CN102020762A - Novel silver-containing PET (polyethylene terephthalate)-based composite and in-situ assembly preparation method and application thereof - Google Patents
Novel silver-containing PET (polyethylene terephthalate)-based composite and in-situ assembly preparation method and application thereof Download PDFInfo
- Publication number
- CN102020762A CN102020762A CN 201010513405 CN201010513405A CN102020762A CN 102020762 A CN102020762 A CN 102020762A CN 201010513405 CN201010513405 CN 201010513405 CN 201010513405 A CN201010513405 A CN 201010513405A CN 102020762 A CN102020762 A CN 102020762A
- Authority
- CN
- China
- Prior art keywords
- matrix material
- preparation
- agx
- ethylene glycol
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a novel PET (polyethylene terephthalate)/Ag (silver)-AgX (X is Cl, Br, I and CH3COO) composite and a preparation method thereof, and the novel PET/Ag-AgX composite is prepared by in-situ assembly of a monomer which is p-phthalic acid (PTA) or dimethyl terephthalate (DMT) for synthesizing the PET and colloidal solution of a precursor which is AgX-ethylene glycol (EG) during the polymerization process. The PET/Ag-AgX composite has great spinnability and bacterinertness, and the preparation method has ingenious concept, simple process, short preparation cycle, low production cost and no pollution, and is applicable to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of matrix material, relate in particular to a kind of novel argentiferous PET based composites and preparation method thereof.
Background technology
Composite organic-inorganic material combines the good characteristic of organic polymer and inorganic materials, with corresponding pure organic or inorganic materials comparatively speaking, they have performances such as better machinery, calorifics, biology, magnetic, optics and electricity, study focus and new growth point for one that has become material science.In recent years, people utilize inorganic nano-particle that PET (polyethylene terephthalate) is carried out modification, preparation has the PET base organic-inorganic nano composite material of multifunctional usage to satisfy the demand of diversified functionalization, main focus mainly concentrates on and utilizes nano imvite, nano-calcium carbonate, nano silicon, nano titanium oxide, nano zine oxide, carbon nanotube to wait modified PET at present, improve its mechanical property, thermal characteristics and crystal property etc., give its some function simultaneously, as uvioresistant, function such as antibiotic, antistatic.
Simultaneously, studies show that the silver salt crystal that the nanometer silver and the utmost point are insoluble in water has very strong anti-microbial activity, can give material excellent antibiotic performance after compound itself and polymer materials.
Summary of the invention
The purpose of this invention is to provide a kind of finely dispersed novel argentiferous PET based composites and preparation method thereof,, and improve material property with the limitation of breakthrough current material.
The present inventor finds under study for action, can prepare novel argentiferous PET matrix material by assemble in situ in the building-up process of PET, i.e. PET/Ag-AgX matrix material, and it has good spinning property and anti-microbial property.
Specifically, (X is Cl, Br, I, CH to PET/Ag-AgX matrix material of the present invention
3COO) be that the monomers terephthalic acid (PTA) of synthetic PET or dimethyl terephthalate (DMT) (DMT) and precursor AgX-ethylene glycol (EG) colloidal solution are formed by assemble in situ in polymerization process.
The preparation method of PET/Ag-AgX matrix material disclosed by the invention comprises: prepare precursor AgX-ethylene glycol colloidal solution by the precipitator method earlier in ethylene glycol 1.; 2. utilize then in the esterification process of synthetic PET under the high-temperature and high-pressure conditions, precursor AgX-ethylene glycol slowly releases Ag by sedimentation equilibrium control
+And because homo-ion adsorption effect Ag
+Be attracted to AgX particulate surface, and ethylene glycol at high temperature has strong reductibility simultaneously, with AgX particulate surfaces A g
+In-situ reducing becomes Ag, thereby realizes that nanometer silver generates and assembling in AgX particle surface original position; 3. under vacuum, carry out polycondensation after esterification is finished, obtain the PET/Ag-AgX matrix material.Wherein, Ag in the 2nd step
+In-situ reducing becomes the reaction principle of Ag as follows:
Assemble in situ provided by the invention prepares the method for PET/Ag-AgX matrix material, both available terephthalic acid (PTA) and the esterification of AgX-ethylene glycol colloidal solution, also available dimethyl terephthalate (DMT) (DMT) and the reaction of AgX-ethylene glycol colloidal solution promptly prepare this matrix material and can adopt 1. PTA direct esterification method or 2. DMT ester-interchange method different process technological line.
