CN107200828B - Polyurethane for single-component coating and preparation method thereof - Google Patents
Polyurethane for single-component coating and preparation method thereof Download PDFInfo
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- CN107200828B CN107200828B CN201710344081.0A CN201710344081A CN107200828B CN 107200828 B CN107200828 B CN 107200828B CN 201710344081 A CN201710344081 A CN 201710344081A CN 107200828 B CN107200828 B CN 107200828B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
- C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/808—Monoamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention provides polyurethane for a single-component coating and a preparation method thereof, wherein the preparation method comprises the following steps: step S1, reacting diisocyanate with a blocking agent to obtain a first mixture, wherein the molar ratio of the diisocyanate to the blocking agent is 0.9:1-1: 1; step S2, adding water into the first mixture, and carrying out chain extension reaction to obtain the product; in the preparation process, the quality of the polyurethane can be effectively controlled by controlling the molar ratio of the diisocyanate to the sealant and/or the molar ratio of the diisocyanate to the water and controlling the reaction temperature. Compared with the problems of complex control of the polyurethane preparation process, multiple types of reagents and high cost in the prior art, the polyurethane for the single-component coating and the preparation method thereof have the advantages of few types of reagents and low cost.
Description
Technical Field
The invention relates to a coating material, in particular to polyurethane for a single-component coating and a preparation method thereof.
Background
Electrophoresis is one of the most common and effective methods for coating metal workpieces. The electrophoretic coating is that the object to be coated with electric conductivity is dipped in a trough filled with electrophoretic paint as a cathode/anode, a corresponding anode/cathode is additionally arranged in the trough, and a current is applied between the two electrodes for a period of time to deposit a uniform and fine coating on the surface of the object to be coated. Among them, the electrophoretic paint, also called electrophoretic paint, is an important factor affecting the quality of the final coating film in the electrophoretic coating process.
The coating is a coating material for protecting and decorating the surface of an object, and can form a film when being applied to the surface of the object to endow the object with protection, beautification or other required effects. Polyurethane resin is a common resin for coating materials.
At present, the preparation of the closed polyurethane generally utilizes glycerin, trimethylolpropane, pentaerythritol and the like to carry out chain extension on diisocyanate with difunctional degree, thereby increasing the reaction point of the closed polyurethane and increasing the crosslinking density of a coating film of the coating; alternatively, blocked polyurethanes can also be synthesized using trimers of polyisocyanates as starting materials.
The reagents such as glycerin, trimethylolpropane, pentaerythritol and the like are used, so that the phenomena of high chain extension cost, harsh reaction control conditions, high viscosity, easy occurrence of gel and the like exist, particularly, the trimethylolpropane and the pentaerythritol are solid and need to be dissolved by a solvent and then added, and the control on the reaction process is also very strict; the price of the blocked polyurethane synthesized by polyisocyanate trimer is high, the blocking agent of binary polyisocyanate must be added to adjust the performance of the coating film, several raw materials are needed, and the blocked polyurethane is a test for the storage and the enterprise liquidity of a company.
When the conventional method is used for preparing the closed polyurethane at present, the general technological process is complex, the control conditions are more, the types of used reagents are more, and the cost is high.
Disclosure of Invention
The invention provides polyurethane for a single-component coating and a preparation method thereof, which overcome the problems or at least partially solve the problems so as to solve the technical problems of complex preparation process, difficult control and high cost of the polyurethane.
In the present invention, the parts may be in the unit of weight known in the art, such as μ g, mg, g, kg, etc., or in multiples thereof, such as 1/10, 1/100, 10, 100, etc.
According to one aspect of the present invention, there is provided a method of preparing a polyurethane for a one-pack paint, comprising:
step S1, reacting diisocyanate with a blocking agent to obtain a first mixture, wherein the molar ratio of the diisocyanate to the blocking agent is 0.9:1-1: 1;
and step S2, adding water into the first mixture, and carrying out chain extension reaction.
In the prior art, the blocked polyurethane generally utilizes glycerin, trimethylolpropane, pentaerythritol and the like to carry out chain extension on diisocyanate with difunctional degree, thereby increasing the reaction point of the blocked polyurethane and increasing the crosslinking density of a coating film of the coating; alternatively, blocked polyurethanes are synthesized from trimers of polyisocyanates.
Because trimethylolpropane and pentaerythritol are solid, the reaction process needs to be strictly controlled when the trimethylolpropane and pentaerythritol are directly added, and the process is complex to control. In addition, the method for preparing the closed polyurethane has the advantages of various related raw materials and high price and cost.
Water is directly used as a chain extender, under a proper control condition, after a part of-NCO bonds in diisocyanate and a blocking agent are subjected to end-capping reaction, under the action of water, chain extension reaction is further performed on the-NCO bonds in the obtained first mixture to obtain the blocked polyurethane, so that the process is simplified, and the cost is effectively reduced.
It will be appreciated that during the preparation, i.e. during the blocking reaction of the diisocyanate with the blocking agent and/or the chain extension reaction of the resulting first mixture under the action of water, a co-solvent is added to allow the reaction to proceed more smoothly. The cosolvent is preferably one or more of dimethylbenzene, ethyl acetate, butyl acetate, acetone, butanone and methyl isobutyl ketone; more preferably, the co-solvent may be selected from methyl isobutyl ketone, butyl acetate and/or acetone.
Specifically, in the reaction of the diisocyanate with the blocking agent, the diisocyanate is first dissolved in a co-solvent, for example, methyl isobutyl ketone, or methyl isobutyl ketone and butyl acetate. Then, the blocking agent is added to the above mixture. Both the diisocyanate and the blocking agent can be dissolved in the cosolvent to better promote the reaction. It will be appreciated that the amount of co-solvent may be suitably adjusted to the amount of diisocyanate so that the resulting mixture after mixing has a solids content of 70% to 85%.
Specifically, the molar ratio of the diisocyanate to the blocking agent is 0.9:1-1: 1. The molar ratio of the diisocyanate to the blocking agent is kept in a proper range, and when the diisocyanate reacts with the blocking agent under certain conditions, partial-NCO bonds of the diisocyanate and the blocking agent are subjected to blocking reaction, but the diisocyanate does not completely react with the blocking agent, so that the subsequent reaction cannot be normally carried out.
Meanwhile, the proportion of the diisocyanate and the blocking agent is controlled to control the number of-NCO bonds in the obtained first mixture, when partial-NCO bonds of the diisocyanate are subjected to blocking reaction and then chain extension reaction is carried out under the action of chain extender water, the reaction efficiency and products can be better controlled, and the chain length or molecular weight of the obtained blocked polyurethane is kept in a proper range, so that the blocked polyurethane meeting the quality requirement is obtained.
Preferably, the step S1 further includes: the NCO% content of the first mixture is determined so that the ratio of the NCO% value in the first mixture to the NCO% value in the diisocyanate is from 48:100 to 52: 100. The NCO% in the present invention means a content of-NCO in percentage by mass unless otherwise specified.
And detecting the NCO% content in the obtained first mixture by controlling reaction conditions so as to control the degree or progress of the reaction and ensure the smooth proceeding of subsequent reaction and the quality of a final product.
Preferably, the molar ratio of the diisocyanate to water is from 2:1 to 5: 1. On the basis of controlling the end-capping reaction of the diisocyanate and the blocking agent, the molar ratio of the diisocyanate to the water used as the chain extender is kept in a proper range by adjusting the amount of the added chain extender, the degree of the chain extension reaction is controlled, and the degree of the reaction is further regulated to control the quality of the final product.
Preferably, after the diisocyanate and the blocking agent are mixed, the temperature for the blocking reaction is 60-100 ℃; more preferably, the temperature at which the diisocyanate is reacted with the blocking agent is from 50 to 80 ℃. It will be appreciated that on the basis of maintaining the molar ratio of diisocyanate to blocking agent within a reasonable range, the blocking reaction of the diisocyanate and blocking agent takes place at this temperature, and the success of the subsequent reaction is controlled by monitoring the reaction time reasonably so that the ratio of the% NCO value in the first mixture to the% NCO value in said diisocyanate is maintained between 48:100 and 52: 100.
The temperature of the end-capping reaction is kept in a suitable range, which is beneficial for controlling the process of the reaction so as to control the quality of the final product. The reaction temperature is too high, the faster the-NCO content is reduced in the reaction, the more difficult the reaction is to control, the higher the degree of side reaction is, and the stability of polyurethane is not facilitated; the temperature is too low, the reaction speed is slow, the reaction heat release is smooth and easy to control, but the reaction period is too long, and the production efficiency is low. The reaction temperature is kept within a proper temperature range, side reactions are few, the reaction period is moderate, and the reaction is easy to control.
Preferably, the molecular weight of the diisocyanate is within a suitable range, i.e., a specific kind of diisocyanate is selected,
preferably, the diisocyanate is toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or methylene bis (4-cyclohexyl isocyanate) cyclohexylmethane diisocyanate, which is more favorable for controlling the reaction degree and ensuring the product quality.
More preferably, the diisocyanate is toluene diisocyanate or isophorone diisocyanate.
Preferably, the blocking agent is methyl salicylate, 3, 5-dimethylpyrazole, acetanilide, phenol, caprolactam, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether or ethylene glycol monohexyl ether; more preferably, the blocking agent is ethylene glycol monoethyl ether or ethylene glycol monohexyl ether.
Preferably, under the action of water, the temperature of the chain extension reaction is 50-120 ℃; more preferably, the temperature of the chain extension reaction is in the range of 70 to 120 ℃. On the basis of controlling the proportion of reactants, the temperature of the chain extension reaction is further controlled so as to better control the degree of the reaction. It will be appreciated that when the first mixture is subjected to the chain extension reaction with water at this temperature, the time of reaction is suitably monitored so that the NCO% of the final product is<8×10-3Percent, thus obtaining the closed polyurethane product meeting the quality requirement.
Specifically, in step S2, while the chain extender water is added to the first mixture, water is added to the first mixture together with a cosolvent, for example, water is added to the first mixture together with acetone. Both the first mixture and water can be dissolved in the co-solvent to better facilitate the reaction.
Preferably, a method for preparing polyurethane comprises:
step S1, reacting diisocyanate with a blocking agent to obtain a first mixture, wherein the molar ratio of the diisocyanate to the blocking agent is 0.9:1-1:1, and the molar ratio of the diisocyanate to water is 3:1-5: 1;
step S2, adding water into the first mixture, and carrying out chain extension reaction to obtain the product;
the reaction temperature of the mixed diisocyanate and the sealant is 60-100 ℃, and the chain extension reaction temperature is 50-120 ℃.
By controlling the relative amounts of the diisocyanate, the blocking agent and the water, the degree of reaction progress is controlled, and the problem that the chain extension reaction is difficult to control so that the final product is easy to cure or cannot meet the requirement of polymerization is avoided.
The invention also provides the closed polyurethane prepared by the method, and the closed polyurethane is used as a raw material of the single-component coating. Water is directly used as a chain extender, and a blocking reaction and a chain extension reaction respectively occur within a proper molar ratio range of diisocyanate and a sealant at proper temperature, so that the reaction progress can be reasonably controlled, the generation of side reactions can be reduced as much as possible, and the quality of the obtained polyurethane can be improved.
The beneficial effects of the invention are mainly as follows:
(1) under the condition that the molar ratio of the diisocyanate to the sealant is kept in a proper range, water is directly used as a chain extender, and a chain extension reaction is carried out to obtain the closed polyurethane, so that the cost is effectively reduced, and the process is simplified;
(2) the molar ratio of the diisocyanate to the water is kept in a proper range, the reaction degree can be further controlled, and the quality of a final product is ensured;
(3) the reaction temperature is kept in a proper range in the preparation process, so that the side reaction can be effectively reduced, the reaction period is moderate, and the reaction is easy to control.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The parts in the following examples are by weight.
Example 1
504 parts of Hexamethylene Diisocyanate (HDI) and 150 parts of methyl isobutyl ketone are placed at the bottom of a reaction kettle, the temperature is increased to 70 ℃, 270 parts of ethylene glycol monoethyl ether is added dropwise, the temperature is kept between 70 and 80 ℃, the detected NCO percent is 13.64 +/-0.1 percent, 18 parts of deionized water and 50 parts of acetone are added dropwise, the temperature is kept between 70 and 80 ℃, after the exothermic reaction disappears, the temperature is increased to 110 plus-120 ℃, the detected NCO percent is less than 8 multiplied by 10-3Percent, and then the closed polyurethane is obtained.
Example 2
Putting 890 parts of isophorone diisocyanate (IPDI), 150 parts of methyl isobutyl ketone and 100 parts of butyl acetate at the bottom of a reaction kettle, heating to 70 ℃, dropwise adding 360 parts of ethylene glycol monoethyl ether, keeping the temperature at 70-80 ℃, detecting that NCO percent is 18.75 +/-0.1%, dropwise adding 18 parts of deionized water and 50 parts of acetone, keeping the temperature at 70-80 ℃, after exothermic reaction disappears, heating to 110-120 ℃, detecting that NCO percent is less than 8 multiplied by 10-3Percent, and then the closed polyurethane is obtained.
Example 3
Putting 696 parts of Toluene Diisocyanate (TDI), 150 parts of methyl isobutyl ketone and 150 parts of butyl acetate at the bottom of a reaction kettle, heating to 50 ℃, dropwise adding 730 parts of ethylene glycol monohexyl ether, keeping the temperature at 50-60 ℃, detecting NCO percent as 7.99 +/-0.1%, dropwise adding 18 parts of deionized water and 50 parts of acetone, keeping the temperature at 70-80 ℃, heating to 110 ℃ after exothermic reaction disappears, detecting NCO percent as less than 8 multiplied by 10, and heating to 100--3Percent, and then the closed polyurethane is obtained.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing polyurethane, comprising:
step S1, reacting diisocyanate with a blocking agent to obtain a first mixture, wherein the molar ratio of the diisocyanate to the blocking agent is 0.9:1-1:1, detecting the NCO% value of the first mixture, and enabling the ratio of the NCO% value in the first mixture to the NCO% value in the diisocyanate to be 48:100-52: 100;
and step S2, adding water into the first mixture, and carrying out chain extension reaction, wherein the molar ratio of the diisocyanate to the water is 3:1-4:1, and the temperature of the chain extension reaction is 50-120 ℃.
2. The method for producing polyurethane according to claim 1, wherein:
the reaction temperature of the diisocyanate and the blocking agent in the step S1 is 50-80 ℃.
3. The process for producing a polyurethane as claimed in claim 1 or 2, wherein: the diisocyanate is toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or methylene bis (4-cyclohexyl isocyanate) cyclohexyl methane diisocyanate.
4. A process for the preparation of a polyurethane as claimed in claim 3, characterized in that:
the diisocyanate is toluene diisocyanate or isophorone diisocyanate.
5. The process for preparing a polyurethane as claimed in claim 1, 2 or 4, wherein the blocking agent is: methyl salicylate, 3, 5-dimethylpyrazole, acetanilide, phenol, caprolactam, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether or ethylene glycol monohexyl ether.
6. The method of claim 3, wherein the blocking agent is: methyl salicylate, 3, 5-dimethylpyrazole, acetanilide, phenol, caprolactam, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether or ethylene glycol monohexyl ether.
7. The process for producing polyurethane according to claim 5,
the blocking agent is ethylene glycol monoethyl ether or ethylene glycol monohexyl ether.
8. The process for producing polyurethane according to claim 6,
the blocking agent is ethylene glycol monoethyl ether or ethylene glycol monohexyl ether.
9. The process for producing polyurethane according to claim 1, wherein: the temperature of the chain extension reaction is 70-120 ℃.
10. A blocked polyurethane prepared by the process of any one of claims 1-9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710344081.0A CN107200828B (en) | 2017-05-16 | 2017-05-16 | Polyurethane for single-component coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710344081.0A CN107200828B (en) | 2017-05-16 | 2017-05-16 | Polyurethane for single-component coating and preparation method thereof |
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| CN107200828A CN107200828A (en) | 2017-09-26 |
| CN107200828B true CN107200828B (en) | 2020-02-18 |
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| CN111320742B (en) * | 2020-04-07 | 2022-03-25 | 湖南湘江关西涂料(长沙)有限公司 | Blocked isocyanate curing agent, preparation method thereof, single-component coating and coating product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61235476A (en) * | 1985-04-10 | 1986-10-20 | Nippon Paint Co Ltd | Cationic electrodeposition paint composition |
| CN102731746A (en) * | 2012-06-29 | 2012-10-17 | 上海东升新材料有限公司 | Enclosed type aqueous polyurethane emulsion papermaking wet strength agent and its preparation method |
| CN103319689A (en) * | 2013-06-24 | 2013-09-25 | 浩力森涂料（上海）有限公司 | Emulsion resin for high-throwing-power cathode electrophoretic paint and preparation method thereof |
| CN105504206A (en) * | 2015-12-24 | 2016-04-20 | 山东一诺威新材料有限公司 | Synthetic method of castor oil based enclosed type waterborne polyurethane |
-
2017
- 2017-05-16 CN CN201710344081.0A patent/CN107200828B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61235476A (en) * | 1985-04-10 | 1986-10-20 | Nippon Paint Co Ltd | Cationic electrodeposition paint composition |
| CN102731746A (en) * | 2012-06-29 | 2012-10-17 | 上海东升新材料有限公司 | Enclosed type aqueous polyurethane emulsion papermaking wet strength agent and its preparation method |
| CN103319689A (en) * | 2013-06-24 | 2013-09-25 | 浩力森涂料（上海）有限公司 | Emulsion resin for high-throwing-power cathode electrophoretic paint and preparation method thereof |
| CN105504206A (en) * | 2015-12-24 | 2016-04-20 | 山东一诺威新材料有限公司 | Synthetic method of castor oil based enclosed type waterborne polyurethane |
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Address after: 441200 Elite River Village, Zaoyang City, Xiangfan City, Hubei Province Applicant after: Hubei Tongbangda Technology Co.,Ltd. Address before: 441200 Elite River Industrial Park, Zaoyang City, Xiangfan City, Hubei Province Applicant before: ZAOYANG TONGBANGDA TECHNOLOGY CO.,LTD. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200218 Termination date: 20210516 |