CN1300246C - Method for preparing uvioresistant polyester by nanometer titania generated in situ - Google Patents
Method for preparing uvioresistant polyester by nanometer titania generated in situ Download PDFInfo
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- CN1300246C CN1300246C CNB2003101227461A CN200310122746A CN1300246C CN 1300246 C CN1300246 C CN 1300246C CN B2003101227461 A CNB2003101227461 A CN B2003101227461A CN 200310122746 A CN200310122746 A CN 200310122746A CN 1300246 C CN1300246 C CN 1300246C
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a preparation method of uvioresistant polyester by generating nanometer titanium dioxide in situ, which belongs to the technical field of composite materials. The preparation method comprises the following steps: firstly, synthesizing titanium glycolate whose hydrolysis speed is controllable; then, processing the titanium glycolate in an organic stabilizing treatment mode in order to decrease the hydrolysis speed further; subsequently, homogeneously dispersing the titanium glycolate over dibasic alcohol in order to prepare stable precursor slurry; finally, polymerizing or copolymerizing the precursor slurry with other monomers of polyester; generating nanometer titanium oxide particles uniformly distributed in situ; obtaining the uvioresistant nanometer titanium dioxide/polyester composite material which has excellent mechanical property and thermology property. The ultraviolet shielding index of fabrics obtained by spinning and weaving the composite materials is larger than 50, the ultraviolet shielding rate of thin films prepared from the materials is larger than 99%, and the mechanical property is decreased by smaller than 5% after the materials are irradiated by ultraviolet rays for 1000 hours. The nanometer titanium oxide/polyester composite material prepared by the present invention can be applied to the technical fields of fiber, thin films, engineering plastics, etc. in order to enhance the capabilities of shielding ultraviolet rays and resisting aging of the materials.
Description
Technical field
The present invention relates to a kind of preparation method of polyester, particularly a kind of anti-ultraviolet radiation poly ester original position generates the preparation method.Belong to field of compound material.
Technical background
In recent years, because forest vegetation is destroyed aggravation, Sunspot Activities is frequent and factors such as a large amount of uses freon refrigerant make the mankind be faced with enhanced ultraviolet radiation day by day, ultraviolet ray be divided into UVC (200～280nm), UVB (280～320nm), UVA (320～400nm) three districts.UVC is absorbed by ozonosphere, does not reach ground, to the basic not damaged effect of human body.UVB can be absorbed by dermis of skin, and permanent irradiation erythema, inflammation, skin aging can occur, can cause skin carcinoma when serious.The UVA penetrance is dark more than UVB, can make skin pitch-dark, and long-term accumulation will cause skin aging.Simultaneously, the energy that ultraviolet ray has is about 314～419KJ/mol, is enough to destroy chemical bond, the initiation autoxidation reaction of polymkeric substance, causes the degradation with aging of polymkeric substance such as plastics, rubber, coating resin, and the loss that therefore cause every year is huge.
At present, the polyester with the ageing-resistant function of uvioresistant mainly adopts interpolation uvioresistant additive to carry out the preparation of blended melting method.The uvioresistant additive is divided into organic and inorganic two big classes.Inorganic UV shield agent becomes research and uses focus with characteristics such as the chemistry of its brilliance and thermostability, non-migrating, tasteless, nontoxic, nonirritants.Find by literature search, the name that people such as Lin Dalin delivered in " synthon " May calendar year 2001 is called: the high-speed spinning long filament experiment of uvioresistant modified poly ester, this article has proposed a kind of preparation method of trevira of anti-ultraviolet radiation, it is few promptly to filter out a kind of addition, the inorganic additives refinement in advance processing that ultraviolet screener usefulness is high, be distributed to and prepare slurries in the polymerization single polymerization monomer, on semicontinuous polyester production equipment, produce superior in quality uvioresistant modified poly ester section, and carried out POY, the spinning experiment of kind such as FDY and DTY, section reaches common half delustring levels of polyester with the every performance of fiber, adopt redness that the modification anti-ultraviolet polyester fiber makes or color prime white fabric to ultraviolet transmitance less than 92%.Though this method has adopted inorganic anti ultraviolet ray additive, the fiber of preparation and the ultraviolet shielding effect of fabric are better, but do not provide the kind and the title of additive, though simultaneously additive has been carried out thinning processing in advance, but because the reagent particle diameter that adds is still bigger, so the addition in polymerization process must be more, cause component pressure rising in spinning process, not only shortened the life cycle of filter and assembly, and the mechanical property of fiber only can be suitable with half delustring polyester, do not play enhancement.
Summary of the invention
The present invention is directed to the problems referred to above that exist in the background technology, a kind of preparation method of anti-ultraviolet radiation poly ester is provided, the present invention has at first abandoned and has added ultraviolet screening agent carry out the method that polymerization prepares uvioresistant polyester in polyester monocase, but synthesized the dibasic alkoxide of the controlled titanium of a kind of hydrolysis rate, make its original position in the polyester process generate nano titanium oxide, and then in-situ polymerization has prepared the polyester with anti-ultraviolet function.The present invention has solved UV light absorber fully and has reunited in polymkeric substance and disperse disadvantages such as intensity irregular, material is low, heat resistance difference, and the fiber spinnability of blend melt spinning method preparation and problems such as mechanical property is relatively poor and anti-ultraviolet property falls flat, deficiencies such as having overcome back finishing technique fabric feeling simultaneously, breathe freely, wearing comfort and function weather resistance are not good.The uvioresistant polyester that the present invention makes is compared with conventional polyester, and the processibility of material, mechanical property and resistance toheat are unaffected, the remarkable long-acting environment friendly of uvioresistant effect.
The present invention is achieved by the following technical solutions, the preparation method of the uvioresistant polyester that the present invention proposes is as follows: the ethylene glycol salt of the presoma-titanium of at first synthetic hydrolysis speed-controllable, ethylene glycol salt to titanium carries out surperficial organic stabilization treatment then, and the ethylene glycol salt of the more simple titanium of its hydrolysis rate is further descended.Thereafter it is dispersed in and makes stable precursor pulp in the dibasic alcohol.Last and the necessary another kind of monomer of synthesizing polyester ...-aromatic binary carboxylic acid carries out polymerization, make the ethylene glycol salt of presoma titanium that hydrolysis reaction take place in polymerization process, original position generates the even particle size distribution titanium dioxide nanoparticle, it is compound that titanium dioxide nanoparticle that generates and polyester carry out original position simultaneously, and then obtain having the nano titanium oxide/polyester composite of anti-ultraviolet property.
This material can be used for preparing antiultraviolet fiber, film and various ageing-resistant injection moulding polyester articles etc.Thus the matrix material spinning weave the fabric that obtains the ultraviolet screener index greater than 50, material is made the rate of ultraviolet shield of film greater than 99%.After 1000 hours, the mechanical properties decrease amplitude is less than 5% in uviolizing for material.
Below method of the present invention is further described, concrete steps are as follows:
(1) preparation of the ethylene glycol salt of presoma titanium is at protective atmosphere N
2Down, add 100mL ethylene glycol in the reactor that has water distilling apparatus, and carry out intensive and stir, and use the ice-water bath cooling reactor, add 10～20ML titanium tetrachloride in the ethylene glycol lentamente, keep stirring after 30 minutes, remove ice-water bath, and feed the exsiccant ammonia lentamente, stir after 30 minutes, there are a large amount of ammonium salts to produce in the solution, when the pH value of solution value is neutrality, stop ammonia and feed, keep stirring 20 minutes, filter, the filtrate decompression distillation obtains a large amount of white solid things, filters, use the washing with acetone solid product, obtain the ethylene glycol salt of titanium.
(2) the ethylene glycol salt with above-mentioned titanium is dispersed in the dibasic alcohol, solid content is 15～30% mass percents, generate the content of nano titanium oxide by hydrolysis, adding organic agent or coupling agent carry out surface organic modification to it in slurry simultaneously, consumption is 2～10% quality percentages of the nano titanium oxide amount of generation, adopt high speed dispersor that the ethylene glycol/dibasic alcohol slurry of titanium is mixed then, standby.
(3) another monomer-aromatic binary carboxylic acid of the ethylene glycol of the titanium that above-mentioned steps is obtained/dibasic alcohol slurry and polyester carries out polyreaction under the condition of catalyzer and stablizer existence, and the nanometer titanium dioxide titanium content that in-situ hydrolysis generates in polymerization process accounts for 0.3%～3% of polyester total amount.According to the different field that final material is used, original position obtains the nano titanium oxide/polyester composite of different molecular weight.
Organic agent of the present invention is one or both in polyoxyethylene glycol, the polyvinylpyrrolidone.Described coupling agent is meant silane coupling agent.
Dibasic alcohol of the present invention is a kind of in ethylene glycol, propylene glycol, the butyleneglycol.
