CN1259357C - Chemical fibre grade polyester resin with health function and making method thereof - Google Patents
Chemical fibre grade polyester resin with health function and making method thereof Download PDFInfo
- Publication number
- CN1259357C CN1259357C CN 02111349 CN02111349A CN1259357C CN 1259357 C CN1259357 C CN 1259357C CN 02111349 CN02111349 CN 02111349 CN 02111349 A CN02111349 A CN 02111349A CN 1259357 C CN1259357 C CN 1259357C
- Authority
- CN
- China
- Prior art keywords
- micro
- micro mist
- ethylene glycol
- polyester resin
- nano
- 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.)
- Expired - Fee Related
Links
Landscapes
- Artificial Filaments (AREA)
Abstract
The present invention relates to a chemical fiber grade polyester resin having the health-care function and a preparation method thereof. The chemical fiber grade polyester resin is prepared into high molecular polymer taking the raw materials of the proportion by weight: 100 of dimethyl terephthalate, 70 of ethylene glycol, 2 to 5 of anion miropowder, 0 to 5 of far-infrared miropowder, 0 to 5 of inorganic bacterium resistant miropowder, 0.03 to 0.04 of ester exchange catalyst, 0.03 to 0.04 of polycondensation catalyst and 0.05 of stabilizing agent. The preparation method comprises the technical steps: esterification reaction, functional powder pulping, preproportioning, pressure reduction, polycondensation, discharge, etc. Compared with the prior art, the present invention has various health-care functions of anion, far-infrared, bacterium resistance, electromagnetic absorption, etc. The present invention has the advantage of reasonableness, and poducts prepared by the method of the present invention has good spinnability.
Description
Technical field
The present invention relates to a kind of have negative ion, far infrared, antibiotic, absorb chemical fibre level synthesizing polyester (PET) resin and the manufacture method thereof of plurality of health care functions such as hertzian wave.
Background technology
It is existing on the market that to have anion function chemical fibre level generally be to adopt micro-nano anion function powder with the PET resin, handle back and general fibre PET resin with certain proportioning blend through activity, and under the certain temperature condition, produce function PET master batch, then with master batch and the fusion of general fibre level PET resin alloy, extruding spinning.Adopt aforesaid method to make the defective that the anion function chemical fibre has following three aspects at least:
1.PET resin under 265 ℃ of fusing point situations, the molecular weight depression of order secondary, thereby influenced the structure and the intensity of material;
2. the agglomeration that produces owing to the high surface energy of micro-nano function powder tends to cause the system incomplete mixing of function powder and resin, produces brilliant point and aggregated particle, makes filter screen easily stifled, influences spinning;
3. a part of micro-nano function powder gets lodged on the filter screen, causes the function of fiber to descend to some extent, and influences a rate.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of health care chemical fibre grade polyester resin and manufacture method thereof with superpower negative ion releasing function for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions: a kind of chemical fibre grade polyester resin with nourishing function is characterized in that it is the high molecular polymer of being made for raw material by following prescription (parts by weight):
Dimethyl terephthalate (DMT) (DMT) 100
Ethylene glycol 70
Negative ion micro mist 2~5
Far infrared micro mist 0~5
Inorganic antibacterial micro mist 0~5
Transesterification catalyst 0.03~0.04
Polycondensation catalyst 0.03~0.04
Stablizer 0.05
Described negative ion micro mist is selected from the electric stone ore of high boron content, and its Chemical Composition is the silicate that contains B, Al, Si, Mg, Mn, Zn, Ti, and its granularity is a micro/nano level.
Described far infrared micro mist is selected from ZrO
2, ZrSiO
3, SiO
2, SiC one or more, its granularity is a micro/nano level.
Described inorganic antibacterial micro mist is selected from Ag
2One or more of O, ZnO, CuO, its granularity are micro/nano level.
Described transesterification catalyst is selected from Mn (Ac)
2, Zn (Ac)
2, Ca (Ac)
2In a kind of.
Described polycondensation catalyst is selected from Sb
2O
3, Sb (Ac)
3, GeO
2In a kind of.
Described stablizer is selected from one or more in triphenylphosphate, triphenyl phosphite, the trimethyl phosphite 99.
A kind of manufacture method with chemical fibre grade polyester resin of nourishing function is characterized in that, it is to be made for raw material by following prescription (parts by weight):
Dimethyl terephthalate (DMT) (DMT) 100
Ethylene glycol 70
Negative ion micro mist 2~5
Far infrared micro mist 0~5
Inorganic antibacterial micro mist 0~5
Transesterification catalyst 0.03~0.04
Polycondensation catalyst 0.03~0.04
Stablizer 0.05
This method adopts following processing step:
A. esterification, with dimethyl terephthalate (DMT) and ethylene glycol, transesterification catalyst, polycondensation catalyst, drop in the reaction kettle of the esterification with said ratio, temperature is carried out esterification for 180 ℃~220 ℃ in being warming up to, and deviates from methyl alcohol and makes the diglycol terephthalate monomer;
B. function powder slurrying, to add that ethylene glycol carries out abundant depolymerization with 1: 1 weight proportion in small-sized shredder high speed stirring by the micro-nano function powder that negative ion micro mist, far infrared micro mist, inorganic antibacterial micro mist constitute, micro-nano function powder is uniformly dispersed in ethylene glycol, evenly coat with molecularity, the ethylene glycol slurry that makes micro-nano function powder is standby;
C. prepare burden in advance, after esterification finishes, in the reaction kettle of the esterification charging opening, slowly pour the above-mentioned slurry that makes into, the limit edged evenly stirs, the slurry that contains function powder is distributed in the diglycol terephthalate monomer with molecularity, time is 10~15 minutes and adds stablizer simultaneously, is discharged in the batch condensation polymerization reactor through fondant filter;
D. vacuum pump is opened in decompression, and then extracts excessive ethylene glycol in the extraction pipe of batch condensation polymerization reactor out, and speed until extracting all excessive ethylene glycol out, enters high vacuum stage of Fig with the method for per 10 minutes decompression 100mmHg;
E. polycondensation, at high vacuum state, vacuum overbottom pressure 0.1~0.3mmHg, under 275~280 ℃ of the temperature, the diglycol terephthalate monomer that contains the function powder slurry carries out polycondensation, deviates from ethylene glycol, obtains functional polyester resin, at this moment, micro-nano function powder will be evenly distributed in this vibrin with molecularity;
F. discharging, treat that molecular weight is up to standard, be limiting viscosity [η] be 0.66 ± 0.02 o'clock can discharging, temperature keeps 275~280 ℃, open the bottom valve inflated with nitrogen, the melt vibrin will be with strip or metamict chilling in cooling trough, with its pelletizing, promptly obtain having the chemical fibre grade polyester resin product of nourishing function, can be used for spinning.
Compared with prior art, function PET resin of the present invention, good spinnability, multiple functional, have the release of continuing negative ion and emission far-infrared functional, the negative ion release rate can reach after measured: 2000~3000/CM
3, far infrared transmissivity reaches 85~90% (4~14 μ wavelength), and the negative-ion fiber that is made by function PET resin has release [OH] continually
-And active oxygen and far-infrared functional, impel the obnoxious flavour microbiological oxidation of air, human body to decompose, and human body is produced the bioelectric current of same frequency, reach static massage, relax the muscles and stimulate the blood circulation and the effect of strengthening immunity; In addition, the inventive method reaches molecularity and evenly coats because micro-nano function powder is uniformly dispersed in ethylene glycol, reduced its surface energy, can not produce agglomeration, so function powder disperses very even in resin system, can not stop up filter screen, but the product spinnability is good.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of chemical fibre grade polyester resin with plurality of health care functions, it is made for raw material by following prescription (parts by weight):
Dimethyl terephthalate (DMT) (DMT) 100
Ethylene glycol 70
Negative ion micro mist tourmaline powder 5
Far infrared micro mist ZrO
25
Inorganic antibacterial micro mist AgO 2
CuO 1
ZnO 2
Inhale ripple ferrite ferrophosphorus breeze 3
Transesterification catalyst Mn (Ac)
20.04
Polycondensation catalyst Sb
2O
30.04
Stablizer triphenylphosphate 0.03
Stablizer triphenyl phosphite 0.02
Above-mentioned manufacture method with chemical fibre vibrin of plurality of health care functions, it adopts following processing step to make:
1. esterification, at first, with 100 parts of terephthaldehyde's ester dimethyl esters [being DMT] and 70 parts of ethylene glycol, 0.04 part of transesterification catalyst manganese acetate, 0.04 part of polycondensation catalyst antimonous oxide drops in the reaction kettle of the esterification, treat that temperature rises to 180 ℃~220 ℃ material meltings after, start stirring motor again, carry out esterification, deviate from methyl alcohol, treat methyl alcohol metering reach a certain amount of after, finish esterification when no longer going out methyl alcohol, make the diglycol terephthalate monomeric compound.
