CN101302265A - Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof - Google Patents
Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof Download PDFInfo
- Publication number
- CN101302265A CN101302265A CNA2008100537105A CN200810053710A CN101302265A CN 101302265 A CN101302265 A CN 101302265A CN A2008100537105 A CNA2008100537105 A CN A2008100537105A CN 200810053710 A CN200810053710 A CN 200810053710A CN 101302265 A CN101302265 A CN 101302265A
- Authority
- CN
- China
- Prior art keywords
- suspension
- tio
- microsphere
- suction filtration
- ultra
- 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
- Compositions Of Macromolecular Compounds (AREA)
- Dental Preparations (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for making suspension polymerization polymethyl methacrylate/titanium dioxide nano composite microsphere. The nano composite microsphere made by the method is pearly powder with the average diameter of between 40 and 80 mu m; and the mass ratios of the components are: 99.9 to 90 percent of polymethyl methacrylate and 0.1 to 10 percent of TiO2. The material made by the method has proper molecular weight and molecular weight distribution and better mechanical property.
Description
Technical field
The invention belongs to field of compound material, particularly relate to a kind of resin-base nano matrix material, particularly suspension polymerization polymethacrylic acid methyl esters/titanic oxide composite nano-microsphere and preparation method.
Background technology
Polymethylmethacrylate (PMMA) be most important in the esters of acrylic acid also be the most frequently used a kind of material because its excellent property is of many uses, become one of plastic prod of being used widely in the national economy all departments.Wherein, the PMMA microballoon has been successfully applied to fields such as artificial tooth reparation and bone cement, but because its toughness and intensity are not high, need carry out modification to it and strengthen.
Continuous development along with nanotechnology, the research of polymkeric substance-inorganic nano composite material has also obtained develop rapidly, become one of new vegetative point of current matrix material, for preparation high-performance, multifunctional novel material provide a new way, and had wide business development and application prospect.
Summary of the invention
Add nano titanium oxide (TiO
2) after can improve the mechanical property of PMMA resin.We with PMMA as matrix resin, with the nano-TiO of silane coupling agent KH-570 surface modification
2Carry out in-situ suspension polymerization as strongthener, the preparation composite nano-microsphere.
The present invention makes the polymethyl methacryate/titanic oxide composite nano-microsphere, and microballoon is the pearl powder, and median size is 40～80 μ m, and each component quality proportioning is:
Polymethylmethacrylate 99.9%～90%,
TiO
2 0.1％～10％。
The preparation method of polymethyl methacryate/titanic oxide composite nano-microsphere of the present invention, step is as follows:
1) with mass concentration is 1～10% TiO
2Toluene or dimethylbenzene suspension fully stir, add reactor through ultra-sonic dispersion processing back, stir, heat up and dropping treatment agent γ-methacryloxypropyl trimethoxy silane (KH-570), isothermal reaction 6～8h under boiling state, the relative and TiO of dripping quantity
2Massfraction be 10～200%.With the TiO after handling
2The suspension suction filtration, with washing with acetone repeatedly after suction filtration drying again, obtain pressed powder A.
2) deionized water solution of configuration 0.5～2% Natvosol, and add 0.01～0.1% sodium laurylsulfonate or Sodium dodecylbenzene sulfonate, obtain solution B.
3) powders A is joined in the MMA monomer, fully stir and with ultrasonic grinding machine ultra-sonic dispersion, obtain suspension, the massfraction of A is 0.1～10%.Suspension behind the ultra-sonic dispersion and solution B are added reactor, and heating is stirred, and stir speed (S.S.) is 400～900rpm.Behind the logical nitrogen protection 30min, be warming up to 65-85 ℃ of adding and be BPO initiated polymerization 5～8h of 0.5～2% with respect to the massfraction of MMA.Products therefrom is repeatedly washed with clear water, suction filtration, drying obtains final product.Water and MMA monomer mass ratio are 3～5 in the suspension polymerization.
Effect of the present invention is:
The PMMA/TiO that obtains by the present invention
2Composite nano-microsphere, can carry out performance evaluation in the following ways:
One, the median size of microballoon
The optical microscope photograph of the median size of the resulting microballoon of the present invention as shown in Figure 1, median size is about 40～80 μ m.
Two, the molecular weight of polymkeric substance and distribution thereof
Get a certain amount of oven dry back mixture, in apparatus,Soxhlet's, use 100ml hot acetone extracting 48h, with PMMA acetone soln cooling in the flask after the extracting and to wherein adding 100ml distilled water.With the floss oven dry of separating out, make solvent with tetrahydrofuran (THF), be made into the solution of 0.005g/ml.Molecular weight and distribution thereof by PMMA in gel permeation chromatography (GPC) the test compound thing.
Three, mechanical property evaluation
The microballoon of gained is mixed by mass ratio with the hot type dental basse acrylic resin liquid that coagulates at 2: 1, by the time dough period is inserted it in plaster mold, in 70 ℃ water, heat 1.5h, be rapidly heated again to 100 ℃, die sinking behind the maintenance 1h, with No. 280, No. 400, No. 800 sand paper it is polished, the gained sample stretches, deflection and rockwell hardness testing.
Specimen size: tension specimen is 50mm * 7mm * 3mm; Transverse test-piece is 64mm * 10mm * 3.3mm; The hardness sample is 50mm * 50mm * 6mm.
Description of drawings
Fig. 1: suspension polymerization PMMA/TiO
2The optical microscope photograph of composite nano-microsphere.
Embodiment
Embodiment 1
TiO with 2g
2Pour in the 198g dimethylbenzene, fully stirring through pouring in the reactor after the ultra-sonic dispersion processing, is stirred, and heats up and dropping 4g treatment agent KH-570 isothermal reaction 6h under boiling state.With the TiO after handling
2The suspension suction filtration, with washing with acetone repeatedly after suction filtration drying again, obtain pressed powder A.The 0.1g powders A is joined in the 99.9gMMA monomer, ultra-sonic dispersion, and with in this suspension adding solution B (being dissolved with the 300ml deionized water of 2% Natvosol and 0.1% Sodium dodecylbenzene sulfonate), with the speed stirring of 900rpm.Behind the logical nitrogen protection 30min, be warming up to 65 ℃ and add 0.5gBPO initiation reaction 5h.Products therefrom is repeatedly washed with clear water, suction filtration, drying obtains the PMMA complex microsphere, packages spare.
Use the observation by light microscope thus obtained microsphere, its median size is about 40 μ m.Get the microballoon of 1.5g, in apparatus,Soxhlet's, use 100ml hot acetone extracting 48h, with PMMA acetone soln cooling in the flask after the extracting and to wherein adding 100ml distilled water.With the floss oven dry of separating out, make solvent with tetrahydrofuran (THF), be made into the solution of 0.005g/ml.The weight-average molecular weight that records PMMA in the mixture by gel permeation chromatography (GPC) is 87.7 * 10
4, polydispersity coefficient is 2.59.
Embodiment 2
TiO with 10g
2Pour in the 90g dimethylbenzene, fully stirring through pouring in the reactor after the ultra-sonic dispersion processing, is stirred, and heats up and dropping 1g treatment agent KH-570 isothermal reaction 8h under boiling state.With the TiO after handling
2The suspension suction filtration, with washing with acetone repeatedly after suction filtration drying again, obtain pressed powder A.The 2g powders A is joined in the 18gMMA monomer, ultra-sonic dispersion, and with in this suspension adding solution B (being dissolved with the 90ml deionized water of 0.5% Natvosol and 0.01% Sodium dodecylbenzene sulfonate), with the speed stirring of 400rpm.Behind the logical nitrogen protection 30min, be warming up to 85 ℃ and add 0.36gBPO initiation reaction 8h.Products therefrom is repeatedly washed with clear water, suction filtration, drying obtains the PMMA complex microsphere, packages spare.
Use the observation by light microscope thus obtained microsphere, its median size is about 80 μ m.Get the powder of 1.5g, in apparatus,Soxhlet's, use 100ml hot acetone extracting 48h, with PMMA acetone soln cooling in the flask after the extracting and to wherein adding 100ml distilled water.With the floss oven dry of separating out, make solvent with tetrahydrofuran (THF), be made into the solution of 0.005g/ml.The weight-average molecular weight that records PMMA in the mixture by gel permeation chromatography (GPC) is 73.9 * 10
4, polydispersity coefficient is 2.86.
Embodiment 3
TiO with 5g
2Pour in the 95g toluene, fully stir, pour in the reactor after handling through ultra-sonic dispersion, stir, heat up and Dropwise 5 g treatment agent KH-570 isothermal reaction 7h under boiling state.With the TiO after handling
2The suspension suction filtration, with washing with acetone repeatedly after suction filtration drying again, obtain pressed powder A.The 2.5g powders A is joined in the 47.5gMMA monomer, ultra-sonic dispersion, and with in this suspension adding solution B (being dissolved with the 190ml deionized water of 1% Natvosol and 0.05% sodium laurylsulfonate), with the speed stirring of 700rpm.Behind the logical nitrogen protection 30min, be warming up to 75 ℃ and add 0.48gBPO initiation reaction 7h.Products therefrom is repeatedly washed with clear water, suction filtration, drying obtains the PMMA complex microsphere, packages spare.
Use the observation by light microscope thus obtained microsphere, its median size is about 61 μ m.Get the microballoon of 1.5g, in apparatus,Soxhlet's, use 100ml hot acetone extracting 48h, with PMMA acetone soln cooling in the flask after the extracting and to wherein adding 100ml distilled water.With the floss oven dry of separating out, make solvent with tetrahydrofuran (THF), be made into the solution of 0.005g/ml.The weight-average molecular weight that records PMMA in the mixture by gel permeation chromatography (GPC) is 89.3 * 10
4, polydispersity coefficient is 2.13.
The microballoon of gained is mixed by mass ratio with the hot type dental basse acrylic resin liquid that coagulates at 2: 1, by the time dough period is inserted it in plaster mold, in 70 ℃ water, heat 1.5h, be rapidly heated again to 100 ℃, die sinking behind the maintenance 1h, with No. 280, No. 400, No. 800 sand paper it is polished, the gained sample stretches, deflection and hardness test.Tensile strength is 60.1MPa, and flexural strength is 122.8MPa, and Rockwell hardness is 113.
Embodiment 4
TiO with 4g
2Pour in the 96g toluene, fully stirring through pouring in the reactor after the ultra-sonic dispersion processing, is stirred, and heats up and dropping 4.5g treatment agent KH-570 isothermal reaction 7h under boiling state.With the TiO after handling
2The suspension suction filtration, with washing with acetone repeatedly after suction filtration drying again, obtain pressed powder A.The 1g powders A is joined in the 50gMMA monomer, ultra-sonic dispersion, and with in this suspension adding solution B (being dissolved with the 200ml deionized water of 0.8% Natvosol and 0.03% sodium laurylsulfonate), with the speed stirring of 600rpm.Behind the logical nitrogen protection 30min, be warming up to 75 ℃ and add 0.5gBPO initiation reaction 8h.Products therefrom is repeatedly washed with clear water, suction filtration, drying obtains the PMMA complex microsphere, packages spare.
The microballoon of gained is mixed by mass ratio with the hot type dental basse acrylic resin liquid that coagulates at 2: 1, by the time dough period is inserted it in plaster mold, in 70 ℃ water, heat 1.5h, be rapidly heated again to 100 ℃, die sinking behind the maintenance 1h, with No. 280, No. 400, No. 800 sand paper it is polished, the gained sample stretches, deflection and hardness test.Tensile strength is 61.3MPa, and flexural strength is 120.2MPa, and Rockwell hardness is 116.
The preparation method of the open and polymethyl methacryate/titanic oxide composite nano-microsphere that proposes of the present invention, those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, processing parameter realize.Method of the present invention and product and method are described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to method as herein described with product is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (2)
1. a polymethyl methacryate/titanic oxide composite nano-microsphere is characterized in that microballoon is the pearl powder, and median size is 40～80 μ m, and each component quality proportioning is:
Polymethylmethacrylate 99.9%～90%,
TiO
2 0.1％～10％。
2. the preparation method of the polymethyl methacryate/titanic oxide composite nano-microsphere of claim 1 is characterized in that method steps is as follows:
1) with mass concentration is 1～10% TiO
2Toluene or dimethylbenzene suspension fully stir, and through adding reactor after the ultra-sonic dispersion processing, stir, and heat up and dropping treatment agent γ-methacryloxypropyl trimethoxy silane the relative and TiO of dripping quantity
2Massfraction be 10～200%, isothermal reaction 6～8h under boiling state is with the TiO after handling
2The suspension suction filtration, with washing with acetone repeatedly after suction filtration drying again, obtain pressed powder A.
2) deionized water solution of configuration 0.5～2% Natvosol, and add 0.01～0.1% sodium laurylsulfonate or Sodium dodecylbenzene sulfonate, obtain solution B.
3) powders A is joined in the methyl methacrylate monomer, fully stir and with ultrasonic grinding machine ultra-sonic dispersion, obtain suspension, the massfraction of A is 0.1～10%; Suspension behind the ultra-sonic dispersion and solution B are added reactor, and heating is stirred, and stir speed (S.S.) is 400～900rpm; Behind the logical nitrogen protection 30min, be warming up to 65-85 ℃ of adding and be BPO initiated polymerization 5～8h of 0.5～2% with respect to the massfraction of MMA; Products therefrom is repeatedly washed with clear water, suction filtration, drying obtains final product; Water MMA monomer mass ratio is 3～5 in the suspension polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100537105A CN101302265B (en) | 2008-06-30 | 2008-06-30 | Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100537105A CN101302265B (en) | 2008-06-30 | 2008-06-30 | Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101302265A true CN101302265A (en) | 2008-11-12 |
| CN101302265B CN101302265B (en) | 2011-05-11 |
Family
ID=40112378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100537105A Expired - Fee Related CN101302265B (en) | 2008-06-30 | 2008-06-30 | Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101302265B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068387A (en) * | 2010-12-02 | 2011-05-25 | 天津大学 | Methyl acrylate (MA)-methyl methacrylate (MMA) copolymer-base denture base material as well as preparation method and application thereof |
| CN102604135A (en) * | 2012-03-02 | 2012-07-25 | 上海交通大学 | Preparation method of polymethyl methacrylate/titanium dioxide nano-grade composite material |
| CN103665279A (en) * | 2013-11-25 | 2014-03-26 | 江苏金太阳布业有限公司 | Preparation method and application of modified nano TiO2 finishing agent |
| CN105254797A (en) * | 2015-09-24 | 2016-01-20 | 衢州市中通化工有限公司 | Preparation method of fluorine-containing light diffusion agent |
| CN106188380A (en) * | 2016-08-03 | 2016-12-07 | 台州艾斐建材有限公司 | A kind of tap of composite clad surface |
| CN106279502A (en) * | 2016-08-03 | 2017-01-04 | 台州艾斐建材有限公司 | A kind of faucet of heat-resisting reinforced resins composite cladding |
| CN108136358A (en) * | 2015-10-22 | 2018-06-08 | 巴斯夫欧洲公司 | The method for preparing the aqueous dispersion of particle |
| CN108559212A (en) * | 2018-05-11 | 2018-09-21 | 东华理工大学 | A kind of nanometer of toughened plastics |
| CN112790999A (en) * | 2021-01-21 | 2021-05-14 | 邱璟 | Toilet powder for infants and preparation method thereof |
| CN113429844A (en) * | 2021-07-15 | 2021-09-24 | 北京世纪海森防水材料有限公司 | Metal roof acrylic acid high-elasticity waterproof coating and preparation method thereof |
| CN114272864A (en) * | 2021-12-23 | 2022-04-05 | 中国科学院重庆绿色智能技术研究院 | White particle, black-white electronic ink microcapsule and preparation method thereof |
| CN116922914A (en) * | 2023-07-24 | 2023-10-24 | 青岛伟东包装有限公司 | High-gloss low-haze plastic film and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102836680B (en) * | 2012-09-14 | 2014-07-02 | 湖北鼎龙化学股份有限公司 | Antimony-doped titania composite microsphere, carrier and electrostatic image developer |
-
2008
- 2008-06-30 CN CN2008100537105A patent/CN101302265B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068387A (en) * | 2010-12-02 | 2011-05-25 | 天津大学 | Methyl acrylate (MA)-methyl methacrylate (MMA) copolymer-base denture base material as well as preparation method and application thereof |
| CN102604135A (en) * | 2012-03-02 | 2012-07-25 | 上海交通大学 | Preparation method of polymethyl methacrylate/titanium dioxide nano-grade composite material |
| CN103665279A (en) * | 2013-11-25 | 2014-03-26 | 江苏金太阳布业有限公司 | Preparation method and application of modified nano TiO2 finishing agent |
| CN105254797A (en) * | 2015-09-24 | 2016-01-20 | 衢州市中通化工有限公司 | Preparation method of fluorine-containing light diffusion agent |
| CN108136358A (en) * | 2015-10-22 | 2018-06-08 | 巴斯夫欧洲公司 | The method for preparing the aqueous dispersion of particle |
| CN106279502A (en) * | 2016-08-03 | 2017-01-04 | 台州艾斐建材有限公司 | A kind of faucet of heat-resisting reinforced resins composite cladding |
| CN106188380A (en) * | 2016-08-03 | 2016-12-07 | 台州艾斐建材有限公司 | A kind of tap of composite clad surface |
| CN108559212A (en) * | 2018-05-11 | 2018-09-21 | 东华理工大学 | A kind of nanometer of toughened plastics |
| CN112790999A (en) * | 2021-01-21 | 2021-05-14 | 邱璟 | Toilet powder for infants and preparation method thereof |
| CN113429844A (en) * | 2021-07-15 | 2021-09-24 | 北京世纪海森防水材料有限公司 | Metal roof acrylic acid high-elasticity waterproof coating and preparation method thereof |
| CN114272864A (en) * | 2021-12-23 | 2022-04-05 | 中国科学院重庆绿色智能技术研究院 | White particle, black-white electronic ink microcapsule and preparation method thereof |
| CN114272864B (en) * | 2021-12-23 | 2023-03-14 | 中国科学院重庆绿色智能技术研究院 | White particle, black-white electronic ink microcapsule and preparation method thereof |
| CN116922914A (en) * | 2023-07-24 | 2023-10-24 | 青岛伟东包装有限公司 | High-gloss low-haze plastic film and preparation method thereof |
| CN116922914B (en) * | 2023-07-24 | 2024-04-05 | 青岛伟东包装有限公司 | High-gloss low-haze plastic film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101302265B (en) | 2011-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101302265B (en) | Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof | |
| CN101787171B (en) | Silicon oxide (SiOX)/polymethyl methacrylate (PMMA) nano composite resin and preparation and application thereof | |
| CN101305966B (en) | Denture base polymethyl methacrylate/silicon dioxide nano composite microsphere and its preparation method | |
| CN113026364B (en) | Modified nano silicon dioxide shear thickening protective liquid and preparation method and application thereof | |
| CN103319832B (en) | Photo-curing compound resin used for dental repair and preparation method thereof | |
| CN102153912B (en) | Single-component glass printing ink | |
| CN105985480B (en) | Polymethyl methacrylate-carbon nano tube compound material based on conjugation and preparation method thereof | |
| CN101418063B (en) | Method for preparing natural rubber-silicon dioxide nano composite material by in-situ grafting polymerization | |
| CN106700372A (en) | Application of methacrylatoethyl dodecyl dimethyl ammonium bromide in disperse silicon dioxide as well as composite material and preparation method of composite material | |
| CN105985602B (en) | Polymethyl methacrylate-carbon nano tube compound material based on charge effect and preparation method thereof | |
| CN101381435B (en) | Preparation method of spherical polyelectrolyte brush and use thereof | |
| CN102973416A (en) | Preparation method of dental restoring resin taking silicon dioxide and cluster of silicon dioxide as stuffing | |
| CN100586416C (en) | Polymethyl methacrylate/montmorillonite nano composite denture base material and its preparation method | |
| CN104497362B (en) | A kind of preparation method of cellulose/nanometer silicon nitride composite membrane | |
| CN107236078B (en) | Preparation method of flexible soft monomer colloid photonic crystal emulsion | |
| CN102552045B (en) | Polymethylmethacrylate-silica composite denture base material as well as preparation method and application thereof | |
| CN101220127B (en) | Nucleocapsid type rubber coordination crosslinking agent | |
| TWI526414B (en) | Modified bone cement composition | |
| Deng et al. | A novel approach for the preparation of PMMA–PDMS core–shell particles with PDMS in the shell | |
| CN104287976B (en) | Antibacterial denture powder with excellent anti-bending performance and preparation method thereof | |
| CN103059491B (en) | Liquid phase laser sputtering-based preparation method of inorganic-polymer nanocomposite material | |
| CN106661384B (en) | Multi-part acrylic cold-setting composition | |
| CN103622836B (en) | Poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material and preparation method | |
| CN103627213A (en) | Preparation method of modified nano hydroxyapatite | |
| CN112521705A (en) | Method for preparing modified aramid pulp/PMMA (polymethyl methacrylate) composite material by supercritical carbon dioxide polymerization |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201218 Address after: No.1301, business office building, Xiuyi Suzhou Hangzhou urban complex, No.8 Lingzhou East Road, Haizhou District, Lianyungang City, Jiangsu Province 222000 Patentee after: Lianyungang bangben Technology Co.,Ltd. Address before: Room 402, building 24, Yuzhou Zunfu, Jinghai Town, Jinghai District, Tianjin Patentee before: Tianjin Dingsheng Technology Development Co.,Ltd. Effective date of registration: 20201218 Address after: Room 402, building 24, Yuzhou Zunfu, Jinghai Town, Jinghai District, Tianjin Patentee after: Tianjin Dingsheng Technology Development Co.,Ltd. Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92, Tianjin University Patentee before: Tianjin University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210330 Address after: 226200 No. 101 Nanhai Road, Qidong high tech Industrial Development Zone, Qidong, Nantong, Jiangsu Patentee after: QIDONG CHUANGLU NEW MATERIAL Co.,Ltd. Address before: No.1301, business office building, Xiuyi Suzhou Hangzhou urban complex, No.8 Lingzhou East Road, Haizhou District, Lianyungang City, Jiangsu Province 222000 Patentee before: Lianyungang bangben Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110511 Termination date: 20210630 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |