CN108250896B - Antifouling paint based on urushiol benzoxazine copper polymer and preparation method thereof - Google Patents
Antifouling paint based on urushiol benzoxazine copper polymer and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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Abstract
The invention relates to antifouling paint based on urushiol benzoxazine copper polymer, which comprises, by weight, 95-105 parts of urushiol benzoxazine copper polymer, 0-30 parts of cuprous oxide, 3-10 parts of auxiliary antifouling agent, 3-10 parts of antibacterial agent, 1-3 parts of auxiliary agent and 20-60 parts of solvent.
Description
Technical Field
The invention relates to an antifouling paint, in particular to antifouling paints based on urushiol benzoxazine copper polymer and a preparation method thereof.
Background
In order to solve the problem, a plurality of antifouling technologies are invented, wherein the most effective and convenient method is to coat a marine antifouling paint, the development of the marine antifouling paint depends on the development of an antifouling agent to a great extent, as early as 50 th century, cuprous oxide becomes a main antifouling agent, and the subsequently appearing organotin antifouling agents rapidly replace the cuprous oxide due to excellent antifouling performance, but as of 80 th century, organotin is banned from using by countries all over the world due to serious pollution problems, and the cuprous oxide becomes a main antifouling agent again.
As a main antifouling agent, cuprous oxide has the defects of large using amount, low using efficiency and the like in an antifouling paint, and the using amount of the cuprous oxide in a marine antifouling paint for ships reaches more than 40-50 wt%. Therefore, the cuprous oxide burst release phenomenon occurs in the earlier stage of the use of the antifouling paint, so that a lot of adverse effects are generated on the marine environment, and the control of the dosage of the cuprous oxide in the antifouling paint is imperative.
The most key concept of the invention is that the urushiol type benzoxazine copper polymer is used as a film forming material of the antifouling paint, and the urushiol type benzoxazine copper polymer can release quantitative copper ions, so that the dosage of cuprous oxide is greatly reduced2D or more, shows that the copper ion leaching rate is higher than 10. mu.g/cm2D, the anti-fouling effect is achieved, and the urushiol type benzoxazine copper polymer has the anti-fouling performance of .
Disclosure of Invention
The invention aims to solve the technical problem of providing urushiol benzoxazine-copper polymer-based antifouling paint and a preparation method thereof, and the amount of cuprous oxide can be reduced.
In order to solve the technical problems, the invention adopts the technical scheme that:
anti-fouling paint based on urushiol benzoxazine copper polymer comprises, by weight, 95-105 parts of urushiol benzoxazine copper polymer, 0-30 parts of cuprous oxide, 3-10 parts of auxiliary anti-fouling agent, 3-10 parts of antibacterial agent, 1-3 parts of auxiliary agent and 20-60 parts of solvent.
The invention also relates to a preparation method of antifouling paint based on urushiol benzoxazine copper polymer, which comprises the following steps:
and weighing cuprous oxide, an auxiliary antifouling agent, an antibacterial agent, an auxiliary agent and a solvent according to the weight parts, mixing, performing th dispersion treatment until the fineness of the mixed raw materials is below 100 mu m, weighing a urushiol benzoxazine copper polymer solution according to the weight parts, adding the urushiol benzoxazine copper polymer solution into the mixed raw materials, and performing second dispersion treatment to obtain the antifouling paint based on the urushiol benzoxazine copper polymer.
The invention has the beneficial effects that:
the urushiol type copper benzoxazine polymer is used as a film forming material of the antifouling paint, the synthesized urushiol raw material belongs to a natural polymer and belongs to a renewable environment-friendly resource, and an amine source pan required for synthesis.
Drawings
FIG. 1 is a graph showing the copper ion leaching rate of a urushiol benzoxazine copper polymer-based antifouling paint according to an embodiment of the present invention;
FIGS. 2a-h are photographs of the surface of a sample after a shallow sea immersion test of an antifouling paint based on urushiol benzoxazine copper polymer according to an embodiment of the present invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The most key concept of the invention is that the urushiol type benzoxazine copper polymer is used as a film forming material of the antifouling paint, and can release quantitative copper ions, so that the consumption of cuprous oxide is greatly reduced.
