CN1958652A - Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent - Google Patents
Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent Download PDFInfo
- Publication number
- CN1958652A CN1958652A CN 200510101144 CN200510101144A CN1958652A CN 1958652 A CN1958652 A CN 1958652A CN 200510101144 CN200510101144 CN 200510101144 CN 200510101144 A CN200510101144 A CN 200510101144A CN 1958652 A CN1958652 A CN 1958652A
- Authority
- CN
- China
- Prior art keywords
- toluene diisocyanate
- trimerization
- curing agent
- preparing
- mixture
- 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.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
This invention provides a method for preparing highly compatible mixed curing agent by toluene diisocyanate addition and trimerization. The raw materials are: (A) toluene diisocyanate or a mixture of two kinds of toluene diisocyanates 40-65 parts, (B) ester or hydrocarbon solvent with boiling point lower than 200 deg.C 25-50 parts, (C) C3-C8 fatty diol 11-15 parts, (D) isocyanate trimerization catalyst 0.005-0.018 part, and (E) isocyanate trimerization inhibitor 0.01-0.036 part (twice the amount of isocyanate trimerization catalyst). The method comprises: adding A and B into a reaction kettle, stirring, introducing N2, adding C every half an hour for four times, reacting at 30-80 deg.C for 3 h, adding D every half an hour for two times, reacting at 70-80 deg.C, determining the weight percentage of dissociated NCO every 1 h, adding E when the relative solid content is 50% and the weight percentage of NCO is 7.2-8.2%, cooling to below 40 deg.C, and discharging. The product can be used in flat paint or glossy paint, and has good compatibility.
Description
Technical Field
The present invention relates to paint industry, and is especially the preparation process of toluene diisocyanate addition and trimerization mixed curing agent with high compatibility.
Background
At present, the toluene diisocyanate addition curing agent widely used in the market is realized by adding a trimerization catalyst to trimerize free TDI after toluene diisocyanate (TDI for short) and trimethylolpropane (TMP for short) are added, and simultaneously, the way of reducing the free TDI is realized:
taking 2, 4-toluene diisocyanate as an example, the adduct, trimerized, is as follows:
this production method has two disadvantages:
1. the cost of raw materials is high, and the price of Trimethylolpropane (TMP) is high.
2. Poor compatibility, low xylene dilution rate, high cost and need of using a large amount of true solvent in production and paint preparation.
Disclosure of Invention
The invention aims to provide a preparation method of a toluene diisocyanate addition and trimerization mixed type curing agent with low raw material price and good intermiscibility aiming at the defects of the existing toluene diisocyanate addition curing agent, so that the prepared toluene diisocyanate addition curing agent has good intermiscibility and low cost, and can be used for matte paint and bright paint.
The purpose of the invention is realized as follows: the raw materials are as follows: (A) toluene diisocyanate or two kinds of toluene diisocyanates40-65 parts of the mixed mixture; (B) 25-50 parts of ester or hydrocarbon solvent with the boiling point less than or equal to 200 ℃; (C) c3-C811-15 parts of aliphatic diol; (D) 0.005-0.018 portion of isocyanate trimerization catalyst. The parts are all parts by weight.
The preparation steps are as follows:firstly, raw material A, B is put into a reaction kettle, and N is stirred and introduced2And (2) performing protection reaction, namely adding the material C for reaction at the temperature of 30-80 ℃, adding the material C once every half hour, finishing adding the material C four times, continuing to perform heat preservation reaction for 3 hours at the temperature of 70-80 ℃, then adding the material D twice, continuing to perform heat preservation reaction at the temperature of 70-80 ℃ once every half hour, detecting the weight percentage content of free NCO groups once every 1 hour, immediately adding an isocyanate trimerization inhibitor when the relative solid content is 50% and the weight percentage content of NCO is 7.2-8.2%, and cooling to the temperature below 40 ℃ for discharging.
Compared with the traditional toluene diisocyanate and trimethylolpropane adduct, the invention has the following differences: the hydroxyl component of the invention which is subjected to addition reaction with toluene diisocyanate is not trimethylolpropane butaliphatic diol, and in addition, after the addition product is generated, a large amount of trimerization reaction is carried out, and the product forms a mixed type curing agent comprising the addition product and the trimer.
The toluene diisocyanate addition and trimerization mixed curing agent produced by the invention has the following advantages:
1. the cost is low, and the addition reactant is aliphatic dihydric alcohol, so that the cost is lower than that of the traditional addition reactant Trimethylolpropane (TMP).
2. The applicability is wide, and the paint can be used in matte paint and bright paint.
3. The advantages are obvious, when the paint is used in the matte paint, the quick drying can be achieved, the matte degree can be improved, and the matte powder can be saved. The paint is used in the bright paint, solves the problem that the bright paint is dried slowly in winter, and does not lose light.
4. The compatibility is good, the xylene dilution rate is high, can completely meet the requirement of true solvent content in common diluent, and the common TDI/TMP addition product has a large amount of or all true solvents in production and paint preparation, so that the product of the invention has wide paint preparation range and low production and paint preparation cost.
Detailed Description
The preparation method of the toluene diisocyanate addition and trimerization mixed type curing agent with good intermiscibility can be summarized as follows:
in a first step, toluene diisocyanate plus an adduct of aliphatic diol and toluene diisocyanate.
In the second step, the first step is that,
the raw material A of the invention is selected from one of the following materials: 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, any mixture of ester ratios of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate. 2, 4-tolylene diisocyanate or a mixture of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate having a 2, 4-tolylene diisocyanate content of not less than 80% is preferable.
The raw material B of the invention is selected from one of the following materials: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, a mixture of ethyl acetate and butyl acetate, a mixture of butyl acetate and toluene, a mixture of butyl acetate and xylene, and xylene. Preferably one of the following: ethyl acetate, butyl acetate, a mixture of ethyl acetate and butyl acetate, a mixture of butyl acetate and toluene, a mixture of butyl acetate and xylene, and xylene.
The raw material C of the invention is selected from one of the following materials: neopentyl glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-ethyl-1, 3-hexanediol. Preference is given to neopentyl glycol or 1, 2-propanediol.
The raw material isocyanate trimerization catalyst of the invention is selected from one of the following: tributyl phosphine, trialkyl phosphine, tertiary amine and phenyl glycidyl ether, lead naphthenate, alkaline potassium salt or sodium salt or lithium salt, lithium salicylate and stannous isooctanoate, lithium isooctanoate and stannous isooctanoate. Preference is given to tri-n-butylphosphine, tertiary amines plus phenyl glycidyl ether, lithium salicylate plus stannous isooctanoate.
The raw material isocyanate trimerization inhibitor is selected from one of the following: anhydrous hydrogen chloride, sulfuric acid, bis (2-ethylhexyl) hydrogen phosphate,benzoyl chloride, phosphoric acid, etc., in an amount of 2 times the equivalent amount of the isocyanate trimerization catalyst.
In the preparation process, the aliphatic diol must be added in batches to slow down the heat release rate and facilitate the control of the reaction temperature.
The molecular weight of the toluene diisocyanate and aliphatic diol adduct generated in the preparation process is smaller than that of the toluene diisocyanate and trimethylolpropane adduct, and the paint matching performance can not meet the requirement. Therefore, more trimerization reaction is introduced in the later stage of the process, and the aim is to increase the average molecular weight of the curing agent and enable part of molecules to form a three-dimensional network structure, so that the paint matching performance of the curing agent disclosed by the invention and the curing agent of the addition product of the toluene diisocyanate and the trimethylolpropane is equivalent, and the intermiscibility is better. In addition, the curing agent of the invention can be used alone in paint preparation and can also be used together with a toluene diisocyanate trimer curing agent to provide NCO groups for cross-linking with-OH groups contained in other components in paint, and the toluene diisocyanate trimer curing agent must be matched with a toluene diisocyanate and polyol adduct for use.
The present invention is further illustrated by the following examples.
In the following examples, the abbreviations for the starting materials are as follows:
TDI: a mixture containing 80% 2, 4-toluene diisocyanate and 20% 2, 6-toluene diisocyanate.
TBI: a mixture containing 90% 2, 4-toluene diisocyanate and 10% 2, 6-toluene diisocyanate.
The first embodiment is as follows:
in a device equipped with a stirrer, a thermometer and a tube N2200g of TDI, 200g of dimethylbenzene and 50g of butyl acetate are added into a protected 1000ml four-neck flask, the temperature is raised by stirring and heating, 12.5g of neopentyl glycol is added at 50 ℃ for reaction, the rest 37.5g of neopentyl glycol is added at 60-80 ℃ in three times, the addition is completed at half an hour interval each time, the temperature is kept at 80 ℃ for reaction for 3 hours, then 0.035g of lithium salicylate and 0.002g of stannous isooctanoate are added for reaction at 80 ℃, the weight percentage content of free NCO groups is detected every 1 hour, when the weight percentage content of NCO is 7.9 percent and the solid content is 50 percent, 0.18g of benzoyl chloride is immediately added, and the temperature is reduced to 40 ℃ for discharging.
Example two:
the implementation method is the same as the first embodiment. In a device equipped with a stirrer, a thermometer and a tube N2Adding 260g of TDI and 200g of dimethylbenzene into a protected 1000ml four-neck flask, stirring, heating, raising the temperature, adding 18g of neopentyl glycol at 50 ℃ for reaction, adding the rest 54g of neopentyl glycol at 60-80 ℃ in three times at intervals of half an hour, keeping the temperature at 75 ℃ for reaction for 3 hours, adding 0.045g of lithium salicylate and 0.0018g of stannous isooctanoate, reacting at 75 ℃, and detecting for one hour every 1 hourWhen the weight percentage of NCO is 8.9% and the solid content is 60%, 0.32g of benzoyl chloride is immediately added, and the temperature is reduced to 40 ℃ for discharging.
Example three:
the implementation method is the same as the first embodiment. In a device equipped with a stirrer, a thermometer and a tube N2Adding 305g of TBI and 125g of xylene into a protected 1000ml four-neck flask, stirring, heating, raising the temperature, adding 17.5g of neopentyl glycol at 50 ℃ for reaction, adding the rest 52.5g of neopentyl glycol at 60-80 ℃ in three times, finishing the addition at intervals of half an hour, keeping the temperature at 70 ℃ for reaction for 3 hours, then adding 0.04g of lithium salicylate and 0.0015g of stannous isooctanoate, reacting at 70 ℃, detecting the weight percentage content of free NCO groups every 1 hour, immediately adding 0.35g of benzoyl chloride when the weight percentage content of NCO is 11.2% and the solid content is 75%, and cooling to 40 ℃ for discharging.
Example four:
the implementation method is the same as the first embodiment. In a device equipped with a stirrer, a thermometer and a tube N2Adding 260g of 2, 4-toluene diisocyanate and 200g of xylene into a protected 1000ml four-neck flask, stirring and heating to raise the temperature, adding 11g of 1, 2-propylene glycol at 50 ℃, adding the rest 33g of 1, 2-propylene glycol at 60-80 ℃ in three times at intervals of half an hour, finishing the addition, keeping the temperature at 80 ℃ for reaction for 3 hours, then adding 0.045g of lithium salicylate and 0.0015g of stannous isooctanoate, reacting at 75 ℃, detecting the weight percentage content of free radicals every 1 hour, immediately adding 0.4g of benzoyl chloride when the weight percentage content of NCO is 9.8 percent and the solid content is 60 percent,cooling to 40 ℃ and discharging.
In the above embodiment, one of ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, a mixture of ethyl acetate and butyl acetate, and a mixture of butyl acetate and toluene may be used as the solvent, and ester and hydrocarbon organic solvents commonly used in the industry may also be used, with similar results.
In the above examples, tributylphosphine, trialkylphosphine, tertiary amine plus phenyl glycidyl ether, lead naphthenate, basic potassium or sodium or lithium salt, lithium isooctanoate plus stannous isooctanoate or zinc isooctanoate can also be used as the trimerization catalyst for toluene diisocyanate, and the results are similar.
In the above examples, one of anhydrous hydrogen chloride, sulfuric acid, bis (2-ethylhexyl) hydrogen phosphate, and phosphoric acid was used as a toluene diisocyanate trimerization inhibitor, and the results were similar.
In the above examples, the weight percent of free NCO groups was determined by dibutylamine titration.
Description of the properties of the formulations
The paint matching application of the toluene diisocyanate addition and trimerization mixed type curing agent prepared by the invention is described as follows:
the mixed curing agents prepared in the first embodiment, the second embodiment and the third embodiment of the invention are mixed with polyurethane matt finish paint in proper amount, diluted by the common diluent in the field, sprayed on a tinplate, and compared by the common toluene diisocyanate and the additive trimethylolpropane adduct curing agent JK-50 (produced by Shenzhen Shenyang Engineered industries, Ltd.), the obtained paint film has the following physical properties:
from the above table, it can be seen that the curing agent prepared by the invention has the same performance as the curing agent widely used in the market, and the drying speed is faster, and the gloss can be reduced under the same condition in the matte paint, so that the amount of the matte powder in the paint can be reduced under the same gloss, thereby achieving the effects of reducing the cost and improving the transparency of the paint film. In conclusion, the curing agent produced by the invention has wide applicability and excellent economical efficiency.
The foregoing merely illustrates the specific manner in which the invention may be practiced and the spirit and scope of the present invention is not limited to the foregoing examples.
Claims (10)
1. A preparation method of a toluene diisocyanate addition and trimerization mixed type curing agent with good phase solubility comprises the following raw materials in parts by weight:
(A) 40-65 parts of toluene diisocyanate or a mixture of two toluene diisocyanates, (B) 25-50 parts of ester or hydrocarbon solvent with the boiling point less than or equal to 200 ℃, and (C) C3-C811-15 parts of aliphatic diol, (D) 0.005-0.018 part of isocyanate trimerization catalyst, and (F) 2 times of isocyanate trimerization polymerization inhibitor in equivalent weight, wherein the parts are parts by weight;
the preparation steps are as follows: firstly, raw material A, B is put into a reaction kettle, and N is stirred and introduced2And (2) performing protection reaction, namely adding the material C for reaction at the temperature of 30-80 ℃, adding the material C once every half hour, finishing adding the material C four times, continuing to perform heat preservation reaction for 3 hours at the temperature of 70-80 ℃, then adding the material D twice at intervals of half an hour, continuing to perform heat preservation reaction at the temperature of 70-80 ℃, detecting the weight percentage content of free NCO groups once every 1 hour, immediately adding the material F when the relative solid content is 50 percent and the weight percentage content of NCO is 7.2-8.2 percent, and cooling to the temperature below 40 ℃ to discharge the material.
2. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 1, which is characterized in that: the raw material A is selected from one of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate according to any proportion.
3. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 2, wherein the curing agent comprises: the raw material A is 2, 4-toluene diisocyanate or a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, wherein the weight percentage of the 2, 4-toluene diisocyanate is not less than 80%.
4. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 1, which is characterized in that: the raw material B is selected from one of the following materials: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, a mixture of ethyl acetate and butyl acetate, a mixture of butyl acetate and toluene, a mixture of butyl acetate and xylene, and xylene.
5. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 4, wherein the curing agent comprises the following components: the raw material B is selected from one of the following materials: ethyl acetate, butyl acetate, a mixture of ethyl acetate and butyl acetate, a mixture of butyl acetate and toluene, a mixture of butyl acetate and xylene, and xylene.
6. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 1, which is characterized in that: the raw material C is selected from one of the following materials: neopentyl glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol and 2-ethyl-1, 3-hexanediol.
7. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 6, wherein the curing agent comprises the following components: the raw material C is neopentyl glycol or 1, 2-propylene glycol.
8. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 1, which is characterized in that: the isocyanate trimerisation catalyst is selected from one of the following: tributyl phosphine, trialkyl phosphine, tertiary amine and phenyl glycidyl ether, lead naphthenate, alkaline potassium salt or sodium salt or lithium salt, lithium salicylate and stannous isooctanoate, lithium isooctanoate and stannous isooctanoate or zinc isooctanoate.
9. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 8, wherein the curing agent comprises: the isocyanate trimerisation catalyst is selected from one of the following: tri-n-butylphosphine, tertiary amine plus phenyl glycidyl ether, lithium salicylate plus stannous isooctanoate.
10. The method for preparing the toluene diisocyanate addition and trimerization hybrid curing agent with good compatibility according to claim 1, wherein the curing agent comprises: the isocyanate trimerization inhibitor is selected from one of the following acidic substances: anhydrous hydrogen chloride, sulfuric acid, bis (2-ethylhexyl) hydrogen phosphate, benzoyl chloride and phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510101144 CN1958652A (en) | 2005-11-04 | 2005-11-04 | Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510101144 CN1958652A (en) | 2005-11-04 | 2005-11-04 | Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1958652A true CN1958652A (en) | 2007-05-09 |
Family
ID=38070515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510101144 Pending CN1958652A (en) | 2005-11-04 | 2005-11-04 | Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1958652A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086991A (en) * | 2013-01-04 | 2013-05-08 | 甘肃银光聚银化工有限公司 | Method for preparing low-free curing agent with solid content of 75% by synthesis of 65/35 toluene diisocynate (TDI) |
| CN104403085A (en) * | 2014-11-26 | 2015-03-11 | 广东东旭化学工业制造有限公司 | European standard-reached low free matte trimer curing agent and preparation method thereof |
| CN104592483A (en) * | 2015-01-14 | 2015-05-06 | 嘉宝莉化工集团股份有限公司 | Environment-friendly polyurethane curing agent as well as preparation method and application of curing agent |
| CN115850656A (en) * | 2022-12-31 | 2023-03-28 | 韶关东森合成材料有限公司 | High-compatibility low-free trimer and preparation method thereof |
-
2005
- 2005-11-04 CN CN 200510101144 patent/CN1958652A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086991A (en) * | 2013-01-04 | 2013-05-08 | 甘肃银光聚银化工有限公司 | Method for preparing low-free curing agent with solid content of 75% by synthesis of 65/35 toluene diisocynate (TDI) |
| CN103086991B (en) * | 2013-01-04 | 2016-01-06 | 甘肃银光聚银化工有限公司 | A kind of use 65/35 tolylene diisocyanate synthesizes the preparation method of 75% solid content, low free solidifying agent |
| CN104403085A (en) * | 2014-11-26 | 2015-03-11 | 广东东旭化学工业制造有限公司 | European standard-reached low free matte trimer curing agent and preparation method thereof |
| CN104592483A (en) * | 2015-01-14 | 2015-05-06 | 嘉宝莉化工集团股份有限公司 | Environment-friendly polyurethane curing agent as well as preparation method and application of curing agent |
| CN104592483B (en) * | 2015-01-14 | 2017-06-06 | 嘉宝莉化工集团股份有限公司 | Environment-protecting polyurethane curing agent and its preparation method and application |
| CN115850656A (en) * | 2022-12-31 | 2023-03-28 | 韶关东森合成材料有限公司 | High-compatibility low-free trimer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10093765B2 (en) | Alkoxysilane-functionalized allophanates | |
| US10093826B2 (en) | Alkoxysilane-functionalized allophanate-containing coating compositions | |
| US9382375B2 (en) | Curable polyisocyanate composition | |
| US10358519B2 (en) | Modified polycarbodiimide compound, curing agent, and thermosetting resin composition | |
| US10689503B2 (en) | Epoxy resin composition | |
| EP1445271B1 (en) | Polyisocyanate composition having allophanate group and high-solid coating material | |
| US10336854B2 (en) | Alkoxysilane-functionalized and allophanate-functionalized urethanes | |
| US10538684B2 (en) | Coating compositions comprising monoallophanates based on alkoxysilane alkyl isocyanates | |
| US20170369631A1 (en) | Alkoxysilane- and allophanate-functionalized coating materials | |
| US20100168297A1 (en) | High-gloss polyurethane coatings prepared from allophanate/polyisocyanate hardener compositions | |
| EP2782945A1 (en) | Curable polyisocyanate composition comprising an epoxy resin | |
| JP2015127368A (en) | Polyisocyanate composition, coating composition and cured article | |
| CN1958652A (en) | Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent | |
| US8940853B2 (en) | Cationic blocked polyisocyanate and aqueous composition comprising the same | |
| JP7037952B2 (en) | Blocked isocyanate composition, aqueous dispersion, aqueous coating composition, coating substrate and aggregation method | |
| CN1186405C (en) | Preparation of dissolvable curing agent for tripolymer of toluene diisocyanate | |
| CN1762988A (en) | Blocked biuretized isocyanates | |
| EP3075755B1 (en) | Ambient temperature curable isocyanate-free compositions for preparing crosslinked polyurethanes | |
| US5925711A (en) | Polyamines and their use in aqueous coating compositions | |
| CN1840560A (en) | Low surface energy polyisocyanates and their use in one- or two-component coating compositions | |
| CN1762987A (en) | Biuretized polyisocyanates and blocked biuretized polyisocyanates | |
| JP2017114959A (en) | Block polyisocyanate composition, curable composition and article | |
| CN1501950A (en) | Liquid partially trimerized polyisocyanates based on toluene diisocyanate and diphenylmethane diisocyanate | |
| JP7124226B2 (en) | Blocked polyisocyanate composition, one-component coating composition, coating film and coated article | |
| JP2014019752A (en) | Blocked polyisocyanate composition, curable composition and cured product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHUHAI FEIYANG CHEMICAL INDUSTRY CO., LTD. Free format text: FORMER OWNER: SHENZHEN FEIYANG INDUSTRY CO.,LTD Effective date: 20100511 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 518104 NO.1, FEIYANG ROAD, SHASI VILLAGE, SHAJING TOWN, SHENZHEN CITY, GUANGDONG PROVINCE TO: 519050 ROOM 505, OFFICE ROOM, ECONOMIC DEVELOPMENT BUREAU, LINGANG INDUSTRIAL DISTRICT, ZHUHAI CITY |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20100511 Address after: 519050 room 505, office of Economic Development Bureau, Zhuhai Lingang Industrial Zone Applicant after: Zhuhai Feiyang Chemical Co., Ltd. Address before: 518104, flying No. 1, Sha four village, manholes Town, Shenzhen, Guangdong Applicant before: Feiyang Industrial Co., Ltd., Shenzhen City |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20070509 |