out oven dry.
2) adhesion of dopamine:
The Tris taking 0.0605-0.1210g is dissolved in 200ml water, and adjust ph to 8.5, takes the dopamine of 0.2-0.4g subsequently, to be dissolved in above-mentioned Tris solution and to stir.Polypropylene fibre is immersed this solution, dopamine-Tris mixed solution brownly finally can become black from colourless becoming in the process, and polypropylene fibre also can become black from white.After reaction 6-48h, polypropylene fibre is taken out, repeatedly rinses with deionized water, dry stand-by;
3) grafting titanium dioxide:
Configuration 0.01-0.1mol/L ammonium titanium fluoride and the mixed solution of 0.03-0.3mol/L boric acid, adjust ph to 3.gg, then by 2) fiber that obtains steeps in mixed solution, 1min-1h is reacted under room temperature, take out and repeatedly rinse with deionized water, drying, obtained uvioresistant polypropylene.
The principle of the invention is: dopamine can be oxidized autohemagglutination under weak basic condition, and can stick to matrix surface.And ammonium titanium fluoride hydrolysis generate titanium dioxide can on the catechol group of poly-dopamine growth in situ, finally at polypropylene fibre Surface Creation titanium dioxide layer, thus make polypropylene fibre have uvioresistant characteristic.
The method applied in the present invention, can be applied to the surface modification of most of material, simple to operate, requires low, green non-pollution, and can not change the original mechanical property of fiber, can be widely used in outdoor fabric to appointed condition.
[specific embodiments]
Embodiment 1:
1) preliminary treatment of polypropylene fiber.Polypropylene fibre is cut to certain length, soaks a period of time in ethanol, remove organic solvent residual on polypropylene fibre, then taking-up is dried stand-by.
2) deposition of dopamine.Take 0.0605gTris to be dissolved in 200ml deionized water, then take 0.2g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 6h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Preparation 0.01mol/L ammonium titanium fluoride and the mixed solution of 0.03mol/L boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 1min under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Embodiment 2:
1) preliminary treatment of polypropylene fiber.With embodiment 1.
2) deposition of dopamine.Take 0.121gTris to be dissolved in 200ml deionized water, then take 0.4g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 12h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Preparation 0.02mol/L ammonium titanium fluoride and the mixed solution of 0.06mol/L boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 2min under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Embodiment 3:
1) preliminary treatment of polypropylene fiber.With embodiment 1.
2) deposition of dopamine.Take 0.121gTris to be dissolved in 200ml deionized water, then take 0.4g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 18h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Preparation 0.03mol/L ammonium titanium fluoride and the mixed solution of 0.09mol/L boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 3min under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Embodiment 4:
1) preliminary treatment of polypropylene fiber.With embodiment 1.
2) deposition of dopamine.Take 0.0605gTris to be dissolved in 200ml deionized water, then take 0.2g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 18h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Preparation 0.04M ammonium titanium fluoride and the mixed solution of 0.12M boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 5min under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Embodiment 5:
1) preliminary treatment of polypropylene fiber.With embodiment 1.
2) deposition of dopamine.Take 0.121gTris to be dissolved in 200ml deionized water, then take 0.4g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 24h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Preparation 0.05mol/L ammonium titanium fluoride and the mixed solution of 0.15mol/L boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 7min under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Embodiment 6:
1) preliminary treatment of polypropylene fiber.With embodiment 1.
2) deposition of dopamine.Take 0.0605gTris to be dissolved in 200ml deionized water, then take 0.2g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 30h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Prepare the mixed solution of 0.07 ammonium titanium fluoride and 0.21mol/L boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 10min under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Embodiment 7:
1) preliminary treatment of polypropylene fiber.With embodiment 1.
2) deposition of dopamine.Take 0.121gTris to be dissolved in 200ml deionized water, then take 0.4g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 36h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Preparation 0.09mol/L ammonium titanium fluoride and the mixed solution of 0.27mol/L boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 30min under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Embodiment 8:
1) preliminary treatment of polypropylene fiber.With embodiment 1.
2) deposition of dopamine.Take 0.0605gTris to be dissolved in 200ml deionized water, then take 0.2g dopamine and be dissolved in Tris solution, to be soaked by polypropylene fibre in solution then fast, reaction condition is: room temperature, 48h.Repeatedly rinse with deionized water after taking-up, dry stand-by.
3) grafting titanium dioxide.Preparation 0.1mol/L ammonium titanium fluoride and the mixed solution of 0.3mol/L boric acid, adjust ph to 3.88, then by 2) fiber that obtains steeps in mixed solution, reacts 1h under room temperature.Repeatedly rinse with deionized water after taking-up, dry, obtained described uvioresistant polypropylene.