Particularly, earlier with soluble silver salt (as AgNO
3) be precursor, Ju Yi Xi Bi Ka Wan ketone (PVP) is made stablizer, and (its general formula is RX, and wherein R is Na, K or H, and X is Cl, Br, I or CH for solubility halide salt, haloid acid, solubility acetate or acetic acid
3COO) do precipitation agent, ethylene glycol is made solvent, make AgX-ethylene glycol colloidal solution by the precipitator method, then the AgX-ethylene glycol colloidal solution that obtains and PTA or DMT and catalyzer adding polymeric kettle are carried out esterification, temperature of reaction is 220-250 ℃, reaction times is about 3 hours, generally at 2.5-3.5 hour, reaction pressure 0-0.4MPa, water outlet (alcohol) amount is that esterification (transesterify) is finished greater than 95% of theoretical value, after esterification (transesterify) is finished, and under 260-280 ℃ of temperature and vacuum polycondensation 2-3 hour, preferable reaction pressure is 0-600Pa, obtains the PET/Ag-AgX matrix material.
Proportioning raw materials is in preparation method's reaction system provided by the invention:
Soluble silver salt: 0.5-2wt% (with respect to the weight percent of PTA or DMT)
EG: PTA=1.5: 1-2.1: 1, preferred 1.7: 1-1.9: 1, optimum 1.8: 1 (mol ratio) or EG: DMT=2.1: 1-2.7: 1, preferred 2.3: 1-2.5: 1, optimum 2.4: 1 (mol ratio)
PVP:0.3-0.7wt%, preferred 0.4-0.6wt%, optimum 0.5wt% (with respect to the weight percent of PTA or DMT)
X in the precipitation agent
-(X is Cl, Br, I, CH
3COO): soluble silver salt=1.2: 1-1.8: 1, preferred 1.4: 1-1.6: 1, optimum 1.5: 1 (mol ratio)
Wherein, the step of the 1st step preparation AgX-ethylene glycol colloidal solution is as follows among the preparation method of the present invention: the consumption of determining EG by the above-mentioned raw materials proportioning, earlier make precipitant solution with 1/3 part of EG dissolution precipitation agent RX, make solvent with 2/3 part of EG again and dissolve PVP (consumption is determined by the above-mentioned raw materials proportioning) fully, add soluble silver salt (consumption is determined by the above-mentioned raw materials proportioning) again, vigorous stirring to soluble silver salt dissolves fully, under vigorous stirring, slowly drip precipitant solution then, continue to stir 0.5-1.5 hour after dripping precipitation agent, be preferably 1 hour, obtain milky AgX-ethylene glycol colloidal solution.The AgX particles dispersed is even in this solution, and median size is between 30-250nm.
The reaction mechanism that adopts the present invention to prepare the PET/Ag-AgX matrix material does not have tangible difference with pure PET is synthetic, so does not need to add special catalyst.When adopting the PTA path of preparing, esterification can add catalyzer, and still available antimony glycol commonly used of the catalyzer of polycondensation or antimonous oxide, consumption are also suitable with the pure PET of preparation; When adopting the DMT path of preparing, the acetate of the still available manganese of the catalyzer in the transesterification reaction, magnesium, zinc etc., still available antimony glycol commonly used of the catalyzer of polycondensation or antimonous oxide, consumption are also suitable with the pure PET of preparation.
The present invention prepares the nanometer silver and AgX being uniformly dispersed in the PET matrix of gained PET/Ag-AgX matrix material, median size is between 30-350nm, its molecular weight and distribute and not to be subjected to the influence of content of nanometer silver can prepare the PET matrix material of higher molecular weight and narrower molecular weight distribution.
PET/Ag-AgX matrix material of the present invention has been broken through the limitation of current material, improved the performance of material, have good spinning property and germ resistance, can adopt common melt processing to be processed into fiber, gram-positive microorganism and gram-positive microorganism there are the strong antibiotic effect, can be used for preparing engineering plastics, functional fibre, film and sizing agent etc. with antibacterial.
The method that the present invention prepares the PET/Ag-AgX matrix material has the following advantages:
(1) the inventive method is skillfully constructed, and the monoethylene glycol that utilizes the monomer that synthesizes PET avoids additional reducing agent to bring impurity to system as solvent and reductive agent;
(2) utilize AgX-ethylene glycol colloidal solution to do precursor, the Ag that the Esterification Stage in the PET building-up process is slowly released by sedimentation equilibrium control by precursor AgX
+Form nano silver particles, control reduction reaction speed realizes that the original position generation of nanometer silver and AgX and assembling take place simultaneously with esterification, improves the dispersiveness of inorganic nano component in the PET matrix, the problem with difficulties in dispersion of avoiding occurring reuniting;
(3) the inventive method technology is simple, and preparation cycle is short, and production cost is low, and is pollution-free, is suitable for large-scale industrial production.
Description of drawings
For can clearer understanding purpose of the present invention, characteristics and advantage, below with reference to accompanying drawing preferred embodiment of the present invention is described in detail, wherein:
Fig. 1 is the TEM photo of the AgCl-ethylene glycol colloidal solution of the inventive method preparation;
Fig. 2 is the TEM photo of the PET/Ag-AgCl matrix material of the inventive method preparation;
Fig. 3 is the XRD figure of the PET/Ag-AgCl matrix material of the inventive method preparation;
Fig. 4 is the digital photograph of the PET/Ag-AgCl compound resin section of the inventive method preparation.
Embodiment
Embodiment 1
Take by weighing 2.58 gram NaCl and add in the ethylene glycol of 200ml and at room temperature be stirred to dissolving fully, obtain the NaCl ethylene glycol solution; Take by weighing 5 gram PVP and add in the ethylene glycol of 400ml and at room temperature be stirred to dissolving fully, add 5 gram AgNO again
3Vigorous stirring is to AgNO
3Dissolving fully slowly drips the NaCl ethylene glycol solution then under vigorous stirring, drip the back and continue to stir 1 hour, obtains milky AgCl-ethylene glycol colloidal solution.The PTA that in the polymeric kettle that has import and export of nitrogen and churned mechanically 5L, adds obtained AgCl-ethylene glycol colloidal solution and 1000 grams, 0.3 gram Sb
2O
3, start mechanical stirring it is stirred, and, replace 4 times simultaneously with the air in the high pure nitrogen displacement still, be warming up to 230 ℃ and carry out esterification, the water that the collection reaction generates is that esterification is finished to the amount of theoretical volume.Be warming up to gradually then between 265-275 ℃, be evacuated to the beginning polycondensation with vacuum pump simultaneously, 1 hour pressure of first precondensation keeps opening the high vacuum polycondensation then about 600Pa, keep-up pressure under 60Pa, and about 2 hours of polymerization, discharging gets final product.Obtain product P ET/Ag-AgCl matrix material 700 grams.
Take by weighing 5.16 gram NaCl and add in the ethylene glycol of 200ml and at room temperature be stirred to dissolving fully, obtain the NaCl ethylene glycol solution; Take by weighing 4 gram PVP and add in the ethylene glycol of 400ml and at room temperature be stirred to dissolving fully, add 10 gram AgNO again
3Vigorous stirring is to AgNO
3Dissolving fully slowly drips the NaCl ethylene glycol solution then under vigorous stirring, drip the back and continue to stir 1 hour, obtains milky AgCl-ethylene glycol colloidal solution.The PTA that in the polymeric kettle that has import and export of nitrogen and churned mechanically 5L, adds obtained AgCl-ethylene glycol colloidal solution and 1000 grams, 0.3 gram Sb
2O
3, start mechanical stirring it is stirred, and, replace 4 times simultaneously with the air in the high pure nitrogen displacement still, be warming up to 230 ℃ and carry out esterification, the water that the collection reaction generates is that esterification is finished to the amount of theoretical volume.Be warming up to gradually then between 265-275 ℃, be evacuated to the beginning polycondensation with vacuum pump simultaneously, 1 hour pressure of first precondensation keeps opening the high vacuum polycondensation then about 600Pa, keep-up pressure under 60Pa, and about 2 hours of polymerization, discharging gets final product.Obtain product P ET/Ag-AgCl matrix material 680 grams.
