CN100455601C - Modification method of cellulose ether product - Google Patents
Modification method of cellulose ether product Download PDFInfo
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- CN100455601C CN100455601C CNB2005101023815A CN200510102381A CN100455601C CN 100455601 C CN100455601 C CN 100455601C CN B2005101023815 A CNB2005101023815 A CN B2005101023815A CN 200510102381 A CN200510102381 A CN 200510102381A CN 100455601 C CN100455601 C CN 100455601C
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Abstract
The present invention discloses a modification method of cellulose ether products, which comprises that reaction raw material and solvents are mixed and react to obtain the products, and then the products are washed, dried and pulverized, wherein in the reaction process and the washing process, the solvents are water, isopropyl alcohol and normal butanol, or the solvents are water, isopropyl alcohol and isobutyl alcohol, or the solvents are water, isopropyl alcohol and tertiary butyl alcohol. The present invention has the advantages of low environment pollution, high reaction efficiency, easy solvent elimination and high washing efficiency of the products, and effectively raises the quality of the cellulose ether products, such as hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), ethyl cellulose (EC), cation type cellulose, etc.
Description
Technical field
The present invention relates to the material field, particularly the preparation method of ether of cellulose.
Background technology
Cellulose ether product comprises non-ionic type Mierocrystalline cellulose, anionic Mierocrystalline cellulose and cationic Mierocrystalline cellulose, wherein, the non-ionic type fiber have hydroxypropylcellulose (HPC), Natvosol (HEC), Vltra tears (HPMC) and ethyl cellulose (EC) etc.; The anionic fiber have carboxymethyl cellulose etc.; Cationic Mierocrystalline cellulose mainly is a kind of weak cation, high-molecular weight polymeric quaternary ammonium salts, presses it by the difference different or bonded quaternary ammonium group number on the cellulosic molecule of same length of hair adsorptive capacity, and is divided into JR, LR, SR Three Estate.These cellulose ether products have become the important industrial chemicals of dozens of industries such as daily-use chemical industry, food, coating, medicine, agricultural chemicals, oil field, explosive, pottery, papermaking.But some is from external import for the plain ether product of the high quality fiber that China uses.This mainly is that it is reasonable inadequately that dissolvant of reaction system is formed, and influenced the reaction efficiency of etherifying agent and the detersive efficiency of reaction effect and product, and then influenced the quality of product because the modified technique of China's cellulose ether product is poor.The most of cellulose modified etherification reactions of China all be in multiphase medium the beginning and finish, in multiphase medium, have the feature of topochemical reaction, chemical reaction velocity is usually greater than velocity of diffusion, both differences are big more, the replacement homogeneity of products obtained therefrom is poor more.Usually the inert solvent that adopts has methyl alcohol, ethanol, Virahol, toluene, and these solvent types and form influentially for the reaction of multiphase medium also easily cause environmental pollution during the solvent recuperation that has.Such as the solvent that adopts when producing hydroxypropylcellulose (HPC) often is the same toluene of water, and toluene pollutes big to production environment, solvent recuperation cost height; The solvent of using when producing cationic cellulose and Natvosol (HEC) etc. is water, Virahol, the solvent of using during washing is water, Virahol, because the content of water can not be too high, too high meeting causes the reaction mass transfer decrease in efficiency, hangs down excessively to make detersive efficiency descend; The use of these solvents has reduced reaction efficiency, and the subsequent wash efficient and the product drying efficient of product is had a negative impact, and has directly caused quality product well not improved.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of environmental friendliness, reaction efficiency and detersive efficiency height, cost are low, the preparation method of the simple ether of cellulose of technology.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of this ether of cellulose comprises Mierocrystalline cellulose, sodium hydroxide, etherifying agent and solvent and reaction are obtained product, then to product wash, dry and pulverize, wherein the solvent that adopts in the reaction process is water, Virahol and propyl carbinol; Or the solvent that adopts is water, Virahol and isopropylcarbinol; Or the solvent that adopts is water, Virahol and the trimethyl carbinol.
Described cellulose ether product comprises hydroxypropylcellulose (HPC), Vltra tears (HPMC), Natvosol (HEC), hydroxyethyl hydroxypropylcellulose (HEHPC), ethyl cellulose (EC) and cationic Mierocrystalline cellulose etc.