Claims (5)
1. a preparation method for uvioresistant polypropylene, comprises the steps:
1) cleaning of polypropylene fibre
The polypropylene fibre commercially bought is soaked a period of time in ethanol, removes the organic solvent that fiber surface is residual, then take out oven dry;
2) deposition of dopamine
The Tris taking 0.0605-0.121g is dissolved in 200ml water, adjust ph to 8.5, take the dopamine of 0.2-0.4g subsequently, being dissolved in above-mentioned Tris solution and stirring, being immersed by polypropylene fibre in this solution, dopamine solution brownly finally can become black from colourless becoming in the process, and polypropylene fibre also can become black from white, after 6-48h, polypropylene fibre is taken out and dries, stand-by;
3) grafting titanium dioxide
The preparation ammonium titanium fluoride of 0.01-0.1mol/L and the mixed solution of 0.03-0.3mol/L boric acid, adjust ph to 3.88, is soaked in fiber in this solution, reacts 1min-1h under room temperature, and take out and dry, so far uvioresistant polypropylene is successfully prepared.
2. the preparation method of a kind of uvioresistant polypropylene according to claim 1, is characterized in that: the modifier of use is dopamine-Tris mixed solution.
3. the preparation method of a kind of uvioresistant polypropylene according to claim 1, is characterized in that: dopamine is oxidized autohemagglutination in Tris solution, adheres to polypropylene fibre surface.
4. the preparation method of a kind of uvioresistant polypropylene according to claim 1, is characterized in that: ammonium titanium fluoride is hydrolyzed and generates titania molecule in BAS.
5. the preparation method of a kind of uvioresistant polypropylene according to claim 1, its characteristic is: dopamine exists catechol group, titanium dioxide can on catechol group growth in situ, finally fiber surface formed titanium dioxide layer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106436288A (en) * | 2016-09-30 | 2017-02-22 | 天津工业大学 | Preparation method of conductive spandex or cotton fabric |
| CN108103778A (en) * | 2018-02-07 | 2018-06-01 | 盐城工学院 | Preparation method and fabric obtained by this method with antifouling sun-proof complex function fabric and include its dress ornament |
| CN108755125A (en) * | 2018-05-28 | 2018-11-06 | 苏州大学 | Fire-retardant ultraviolet resistant nylon fabric and preparation method thereof |
| CN110714272A (en) * | 2019-10-14 | 2020-01-21 | 江苏盛纺纳米材料科技股份有限公司 | Degradable high-flexibility non-woven fabric and manufacturing method thereof |
| CN111394993A (en) * | 2020-04-29 | 2020-07-10 | 界首市宏利塑料有限公司 | Anti-aging plastic rope and preparation method thereof |
| CN112726206A (en) * | 2020-12-28 | 2021-04-30 | 安徽省临泉县万隆塑料包装有限公司 | Ultraviolet-resistant polyethylene non-woven fabric and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891829A (en) * | 2015-06-11 | 2015-09-09 | 济南大学 | Method for growing nano titanium dioxide on glass fiber surface |
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2015
- 2015-11-18 CN CN201510800159.6A patent/CN105220453A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891829A (en) * | 2015-06-11 | 2015-09-09 | 济南大学 | Method for growing nano titanium dioxide on glass fiber surface |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106436288A (en) * | 2016-09-30 | 2017-02-22 | 天津工业大学 | Preparation method of conductive spandex or cotton fabric |
| CN108103778A (en) * | 2018-02-07 | 2018-06-01 | 盐城工学院 | Preparation method and fabric obtained by this method with antifouling sun-proof complex function fabric and include its dress ornament |
| CN108103778B (en) * | 2018-02-07 | 2019-11-15 | 盐城工学院 | Preparation method and fabric obtained by this method with antifouling sun-proof complex function fabric and include its dress ornament |
| CN108755125A (en) * | 2018-05-28 | 2018-11-06 | 苏州大学 | Fire-retardant ultraviolet resistant nylon fabric and preparation method thereof |
| CN110714272A (en) * | 2019-10-14 | 2020-01-21 | 江苏盛纺纳米材料科技股份有限公司 | Degradable high-flexibility non-woven fabric and manufacturing method thereof |
| CN111394993A (en) * | 2020-04-29 | 2020-07-10 | 界首市宏利塑料有限公司 | Anti-aging plastic rope and preparation method thereof |
| CN112726206A (en) * | 2020-12-28 | 2021-04-30 | 安徽省临泉县万隆塑料包装有限公司 | Ultraviolet-resistant polyethylene non-woven fabric and preparation method thereof |
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Application publication date: 20160106 |