CN1204196C - Uvioresistant composite zinc oxide-polyester material and its prepn - Google Patents
Uvioresistant composite zinc oxide-polyester material and its prepn Download PDFInfo
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- CN1204196C CN1204196C CN 03138993 CN03138993A CN1204196C CN 1204196 C CN1204196 C CN 1204196C CN 03138993 CN03138993 CN 03138993 CN 03138993 A CN03138993 A CN 03138993A CN 1204196 C CN1204196 C CN 1204196C
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- zinc oxide
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- ethylene glycol
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Abstract
The present invention relates to ultraviolet resisting polyester compounded with zinc oxide, and a preparing method thereof, which belongs to the technical field of macromolecular materials. The ultraviolet resisting polyester compounded with the zinc oxide is obtained by the following method: zinc oxide is dissolved in the mixed glycol solution of ammonia and ammonium carbonate to form the glycol suspension of zinc carbonate hydroxide by heating, and then water in the glycol suspension of the zinc carbonate hydroxide is removed; the glycolic suspension of the zinc carbonate hydroxide is added in the synthesizing process of polyethylene glycol terephthalate, the zinc carbonate hydroxide is decomposed to generate the zinc oxide when the polyester is generated by a polymerization reaction, and the polyester compounded with the zinc oxide which has the content as (0.1 to 5)% of the weight of the polyester is obtained. By changing the generating process of the zinc oxide by the present invention, the zinc oxide is generated synchronously with the synthesis of the polyester, so the production cost of the ultraviolet resisting polyester is reduced, and the spinnability and the ultraviolet resisting effect of the polyester are improved; the present invention has simple technological process and is easy of large-scale commercial process.
Description
(1) technical field
The present invention relates to a kind of preparation method who has reflection or absorb the trevira of ultraviolet function, be specifically related to a kind of zinc oxide complex polyester and preparation method thereof, belong to technical field of polymer materials.
(2) background technology
Uvioresistant polyester is meant that polyester can be used for producing and has reflection or to absorb ultraviolet functional fibre.Have anti-UV fabric and be used widely, as uvioresistant umbrella, anti-aging outer packaging, sunbonnet etc.Adopting the inorganic anti ultraviolet agent of interpolation that polyester is carried out modification, obtain the uvioresistant terylene, is current application technology more widely.Prior art is directly to adopt inorganic anti ultraviolet powder to produce uvioresistant polyester, make master batch with the direct blend of polyester, or after disperseing, in the polyester building-up process, add, complicated process of preparation, production unit is relied on big, energy consumption is big, can produce dust, environmental pollutions such as noise, application number ZL 98116588.5 discloses a kind of preparation method of anti-ultraviolet polyester, adds a kind of inorganic screening agent in polycondensation, through transesterification reaction, the anti-ultraviolet polyester section is produced in polycondensation, there is following defective in this technology, inorganic powder manufacturing technology complexity also can produce dust, contaminate environment, before adding, to grind dispersion treatment to powder, to the equipment requirements height, complex process, energy consumption height.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of uvioresistant zinc oxide complex polyester and preparation method thereof is provided.
Uvioresistant zinc oxide complex polyester of the present invention obtains by the following method:
Zinc oxide is dissolved in the ethylene glycol mixing solutions of ammonia and carbonic acid ammonia, generate the suspension of zinc subcarbonate ethylene glycol through heating, and remove moisture, the suspension that in the polyethylene terephthalate building-up process, adds this zinc subcarbonate ethylene glycol, when polyreaction generates polyester, zinc subcarbonate decomposes generation zinc oxide, obtains the zinc oxide complex polyester, and the content of zinc oxide is 0.1%～5% of weight polyester.
The suspension of described zinc subcarbonate ethylene glycol is that esterification finishes back adding reaction system in the synthetic reaction process of polyethylene terephthalate.
Preparation method's step of uvioresistant zinc oxide complex polyester of the present invention is as follows:
(1) preparation of the suspension of anti ultraviolet agent intermediate zinc subcarbonate ethylene glycol
Ammoniacal liquor and ethylene glycol are mixed in proportion, add carbonic acid ammonia, stirring and dissolving, add zinc oxide again, be dissolved to settled solution, filter, add hot filtrate to 140 ℃～160 ℃, remove moisture, the gained suspended substance is the suspension of anti ultraviolet agent intermediate zinc subcarbonate ethylene glycol, suspension particle 20nm～100nm.
(2) polyester is synthetic
In reactor, add pure terephthalic acid, ethylene glycol, catalyzer, stablizer, heat up and carry out esterification, esterification 2 hours～3 hours, 230 ℃～269 ℃ of esterification temperatures; After esterification finishes, add the suspension of above-mentioned zinc subcarbonate ethylene glycol, rough vacuum polycondensation 1 hour～1.5 hours, 269～283 ℃ of temperature continue to heat up and carry out polycondensation, high vacuum polycondensation 1～2 hour, 283 ℃～290 ℃ of temperature can make uvioresistant zinc oxide complex polyester.