When described cellulose ether product was hydroxypropylcellulose (HPC), used etherifying agent was a propylene oxide; When described cellulose ether product was Natvosol (HEC), used etherifying agent was an oxyethane; When described cellulose ether product was Vltra tears (HPMC), used etherifying agent was propylene oxide and monochloro methane; When described cellulose ether product was hydroxyethyl hydroxypropylcellulose (HEHPC), used etherifying agent was oxyethane and propylene oxide; When described cellulose ether product was cationic Mierocrystalline cellulose, used etherifying agent was 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride and/or oxyethane; When described cellulose ether product was ethyl cellulose (EC), used etherifying agent was a monochloroethane.
In the described reaction process, the weight percent of solvent is a water: Virahol: (propyl carbinol or isopropylcarbinol or the trimethyl carbinol) equals 5%～37%: 5%～90%: 1%～90%.
In the described reaction process, the liquid-solid ratio of reaction raw materials and solvent (weight ratio) is 2～15.
In the described reaction process, elder generation is with reaction raw materials and solvent and stir 1～120 fen kind, then temperature of reaction is elevated to 45 ℃～117 ℃ from charge temperature, reacts 30～300 fens kinds.
The preparation method of above-mentioned ether of cellulose, the solvent that product carries out adopting in the washing process is water, Virahol and propyl carbinol; Or the solvent that adopts is water, Virahol and isopropylcarbinol; Or the solvent that adopts is water, Virahol and the trimethyl carbinol.
In the described washing process, adopting the weight percent of solvent is water: Virahol: (propyl carbinol or isopropylcarbinol or the trimethyl carbinol) equals 10%～45%: 5%～88%: 1%～85%.
In the described washing process, when the liquid-solid ratio (weight ratio) of washing when being 0.5～25, the solvent wash product once, the ash content of coal of dry back product is less than 5%; Solvent wash product secondary, the ash content of coal of dry back product is less than 3%; Solvent wash product three times, the ash content of coal of dry back product is less than 1%.
The present invention compared with prior art has following advantage and effect:
(1) the present invention is in the process of production of cellulose ether product, and the solvent that is adopted can improve reaction efficiency, helps removing and washing of solvent simultaneously.
(2) the present invention is in the washing process of cellulose ether product, and the solvent that is adopted can improve product detersive efficiency and product drying efficient, reduces salt content 3～30% weight of cellulose ether product simultaneously.
(3) the present invention can save the consumption of etherifying agent in the reaction, and its amount ratio ordinary method is saved 3%-30% weight, improves the replacement homogeneity of product.
(4) environmental pollution of the present invention is little, and the solvent recuperation cost is low, has effectively improved the quality of cellulose ether product.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
Produce hydroxypropylcellulose (HPC):
At first the purified cotton fibre element is carried out powder essence, 1000 kilograms of purified cottons after will pulverizing then, 1200 kilograms of propylene oxide (etherifying agent), sodium hydroxide double centner and solvent 6000 kilograms (weight percent of each component of solvent is a water: Virahol: the trimethyl carbinol equals 15%: 25%: 60%) mix and add in the reactor, stirred 25 minutes down at 20 ℃ earlier, in 30 minutes, temperature of reaction is elevated to 97 ℃ from 20 ℃ then, in 180 fens kinds of 97 ℃ of reactions; The pH value that then product neutralized dropped to 37 ℃ with product temperature again for neutral in 50 minutes, the solvent major part in the product is removed; Add 1400 kilograms of 600 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols in product, agitator treating 30 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 1400 kilograms of 600 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols again in product, agitator treating 30 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 1400 kilograms of 600 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols for the third time, agitator treating 30 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.7% after the gained drying; At last hydroxypropylcellulose (HPC) product is carried out the pure and packing of powder.
Embodiment 2
Produce hydroxypropylcellulose (HPC):
At first the purified cotton fibre element is carried out powder essence, 1000 kilograms of purified cottons after will pulverizing then, 1100 kilograms of propylene oxide (etherifying agent), sodium hydroxide double centner and solvent 6000 kilograms (weight percent of each component of solvent is a water: Virahol: the trimethyl carbinol equals 5%: 5%: 90%) mix and add in the reactor, stirred 25 minutes down at 20 ℃ earlier, then in 30 minutes, temperature of reaction is elevated to 65 ℃ from 20 ℃, in 300 fens kinds of 65 ℃ of reactions; The pH value that then product neutralized dropped to 37 ℃ with product temperature again for neutral in 50 minutes, the solvent major part in the product is removed; Add 2200 kilograms of 300 kilograms of entry, 500 kilograms of Virahols and the trimethyl carbinols in product, agitator treating 30 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 2200 kilograms of 300 kilograms of entry, 500 kilograms of Virahols and the trimethyl carbinols again in product, agitator treating 30 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 2200 kilograms of 300 kilograms of entry, 500 kilograms of Virahols and the trimethyl carbinols for the third time, agitator treating 30 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.9% after the gained drying; At last hydroxypropylcellulose (HPC) product is carried out the pure and packing of powder.
