CN102775601A - Preparation method of semi-aromatic polyamide-polyamide 11 copolymer - Google Patents
Preparation method of semi-aromatic polyamide-polyamide 11 copolymer Download PDFInfo
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Abstract
The invention relates to the field of copolymer of high molecular material, in particular to a preparation method of a semi-aromatic polyamide-polyamide 11 copolymer. According to the invention, the following components in part by weight, namely 1-50 parts of semi-aromatic polyamide salt and 1-50 parts of aminoundecanoic acid, are reacted: under a protective gas to obtain the semi-aromatic polyamide-polyamide 11 copolymer. The copolymer provided by the invention has the following beneficial effects: (1) the used aminoundecanoic acid is made from castor oil, so the prepared copolymer reduces dependence on petrochemical resources and has a certain environmental value; (2) the prepared copolymer has improved tensile strength, elongation at break and processing property; and (3) the preparation process is continuous and compact, which shortens the polymerization cycle effectively.
Description
Technical field
The present invention relates to the copolymer field of macromolecular material, specifically is a kind of preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers.
Background technology
Polyamide resin (PA) has mechanical mechanics properties such as excellent wear-resisting, self-lubricating, oil resistant, heatproof, is domestic and international application engineering plastics the most widely, first of the row five large-engineering plastics.Wherein, advantage such as polymeric amide 11 (PA11) has that water-absorbent is low, dimensional stability good, low temperature resistant and electrical insulation capability is good, and stress cracking resistance is good, it is not easy to crack to embed metal parts, has excellent shock resistance and oil resistant solvent resistance.The polymerization single polymerization monomer of PA11 is an aminoundecanoic acid, and the synthesis material of aminoundecanoic acid derives from Viscotrol C, does not rely on oil, is a kind of renewable macromolecular material of biomass, and market application foreground is wide.
Semiaromatic polyamide composition is diamines or dicarboxylicacid and the aliphatic dicarboxylic acid or the diamines of band aromatic nucleus, the polyamide resin that is prepared from through polycondensation.Owing in the polymeric amide molecular backbone chain, imported aromatic nucleus; Thereby thermotolerance and mechanical property have been improved; Reduced water-intake rate; And more suitable cost performance is arranged, and is the high heat resistance resin between general engineering plastic polymeric amide and thermostability engineering plastic, is mainly used in automobile and electric and electronic industry.Develop rapidly along with high-tech, its application has new breakthrough and progress, market requirement cumulative year after year.The semiaromatic polyamide composition product mainly contains polymeric amide MXD6,6T/66,6T/6I, 6T/6I/66,6T/M-5T and 9T etc. at present.
Among the English Patent GB1070416, the Davis Anthony Charles of ICI company etc. has disclosed the compound method of a series of semiaromatic polyamide compositions such as PA7T, PA9T, PA10T, PA12T; In the U.S. Pat 5502155, DUPONT company has also mentioned with terephthalic acid and the synthetic PA10T polymkeric substance of decamethylene diamine; Patent US4022756, GB1526329, US4113708, US4246395, US4663166, US4863991, WO9210525, US560167, JP02251352, JP034317, JP03161507 and JP0408730 etc. have all disclosed the preparation method of PA6T.Because semiaromatic polyamide composition is compared with fatty polyamide, its maximum characteristics are fine heat-resisting performance; Compare with fully aromatic polyamide, though moulding processability has some improvement, fusing point is still too high, and is comparatively approaching with the decomposition temperature of polymeric amide, needs to add the 3rd monomer and reduces fusing point, further to satisfy the requirement of forming process.Patent US5516882, US5981692, US962628, US6140459 and US5663284 etc. disclose the method for the multiple PA6T of preparation multipolymer.In addition, Chinese patent CN1032363C, CN1537881A, CN101724152A etc. disclose the different methods for preparing the semiaromatic polyamide composition alloy.
But, not having in the prior art with renewable resources---aminoundecanoic acid is a raw material, obtains the relevant report of semiaromatic polyamide composition-polymeric amide 11 multipolymers.