Embodiment 3
Take by weighing 7.74 gram NaCl and add in the ethylene glycol of 300ml and at room temperature be stirred to dissolving fully, obtain the NaCl ethylene glycol solution; Take by weighing 5 gram PVP and add in the ethylene glycol of 600ml and at room temperature be stirred to dissolving fully, add 15 gram AgNO again
3Vigorous stirring is to AgNO
3Dissolving fully slowly drips the NaCl ethylene glycol solution then under vigorous stirring, drip the back and continue to stir 0.8 hour, obtains milky AgCl-ethylene glycol colloidal solution.The DMT that in the polymeric kettle that has import and export of nitrogen and churned mechanically 5L, adds obtained AgCl-ethylene glycol colloidal solution and 1000 grams, 0.5 gram magnesium acetate, 0.3 gram Sb
2O
3, start mechanical stirring it is stirred, and, replace 4 times simultaneously with the air in the high pure nitrogen displacement still, be warming up to 240 ℃ and carry out esterification, the water that the collection reaction generates is that esterification is finished to the amount of theoretical volume.Be warming up to gradually then between 265-275 ℃, be evacuated to the beginning polycondensation with vacuum pump simultaneously, 1 hour pressure of first precondensation keeps opening the high vacuum polycondensation then about 600Pa, keep-up pressure under 60Pa, and about 2 hours of polymerization, discharging gets final product.Obtain product P ET/Ag-AgCl matrix material 720 grams.
Embodiment 4
Take by weighing 10.50 gram KBr and add in the ethylene glycol of 200ml and at room temperature be stirred to dissolving fully, obtain the KBr ethylene glycol solution; Take by weighing 6 gram PVP and add in the ethylene glycol of 400ml and at room temperature be stirred to dissolving fully, add 10 gram AgNO again
3Vigorous stirring is to AgNO
3Dissolving fully slowly drips the KBr ethylene glycol solution then under vigorous stirring, drip the back and continue to stir 1.3 hours, obtains milky AgBr-ethylene glycol colloidal solution.The PTA that in the polymeric kettle that has import and export of nitrogen and churned mechanically 5L, adds obtained AgBr-ethylene glycol colloidal solution and 1000 grams, 0.3 gram Sb
2O
3, start mechanical stirring it is stirred, and, replace 4 times simultaneously with the air in the high pure nitrogen displacement still, be warming up to 220 ℃ and carry out esterification, the water that the collection reaction generates is that esterification is finished to the amount of theoretical volume.Be warming up to gradually then between 265-275 ℃, be evacuated to the beginning polycondensation with vacuum pump simultaneously, 1 hour pressure of first precondensation keeps opening the high vacuum polycondensation then about 600Pa, keep-up pressure under 60Pa, and about 2 hours of polymerization, discharging gets final product.Obtain product P ET/Ag-AgBr matrix material 713 grams.
Embodiment 5
Take by weighing 14.66 gram KI and add in the ethylene glycol of 300ml and at room temperature be stirred to dissolving fully, obtain the KI ethylene glycol solution; Take by weighing 7 gram PVP and add in the ethylene glycol of 600ml and at room temperature be stirred to dissolving fully, add 10 gram AgNO again
3Vigorous stirring is to AgNO
3Dissolving fully slowly drips the KI ethylene glycol solution then under vigorous stirring, drip the back and continue to stir 1.5 hours, obtains milky AgI-ethylene glycol colloidal solution.The DMT that in the polymeric kettle that has import and export of nitrogen and churned mechanically 5L, adds obtained AgI-ethylene glycol colloidal solution and 1000 grams, 0.5 gram manganese acetate, 0.3 gram Sb
2O
3, start mechanical stirring it is stirred, and, replace 4 times simultaneously with the air in the high pure nitrogen displacement still, be warming up to 250 ℃ and carry out esterification, the water that the collection reaction generates is that esterification is finished to the amount of theoretical volume.Be warming up to gradually then between 265-275 ℃, be evacuated to the beginning polycondensation with vacuum pump simultaneously, 1 hour pressure of first precondensation keeps opening the high vacuum polycondensation then about 600Pa, keep-up pressure under 60Pa, and about 2 hours of polymerization, discharging gets final product.Obtain product P ET/Ag-AgI matrix material 692 grams.
Effect embodiment
With embodiment 2 is that example is carried out TEM, XRD analysis, from Fig. 1 as seen, prepared AgCl-ethylene glycol colloidal solution, the AgCl particles dispersed is even, and particle diameter is between 50-200nm; From Fig. 2 as seen, prepared PET/Ag-AgCl matrix material, nanometer silver and AgCl being uniformly dispersed in the PET matrix, the Ag-AgCl particle grain size is between 250-350nm, amplify the visible circumgranular small-particle of AgCl in back and be nanometer silver, particle diameter is at 20-100nm.
The XRD figure of prepared PET/Ag-AgCl matrix material is asked for an interview Fig. 3, and from Fig. 3 as seen, prepared matrix material has tangible Ag crystal and AgCl crystalline diffraction peak; The digital photograph of resin slicer is asked for an interview Fig. 4.
Claims (15)
1. PET/Ag-AgX matrix material, wherein, X is Cl, Br, I or CH
3COO.
2. matrix material according to claim 1, the median size of Ag-AgX wherein are 30-350nm.
3. matrix material according to claim 1, it is to be prepared from by assemble in situ in the PET building-up process.
4. the preparation method of each described matrix material of claim 1 to 3 comprises:
A. in ethylene glycol, prepare precursor AgX-ethylene glycol colloidal solution by the precipitator method;
B. a gained AgX-ethylene glycol colloidal solution and PTA or DMT are carried out esterification;
C. the b products therefrom is carried out polycondensation, get the PET/Ag-AgX matrix material.
5. the preparation method of matrix material according to claim 4, comprise in the described a step: precipitant solution is made in the agent of spent glycol dissolution precipitation; Add soluble silver salt again after the agent of spent glycol steady dissolution, be stirred to dissolving fully; Drip precipitant solution while stirring, drip the back and continue to stir; Obtain AgX-ethylene glycol colloidal solution.
6. the preparation method of matrix material according to claim 5, described precipitation agent is solubility halide salt, haloid acid, solubility acetate or acetic acid, and its general formula is RX, and wherein R is Na, K or H, and X is Cl, Br, I or CH
3COO; Described stablizer is PVP; Described soluble silver salt is AgNO
3
7. the preparation method of matrix material according to claim 6, described soluble silver salt is 0.5-2wt% with respect to the mass percent of PTA or DMT; Described stablizer is 0.3-0.7wt% with respect to the mass percent of PTA or DMT; X in the described precipitation agent
-With the mol ratio of soluble silver salt be 1.2: 1-1.8: 1.
8. the preparation method of matrix material according to claim 4, the mol ratio of described ethylene glycol and PTA is 1.5: 1-2.1: 1, the mol ratio of ethylene glycol and DMT is 2.1: 1-2.7: 1.
9. the preparation method of matrix material according to claim 4, the median size of AgX is 30-250nm in the described AgX-ethylene glycol colloidal solution.
10. the preparation method of matrix material according to claim 4, the temperature of reaction of described b step is 220-250 ℃, and the reaction times is 2.5-3.5 hour, and reaction pressure is 0-0.4MPa.
11. the preparation method of matrix material according to claim 4 selects DMT for use in the described b step, then selects the catalyzer of the acetate of manganese, magnesium, zinc as the b step for use.
12. the preparation method of matrix material according to claim 4, the temperature of reaction of described c step are 260-280 ℃, the reaction times is 2-3 hour, and reaction pressure is a vacuum.
13. the preparation method of matrix material according to claim 12, the reaction pressure of described c step are 0-600Pa.
14. the preparation method of matrix material according to claim 4 selects antimony glycol or the antimonous oxide catalyzer as the c step for use.