Embodiment 3
Produce hydroxypropylcellulose (HPC):
At first the purified cotton fibre element is carried out powder essence, 1000 kilograms of purified cottons after will pulverizing then, 1000 kilograms of propylene oxide (etherifying agent), sodium hydroxide double centner and solvent 6000 kilograms (weight percent of each component of solvent is a water: Virahol: the trimethyl carbinol equals 35%: 5%: 60%) mix and add in the reactor, stirred 25 minutes down at 20 ℃ earlier, then in 60 minutes, temperature of reaction is elevated to 117 ℃ from 20 ℃, in 30 fens kinds of 117 ℃ of reactions; The pH value that then product neutralized dropped to 37 ℃ with product temperature again for neutral in 70 minutes, the solvent major part in the product is removed; Add 1700 kilograms of 1400 kilograms of entry, 200 kilograms of Virahols and the trimethyl carbinols in product, agitator treating 30 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 1700 kilograms of 1400 kilograms of entry, 200 kilograms of Virahols and the trimethyl carbinols again in product, agitator treating 30 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 1700 kilograms of 1400 kilograms of entry, 200 kilograms of Virahols and the trimethyl carbinols for the third time, agitator treating 30 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.1% after the gained drying; At last hydroxypropylcellulose (HPC) product is carried out the pure and packing of powder.
Embodiment 4
Produce Vltra tears (HPMC).
At first the purified cotton fibre element is carried out powder essence, 6000 kilograms (weight percent of each component of solvent is a water: Virahol: propyl carbinol equals mixing in 20%: 25%: 55% for 1000 kilograms of purified cottons after will pulverizing then, 800 kilograms of propylene oxide (etherifying agent), 300 kilograms of monochloro methanes (etherifying agent), 240 kilograms in sodium hydroxide and solvent, and in the adding reactor, stirred 25 minutes down at 20 ℃ earlier, then in 50 minutes, temperature of reaction is elevated to 95 ℃ from 20 ℃, in 200 fens kinds of 95 ℃ of reactions; The pH value that then product neutralized dropped to 35 ℃ with product temperature again for neutral in 45 minutes, the solvent major part in the product is removed; Add 1300 kilograms of 800 kilograms of entry, 900 kilograms of Virahols and propyl carbinols in product, agitator treating 50 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 1300 kilograms of 800 kilograms of entry, 900 kilograms of Virahols and propyl carbinols again in product, agitator treating 50 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 1300 kilograms of 800 kilograms of entry, 900 kilograms of Virahols and propyl carbinols for the third time, agitator treating 50 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.5% after the gained drying; At last Vltra tears (HPMC) product is carried out the pure and packing of powder.
Embodiment 5
Produce Natvosol (HEC).
At first the purified cotton fibre element is carried out powder essence, 1000 kilograms of purified cottons after will pulverizing then, 900 kilograms in oxyethane (etherifying agent), sodium hydroxide double centner and solvent 6000 kilograms (adopting the weight percent of solvent in the reaction process is water: Virahol: the trimethyl carbinol equals 22%: 28%: 50%) mix, and in the adding reactor, stirred 30 minutes down at 25 ℃ earlier, then in 45 minutes, temperature of reaction is elevated to 75 ℃ from 25 ℃, in 120 fens kinds of 75 ℃ of reactions; The pH value that then product neutralized dropped to 37 ℃ with product temperature again for neutral in 30 minutes, the solvent major part in the product is removed; Add 1400 kilograms of 400 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols in product, agitator treating 50 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 1400 kilograms of 400 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols again in product, agitator treating 50 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 1400 kilograms of 400 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols for the third time, agitator treating 50 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.5% after the gained drying; At last Natvosol (HEC) product is carried out the pure and packing of powder.
Comparative Examples:
During present industrial production Natvosol (HEC), the solvent that reaction process adopts is water and Virahol, and other reaction conditionss are with present embodiment 5, and after measured, the reaction efficiency of Comparative Examples is than the reaction efficiency low 10% of present embodiment 5; The solvent that washing process adopts is water and Virahol, other wash conditions are with present embodiment 5, after measured, the detersive efficiency of Comparative Examples is lower more than 30% than the detersive efficiency of present embodiment 5, the ash content of coal of dry back product is 5.5% in the Comparative Examples, is higher than the product the ash content of coal (0.5%) of present embodiment 5.