2. function powder slurrying is with 5 parts of tourmaline powders, far infrared micro mist ZrO
25 parts, the micro-nano function powder of 0.5 part of 2 parts of inorganic antibacterial micro mist AgO, CuO, 2 parts of formations of ZnO add that ethylene glycol stirred 0.5 hour to 1 hour in small-sized shredder high speed with 1: 1 part by weight, carry out abundant depolymerization, micro-nano function powder is uniformly dispersed in ethylene glycol, and it is standby evenly to clad the ethylene glycol slurry that makes the composite powder of micro-nano function with molecularity.
3. pre-batching, after esterification finishes, in the charging opening of reaction kettle of the esterification, slowly pour the slurry that makes by the 2nd step into, the limit edged stirs, time is 10 minutes to 15 minutes, and add 0.03 part of stablizer triphenylphosphate, and 0.02 part of stirring of triphenyl phosphite can not pause, and the melt filtration device of monomer in charge tube is discharged in the batch condensation polymerization reactor after the esterification.
4. decompression phase starts vacuum pump, and then slowly extracts excessive ethylene glycol, speed in the extraction pipe of batch condensation polymerization reactor out: until extracting all excessive ethylene glycol out, enter high vacuum stage of Fig with the method for per 10 minutes decompression 100mmHg then.
5. polycondensation stage is in high vacuum (vacuum overbottom pressure 0.1~0.3mmHg), temperature of reaction: under 275 ℃~280 ℃ situations, carry out polycondensation.At this moment, micro-nano function powder will be evenly distributed in the high molecular polymer of PET with molecularity, and polymer segment constantly increases, and molecular weight is rising always.
6. discharging: treat that the PET molecular weight is up to standard; that is limiting viscosity [η] reaches at 0.66 ± 0.02 o'clock; promptly can discharging; discharging condition: temperature keeps 275~280 ℃ and opens bottom valve; the melt PET resin that inflated with nitrogen is qualified will be with strip or metamict; in cooling trough, chilling, and in dicing machine, be cut into finished particle (as grain of rice size).
The multi-functional PET resin that adopts above-mentioned prescription and technology to make, its performance data is as follows after measured:
1.[η]:0.66±0.02
2. fusing point: 260~265 ℃
3. crystal habit: crystallite
4. spinning property: good
5. make the fundamental characteristics of functional fibre:
A. the anion emission rate can reach 3000/cm
3
B. far infrared transmissivity reaches 80% (4~14 μ wavelength);
C. germ resistance: up to standard
D. anti-electromagnetic wave: hertzian wave (high frequency waves) specific absorption reaches 85~90%.
Embodiment 2
A kind of chemical fibre grade polyester resin with plurality of health care functions, it is made for raw material by following prescription (parts by weight):
Dimethyl terephthalate (DMT) (DMT) 100
Ethylene glycol 70
Negative ion micro mist tourmaline powder 4
Nano-TiO
23
Far infrared micro mist ZrSiO
32
ZrO
2 1
Inorganic antibacterial micro mist ZnO 3
Inhale ripple ferrite kakoxene 3
Transesterification catalyst Mn (Ac)
20.03
Co(Ac)
2 0.01
Polycondensation catalyst Sb (Ac)
30.04
Stablizer triphenylphosphate 0.05
The manufacture method of above-mentioned functions PET resin is identical with embodiment 1.