Ethylene glycol salt of the present invention generated in-situ nano titanium oxide in the polyester process can participate in the polyester reaction separately, also can together carry out polyreaction with chemical fibre of titanium dioxide.
In-situ polymerization of the present invention prepares nano titanium oxide/polyester composite and can be used on fields such as fiber, film and engineering plastics.
Compared with prior art, the present invention has at first utilized the ethylene glycol salt of the controlled titanium of hydrolysis rate as the presoma that generates ultraviolet screening agent----nano titanium oxide, and it is carried out organic stabilizing modification, further reduced the hydrolysis rate of the ethylene glycol salt of titanium on the one hand, guaranteed its in the polyester process steadily hydrolysis generate the little and titanium dioxide nanoparticle that is evenly distributed of particle diameter, and, improve PET hue through reducing the catalytic activity of nano titanium oxide behind the organic modification greatly to the polyester degraded.It is worthy of note that the present invention adopts the method for original position generation nano particle in polymerization process, solved the agglomeration traits of titanium dioxide nanoparticle in matrix at all, truly realized nanometer homodisperse and composite effect.Nano titanium oxide/polyester composite of obtaining of method can be used for preparing antiultraviolet fiber, film and various ageing-resistant injection moulding polyester articles etc. thus.Thus the matrix material spinning weave the fabric that obtains the ultraviolet screener index greater than 50, material is made the rate of ultraviolet shield of film greater than 99%.
Embodiment
Provide following examples in conjunction with content of the present invention:
Embodiment 1
In the reactor that has agitator, water distilling apparatus, add 100ml ethylene glycol, and carry out violent stirring and ice-water bath cooling; At protective atmosphere N
2Down, slowly add the 10ml titanium tetrachloride, stirred lasting 30 minutes, remove refrigerating unit, by separating funnel, slowly feed the exsiccant ammonia, when treating that solution is neutrality, maintenance stirred 20 minutes, left standstill and was cooled to normal temperature, filtered, and obtained the liquid of facile hydrolysis; Moving into then in the reliever, is 1000Pa in vacuum tightness, and temperature is 80 ℃ of down distillations, and after 15 minutes, a large amount of white precipitates generates, and leaves standstill and is cooled to normal temperature, filters, and uses the washing with acetone filtrate, and drying promptly gets the ethylene glycol salt solid of titanium.
In the 2000mL beaker, add ethylene glycol 1470 grams, stir the 30 gram polyvinylpyrrolidones of adding down, be heated to 70 ℃, after treating that polyvinylpyrrolidone dissolves fully, take by weighing ethylene glycol salt solid 630 gram of above-mentioned titanium, and at 70 ℃ of following stirring reactions after 1 hour, standby.
Ethylene glycol salt/ethylene glycol slurry 1960 grams of 8000g terephthalic acid, 2630g ethylene glycol and above-mentioned titanium are together added in 30 liters of polyester stills the making beating back, use antimony glycol to be polymerization stabilizer, carry out polyreaction as polycondensation catalyst, trimethyl phosphite 99.Feed nitrogen, the esterification of this process is carried out under 0.2Mpa pressure, polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 150 minutes, obtain nano titanium oxide/polyester composite.The form and aspect L value 85.79 of resin, form and aspect b value 6.08, limiting viscosity are 0.657,260.8 ℃ of fusing points, carboxyl-content are 24mol.t
-1, glycol ether content is 1.4%.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 163.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.07%.
Embodiment 2
Be dispersed in the ethylene glycol according to the glycol salt of embodiment 1 described method the second of modification, different is that solid content of slurry is 15%, the organic modifiers of selecting for use is a polyoxyethylene glycol, the consumption of polyoxyethylene glycol be 8.5 grams (by generate the nano titanium oxide metering 6%).
Ethylene glycol salt/ethylene glycol slurry 1960 grams of 8000g terephthalic acid, 2330g ethylene glycol and above-mentioned titanium are together added in 30 liters of polyester stills the making beating back, use antimony glycol to be polymerization stabilizer, carry out polyreaction as polycondensation catalyst, trimethyl phosphite 99.Esterification is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 185 minutes, obtain nano titanium oxide/polyester composite, the form and aspect L value 88.63 of resin, form and aspect b value 4.59, limiting viscosity are 0.669,261.2 ℃ of fusing points, carboxyl-content are 22mol.t
-1, glycol ether content is 1.2%.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 106.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.11%.
Embodiment 3
Be dispersed in the ethylene glycol according to the glycol salt of embodiment 1 described method the second of modification, different is that solid content of slurry is 22.5%, organic modifiers is silane coupling agent KH560, the consumption of KH560 be 0.56 gram (by generate the nano titanium oxide metering 2%).
Ethylene glycol salt/ethylene glycol slurry 260 grams of 8000g terephthalic acid, 3800 gram ethylene glycol and above-mentioned titanium are together added in 30 liters of polyester stills the making beating back, use antimony glycol to be polymerization stabilizer, carry out polyreaction as polycondensation catalyst, trimethyl phosphite 99.Esterification is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 230 minutes, obtain nano titanium oxide/polyester composite, the form and aspect L value 89.67 of resin, form and aspect b value 2.46, limiting viscosity are 0.681,260.2 ℃ of fusing points, carboxyl-content are 20mol.t
-1, glycol ether content is 0.9%.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 52.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.20%.
Embodiment 4
According to embodiment 1 described method two alkoxide of the second of titanium are carried out surperficial organic stabilization treatment, different is is dispersed in the glycol salt of the second of titanium in the butyleneglycol.
With the 8000g terephthalic acid, the ethylene glycol salt of 5365 gram butyleneglycols and above-mentioned titanium/butyleneglycol slurry 2250 grams together add in 30 liters of polyester stills the making beating back, use tetrabutyl titanate to be polymerization stabilizer, carry out polyreaction as polycondensation catalyst, trimethyl phosphite 99.Esterification is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Keep high vacuum discharging after 210 minutes, obtain nano titanium oxide/polyester composite, the form and aspect L value 86.78 of resin, form and aspect b value 7.26, limiting viscosity are 1.10,220.1 ℃ of fusing points.
80 ℃ of dryings are after 12 hours in vacuum drying oven with above-mentioned nano titanium oxide/polyester composite resin, and behind the injection molding standard testing batten, the tensile strength of sample is 57.8MPa, and notched Izod impact strength is 6.0KJ/M
2, dimension card modification temperature is 171 ℃, and after 1000 hours, the every mechanical properties decrease of material is less than 5% through uviolizing for sample, and material b value is 8.88.
Embodiment 5
According to embodiment 3 described methods, different is in polymerization process, original position generates the nano titanium oxide in polymerization process, chemical fibre of titanium dioxide 28 grams of using as the polyester delustring that also added mean particle size and be 300 nanometers (account for 0.3% of weight polyester, mass percent), behind the in-situ polymerization, obtain nano titanium oxide/delustring polyester composite.The form and aspect L value 90.13 of resin, form and aspect b value 3.03, limiting viscosity are 0.681,261.1 ℃ of fusing points, carboxyl-content are 26mol.t
-1, glycol ether content is 1.0%.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 48 hours in vacuum drying oven, the ultraviolet screener index UPF value of carrying out making after spinning, drawing-off, the manufacturing thickness and be 50 microns plain is 70.
With above-mentioned nano titanium oxide/polyester composite resin 150 ℃ of dryings after 6 hours in vacuum drying oven, the film that carries out making after membrane, the drawing-off thickness and be 20 microns is a transparence, ultraviolet average transmittances (280～400nm) 0.15%.
Claims (4)
1, a kind of original position generates the method that nano titanium oxide prepares uvioresistant polyester, it is characterized in that the preparation method is as follows: presoma--the ethylene glycol salt of-titanium: at protective atmosphere N of at first synthetic hydrolysis speed-controllable
2Down, add 100mL ethylene glycol in the reactor that has water distilling apparatus, and carry out intensive and stir, and use the ice-water bath cooling reactor, add 10～20ML titanium tetrachloride in the ethylene glycol lentamente, keep stirring after 30 minutes, remove ice-water bath, and feed the exsiccant ammonia lentamente, stir after 30 minutes, there are a large amount of ammonium salts to produce in the solution, when the pH value of solution value is neutrality, stop ammonia and feed, keep stirring 20 minutes, filter, the filtrate decompression distillation obtains a large amount of white solid things, filters, use the washing with acetone solid product, obtain the ethylene glycol salt of titanium; Adopt organic agent or silane coupling agent that the ethylene glycol salt of titanium is carried out surperficial organic stabilization treatment then, the ethylene glycol salt of the more simple titanium of its hydrolysis rate is further descended, then it is dispersed in and makes stable precursor pulp in the dibasic alcohol, last and the necessary another kind of monomer of synthesizing polyester----aromatic binary carboxylic acid carries out polymerization, make the ethylene glycol salt of presoma titanium that hydrolysis reaction take place in polymerization process, original position generates the even particle size distribution titanium dioxide nanoparticle, it is compound that titanium dioxide nanoparticle that generates and polyester carry out original position simultaneously, and then obtain having anti-ultraviolet property nano titanium oxide/polyester composite;
Described organic agent is one or both in polyoxyethylene glycol, the polyvinylpyrrolidone, and described coupling agent is meant silane coupling agent.
2, original position according to claim 1 generates the method that nano titanium oxide prepares uvioresistant polyester, it is characterized in that, below the preparation method is done further qualification:
(1) the ethylene glycol salt with above-mentioned titanium is dispersed in the dibasic alcohol, solid content is 15～30% mass percents, generate the content of nano titanium oxide by hydrolysis, adding polyoxyethylene glycol or silane coupling agent carry out surperficial organic stabilization treatment to it in slurry simultaneously, consumption is 2～10% mass percents of the nano titanium oxide amount of generation, adopt high speed dispersor that the ethylene glycol/dibasic alcohol slurry of titanium is mixed then, standby;
(2) another monomer of the ethylene glycol of the titanium that above-mentioned steps is obtained/dibasic alcohol slurry and polyester---aromatic binary carboxylic acid carries out polyreaction under the condition that has catalyzer and stablizer to exist, the nanometer titanium dioxide titanium content that in-situ hydrolysis generates in polymerization process accounts for 0.3%～3% of polyester total amount, according to the field that final material is used, original position obtains nano titanium oxide/polyester composite.
3, original position according to claim 1 and 2 generates the method that nano titanium oxide prepares uvioresistant polyester, it is characterized in that, described ethylene glycol salt generated in-situ nano titanium oxide in the polyester process participates in the polyester reaction separately, perhaps together carries out polyreaction with chemical fibre of titanium dioxide.
4, original position according to claim 1 and 2 generates the method that nano titanium oxide prepares uvioresistant polyester, it is characterized in that, described dibasic alcohol is a kind of in ethylene glycol, propylene glycol, the butyleneglycol.
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| CNB2003101227461A CN1300246C (en) | 2003-12-19 | 2003-12-19 | Method for preparing uvioresistant polyester by nanometer titania generated in situ |
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| CNB2003101227461A CN1300246C (en) | 2003-12-19 | 2003-12-19 | Method for preparing uvioresistant polyester by nanometer titania generated in situ |
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| CN1300246C true CN1300246C (en) | 2007-02-14 |
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| CN100355976C (en) * | 2006-01-13 | 2007-12-19 | 浙江理工大学 | Method for in-situ generating inorganic nanoparticles in textile |
| CN100462492C (en) * | 2006-01-20 | 2009-02-18 | 泉州海天轻纺有限公司 | Textile with ultraviolet resistant , hygroscopic and perspiratory function, and its preparation method |
| CN101020744B (en) * | 2007-03-19 | 2010-04-14 | 四川大学 | Nanometer composite polyester material and its double in-situ preparation process |
| CN102617989A (en) * | 2012-03-21 | 2012-08-01 | 太仓振辉化纤有限公司 | Formula of full-dull master batch and preparation method thereof |
| CN103059519B (en) * | 2012-12-10 | 2015-09-02 | 合肥乐凯科技产业有限公司 | A kind of preparation method of white polyester masterbatch |
| CN104193978B (en) * | 2014-08-30 | 2016-08-17 | 南京大学扬州化学化工研究院 | Chain binary titanium alkoxide catalyst for polyester synthesis and its preparation method and application |
| CN107641196B (en) * | 2017-09-25 | 2019-12-06 | 张家港美景荣化学工业有限公司 | Delustering polyester and low-glossiness elastic composite fiber |
| JP7197607B2 (en) * | 2018-01-29 | 2022-12-27 | 江蘇納盾科技有限公司 | Antibacterial/ultraviolet shielding multifunctional chemical fiber |
| CN112137902B (en) * | 2020-10-06 | 2021-07-23 | 佛山市百分之秀化妆品有限公司 | Moisturizing, concealer and anti-wrinkle composition and preparation method thereof |
| CN113265720A (en) * | 2021-05-17 | 2021-08-17 | 福建师范大学泉港石化研究院 | Polyester fiber with uvioresistant performance and preparation method thereof |
| CN113831517A (en) * | 2021-09-09 | 2021-12-24 | 万凯新材料股份有限公司 | Preparation method of antibacterial and uvioresistant polyester |
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