Embodiment 6
Produce hydroxyethyl hydroxypropylcellulose (HEHPC).
At first the purified cotton fibre element is carried out powder essence, 1000 kilograms of purified cottons after will pulverizing then, 700 kilograms of propylene oxide (etherifying agent), 500 kilograms in oxyethane (etherifying agent), sodium hydroxide double centner and solvent 6000 kilograms (adopting the weight percent of solvent in the reaction process is water: Virahol: the trimethyl carbinol equals 13%: 27%: 60%) mix, and in the adding reactor, stirred 30 minutes down at 25 ℃ earlier, then in 45 minutes, temperature of reaction is elevated to 87 ℃ from 25 ℃, in 120 fens kinds of 87 ℃ of reactions; The pH value that then product neutralized dropped to 37 ℃ with product temperature again for neutral in 30 minutes, the solvent major part in the product is removed; Add 1400 kilograms of 500 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols in product, agitator treating 30 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 1400 kilograms of 500 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols again in product, agitator treating 30 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 1400 kilograms of 500 kilograms of entry, 1000 kilograms of Virahols and the trimethyl carbinols for the third time, agitator treating 30 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.6% after the gained drying; At last hydroxyethyl hydroxypropylcellulose (HEHPC) product is carried out the pure and packing of powder.
Embodiment 7
Production ethyl cellulose (EC).
At first the purified cotton fibre element is carried out powder essence, 1000 kilograms of purified cottons after will pulverizing then, 700 kilograms in monochloroethane (etherifying agent), 400 kilograms in sodium hydroxide and solvent 6000 kilograms (adopting the weight percent of solvent in the reaction process is water: Virahol: the trimethyl carbinol equals 30%: 40%: 30%) mix, and in the adding reactor, stirred 30 minutes down at 25 ℃ earlier, then in 45 minutes, temperature of reaction is elevated to 75 ℃ from 25 ℃, in 120 fens kinds of 75 ℃ of reactions; The pH value that then product neutralized dropped to 37 ℃ with product temperature again for neutral in 30 minutes, the solvent major part in the product is removed; Add 900 kilograms of 1000 kilograms of entry, 1100 kilograms of Virahols and the trimethyl carbinols in product, agitator treating 50 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 900 kilograms of 1000 kilograms of entry, 1100 kilograms of Virahols and the trimethyl carbinols again in product, agitator treating 50 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 900 kilograms of 1000 kilograms of entry, 1100 kilograms of Virahols and the trimethyl carbinols for the third time, agitator treating 50 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.97% after the gained drying; At last ethyl cellulose (EC) product is carried out the pure and packing of powder.
Embodiment 8
Produce cationic cellulose.
At first the purified cotton fibre element is carried out powder essence, 1000 kilograms of purified cottons after will pulverizing then, 800 kilograms in oxyethane (etherifying agent), 180 kilograms in sodium hydroxide and solvent 6000 kilograms (adopting the weight percent of solvent in the reaction process is water: Virahol: the trimethyl carbinol equals 22%: 28%: 50%) mix, and in the adding reactor, stirred 30 minutes down at 25 ℃ earlier, then in 45 minutes, temperature of reaction is elevated to 75 ℃ from 25 ℃, in 120 fens kinds of 75 ℃ of reactions; In reactor, add 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride (etherifying agent) 700 kilograms again; In 120 fens kinds of 60 ℃ of reactions, the pH value that then product neutralized dropped to 37 ℃ with product temperature again for neutral in 30 minutes, the solvent major part in the product is removed; Add 1600 kilograms of 500 kilograms of entry, 800 kilograms of Virahols and the trimethyl carbinols in product, agitator treating 50 minutes is finished for the first time and is cleaned, and the solvent major part in the product is removed; Add 1600 kilograms of 500 kilograms of entry, 800 kilograms of Virahols and the trimethyl carbinols again in product, agitator treating 50 minutes is finished for the second time and is cleaned, and the solvent major part in the product is removed; In product, add 1600 kilograms of 500 kilograms of entry, 800 kilograms of Virahols and the trimethyl carbinols for the third time, agitator treating 50 minutes is finished for the third time and is cleaned, and the solvent major part in the product is removed, again in drying plant with product drying, the ash content of coal of product is 0.7% after the gained drying; At last the cationic cellulose product is carried out the pure and packing of powder.
Comparative Examples:
During present industrial production cationic cellulose, the solvent that reaction process adopts is water and Virahol, and other reaction conditionss are with present embodiment 5, and after measured, the reaction efficiency of Comparative Examples is than the reaction efficiency low 18% of present embodiment 5; The solvent that washing process adopts is water and Virahol, other wash conditions are with present embodiment 5, after measured, the detersive efficiency of Comparative Examples is lower more than 35% than the detersive efficiency of present embodiment 5, the ash content of coal of dry back product is 6.5% in the Comparative Examples, is higher than the product the ash content of coal (0.7%) of present embodiment 5.
Claims (4)
1, a kind of preparation method of ether of cellulose, comprise Mierocrystalline cellulose, sodium hydroxide, etherifying agent and solvent and reaction are obtained product, then to product wash, dry and pulverize, it is characterized in that: the solvent that adopts in the described reaction process is water, Virahol and propyl carbinol; Described product carries out in the washing process, and the solvent of employing is water, Virahol and propyl carbinol.
2, the preparation method of ether of cellulose according to claim 1 is characterized in that: in the described reaction process, the weight percent of each component is a water in the solvent: Virahol: propyl carbinol equals 5%～37%: 5%～90%: 1%～90%.
3, the preparation method of ether of cellulose according to claim 1 is characterized in that: in the described washing process, the weight percent of each component is a water in the solvent: Virahol: propyl carbinol equals 10%～45%: 5%～88%: 1%～85%.
4, the preparation method of ether of cellulose according to claim 1 is characterized in that: described cellulose ether product is hydroxypropylcellulose, Vltra tears, hydroxyethyl hydroxypropylcellulose, ethyl cellulose or cationic Mierocrystalline cellulose.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100543037C (en) * | 2006-09-30 | 2009-09-23 | 广州天赐高新材料股份有限公司 | The preparation method of hydrophobic modified cation cellulose ether |
| JP2010516830A (en) * | 2007-01-22 | 2010-05-20 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method for producing cellulose ether |
| CN101070351B (en) * | 2007-05-17 | 2011-05-11 | 湖州展望天明药业有限公司 | Polysubstituted radical cellulose composite ether and its preparing method |
| CN101260158B (en) * | 2008-04-14 | 2010-08-25 | 浙江中维药业有限公司 | Method for preparing hydroxypropylmethylcellulose |
| CN101798353B (en) * | 2009-02-27 | 2012-05-09 | 河南喜人纤维素有限公司 | Method for preparing hydroxyethyl cellulose with high degree of substitution |
| CN101591448B (en) * | 2009-06-22 | 2012-02-15 | 天津科技大学 | Method for preparing bacterial cellulose membrane with high rehydration |
| JP5683092B2 (en) * | 2009-10-29 | 2015-03-11 | 花王株式会社 | Method for producing cationized hydroxypropylcellulose |
| CN101891827B (en) * | 2010-07-29 | 2012-05-09 | 安徽山河药用辅料股份有限公司 | Method for preparing hydroxypropyl cellulose |
| CN102276733B (en) * | 2011-08-19 | 2013-04-17 | 华南理工大学 | Method for preparing ethyl cellulose with high degree of substitution |
| CN102382311B (en) * | 2011-08-19 | 2013-04-10 | 华南理工大学 | Method for utilizing vegetable fibers at high value |
| CN105384829A (en) * | 2015-12-14 | 2016-03-09 | 山东一滕新材料股份有限公司 | Carboxymethyl hydroxyethyl methyl cellulose ether and preparation method thereof |
| CN105384830A (en) * | 2015-12-14 | 2016-03-09 | 山东一滕新材料股份有限公司 | Hydroxypropyl hydroxyethyl cellulose ether and preparation method thereof |
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Assignee: Huzhou Hopetop Pharmaceutical Co., Ltd. Assignor: South China University of Technology Contract fulfillment period: 2009.1.30 to 2014.1.29 contract change Contract record no.: 2009330000945 Denomination of invention: Process for preparing hydrophobic modified cation cellulose ether Granted publication date: 20090128 License type: Exclusive license Record date: 2009.5.11 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.1.30 TO 2014.1.29; CHANGE OF CONTRACT Name of requester: HUZHOU ZHANWANGTIANMING PHARMACEUTICAL CO., LTD. Effective date: 20090511 |
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