The mensuration performance data of the multi-functional chemical fibre level PET resin of producing through above-mentioned prescription and method is as follows:
1.[η]:0.66±0.02
2. fusing point: 261~265 ℃
3. crystal habit: crystallite or little spherocrystal
4. spinning property: good [1000 meters/minute, spinning speed]
5. the functional fibre fundamental characteristics that makes:
A. the anion emission rate reaches 2800/cm
3
B. far infrared transmissivity 79%[4~14 wavelength]
C. germ resistance: up to standard
D. anti-electromagnetic wave: hertzian wave [high frequency waves] specific absorption reaches 88%
Embodiment 3
A kind of chemical fibre level PET resin with plurality of health care functions, it is the polymkeric substance of being made for raw material by following prescription [parts by weight]:
Dimethyl terephthalate (DMT) [DMT] 100
Ethylene glycol 70
Negative ion micro mist tourmaline powder 2
Nanometer CaCO
33
Far infrared micro mist SiC 2
ZrO
2 2
Inorganic antibacterial micro mist ZnO 2
Inhale ripple ferrite ferrophosphorus powder 4
Transesterification catalyst Ca (Ac)
20.03
Polycondensation catalyst GeO
20.03
Stablizer triphenylphosphate 0.05
The manufacture method of above-mentioned functions PET resin is identical with embodiment 1.
The mensuration performance data of the function chemical fibre level PET resin that makes through above-mentioned prescription and method is as follows:
1. molecular weight [η]: 0.66 ± 0.02
2. fusing point: 262 °~264 ℃
3. crystal habit: crystallite
4. spinning property: good [1000 meters/minute of spinning speeds]
5. the functional fibre fundamental characteristics that makes:
A. the anion emission rate reaches 2600/cm
3
B. far infrared transmissivity 79.1%[4~14 wavelength]
C. germ resistance: up to standard
D. anti-electromagnetic wave: hertzian wave [high frequency waves] specific absorption reaches 89%.
Claims (2)
1, a kind of chemical fibre grade polyester resin with nourishing function is characterized in that, it is to be the high molecular polymer that raw material is made by following formulation weight umber:
Dimethyl terephthalate (DMT) 100,
Ethylene glycol 70,
Negative ion micro mist 2~5,
Far infrared micro mist 0~5,
Inorganic antibacterial micro mist 0~5,
Transesterification catalyst 0.03~0.04,
Polycondensation catalyst 0.03~0.04,
Stablizer 0.05;
Described negative ion micro mist is selected from the electric stone ore of high boron content, and its Chemical Composition is the silicate that contains B, Al, Si, Mg, Mn, Zn, Ti, and its granularity is a micro/nano level;
Described far infrared micro mist is selected from ZrO
2, ZrSiO
3, SiO
2, SiC one or more, its granularity is a micro/nano level;
Described inorganic antibacterial micro mist is selected from Ag
2One or more of O, ZnO, CuO, its granularity are micro/nano level;
Described transesterification catalyst is selected from Mn (Ac)
2, Zn (Ac)
2, Ca (Ac)
2In a kind of;
Described polycondensation catalyst is selected from Sb
2O
3, Sb (Ac)
3, GeO
2In a kind of;
Described stablizer is selected from one or more in triphenylphosphate, triphenyl phosphite, the trimethyl phosphite 99.
2, a kind of manufacture method with chemical fibre grade polyester resin of nourishing function is characterized in that, it is to be that raw material is made by following formulation weight umber:
Dimethyl terephthalate (DMT) 100,
Ethylene glycol 70,
Negative ion micro mist 2~5,
Far infrared micro mist 0~5,
Inorganic antibacterial micro mist 0~5,
Transesterification catalyst 0.03~0.04,
Polycondensation catalyst 0.03~0.04,
Stablizer 0.05;
Described negative ion micro mist is selected from the electric stone ore of high boron content, and its Chemical Composition is the silicate that contains B, Al, Si, Mg, Mn, Zn, Ti, and its granularity is a micro/nano level;
Described far infrared micro mist is selected from ZrO
2, ZrSiO
3, SiO
2, SiC one or more, its granularity is a micro/nano level;
Described inorganic antibacterial micro mist is selected from Ag
2One or more of O, ZnO, CuO, its granularity are micro/nano level;
Described transesterification catalyst is selected from Mn (Ac)
2, Zn (Ac)
2, Ca (Ac)
2In a kind of;
Described polycondensation catalyst is selected from Sb
2O
3, Sb (Ac)
3, GeO
2In a kind of;
Described stablizer is selected from one or more in triphenylphosphate, triphenyl phosphite, the trimethyl phosphite 99;
This method adopts following processing step:
A. esterification, with dimethyl terephthalate (DMT) and ethylene glycol, transesterification catalyst, polycondensation catalyst, drop in the reaction kettle of the esterification with said ratio, temperature is carried out esterification for 180 ℃~220 ℃ in being warming up to, and deviates from methyl alcohol and makes the diglycol terephthalate monomer;
B. function powder slurrying, to add that ethylene glycol carries out abundant depolymerization with 1: 1 weight proportion in small-sized shredder high speed stirring by the micro-nano function powder that negative ion micro mist, far infrared micro mist, inorganic antibacterial micro mist constitute, micro-nano function powder is uniformly dispersed in ethylene glycol, evenly coat with molecularity, the ethylene glycol slurry that makes micro-nano function powder is standby;
C. prepare burden in advance, after esterification finishes, in the reaction kettle of the esterification charging opening, slowly pour the above-mentioned slurry that makes into, the limit edged evenly stirs, the slurry that contains function powder is distributed in the diglycol terephthalate monomer with molecularity, time is 10~15 minutes and adds stablizer simultaneously, is discharged in the batch condensation polymerization reactor through fondant filter;
D. vacuum pump is opened in decompression, and then extracts excessive ethylene glycol in the extraction pipe of batch condensation polymerization reactor out, and speed until extracting all excessive ethylene glycol out, enters high vacuum stage of Fig with the method for per 10 minutes decompression 100mmHg;
E. polycondensation, at high vacuum state, vacuum overbottom pressure 0.1~0.3mmHg, under 275~280 ℃ of the temperature, the diglycol terephthalate monomer that contains the function powder slurry carries out polycondensation, deviates from ethylene glycol, obtains functional polyester resin, at this moment, micro-nano function powder will be evenly distributed in this vibrin with molecularity;
F. discharging, treat that molecular weight is up to standard, be limiting viscosity [η] be 0.66 ± 0.02 o'clock can discharging, temperature keeps 275~280 ℃, open the bottom valve inflated with nitrogen, the melt vibrin will be with strip or metamict chilling in cooling trough, with its pelletizing, promptly obtain having the chemical fibre grade polyester resin product of nourishing function, can be used for spinning.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 02111349 CN1259357C (en) | 2002-04-15 | 2002-04-15 | Chemical fibre grade polyester resin with health function and making method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 02111349 CN1259357C (en) | 2002-04-15 | 2002-04-15 | Chemical fibre grade polyester resin with health function and making method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1451673A CN1451673A (en) | 2003-10-29 |
CN1259357C true CN1259357C (en) | 2006-06-14 |
Family
ID=29220863
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 02111349 Expired - Fee Related CN1259357C (en) | 2002-04-15 | 2002-04-15 | Chemical fibre grade polyester resin with health function and making method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1259357C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101948612A (en) * | 2010-10-18 | 2011-01-19 | 华润包装材料有限公司 | Antistatic polyester and preparation method thereof |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009270218A (en) * | 2008-05-02 | 2009-11-19 | Diatex Co Ltd | Electromagnetic wave suppression flat yarn, electromagnetic wave suppression product using same, and method for producing the same |
CN102345178A (en) * | 2011-06-21 | 2012-02-08 | 江苏鹰翔化纤股份有限公司 | Preparation method of nano silver oxide modified polyester fiber |
CN102345179A (en) * | 2011-06-21 | 2012-02-08 | 江苏鹰翔化纤股份有限公司 | Preparation method of nano zinc oxide modified polyester fiber |
CN104804386A (en) * | 2014-01-26 | 2015-07-29 | 北京赛特瑞科技发展有限公司 | Functional fixing plate, production method and use thereof |
CN107142546B (en) * | 2017-06-07 | 2018-06-01 | 广州市中诚新型材料科技有限公司 | The compound polyester functional fibre of a kind of far infrared, antibacterial mite-removing and its manufacturing method |
CN107648730B (en) * | 2017-09-25 | 2020-12-08 | 东莞理工学院 | A health chair containing traditional Chinese medicine for treating hemorrhoid |
CN109295532B (en) * | 2018-09-29 | 2022-02-01 | 和也健康科技有限公司 | Antibacterial composite functional fiber and preparation method thereof |
CN109695067A (en) * | 2018-12-25 | 2019-04-30 | 上海德福伦化纤有限公司 | A kind of anti-bacterial heat storage polyester fiber and preparation method thereof |
CN109762153B (en) * | 2018-12-29 | 2021-04-16 | 中国纺织科学研究院有限公司 | Preparation method and preparation system of functional polyester product and functional polyester product |
CN109679076B (en) * | 2018-12-29 | 2021-04-23 | 中国纺织科学研究院有限公司 | Functional polyester product and preparation method thereof |
CN109957099A (en) * | 2019-02-28 | 2019-07-02 | 宜兴新乐祺纺织印染有限公司 | A kind of production method of low melting point anionic copolymerization type modified poly ester |
CN113046891B (en) * | 2021-03-22 | 2022-11-29 | 广州日祥纺织有限公司 | Fabric for improving comfort of golf clothes and preparation method thereof |
CN113818263B (en) * | 2021-11-03 | 2023-09-08 | 愉悦家纺有限公司 | Fast-heating warm-feeling textile compounded by tourmaline mineral and preparation method thereof |
-
2002
- 2002-04-15 CN CN 02111349 patent/CN1259357C/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101948612A (en) * | 2010-10-18 | 2011-01-19 | 华润包装材料有限公司 | Antistatic polyester and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1451673A (en) | 2003-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1259357C (en) | Chemical fibre grade polyester resin with health function and making method thereof | |
CN100345908C (en) | Organopolysiloxane granulate | |
CN1528582A (en) | Method for continuously producing silicone composition | |
CN1683614A (en) | Monofilament capable of emitting negative ion, its preparing method and use | |
CN1709989A (en) | Composite electromagnetic wave shielded coating and its preparing method | |
CN1687268A (en) | Controlled released stably coating material capable of purifying air and preparation method thereof | |
CN1714838A (en) | Medical gel and its preparing method and device | |
CN1817951A (en) | Conductive mother paticle, conductive polymer filament, its production and use | |
CN100341790C (en) | Production process of titania-silica mixed crystal particles having a high bulk density, titania-silica mixed crystal particles obtained by the process and uses thereof | |
CN1255471C (en) | Preparation method of biodegradable polyester composite material | |
CN1041194C (en) | Method for making far-infrared radioactive substance and far-infrared radioactive product using said far-infrared radioactive substance | |
CN1371673A (en) | Porous titanium oxide, organic polyorganosiloxane hybridized powder and titanium oxide, silicon oxide composite unit and matched cosmetic material thereof | |
CN1876699A (en) | Microwave radioradiation crosslinked complete biodegradable material and its processing method | |
CN1909870A (en) | Dental or surgical adhesive and polymerization initiator composition therefor | |
CN1031089A (en) | Suspension emulsion polymerization preparation is insoluble to the method for the polymkeric substance and the multipolymer of monomer whose or comonomer composite | |
CN1264497C (en) | External used agent for skin | |
CN1276947C (en) | Foamed plastics additive with bealth care function and its prepn process | |
CN1076377C (en) | Oil repulsive anti-stick coating for cooker hood | |
CN1781980A (en) | High performance elastomer composite material spcially for printing rubber roller and its preparing method | |
CN1546567A (en) | Flame-retardant, smoke-removing type polycarbonate alloy | |
CN1218452A (en) | Synthesis of solid, powdery rare earth carboxylates by precipitation method | |
CN1159226C (en) | Process for preparing rare-earth nano oxide by ball grinding and solid-phase chemical reaction | |
CN1148944A (en) | Health-care powder | |
CN1259055C (en) | Method for preparing azithromycin superfine powder by ultrasound homogenization dissolvent diffusion method | |
CN1288215C (en) | Coating material with photocatalysis decontamination and infrared energy-saving |
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 | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060614 Termination date: 20110415 |