In the ammonia in the above-mentioned steps (1) and the ethylene glycol mixing solutions of carbonic acid ammonia, the mol ratio of ammonia and technical grade zinc oxide is 1: 1～5: 1, and the mol ratio of carbonic acid ammonia and technical grade zinc oxide is 1: 1～3: 1, and the mass ratio of ethylene glycol and ammonia is 1: 4～1: 12.
Suspension particle 20nm～100nm in the suspension of zinc subcarbonate ethylene glycol in the above-mentioned steps (1).
Above-mentioned polyester synthesis condition do not specify all by existing routine techniques.
The present invention decomposes generation zinc oxide with ethylene glycol (EG), terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) by interpolation uvioresistant intermediate in the polyester process makes polyester have uvioresistant performance.The present invention combines the preparation and the synthetic of uvioresistant polyester of inorganic anti ultraviolet agent, and by directly generate the intermediate zinc subcarbonate of anti ultraviolet agent in ethylene glycol, granularity is about 80 nanometers, can and pulverize directly without mechanical separation to add in the polyester.This midbody particle decomposes generation zinc oxide in the polyester process, the disintegration of zinc subcarbonate particle generation simultaneously, played the effect of further refinement, avoided a large amount of reunions of particle in polyester, the zinc oxide of generation still can be kept than small grain size in polyester.The ultraviolet performance of the absorption of zinc oxide is corresponding enhancing along with its particle size reduction, can guarantee that for the present invention zinc oxide has than small grain size, therefore the anti ultraviolet agent add-on is less relatively, and the good physicals of spinning equipment, process and fiber almost do not had an influence.
The present invention is by changing the generative process of zinc oxide, makes its synchronously synthetic with polyester, thereby the production cost of reduction uvioresistant polyester has improved the spinning property and the uvioresistant effect of polyester.This technological process is simple, is easy to large-scale industrial production.
(4) embodiment
By following example the present invention is further specified.
Embodiment 1:
Measure ethylene glycol 280mL, ammoniacal liquor (concentration 25%) 180mL mixes, and takes by weighing carbonic acid ammonia 74.8g, adds in the above-mentioned mixed solution and dissolves; Take by weighing zinc oxide 64.4g and add in the above-mentioned solution, stirring and dissolving is filtered, and adds hot filtrate to 140 ℃, makes pH value＜7.5, can get the glycolic suspension of zinc subcarbonate.The granularity 60nm of zinc subcarbonate～100nm.
Measure ethylene glycol 280mL, take by weighing pure terephthalic acid 700g, add in the reactor; The catalytic antimony trioxide adds in the pure terephthalic acid's slurry that modulates, pressurization 0.36MPa, esterification 2.5 hours, 230～269 ℃ of esterification temperatures; Measure above-mentioned suspension liquid 70mL (wherein containing zinc oxide 16g), add in the esterification products, rough vacuum 150Pa polycondensation 1 hour, 269～283 ℃ of temperature, high vacuum 50Pa polycondensation 1.5 hours, 283～290 ℃ of temperature can make uvioresistant zinc oxide complex polyester.
This polyester is made the film of 0.15mm, utilizes 7530 spectrophotometers to detect, to the specific absorption of UV-A greater than 94%, to the specific absorption of UV-B greater than 90%.
Embodiment 2:
Measure ethylene glycol 280mL, ammoniacal liquor (concentration 25%) 120mL mixes, and takes by weighing carbonic acid ammonia 37.4g, adds in the above-mentioned mixed solution and dissolves; Take by weighing zinc oxide 32.2g and add in the above-mentioned solution, stir, dissolving is filtered, and adds hot filtrate to 140 ℃, makes pH value＜7.5, can get the glycolic suspension of zinc subcarbonate.Granularity 20～the 50nm of zinc subcarbonate.
Measure ethylene glycol 210mL, take by weighing pure terephthalic acid 700g, add in the reactor; Pressurization 0.36MPa, esterification 2.5 hours, 230～269 ℃ of esterification temperatures; Measure above-mentioned suspension (containing zinc oxide 16g) 140mL, add in the esterification products; Rough vacuum 150Pa polycondensation 1 hour, 269～283 ℃ of temperature, high vacuum 50Pa polycondensation 1.5 hours, 283～290 ℃ of temperature, can make uvioresistant zinc oxide complex polyester, this polyester is made the film of 0.15mm, utilize 7530 spectrophotometers to detect, to the specific absorption of UV-A greater than 97%, to the specific absorption of UV-B greater than 93%.