15. each described matrix material of claim 1 to 3 is as the purposes of anti-biotic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105134057A CN102020762B (en) | 2010-10-20 | 2010-10-20 | Novel silver-containing PET (polyethylene terephthalate)-based composite and in-situ assembly preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105134057A CN102020762B (en) | 2010-10-20 | 2010-10-20 | Novel silver-containing PET (polyethylene terephthalate)-based composite and in-situ assembly preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102020762A true CN102020762A (en) | 2011-04-20 |
| CN102020762B CN102020762B (en) | 2012-07-25 |
Family
ID=43862569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105134057A Active CN102020762B (en) | 2010-10-20 | 2010-10-20 | Novel silver-containing PET (polyethylene terephthalate)-based composite and in-situ assembly preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102020762B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044861A (en) * | 2011-10-14 | 2013-04-17 | 合肥杰事杰新材料股份有限公司 | Antibacterial polybutylene terephthalate composition and preparation method thereof |
| CN104212132A (en) * | 2014-09-12 | 2014-12-17 | 北京和时利科技有限公司 | Silver-containing polyester pellet, and synthesis method and application thereof |
| CN106967278A (en) * | 2017-02-14 | 2017-07-21 | 浙江省东阳市塑料有限公司 | A kind of high-temperature resistant antibacterial PET cup and preparation method thereof |
| CN108193308A (en) * | 2018-01-29 | 2018-06-22 | 苏州美纳福健康科技有限公司 | A kind of fast preparation method of antibacterial and deodorizing dacron thread and application |
| CN110042495A (en) * | 2019-03-29 | 2019-07-23 | 南通和清纺织科技有限公司 | A kind of novel silver antibacterial polyester fibre and preparation method thereof |
| CN110387598A (en) * | 2018-04-17 | 2019-10-29 | 南通纺织丝绸产业技术研究院 | A kind of antibacterial ultraviolet-resistannanofiber multifunctional chemical fiber |
| JP2021517613A (en) * | 2018-01-29 | 2021-07-26 | 蘇州大学 | Antibacterial / UV shielding multifunctional chemical fiber |
| KR20220022292A (en) * | 2020-08-18 | 2022-02-25 | 재단법인대구경북과학기술원 | Antibacterial and Antiviral molded body manufacturing method and moled body comprising thereof |
| CN117552127A (en) * | 2023-11-15 | 2024-02-13 | 台州康怡丝新材料科技有限责任公司 | Parallel multidimensional curled PET/PA6 double-component antistatic antibacterial fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851438A (en) * | 1997-08-29 | 1998-12-22 | E. I. Du Pont De Nemours And Company | Thick film compositions for making medical electrodes |
| JP2003228154A (en) * | 2001-11-27 | 2003-08-15 | Fuji Photo Film Co Ltd | Silver halide photographic light-sensitive material |
| WO2003085052A1 (en) * | 2002-04-10 | 2003-10-16 | Fujikura Ltd. | Conductive composition, conductive film, and process for the formation of the film |
| CN101230186A (en) * | 2008-01-07 | 2008-07-30 | 广州市合诚化学有限公司 | Anti-static poly(ethylene terephthalate) material and preparation method thereof |
| CN101629335A (en) * | 2009-08-18 | 2010-01-20 | 太仓市金辉化纤实业有限公司 | Uvioresistant, antibacterial and flame retardant terylene fiber, preparation method and application thereof |
-
2010
- 2010-10-20 CN CN2010105134057A patent/CN102020762B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851438A (en) * | 1997-08-29 | 1998-12-22 | E. I. Du Pont De Nemours And Company | Thick film compositions for making medical electrodes |
| JP2003228154A (en) * | 2001-11-27 | 2003-08-15 | Fuji Photo Film Co Ltd | Silver halide photographic light-sensitive material |
| WO2003085052A1 (en) * | 2002-04-10 | 2003-10-16 | Fujikura Ltd. | Conductive composition, conductive film, and process for the formation of the film |
| CN101230186A (en) * | 2008-01-07 | 2008-07-30 | 广州市合诚化学有限公司 | Anti-static poly(ethylene terephthalate) material and preparation method thereof |
| CN101629335A (en) * | 2009-08-18 | 2010-01-20 | 太仓市金辉化纤实业有限公司 | Uvioresistant, antibacterial and flame retardant terylene fiber, preparation method and application thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044861A (en) * | 2011-10-14 | 2013-04-17 | 合肥杰事杰新材料股份有限公司 | Antibacterial polybutylene terephthalate composition and preparation method thereof |
| CN104212132A (en) * | 2014-09-12 | 2014-12-17 | 北京和时利科技有限公司 | Silver-containing polyester pellet, and synthesis method and application thereof |