The invention provides anti-fouling paint based on urushiol benzoxazine copper polymer, which comprises, by weight, 95-105 parts of urushiol benzoxazine copper polymer, 0-30 parts of cuprous oxide, 3-10 parts of auxiliary antifouling agent, 3-10 parts of antibacterial agent, 1-3 parts of auxiliary agent and 20-60 parts of solvent.
The invention also relates to a preparation method of antifouling paint based on urushiol benzoxazine copper polymer, which comprises the following steps:
and weighing cuprous oxide, an auxiliary antifouling agent, an antibacterial agent, an auxiliary agent and a solvent according to the weight parts, mixing, performing th dispersion treatment until the fineness of the mixed raw materials is below 100 mu m, weighing a urushiol benzoxazine copper polymer solution according to the weight parts, adding the urushiol benzoxazine copper polymer solution into the mixed raw materials, and performing second dispersion treatment to obtain the antifouling paint based on the urushiol benzoxazine copper polymer.
From the above description, the beneficial effects of the present invention are:
the urushiol type copper benzoxazine polymer is used as a film forming material of the antifouling paint, the synthesized urushiol raw material belongs to a natural polymer and belongs to a renewable environment-friendly resource, and an amine source pan required for synthesis.
In the antifouling paint based on urushiol benzoxazine copper polymer of the invention:
, the urushiol type copper benzoxazine polymer is prepared by reacting urushiol type benzoxazine with anhydrous copper chloride, the urushiol type benzoxazine is prepared by performing Mannich condensation reaction on urushiol, paraformaldehyde and primary amine, and the primary amine contains carbon chain with length of C1-C18The primary alkyl amine, the primary cycloalkyl amine, the primary unsaturated alkyl amine or the primary aryl amine.
The above description shows that the urushiol type copper benzoxazine polymer can be urushiol type benzoxazine synthesized by taking urushiol and other natural phenols, paraformaldehyde and primary amine as raw materials through a Mannich condensation reaction, and then anhydrous copper chloride is added into the synthesized urushiol type benzoxazine to react for periods of time under the condition of , so that the urushiol type copper benzoxazine polymer is finally obtained.
, the cuprous oxide is any electrolytic nano cuprous oxide or modified nano cuprous oxide with the particle size less than 100 nm.
From the above description, it can be known that the modified nano cuprous oxide or electrolytic cuprous oxide with the above particle size is used as the antifouling agent, so that the amount of cuprous oxide can be greatly reduced, and the cuprous oxide in the antifouling paint can be stably released, thereby reducing the pollution to the environment.
, the auxiliary antifouling agent is any of copper sulfate, zinc oxide and zineb.
As can be seen from the above description, the auxiliary antifouling agent has the function of improving the marine antifouling capacity, and can reduce the consumption of electrolytic nano cuprous oxide or modified nano cuprous oxide.
, the antimicrobial agent is a Dow antimicrobial agent.
As is apparent from the above description, the selection of the Dow's antibacterial agent as the antibacterial agent has an advantage of reducing the adhesion of substances such as algae in the ocean. The above-mentioned dow antibacterial agent is an antibacterial agent that is proposed by the dow chemical company.
, the assistant is defoaming agent and/or leveling agent.
, the solvent is at least selected from xylene, n-butanol, ethyl acetate, butyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate and isoamyl acetate.
As can be seen from the above description, the solvent may be any kinds of mixed solvents, any two kinds of mixed solvents, or any three kinds of mixed solvents of xylene, n-butanol, ethyl acetate, butyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate, and isoamyl acetate.
, the weight fraction of the urushiol type benzoxazine copper polymer is 100 parts, and the weight fraction of the cuprous oxide is 30 parts.
As can be seen from the above description, as an example of preferable components, the weight fraction of the urushiol type copper benzoxazine polymer is 100 parts and the weight fraction of the cuprous oxide is 30 parts based on 3-10 parts of the auxiliary antifouling agent, 3-10 parts of the antibacterial agent, 1-3 parts of the auxiliary agent and 20-60 parts of the solvent.
The preparation method of the antifouling paint based on the urushiol benzoxazine copper polymer comprises the following steps:
, ball milling to obtain times of dispersion treatment and the second time of dispersion treatment, or high-speed dispersion to obtain times of dispersion treatment and the second time of dispersion treatment.
As is apparent from the above description, the th dispersion treatment and the second dispersion treatment may be performed by a ball milling method or a high-speed dispersion method.
Specifically, the mixed raw materials are sequentially added into a dispersion tank, ball milling is carried out for 2 hours until the fineness reaches below 100 mu m, then the urushiol type benzoxazine copper polymer solution is added into the dispersion tank, ball milling is continued for 1-6 hours, the material with uniform sagging is obtained by filtering with gauze, and uniform dispersion is achieved, otherwise, ball milling is continued until uniform dispersion is achieved.
Or sequentially adding the mixed raw materials into a dispersion tank, and dispersing at high speed for 30-60min until the fineness is below 100 μm; adding the urushiol type benzoxazine copper polymer solution into a dispersion tank, continuously dispersing for 1-6h, and filtering and discharging if the urushiol type benzoxazine copper polymer solution is uniformly dispersed; otherwise, continuing ball milling until the dispersion is uniform.
Example of the present invention is:
the preparation method of the antifouling paint based on urushiol benzoxazine copper polymer in the embodiment comprises the following steps:
(1) the preparation method comprises the following steps of preparing octylamine-based urushiol benzoxazine by carrying out Mannich condensation reaction on urushiol, paraformaldehyde and octylamine, and preparing octylamine-based urushiol-type benzoxazine copper polymer after reacting the octylamine-based urushiol benzoxazine with anhydrous copper chloride;
dissolving a cumyl amine-based urushiol type copper benzoxazine polymer in xylene, wherein the weight ratio of the octylamine-based urushiol type copper benzoxazine polymer to the xylene is 1:2, so as to obtain a octylamine-based urushiol type copper benzoxazine polymer solution;
(2) weighing 0 part of cuprous oxide, 5 parts of auxiliary antifouling agent, 5 parts of antibacterial agent, 3 parts of auxiliary agent and 20 parts of solvent according to parts by weight, mixing, adding into a dispersion tank according to the sequence, and performing ball milling for 2 hours until the fineness reaches 100 mu m; adding 95 parts of octylamine-based urushiol type benzoxazine copper polymer solution into a dispersion tank, continuing ball milling for 1 hour, and filtering and discharging if the dispersion is uniform; otherwise, continuing ball milling until the dispersion is uniform, and obtaining the antifouling paint of the octylamine-based urushiol type benzoxazine copper polymer; the cuprous oxide is modified nano cuprous oxide with the particle size of 50 nm; the auxiliary antifouling agent is copper pyrithione; the antibacterial agent is a Dow antibacterial agent; the auxiliary agent is a defoaming agent and a flatting agent; the solvent is xylene.
The antifouling paint thus obtained was designated as A.
The second embodiment of the invention is as follows:
the preparation method of the antifouling paint based on urushiol benzoxazine copper polymer in the embodiment comprises the following steps:
(1) the preparation method comprises the following steps of preparing octylamine-based urushiol benzoxazine by carrying out Mannich condensation reaction on urushiol, paraformaldehyde and octylamine, and preparing octylamine-based urushiol-type benzoxazine copper polymer after reacting the octylamine-based urushiol benzoxazine with anhydrous copper chloride;
dissolving a cumyl amine-based urushiol type copper benzoxazine polymer in xylene, wherein the weight ratio of the octylamine-based urushiol type copper benzoxazine polymer to the xylene is 1:2, so as to obtain a octylamine-based urushiol type copper benzoxazine polymer solution;
(2) weighing 5 parts of cuprous oxide, 5 parts of auxiliary antifouling agent, 5 parts of antibacterial agent, 3 parts of auxiliary agent and 25 parts of solvent according to parts by weight, mixing, adding into a dispersion tank according to the sequence, and performing ball milling for 2 hours until the fineness reaches 100 mu m; adding 100 parts of octylamine-based urushiol type benzoxazine copper polymer solution into a dispersion tank, continuing ball milling for 1 hour, and filtering and discharging if the dispersion is uniform; otherwise, continuing ball milling until the dispersion is uniform, and obtaining the antifouling paint of the octylamine-based urushiol type benzoxazine copper polymer; the cuprous oxide is modified nano cuprous oxide with the particle size of 50 nm; the auxiliary antifouling agent is copper pyrithione; the antibacterial agent is a Dow antibacterial agent; the auxiliary agent is a defoaming agent and a flatting agent; the solvent is xylene.
The antifouling paint thus obtained was designated as B.
The third embodiment of the invention is as follows:
the preparation method of the antifouling paint based on urushiol benzoxazine copper polymer in the embodiment comprises the following steps:
(1) the preparation method comprises the following steps of preparing octylamine-based urushiol benzoxazine by carrying out Mannich condensation reaction on urushiol, paraformaldehyde and octylamine, and preparing octylamine-based urushiol-type benzoxazine copper polymer after reacting the octylamine-based urushiol benzoxazine with anhydrous copper chloride;
dissolving a cumyl amine-based urushiol type copper benzoxazine polymer in xylene, wherein the weight ratio of the octylamine-based urushiol type copper benzoxazine polymer to the xylene is 1:2, so as to obtain a octylamine-based urushiol type copper benzoxazine polymer solution;
(2) weighing 10 parts of cuprous oxide, 5 parts of auxiliary antifouling agent, 5 parts of antibacterial agent, 3 parts of auxiliary agent and 30 parts of solvent according to parts by weight, mixing, adding into a dispersion tank according to the sequence, and performing ball milling for 2 hours until the fineness reaches 100 mu m; adding 100 parts of octylamine-based urushiol type benzoxazine copper polymer solution into a dispersion tank, continuing ball milling for 1 hour, and filtering and discharging if the dispersion is uniform; otherwise, continuing ball milling until the dispersion is uniform, and obtaining the antifouling paint of the octylamine-based urushiol type benzoxazine copper polymer; the cuprous oxide is modified nano cuprous oxide with the particle size of 50 nm; the auxiliary antifouling agent is copper pyrithione; the antibacterial agent is a Dow antibacterial agent; the auxiliary agent is a defoaming agent and a flatting agent; the solvent is xylene.
The antifouling paint thus obtained was designated as C.
The fourth embodiment of the invention is as follows:
the preparation method of the antifouling paint based on urushiol benzoxazine copper polymer in the embodiment comprises the following steps:
(1) the preparation method comprises the following steps of preparing octylamine-based urushiol benzoxazine by carrying out Mannich condensation reaction on urushiol, paraformaldehyde and octylamine, and preparing octylamine-based urushiol-type benzoxazine copper polymer after reacting the octylamine-based urushiol benzoxazine with anhydrous copper chloride;
dissolving a cumyl amine-based urushiol type copper benzoxazine polymer in xylene, wherein the weight ratio of the octylamine-based urushiol type copper benzoxazine polymer to the xylene is 1:2, so as to obtain a octylamine-based urushiol type copper benzoxazine polymer solution;
(2) weighing 20 parts of cuprous oxide, 5 parts of auxiliary antifouling agent, 5 parts of antibacterial agent, 3 parts of auxiliary agent and 30 parts of solvent according to parts by weight, mixing, adding into a dispersion tank according to the sequence, and performing ball milling for 2 hours until the fineness reaches 100 mu m; adding 100 parts of octylamine-based urushiol type benzoxazine copper polymer solution into a dispersion tank, continuing ball milling for 1 hour, and filtering and discharging if the dispersion is uniform; otherwise, continuing ball milling until the dispersion is uniform, and obtaining the antifouling paint of the octylamine-based urushiol type benzoxazine copper polymer; the cuprous oxide is modified nano cuprous oxide with the particle size of 50 nm; the auxiliary antifouling agent is copper pyrithione; the antibacterial agent is a Dow antibacterial agent; the auxiliary agent is a defoaming agent and a flatting agent; the solvent is xylene. The antifouling paint thus obtained was designated as D.
Effect testing
1. The A, B, C and D samples prepared in the above-mentioned examples to three were sampled and tested for their physical and mechanical properties, respectively, and the results of the tests are shown in table 1 below, where table 1 is the table of the physical and mechanical properties of the antifouling paint A, B, C, D prepared in the above-mentioned examples , two, three and four.
TABLE 1
2. The test results of the shallow sea immersion test of samples A, B, C and D prepared in the above examples to third example are shown in table 2 according to the method of the shallow sea immersion test of the sample of the antifouling paint GB/T5370-2007.
TABLE 2
Referring to FIGS. 2a-h, the results show that: from sample A to D, the dosage (mass percent) of cuprous oxide is 0, 4%, 8% and 15%, respectively, and after 100 days of shallow sea soaking, A, B and sample C have a small amount of marine organism attached to the surface, but no large marine organism attached to the surface, while sample D has no marine organism attached to the surface.
In conclusion, the antifouling paint based on the urushiol type benzoxazine copper polymer provided by the invention has the advantage of greatly reducing the consumption of cuprous oxide.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (10)
1, antifouling paint based on urushiol benzoxazine copper polymer, which is characterized by comprising, by weight, 95-105 parts of urushiol benzoxazine copper polymer, 0-30 parts of cuprous oxide, 3-10 parts of auxiliary antifouling agent, 3-10 parts of antibacterial agent, 1-3 parts of auxiliary agent and 20-60 parts of solvent.
2. The antifouling paint based on urushiol benzoxazine copper polymer according to claim 1, wherein the urushiol benzoxazine copper polymer is prepared by reacting urushiol benzoxazine with anhydrous copper chloride, and the urushiol benzoxazine is prepared by Mannich condensation reaction of urushiol, paraformaldehyde and primary amine.
3. The antifouling paint based on urushiol benzoxazine copper polymer according to claim 1, wherein the cuprous oxide is any kinds of electrolytic cuprous oxide or modified cuprous oxide having particle size less than 100 nm.
4. The antifouling paint based on urushiol benzoxazine copper polymer according to claim 1, wherein the auxiliary antifouling agent is any kinds of copper sulfate pyridine, zinc oxide and zineb.
5. The urushiol benzoxazine copper polymer-based antifouling paint according to claim 1, wherein the antibacterial agent is a dow antibacterial agent.
6. The urushiol benzoxazine copper polymer-based antifouling paint according to claim 1, wherein the auxiliary agent is an antifoaming agent and/or a leveling agent.
7. The antifouling paint based on urushiol benzoxazine copper polymer according to claim 1, wherein the solvent is at least kinds of xylene, n-butanol, ethyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate and isoamyl acetate.
8. The antifouling paint based on urushiol benzoxazine copper polymer according to claim 1, wherein the weight part of the urushiol benzoxazine copper polymer is 100 parts, and the weight part of cuprous oxide is 30 parts.
A process for the preparation of a urushiol benzoxazine copper polymer based antifouling paint according to any of claims 1-8 to , comprising the steps of:
weighing cuprous oxide, an auxiliary antifouling agent, an antibacterial agent, an auxiliary agent and a solvent, mixing, performing th dispersion treatment until the fineness of the mixed raw materials is below 100 mu m, then weighing a urushiol benzoxazine copper polymer, adding the urushiol benzoxazine copper polymer into the mixed raw materials, and performing second dispersion treatment to obtain the antifouling paint based on the urushiol benzoxazine copper polymer.
10. The method for preparing an antifouling paint based on urushiol benzoxazine copper polymer according to claim 9, wherein the th dispersion treatment and the second dispersion treatment are performed by a ball milling method, or the th dispersion treatment and the second dispersion treatment are performed by a high speed dispersion method.
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| CN109796828A (en) * | 2019-01-28 | 2019-05-24 | 福建师范大学 | A kind of environment-friendly type marine anti-pollution anticorrosive paint and preparation method thereof |
| CN111849345B (en) * | 2019-04-29 | 2021-12-03 | 华东理工大学 | Fluorine-free hydrophobic antifouling antibacterial coating composition and preparation method and application thereof |
| CN112707932B (en) * | 2020-12-30 | 2021-12-28 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
| CN113416289B (en) * | 2021-07-15 | 2022-10-11 | 中国科学院宁波材料技术与工程研究所 | Bio-based benzoxazine organic phase change material and preparation method and application thereof |
| CN114410177A (en) * | 2022-02-25 | 2022-04-29 | 浙江鱼童新材料股份有限公司 | Low-surface-energy marine antifouling paint and preparation method thereof |
| CN115181474A (en) * | 2022-06-09 | 2022-10-14 | 广西电网有限责任公司玉林供电局 | Weeding functional type smooth coating and preparation method and use method thereof |
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| CN102432560A (en) * | 2011-09-13 | 2012-05-02 | 华南理工大学 | Preparation method for benzoxazine intermediate and synthetic resin of intermediate |
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| CN102432560A (en) * | 2011-09-13 | 2012-05-02 | 华南理工大学 | Preparation method for benzoxazine intermediate and synthetic resin of intermediate |
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| 漆酚型苯并噁嗪铜聚合物的制备及性能研究;黄坤;《中国化学会第30届学术年会摘要集-第十一分会：应用化学》;20160731 * |
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