Embodiment 3:
Measure ethylene glycol 280mL, ammoniacal liquor (concentration 25%) 180mL mixes, and takes by weighing carbonic acid ammonia 74.8g, adds in the above-mentioned mixed solution and dissolves; Take by weighing zinc oxide 64.4g and add in the above-mentioned solution, stir, dissolving is filtered, and adds hot filtrate to 140 ℃, makes pH value＜7.5, can get the glycolic suspension of zinc subcarbonate.The granularity 60nm of zinc subcarbonate～100nm.
Measure ethylene glycol 256mL, take by weighing pure terephthalic acid 700g, add in the reactor; Pressurization 0.36MPa, esterification 2.5 hours, 230～269 ℃ of esterification temperatures; Measure above-mentioned suspension (containing zinc oxide 24g) 94mL, add in the esterification products; Rough vacuum 150Pa polycondensation 1 hour, 269～283 ℃ of temperature, high vacuum 50Pa polycondensation 1.5 hours, 283～290 ℃ of temperature, can make uvioresistant polyester, this polyester is made the film of 0.15mm, utilize 7530 spectrophotometers to detect, to the specific absorption of UV-A greater than 98%, to the specific absorption of UV-B greater than 94%.
Present embodiment makes polyester through melt-spinning, flat pin down terylene DT silk; The DT silk is through double twisting, be processed into cloth specimen after, recording this cloth specimen UPF value is 50
+The like product cloth specimen UPF value that does not add the uvioresistant intermediate is 20.
Claims (3)
1. the preparation method of a uvioresistant zinc oxide complex polyester, step is as follows:
(1) preparation of the suspension of anti ultraviolet agent intermediate zinc subcarbonate ethylene glycol
Ammoniacal liquor and ethylene glycol are mixed in proportion, add carbonic acid ammonia, stirring and dissolving, add zinc oxide again, be dissolved to settled solution, filter, add hot filtrate to 140 ℃～160 ℃, remove moisture, the gained suspended substance is the suspension of anti ultraviolet agent intermediate zinc subcarbonate ethylene glycol;
(2) polyester is synthetic
In reactor, add pure terephthalic acid, ethylene glycol, catalyzer, stablizer, heat up and carry out esterification, esterification 2 hours～3 hours, 230 ℃～269 ℃ of esterification temperatures; After esterification finishes, the suspension that adds above-mentioned zinc subcarbonate ethylene glycol, rough vacuum polycondensation 1 hour～1.5 hours, 269 ℃～283 ℃ of temperature, continue to heat up and carry out polycondensation, high vacuum polycondensation 1 hour～2 hours, 283 ℃～290 ℃ of temperature, can make uvioresistant zinc oxide complex polyester, the content of zinc oxide is 0.1%～5% of weight polyester.
2. the preparation method of uvioresistant zinc oxide complex polyester as claimed in claim 1, it is characterized in that, in the ammonia in the described step (1) and the ethylene glycol mixing solutions of carbonic acid ammonia, the mol ratio of ammonia and technical grade zinc oxide is 1: 1～5: 1, the mol ratio of carbonic acid ammonia and technical grade zinc oxide is 1: 1～3: 1, and the mass ratio of ethylene glycol and ammonia is 1: 4～1: 12.
3. the preparation method of uvioresistant zinc oxide complex polyester as claimed in claim 1 is characterized in that, suspension particle 20nm～100nm in the suspension of zinc subcarbonate ethylene glycol in the described step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138993 CN1204196C (en) | 2003-08-11 | 2003-08-11 | Uvioresistant composite zinc oxide-polyester material and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138993 CN1204196C (en) | 2003-08-11 | 2003-08-11 | Uvioresistant composite zinc oxide-polyester material and its prepn |
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| CN1487026A CN1487026A (en) | 2004-04-07 |
| CN1204196C true CN1204196C (en) | 2005-06-01 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100385048C (en) * | 2005-08-18 | 2008-04-30 | 济南正昊化纤新材料有限公司 | Preparation method of ultraviolet resistant, quick moisture absorption dry polyester fiber |
| CN101240463B (en) * | 2007-02-05 | 2011-03-23 | 东丽纤维研究所（中国）有限公司 | Water-absorbing fast-drying fiber, producing method thereof and method for producing textile fabric |
| CN104017190B (en) * | 2014-06-20 | 2015-12-30 | 曲铭海 | A kind of preparation method of flame-retardant and anti-dripping PET nano composite material |
| CN105295029B (en) * | 2015-12-04 | 2018-10-30 | 黄淮学院 | A kind of nano zine oxide-polyamide compoiste material and preparation method thereof |
| CN105778070B (en) * | 2016-03-24 | 2017-06-16 | 江苏裕兴薄膜科技股份有限公司 | The preparation method of antifog uvioresistant poly ester film |
| CN116252534B (en) * | 2023-02-28 | 2024-04-26 | 中天科盛科技股份有限公司 | High-load FFS packaging film and preparation method thereof |
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