| CN106967278A (en) * | 2017-02-14 | 2017-07-21 | 浙江省东阳市塑料有限公司 | A kind of high-temperature resistant antibacterial PET cup and preparation method thereof |
| CN106967278B (en) * | 2017-02-14 | 2018-11-06 | 浙江省东阳市塑料有限公司 | A kind of high-temperature resistant antibacterial PET plastic cup and preparation method thereof |
| CN108193308A (en) * | 2018-01-29 | 2018-06-22 | 苏州美纳福健康科技有限公司 | A kind of fast preparation method of antibacterial and deodorizing dacron thread and application |
| JP2021517613A (en) * | 2018-01-29 | 2021-07-26 | 蘇州大学 | Antibacterial / UV shielding multifunctional chemical 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 |
| CN110387598A (en) * | 2018-04-17 | 2019-10-29 | 南通纺织丝绸产业技术研究院 | A kind of antibacterial ultraviolet-resistannanofiber multifunctional chemical fiber |
| CN110042495A (en) * | 2019-03-29 | 2019-07-23 | 南通和清纺织科技有限公司 | A kind of novel silver antibacterial polyester fibre and preparation method thereof |
| KR20220022292A (en) * | 2020-08-18 | 2022-02-25 | 재단법인대구경북과학기술원 | Antibacterial and Antiviral molded body manufacturing method and moled body comprising thereof |
| KR102418999B1 (en) * | 2020-08-18 | 2022-07-08 | 재단법인대구경북과학기술원 | Antibacterial and Antiviral molded body manufacturing method and moled body comprising thereof |
| CN117552127A (en) * | 2023-11-15 | 2024-02-13 | 台州康怡丝新材料科技有限责任公司 | Parallel multidimensional curled PET/PA6 double-component antistatic antibacterial fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102020762B (en) | 2012-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102020762B (en) | Novel silver-containing PET (polyethylene terephthalate)-based composite and in-situ assembly preparation method and application thereof | |
| CN101993527B (en) | Preparation method and application of silver-containing PET based composite resin material | |
| CN1263677C (en) | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly | |
| US9987686B2 (en) | Complex, method for producing complex, dispersion liquid, method for producing dispersion liquid, and optical material | |
| CN101747620B (en) | Preparation method for nanometer composite material of in situ capacity-increased cast nylon/carbon nanometer tube | |
| TWI363771B (en) | Organo-inorganic compound nanofiber, organo-inorganic compound structrue, and method for producing the same | |
| EP3202848B1 (en) | Composite polyester material, composite polyester fibre, preparation method therefor and use thereof | |
| CN101811664A (en) | Cellulose/silver nano composite material and preparation method thereof | |
| CN103059280B (en) | Natural polysaccharide-grafted polycaprolactone in ionic liquid as well as preparation method and application thereof | |
| JP7197607B2 (en) | Antibacterial/ultraviolet shielding multifunctional chemical fiber | |
| CN100484985C (en) | Conductive polyanion/starch shell-core type composite microsphere and its preparation method | |
| CN102071487B (en) | Preparation method of organic-inorganic nanocomposite film | |
| CN100494290C (en) | Preparation method of high dispersed nano-silver particle | |
| CN107325268A (en) | A kind of graphene/PET nano composite materials and preparation method thereof | |
| CN101716684A (en) | Highly dispersible spherical nano-silver powder and preparation method thereof | |
| CN101524762A (en) | Method for preparing ferroplatinum nano-particle | |
| CN111218064A (en) | Antistatic and antibacterial multifunctional polymer composite material and preparation method thereof | |
| CN114085428A (en) | Antibacterial agent for plastic modification and preparation method thereof | |
| CN102167876B (en) | Butyl acrylate-styrene-acrylonitrile copolymer/titanium dioxide composite film and preparation method thereof | |
| CN110181074B (en) | Method for green preparation of high-length-diameter-ratio silver nanowires by composite soft template method | |
| CN105646896A (en) | Nano particle grafted stereoblock polylactic acid, preparation method and application of nano particle grafted stereoblock polylactic acid | |
| CN112337491A (en) | Preparation method and application of nickel phosphide/indium oxide nanocomposite material applied to bifunctional photocatalysis | |
| CN100384573C (en) | Method for preparing copper zinc alloy powder | |
| CN111992735A (en) | Silver nanowire and preparation method thereof | |
| CN113583401B (en) | Preparation method of transparent PET composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |