CN111732716B - Mannich base curing agent for epoxy floor sealing primer and preparation method thereof - Google Patents
Mannich base curing agent for epoxy floor sealing primer and preparation method thereof Download PDFInfo
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- CN111732716B CN111732716B CN202010573718.5A CN202010573718A CN111732716B CN 111732716 B CN111732716 B CN 111732716B CN 202010573718 A CN202010573718 A CN 202010573718A CN 111732716 B CN111732716 B CN 111732716B
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
A Mannich base curing agent for epoxy floor seal primer and a preparation method thereof are disclosed, phenol and a catalyst are placed in a high-pressure reaction kettle, a metered addition reactant is slowly introduced while stirring at 150-160 ℃, the pressure in the kettle is maintained at 0.4-0.5 MPa, the introduction is completed and the temperature is kept for 1-2 h, then the temperature is reduced, alkali liquor and saturated salt solution are added for washing and standing for layering for several times, and the upper layer liquid is taken and dried by anhydrous sodium sulfate to obtain a phenol addition product; the Mannich base curing agent with low viscosity is synthesized by the Mannich condensation reaction of the phenol addition product, the polyamine and the aldehyde. Compared with the existing phenolic aldehyde amine curing agent, the phenolic aldehyde amine curing agent does not contain free phenol, does not need to add a large amount of solvent, and is more environment-friendly; good compatibility with epoxy resin, mild curing reaction, convenient construction and short curing period; the cured product has excellent adhesive force, corrosion resistance and mechanical property.
Description
Technical Field
The invention belongs to the field of thermosetting resin materials, and particularly relates to a Mannich base curing agent for epoxy floor sealing primer and a preparation method thereof.
Background
Epoxy resin is a linear polymer material containing epoxy groups, has a thermoplastic property due to a large change of viscosity range under the influence of temperature, cannot be used independently, is chemically reacted with a curing agent only by adding a proper amount to form a polymer material with a three-dimensional network structure, and is widely applied to various industries due to the fact that the epoxy resin shows excellent adhesive property, mechanical property, electric insulation property, thermal stability and the like. At present, glycidyl ether type epoxy resin is mainly used in the epoxy terrace industry, and the curing agents are relatively more in variety and mainly comprise polyamide, phenolic aldehyde amine and aromatic amine curing agents. The epoxy floor sealing primer needs to have excellent adhesion, good water resistance, oil resistance, acid and alkali resistance, permeability resistance and the like. The polyamide has low volatility, low toxicity, wide compounding range with epoxy resin, low shrinkage of cured product, excellent adhesion, impact resistance, electric performance, water resistance, etc. However, the polyamide has a high viscosity, and in order to ensure leveling property and permeability during construction, a large amount of organic solvent needs to be added, so that environmental pollution and damage to the body of construction personnel are caused, and the curing reaction speed is slow, so that the construction period is influenced. The phenolic aldehyde amine curing agent (T31) is widely used due to simple production process and low price, has good compatibility with epoxy resin, and has good heat resistance and corrosion resistance of a cured product. The weak acidic phenolic hydroxyl group in the molecular structure has a promoting effect on the curing reaction, so that the exothermic peak is high, the pot life is short, the explosive polymerization is easy, the cured product is high in brittleness, poor in toughness, easy to crack and poor in impact resistance, in addition, the contained free phenol has certain toxicity, the product viscosity is high, the workability is influenced, and a large amount of solvent is also required to be added. In order to reduce the viscosity of the phenolic aldehyde amine and improve the brittleness of the cured product, a certain amount of furfuryl alcohol or polyether amine can be added, and dicyclopentadiene or tung oil and the like can be introduced into the molecular structure of the phenolic aldehyde amine to improve the toughness of the cured product. Aromatic amine is weak in alkalinity, large in steric hindrance and low in reaction activity with epoxy resin, a curing reaction accelerator needs to be added, and cured products are good in heat resistance, oil resistance, acid resistance, water resistance, mechanical properties and electrical properties and widely used in epoxy terraces of pharmaceutical factories, power plants and the like. The Mannich reaction refers to a three-molecule dehydration condensation reaction of a compound containing active hydrogen and aldehyde and amine to generate a compound containing amine, and the phenol aldehyde amine is a typical Mannich (Mannich) reaction. Through molecular structure design, ether bond is introduced into a compound with active hydrogen, and then the compound, aldehyde and polyamine are subjected to dehydration condensation reaction to synthesize a Mannich base curing agent, so that the viscosity of phenolic aldehyde amine is reduced, and the flexibility of the phenolic aldehyde amine and an epoxy resin condensate is improved; the phenolic hydroxyl group is easier to form a hydrogen bond with an oxygen atom of an epoxy group than the alcoholic hydroxyl group to promote a ring-opening curing reaction, so that the reaction activity of the Mannich base and the epoxy resin can be reduced by converting the phenolic hydroxyl group into the alcoholic hydroxyl group, and the same effect can be achieved by introducing-CN.
Disclosure of Invention
The technical problem to be solved is as follows:
the invention provides a Mannich base curing agent for epoxy floor sealing primer and a preparation method thereof. Through molecular structure design, an-O-bond and-CN are introduced into the Mannich base curing agent, so that the viscosity of the phenolic aldehyde amine is reduced, the reactivity of the phenolic aldehyde amine with epoxy resin is slowed, and the flexibility of an epoxy cured product is improved.
The technical scheme is as follows:
a Mannich base curing agent for epoxy floor seal primer and a preparation method thereof, the preparation steps are as follows:
(1) adding phenol and a catalyst into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 150-160 ℃, slowly introducing a metered addition reactant, maintaining the pressure in the kettle at 0.4-0.5 MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat for 1-2 hours at the temperature, introducing cooling water to cool to 50-60 ℃, adding alkali liquor and saturated salt solution to wash, standing and layering for several times, taking the supernatant, and drying with anhydrous sodium sulfate to obtain the phenol addition product.
(2) And (3) mixing and stirring the phenol addition product and the polyamine uniformly, slowly dropwise adding aldehyde, controlling the temperature to be less than 50-60 ℃, heating to 85-95 ℃ after the aldehyde is dropwise added, reacting for 3-4 hours, and then carrying out reduced pressure distillation to remove generated water to obtain the Mannich base curing agent.
The phenol in the step (1) is any one selected from phenol, cresol, p-tert-butylphenol, nonylphenol and cardanol.
The catalyst in the step (1) is selected from any one of sodium hydroxide, potassium hydroxide and sodium methoxide.
The addition reactant in the step (1) is selected from any one of ethylene oxide, propylene oxide and acrylonitrile.
The aldehyde in the step (2) is selected from at least one of formaldehyde, butyraldehyde, furfural and benzaldehyde.
The polyamine in the step (2) is at least one selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, 4-diaminodicyclohexylmethane, and 1, 3-cyclohexyldimethylamine.
Has the advantages that:
the Mannich base curing agent has low viscosity and good permeability, does not need to add a large amount of organic solvent, and is more environment-friendly and safer; good compatibility with epoxy resin, insensitive curing reaction to temperature, mild reaction, convenient construction and short curing period; the prepared floor sealing primer has excellent adhesive force and corrosion resistance, and a cured product is tougher.
Drawings
FIG. 1 is an infrared spectrum of example 6.
3100cm in the figure-1～3500cm-1The absorption peak of hydroxyl is overlapped with-NH-absorption peak in Mannich base; 3063cm-1And 3039cm-1Is the stretching vibration absorption peak of CH on the benzene ring; 2969cm-1Is of the formula-CH3Vibration absorption peak of (1); 2927cm-1And 2875cm-1Respectively present in-CH on the side chain of the benzene ring2and-CH vibration absorption peak; 1598cm-1、1586cm-1Characteristic absorption peak of C ═ C that can be assigned to benzene ring; 1110-1241 cm-1Is the C-N stretching vibration absorption peak; 1078cm-1Is a stretching vibration absorption peak of the ether bond.
Detailed Description
Parts not mentioned in the text are the same as or can be realized by the prior art. The following are preferred embodiments of the present invention, but the present invention is not limited to the following embodiments, and some modifications to the embodiments will be considered as the protection scope of the present invention.
Example 1
The first step is as follows: adding 470g of phenol and 23.5g of sodium hydroxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 150 ℃, slowly introducing 220g of ethylene oxide, maintaining the pressure in the kettle at 0.4MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat for 1h at the temperature, introducing cooling water to reduce the temperature to 60 ℃, adding 10% NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking the supernatant, and drying with anhydrous sodium sulfate to obtain the phenol and propylene oxide adduct for later use.
The second step is that: 138g of phenol and ethylene oxide addition product, and 210g of 4, 4-diaminodicyclohexyl methane are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser pipe, uniformly mixed and stirred, 72g of butyraldehyde is slowly dripped, the temperature is controlled to be less than 50 ℃, the temperature is raised to 85 ℃ after the butyraldehyde is dripped, and after reaction is finished for 3 hours, the Mannich base curing agent is obtained by removing generated water through reduced pressure distillation.
Example 2
The first step is as follows: adding 540g of cresol and 27g of sodium hydroxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 160 ℃, slowly introducing 265g of acrylonitrile, maintaining the pressure in the kettle at 0.5MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat for 2 hours at the temperature, introducing cooling water to 50 ℃, adding 10% NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking the supernatant, and drying with anhydrous sodium sulfate to obtain the phenol and propylene oxide adduct for later use.
The second step is that: 161g of cresol and acrylonitrile addition product and 142g of 1, 3-cyclohexyldimethylamine are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser pipe, mixed and stirred uniformly, 72g of butyraldehyde is slowly dripped, the temperature is controlled to be less than 60 ℃, the temperature is raised to 95 ℃ after the butyraldehyde is dripped, and after the reaction is carried out for 4 hours, the generated water is removed by reduced pressure distillation to obtain the Mannich base curing agent.
Example 3
The first step is as follows: adding 750g of p-tert-butylphenol and 37.7g of potassium hydroxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 155 ℃, slowly introducing 220g of ethylene oxide, keeping the pressure in the kettle at 0.45MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat for 1.5 hours at the temperature, introducing cooling water to cool to 55 ℃, adding 10% NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking supernatant, and drying with anhydrous sodium sulfate to obtain the phenol and propylene oxide adduct for later use.
The second step is that: adding 194g of p-tert-butylphenol, an ethylene oxide adduct and 103g of diethylenetriamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, uniformly mixing and stirring, slowly dropwise adding 96g of furfural, controlling the temperature to be less than 55 ℃, heating to 90 ℃ after the dropwise adding of furfural is finished, reacting for 3.5 hours, and then carrying out reduced pressure distillation to remove generated water to obtain the Mannich base curing agent.
Example 4
The first step is as follows: adding 1100g of nonylphenol and 55g of sodium methoxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 155 ℃, slowly introducing 220g of ethylene oxide, maintaining the pressure in the kettle at 0.5MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat at the temperature for 1-2 hours, introducing cooling water to cool to 58 ℃, adding 10% of NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking the upper layer liquid, and drying with anhydrous sodium sulfate to obtain the phenol and propylene oxide adduct for later use.
The second step is that: 264g of nonyl phenol, 264g of ethylene oxide adduct and 146g of triethylene tetramine are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube to be mixed and stirred uniformly, 81g of 37 percent formaldehyde water solution is slowly dripped, the temperature is controlled to be less than 55 ℃, the temperature is raised to 92 ℃ after the dripping of formaldehyde, and after the reaction is carried out for 3 hours, the Mannich base curing agent is obtained by removing the generated water through reduced pressure distillation.
Example 5
The first step is as follows: adding 1200g of cardanol and 60g of sodium methoxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 153 ℃, slowly introducing 176g of ethylene oxide, maintaining the pressure in the kettle at 0.4MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat at the temperature for 1-2 hours, introducing cooling water to cool to 50 ℃, adding 10% of NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking the upper layer liquid, and drying with anhydrous sodium sulfate to obtain phenol and propylene oxide addition products for later use.
The second step is that: adding 344g of cardanol, 344g of ethylene oxide adduct and 189g of tetraethylenepentamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, uniformly mixing and stirring, slowly dropwise adding 106g of benzaldehyde, controlling the temperature to be less than 60 ℃, heating to 90 ℃ after the benzaldehyde is dropwise added, reacting for 3 hours, and removing generated water through reduced pressure distillation to obtain the Mannich base curing agent.
Example 6
The first step is as follows: adding 470g of phenol and 23.5g of sodium hydroxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 160 ℃, slowly introducing 290g of propylene oxide, keeping the pressure in the kettle at 0.5MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, keeping the temperature for 2 hours at the temperature, introducing cooling water to cool to 55 ℃, adding 10% NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking the supernatant, and drying with anhydrous sodium sulfate to obtain the phenol and propylene oxide adduct for later use.
The second step is that: 152g of phenol, propylene oxide adduct and 103g of diethylenetriamine are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube to be mixed and stirred uniformly, 81g of 37 percent formaldehyde water solution is slowly dripped, the temperature is controlled to be less than 55 ℃, the temperature is raised to 95 ℃ after the dripping of benzaldehyde is finished, and after the reaction is carried out for 4 hours, the generated water is removed by reduced pressure distillation to obtain the Mannich base curing agent.
Example 7
The first step is as follows: adding 750g of p-tert-butylphenol and 37.7g of potassium hydroxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 155 ℃, slowly introducing 290g of propylene oxide, keeping the pressure in the kettle at 0.45MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat for 1-2 hours at the temperature, introducing cooling water to cool to 55 ℃, adding 10% NaOH aqueous solution and saturated saline solution to wash, standing and layering for 3 times, taking supernatant, and drying with anhydrous sodium sulfate to obtain the phenol and propylene oxide adduct for later use.
The second step is that: adding 208g of p-tert-butylphenol, an addition product of propylene oxide and 136g of m-xylylenediamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, uniformly mixing and stirring, slowly dropwise adding 96g of furfural, controlling the temperature to be less than 57 ℃, heating to 88 ℃ after dropwise adding of benzaldehyde, reacting for 3 hours, and removing generated water through reduced pressure distillation to obtain the Mannich base curing agent.
Comparative example 1
Mixing 35g of the Mannich base curing agent obtained in example 6 and 100g of epoxy resin E-51 (epoxy equivalent is 184-200 g/eq) uniformly, coating the mixture on a tinplate by using a film coater, wherein the thickness of a paint film is 50 μm, and the curing conditions are as follows: room temperature/24 h +80 ℃/3 h.
Comparative example 2
56g of the Mannich base curing agent obtained in example 5 and 100g of epoxy resin E-51 (epoxy equivalent is 184-200 g/eq) are uniformly mixed and stirred, the mixture is coated on a tinplate sheet by a coating machine, the thickness of a paint film is 50 μm, and the curing conditions are as follows: room temperature/24 h +80 ℃/3 h.
Comparative example 1
27g of T31 curing agent and 100g of epoxy resin E-51 (epoxy equivalent is 184-200 g/eq) are mixed and stirred uniformly, the mixture is coated on a tinplate by a coating machine, the thickness of a paint film is 50 mu m, and the curing conditions are as follows: room temperature/24 h +80 ℃/3 h.
Viscosity was determined by a rotary viscometer as described in GB/T2794-1995; the gel time is tested by a flat knife method; the adhesion of the paint film is determined according to the method GB/T1720-; the mechanical properties of the cast body are tested according to the GB/T2567 + 2008 standard, all the test temperatures are 25 ℃, and the test results are shown in the attached table 1.
TABLE 1 attached Performance comparison of the comparative examples and comparative examples
Claims (1)
1. A preparation method of a Mannich base curing agent for epoxy floor seal primer is characterized by comprising the following preparation steps: the first step is as follows: adding 470g of phenol and 23.5g of sodium hydroxide into a 2L high-pressure stainless steel reaction kettle, introducing nitrogen to replace air for 3 times, starting stirring, slowly heating to 150 ℃, slowly introducing 220g of ethylene oxide, maintaining the pressure in the kettle at 0.4MPa, stopping heating when the pressure in the reaction kettle does not decrease any more, finishing the addition reaction, continuously preserving heat for 1h at the temperature, introducing cooling water to cool to 60 ℃, adding 10% NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking the supernatant, and drying with anhydrous sodium sulfate to obtain phenol and ethylene oxide adduct for later use; the second step is that: 138g of phenol and ethylene oxide addition product, and 210g of 4, 4-diaminodicyclohexyl methane are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser pipe, uniformly mixed and stirred, 72g of butyraldehyde is slowly dripped, the temperature is controlled to be less than 50 ℃, the temperature is raised to 85 ℃ after the butyraldehyde is dripped, and after reaction is finished for 3 hours, the Mannich base curing agent is obtained by removing generated water through reduced pressure distillation.
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| US3992358A (en) * | 1975-04-10 | 1976-11-16 | American Velodur Metal, Inc. | Epoxy resin compositions |
| EP0066447A1 (en) * | 1981-05-25 | 1982-12-08 | Mitsubishi Gas Chemical Company, Inc. | Reaction of a phenol, aldehyde and amine to produce hardening agent for epoxy resins |
| CN101348563A (en) * | 2008-09-17 | 2009-01-21 | 中昊晨光化工研究院 | Tough mannich base curing agent and preparation thereof |
| CN104817677A (en) * | 2015-05-19 | 2015-08-05 | 大连凯华新技术工程有限公司 | High-flexibility epoxy resin curing agent |
| CN110498907A (en) * | 2019-08-20 | 2019-11-26 | 浙江万盛股份有限公司 | A kind of preparation method of anacardol aqueous epoxy curing agent |
| CN112135855A (en) * | 2018-04-26 | 2020-12-25 | 艾伦塔斯贝克印度有限公司 | Modified phenolic aldehyde amine curing agent for epoxy resin composition and application thereof |
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2020
- 2020-06-22 CN CN202010573718.5A patent/CN111732716B/en active Active
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| GB1163502A (en) * | 1967-01-12 | 1969-09-10 | Ruetgerswerke & Teerverwertung | Method for activating cycloaliphatic polyamines as curing agents for reaction with epoxide compounds |
| US3992358A (en) * | 1975-04-10 | 1976-11-16 | American Velodur Metal, Inc. | Epoxy resin compositions |
| EP0066447A1 (en) * | 1981-05-25 | 1982-12-08 | Mitsubishi Gas Chemical Company, Inc. | Reaction of a phenol, aldehyde and amine to produce hardening agent for epoxy resins |
| CN101348563A (en) * | 2008-09-17 | 2009-01-21 | 中昊晨光化工研究院 | Tough mannich base curing agent and preparation thereof |
| CN104817677A (en) * | 2015-05-19 | 2015-08-05 | 大连凯华新技术工程有限公司 | High-flexibility epoxy resin curing agent |
| CN112135855A (en) * | 2018-04-26 | 2020-12-25 | 艾伦塔斯贝克印度有限公司 | Modified phenolic aldehyde amine curing agent for epoxy resin composition and application thereof |
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Address after: No. 16, No. five village, Xuanwu District, Nanjing, Jiangsu Province Applicant after: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF Applicant after: Nanjing Science and Technology Development Co.,Ltd. Institute of Forest Products and Chemical Industry Chinese Academy of Forestry Sciences Address before: 210000 China Academy of forestry (Nanjing) science and Technology Park, No. 1, Yuanyuan North Road, Jiangbei new area, Nanjing, Jiangsu Applicant before: Nanjing Science and Technology Development Co.,Ltd. Institute of Forest Products and Chemical Industry Chinese Academy of Forestry Sciences Applicant before: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF |
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