Summary of the invention
The present invention aims to provide a kind of preparation method with semiaromatic polyamide composition-polymeric amide 11 multipolymers of good heat resistance ability, mechanical property, environmental protection.
The present invention realizes through following technical scheme: the preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, and its preparation process is:
(1) reinforced: with the semiaromatic polyamide composition salt of 1 ~ 50 weight part, the aminoundecanoic acid of 1 ~ 50 weight part, the zero(ppm) water of 5 ~ 40 weight parts or organic solvent, the catalyzer of 0.01 ~ 2 weight part, the end-capping reagent of 0.2 ~ 10 weight part, the acquisition mixture stirs; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or N, and described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, ortho phosphorous acid or their salt compounds, and described end-capping reagent is monocarboxylic acid or monoamine;
(2) reaction is synthetic: mixture is warming up to 220 ~ 270 ℃, is forced into 1.6 ~ 3.5MPa under the shielding gas atmosphere, insulation (220 ~ 270 ℃) pressurize (1.6 ~ 3.5MPa) 1 ~ 4h; 1 ~ 4h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 290 ~ 350 ℃ simultaneously, and insulation (290 ~ 350 ℃) 2 ~ 4h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
When semiaromatic polyamide composition salt is 1 ~ 50 weight part; When aminoundecanoic acid was 1 ~ 50 weight part, if the weight part of zero(ppm) water or organic solvent is during less than 5 parts, the mixing of reaction raw materials was difficult for evenly; Cause the loss of diamines during polymerization easily; If during greater than 40 parts, polymerization rate descends, and polymerization reaction time increases; If the weight part of catalyzer is during less than 0.01 part, if the effect that catalyzer plays is not obvious during greater than 2 parts, and the catalytic effect of catalyzer levels off to a maximum value, and too much use causes the waste of catalyzer easily; If the weight part of end-capping reagent was less than 0.2 o'clock, polymerization velocity is too fast, causes copolymerization product bad phenomenon such as implode to occur easily, if greater than 10 o'clock, the activity of reactive functionality is impacted, and polymerization rate reduces.
Organic solvent of the present invention is methyl alcohol, ethanol, N-Methyl pyrrolidone or N.Above-mentioned organic solvent helps further improving the performance of multipolymer.
Described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, ortho phosphorous acid or their salt compounds.Above-mentioned catalyzer helps the carrying out of copolyreaction.
Described end-capping reagent is monocarboxylic acid or monoamine.Above-mentioned end-capping reagent helps the carrying out of copolyreaction.
Further, added the foam preventer of 0.01 ~ 0.5 weight part in the described addition step in the mixture.When the weight part of foam preventer less than 0.01 the time, foam preventer can not play effect; When the weight part of foam preventer greater than 0.5 the time, too much use foam preventer, the effect of foam preventer increases not obvious, causes the waste of foam preventer easily.Described foam preventer can be selected the conventional foam preventer of preparation polymkeric substance for use.
Foam preventer of the present invention is a silicone oil, adopts silicone oil can more effectively prevent the foaming of material in the reaction process as foam preventer of the present invention.
Further, added the inhibitor of 0.01 ~ 2 weight part in the described addition step in the mixture.When the weight part of inhibitor less than 0.01 the time, inhibitor does not have tangible oxidation resistant effect; When the weight part of inhibitor greater than 2 the time, antioxidant effect reaches peak, increases the consumption of inhibitor, antioxidant effect can not increase, and also can increase cost.Described foam preventer can be selected the conventional inhibitor of preparation polymkeric substance for use.
Inhibitor of the present invention is sodium phosphite, antioxidant 1010 [four { β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester], antioxidant 1076 [β-(3; The 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid], oxidation inhibitor 1098 [N; N '-two-{ 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group } hexanediamine].The present invention selects above-mentioned inhibitor for use, can more help avoiding the oxidation stain of multipolymer.
Further, described preparation process is carried out in autoclave.Described autoclave is available from Chaoyang, Weihai chemical machinery ltd.
Further, described semiaromatic polyamide composition salt be in PA6T salt, PA6I salt, PA7T salt, PA7I salt, PA8T salt, PA8I salt, PA9T salt, PA9I salt, PA10T salt, PA10I salt, PA11T salt, PA12T salt, PA12I salt, the PA13T salt wherein one or more with arbitrary proportion blended mixture.Adopt the mechanical property and the Good Heat-resistance of the multipolymer that above-mentioned semiaromatic polyamide composition salt makes.
According to the inventor to TE of the present invention; Finally confirmed preparation method of the present invention; Multipolymer of the present invention has following beneficial effect: 1) used aminoundecanoic acid comes from Viscotrol C; The multipolymer of preparation decreases to petrochemical industry resource dependency degree, has certain value of environmental protection; 2) tensile strength of the multipolymer of preparation, elongation at break and moulding processability are improved; 3) preparation technology's continuous and compact has effectively shortened polymerization cycle.
Embodiment
All in an embodiment characteristics are all measured by following method.
1. tensile strength (MPa) and elongation at break (%)
Adopt the CMT6104 type microcomputer control electronics universal testing machine of Shenzhen Sans Material Detection Co., Ltd, undertaken by standard method of test GB/T 1040-2006.
2. flexural strength (MPa) and modulus in flexure (MPa)
Adopt the CMT6104 type microcomputer control electronics universal testing machine of Shenzhen Sans Material Detection Co., Ltd, undertaken by standard method of test GB/T 9341-2000.
3. shock strength (KJ/m
2)
Adopt the XJU-22 type socle girder test with notched test piece machine of Chengde trier ltd, undertaken by standard method of test GB1843-2008.
Heat-drawn wire (℃)
Adopt the XRW-300M type thermal distortion vicat softening point temperature determinator of Chengde Jinjian Testing Instrument Co., Ltd., undertaken by standard method of test GB/T 1634-2004.
Fusing point (℃) adopt the DSC822e type DSC of METTLER company, undertaken by standard method of test GB/T 19466-2004.
6. limiting viscosity (dl/g): in 25 ℃ the vitriol oil, measure the limiting viscosity of copolymer sample, undertaken by standard method of test GB/T 12006-2009.
Embodiment 1 (every part is 10 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA10T salt of 500 grams, the aminoundecanoic acid of 500 grams, the zero(ppm) water of 350 grams, the phosphoric acid of 1 gram, the acetate of 1 gram, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 225 ℃, is forced into 2.0MPa, heat-insulation pressure keeping 3h under the shielding gas atmosphere; 2h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 320 ℃ simultaneously, and insulation 4h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
Described preparation process is carried out in autoclave.Described autoclave is available from Chaoyang, Weihai chemical machinery ltd
The performance of copolymer test result is shown in table 1.
Embodiment 2 (every part is 20 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA7T salt of 500 grams, the PA7I salt of 400 grams, the aminoundecanoic acid of 800 grams, the methyl alcohol of 300 grams, the sodium phosphate of 10 grams, the butylamine of 20 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 245 ℃, is forced into 2.5MPa, heat-insulation pressure keeping 2h under the shielding gas atmosphere; 3h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 310 ℃ simultaneously, and insulation 2h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 1.
Embodiment 3 (every part is 15 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA8T salt of 300 grams, the aminoundecanoic acid of 150 grams, the ethanol of 450 grams, the phosphorous acid of 22.5 grams, the LAURIC ACID 99 MIN of 3 grams, the silicone oil of 0.15 gram, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 270 ℃, is forced into 1.6MPa, heat-insulation pressure keeping 1h under the shielding gas atmosphere; 4h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 350 ℃ simultaneously, and insulation 3h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 1.
Embodiment 4 (every part is 20 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA6T salt of 6 grams, the PA8I salt of 7 grams, the PA13T salt of 7 grams, the aminoundecanoic acid of 20 grams, the N-Methyl pyrrolidone of 100 grams, the Hypophosporous Acid, 50 of 40 grams, the Triple Pressed Stearic Acid of 10 grams, the silicone oil of 8 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 220 ℃, is forced into 2.8MPa, heat-insulation pressure keeping 4h under the shielding gas atmosphere; 2h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 290 ℃ simultaneously, and insulation 3h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 1.
Embodiment 5 (every part is 100 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA6I salt of 1000 grams, the PA11T salt of 2000 grams, the aminoundecanoic acid of 2000 grams, the N of 4000 grams; The ortho phosphorous acid of 1 gram, the myristic acid of 700 grams, the MO of 20 grams; The antioxidant 1010 of 200 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 250 ℃, is forced into 3.5MPa, heat-insulation pressure keeping 4h under the shielding gas atmosphere; 3h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 340 ℃ simultaneously, and insulation 2h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 1.
Embodiment 6 (every part is 20 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA12T salt of 800 grams, the aminoundecanoic acid of 900 grams, the zero(ppm) water of 500 grams; The sodium hypophosphite (catalyzer) of 36 grams, the hexahydroaniline of 200 grams, the vegetables oil of 10 grams; 0.2 the sodium phosphite (inhibitor) of gram, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 260 ℃, is forced into 2.2MPa, heat-insulation pressure keeping 2h under the shielding gas atmosphere; 1h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 330 ℃ simultaneously, and insulation 3h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 1.
Embodiment 7 (every part is 10 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA12I salt of 150 grams, the PA9T salt of 100 grams, the aminoundecanoic acid of 250 grams, the methyl alcohol of 100 grams, the sodium phosphite of 10 grams, the Triple Pressed Stearic Acid of 90 grams, the silicone oil of 3 grams, the antioxidant 1076 of 0.5 gram, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 230 ℃, is forced into 1.6MPa, heat-insulation pressure keeping 3h under the shielding gas atmosphere; 1h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 300 ℃ simultaneously, and insulation 4h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 1.
Embodiment 8 (every part is 50 grams)
The preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers, its preparation process is:
(1) reinforced: with the PA9I salt of 1400 grams, the aminoundecanoic acid of 1500 grams, the N-Methyl pyrrolidone of 1000 grams, the ortho phosphorous acid of 0.5 gram, the aniline of 250 grams, the silicone oil of 5 grams, the oxidation inhibitor 1098 of 5 grams, the acquisition mixture stirs;
(2) reaction is synthetic: mixture is warming up to 240 ℃, is forced into 3.0MPa, heat-insulation pressure keeping 1h under the shielding gas atmosphere; 4h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 350 ℃ simultaneously, and insulation 3h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
The performance of copolymer test result is shown in table 1.
Table 1 embodiment 1 ~ 8 prepared performance of copolymer test result
Claims (8)
1. the preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers is characterized in that, its preparation process is:
(1) reinforced: with the semiaromatic polyamide composition salt of 1 ~ 50 weight part, the aminoundecanoic acid of 1 ~ 50 weight part, the zero(ppm) water of 5 ~ 40 weight parts or organic solvent, the catalyzer of 0.01 ~ 2 weight part, the end-capping reagent of 0.2 ~ 10 weight part, the acquisition mixture stirs; Described organic solvent is methyl alcohol, ethanol, N-Methyl pyrrolidone or N, and described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, ortho phosphorous acid or their salt compounds, and described end-capping reagent is monocarboxylic acid or monoamine;
(2) reaction is synthetic: mixture is warming up to 220 ~ 270 ℃, is forced into 1.6 ~ 3.5MPa, heat-insulation pressure keeping 1 ~ 4h under the shielding gas atmosphere; 1 ~ 4h reduces to normal pressure subsequently, reduce to non-pressurizedly to be warming up to 290 ~ 350 ℃ simultaneously, and insulation 2 ~ 4h, discharging makes semiaromatic polyamide composition-polymeric amide 11 multipolymers.
2. the preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers according to claim 1 is characterized in that, has added the foam preventer of 0.01 ~ 0.5 weight part in the described addition step in the mixture.
3. the preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers according to claim 2 is characterized in that, has added the inhibitor of 0.01 ~ 2 weight part in the described addition step in the mixture.
4. the preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers according to claim 3 is characterized in that described preparation process is carried out in autoclave.
5. the preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers according to claim 4; It is characterized in that, described semiaromatic polyamide composition salt be in PA6T salt, PA6I salt, PA7T salt, PA7I salt, PA8T salt, PA8I salt, PA9T salt, PA9I salt, PA10T salt, PA10I salt, PA11T salt, PA12T salt, PA12I salt, the PA13T salt wherein one or more with arbitrary proportion blended mixture.
6. according to the preparation method of any described semiaromatic polyamide composition-polymeric amide 11 multipolymers of claim 1 ~ 5, it is characterized in that described foam preventer is a silicone oil.
7. according to the preparation method of described semiaromatic polyamide composition-polymeric amide 11 multipolymers of claim 1 ~ 5, it is characterized in that described inhibitor is sodium phosphite, antioxidant 1010, antioxidant 1076, oxidation inhibitor 1098.
8. the preparation method of semiaromatic polyamide composition-polymeric amide 11 multipolymers according to claim 6 is characterized in that, described inhibitor is sodium phosphite, antioxidant 1010, antioxidant 1076, oxidation inhibitor 1098.
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Cited By (8)
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| CN103122063A (en) * | 2013-02-05 | 2013-05-29 | 中北大学 | Preparation method of poly-p-aminobenzoylamonoundecylamine |
| CN103122065A (en) * | 2013-02-05 | 2013-05-29 | 中北大学 | Preparation method of transparent polyamide-polyamide 11 copolymer |
| CN104817693A (en) * | 2015-05-21 | 2015-08-05 | 郑州大学 | Semi-aromatic polyamide PA11T and preparation method thereof |
| CN105330844A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Transparent nylon and synthetic method thereof |
| CN105330846A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Bio-based high-temperature-resistant polyamide and synthesis method thereof |
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| CN103122063A (en) * | 2013-02-05 | 2013-05-29 | 中北大学 | Preparation method of poly-p-aminobenzoylamonoundecylamine |
| CN103122065A (en) * | 2013-02-05 | 2013-05-29 | 中北大学 | Preparation method of transparent polyamide-polyamide 11 copolymer |
| CN103122065B (en) * | 2013-02-05 | 2015-01-21 | 中北大学 | Preparation method of transparent polyamide-polyamide 11 copolymer |
| CN103122063B (en) * | 2013-02-05 | 2015-02-11 | 中北大学 | Preparation method of poly-p-aminobenzoylamonoundecylamine |
| CN104817693A (en) * | 2015-05-21 | 2015-08-05 | 郑州大学 | Semi-aromatic polyamide PA11T and preparation method thereof |
| CN105330844A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Transparent nylon and synthetic method thereof |
| CN105330846A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Bio-based high-temperature-resistant polyamide and synthesis method thereof |
| CN105330846B (en) * | 2015-12-07 | 2017-06-06 | 中北大学 | Bio-based heat resistant polyamide and its synthetic method |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
| CN109320716A (en) * | 2018-09-10 | 2019-02-12 | 湖南华曙高科技有限责任公司 | A kind of nylon powder material preparation method applied to selective laser sintering |
| CN109517370A (en) * | 2018-09-10 | 2019-03-26 | 湖南华曙高科技有限责任公司 | A kind of nylon powder material preparation method for selective laser sintering |
| CN109517370B (en) * | 2018-09-10 | 2021-07-02 | 湖南华曙高科技有限责任公司 | Preparation method of nylon powder material for selective laser sintering |
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Inventor after: Hu Guosheng Inventor after: Liu Yuchen Inventor after: Qu Zhen Inventor after: Li Yingchun Inventor after: Yang Yunfeng Inventor after: Wang Zhongqiang Inventor after: Zhang Jingting Inventor before: Hu Guosheng Inventor before: Li Yingchun Inventor before: Liu Yuchen Inventor before: Yang Yunfeng Inventor before: Zhang Jingting Inventor before: Song Jiangfeng Inventor before: Wang Zhiqiang |
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| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: HU GUOSHENG LI YINGCHUN LIU YUCHEN YANG YUNFENG ZHANG JINGTING SONG JIANGFENG WANG ZHIQIANG TO: HU GUOSHENG LIU YUCHEN QU ZHEN LI YINGCHUN YANG YUNFENG WANG ZHONGQIANG ZHANG JINGTING |
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| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20121114 |