CN115386059A - Bio-based benzoxazine precursor and preparation method and application thereof - Google Patents
Bio-based benzoxazine precursor and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a bio-based benzoxazine precursor and a preparation method and application thereof. The preparation method of the bio-based benzoxazine precursor comprises the following steps: the mixed reaction system containing natural flavonoid compounds, monoamine and formaldehyde is subjected to Mannich reaction at 50-70 ℃ for 36-72 h to prepare the bio-based benzoxazine precursor. The method provided by the invention is simple, simple and convenient to operate, good in controllability, easy to implement and suitable for large-scale industrial production; the bio-based benzoxazine precursor prepared by the method can be subjected to ring opening polymerization at a lower temperature to prepare thermosetting polybenzoxazine resin, so that the thermosetting polybenzoxazine resin has excellent corrosion resistance, mechanical property, thermal property, antibacterial and algae killing properties and the like, has the possibility of replacing the existing petroleum-based product, is wide in application range, and can be used for preparing a polybenzoxazine resin coating with marine anti-pollution performance.
Description
Technical Field
The invention belongs to the technical field of bio-based thermosetting resin, particularly relates to a bio-based benzoxazine precursor and a preparation method and application thereof, and particularly relates to a bio-based benzoxazine precursor based on natural flavonoid compounds and application thereof in the field of marine antifouling paint.
Background
The 21 st century is the marine century of mankind worldwide, and the development and utilization of vast ocean resources has become a central focus of social development. However, the engineering structures such as ships, offshore platforms, offshore drilling platforms and aquaculture facilities for developing marine resources are very easy to be attached by a large amount of marine fouling due to long-term marine environment, and the attachment of marine organisms causes serious consequences and huge economic losses. At present, the most effective means is to apply antifouling paint containing antifouling agent, but the currently used marine antifouling agents in the mainstream all have the problem of polluting marine environment and have poor durability, the antifouling effect is weakened along with the continuous extension of the service time of the coating, and the antifouling agent can be continuously precipitated from the resin matrix in the process to continuously pollute the marine environment.
On the other hand, almost all of the matrix resin in the marine antifouling paint at present is derived from petroleum-based products, the production and preparation processes of the petroleum-based products inevitably pollute the natural environment where the petroleum-based products are located, and meanwhile, the petroleum-based products are all obtained from unsustainable and non-renewable petrochemical resources, and the cost of petroleum-based high polymer materials is inevitably increased along with the increasing exhaustion of reserves of the petroleum-based products. Recently, under the multiple pressure of protecting the environment, reducing the production cost and saving petroleum resources, environment-friendly bio-based polymer materials derived from sustainable resources gradually enter the visual field of people, and research, development and utilization of the bio-based polymer materials are increasingly paid more attention by people. Therefore, the preparation of high-performance resin with intrinsic antifouling capacity by using the diversity of the bio-based raw materials is a very important development trend of the future marine antifouling paint.
In recent years, benzoxazine resins have attracted great interest to researchers due to their characteristics of excellent thermal stability, almost zero volume shrinkage, extremely low surface energy, good flame retardancy and electrical insulation properties, excellent corrosion resistance, and the like. Like other polymeric materials, benzoxazines face the same challenges in terms of availability of raw materials, cost, and even environmental friendliness. Therefore, bio-based benzoxazines are also a very important research direction for sustainable development in the current benzoxazine field.
Patent CN110240684A discloses that a benzoxazine monomer containing intramolecular hydrogen bond is prepared from naringenin (hydrogenated flavonoid compound), but the benzoxazine polymer based on the compound does not show antibacterial and seaweed-killing performance. The natural flavonoid (Flavonoids) has C 6 -C 3 -C 6 The general name of a compound with a structure is wide in distribution in the plant world, and the compound has the effects of resisting oxidation, inhibiting the growth of pathological cells and the like. For example, luteolin and baicalein have certain antibacterial effect; quercetin and kaempferol have antiviral effect; the flavonoid monomer separated from chrysanthemum and swertia pseudochinensis has a strong inhibiting effect on HIV virus, genistein and biochanin A (biochanin A) also have a certain inhibiting effect on HIV virus, and the research work at present discovers that epoxy resin and benzoxazine resin based on flavone structures both have excellent thermal and mechanical properties, and have great potential to become a novel bio-based platform compound capable of being used for preparing high-performance resin materials. However, the curing of the benzoxazine resin usually requires a high temperature (120-220 ℃), which is a difficult problem restricting the wide application of the benzoxazine resin, so how to cure the benzoxazine resin under a mild condition is a very important research direction for the benzoxazine resin.
Disclosure of Invention
The invention mainly aims to provide a bio-based benzoxazine precursor, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a bio-based benzoxazine precursor, which has a structure shown as a formula (I):
wherein R is 1 Selected from H, C 6 H 5 、CH 3 OC 6 H 5 、
Any one of (1), R 2 Selected from H, OH, CH 3 O、CH 3 OC 6 H 5 And
any one of (1), R 3 Selected from H, OH and CH 3 Any one of O and R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
The embodiment of the invention also provides a preparation method of the bio-based benzoxazine precursor, which comprises the following steps:
the mixed reaction system containing natural flavonoid compounds, monoamine and formaldehyde is subjected to Mannich reaction (cyclization reaction) to prepare the biobased benzoxazine precursor.
The embodiment of the invention also provides application of the bio-based benzoxazine precursor in preparation of polybenzoxazine resin.
The embodiment of the invention also provides a preparation method of the polybenzoxazine resin, which comprises the following steps:
providing the aforementioned biobased benzoxazine precursor;
and heating and reacting the bio-based benzoxazine precursor at the temperature of 140-170 ℃ for 6-12 h to prepare the polybenzoxazine resin.
Embodiments of the present invention also provide a polybenzoxazine resin prepared by the foregoing method.
The embodiment of the invention also provides application of the bio-based benzoxazine precursor or the polybenzoxazine resin in preparing a marine antibacterial and/or antifouling coating or a marine antibacterial and/or antifouling coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) The bio-based benzoxazine precursor based on natural flavonoid compounds is prepared by directly adopting the flavonoid compounds with bio-based sources as raw materials, has the advantages of simple and efficient preparation method, simple and convenient operation, good controllability, high yield and simple process, can be produced in large scale by utilizing the existing chemical equipment, is suitable for large-scale industrial production, and can reduce the dependence of the existing petroleum-based benzoxazine resin on petrochemical resources and the pollution to the environment;
(2) The bio-based benzoxazine precursor based on natural flavonoid compounds prepared by the invention can be completely cured at a lower temperature, and the finally obtained polybenzoxazine resin product has excellent thermal properties, mechanical properties and antibacterial and algae-killing properties. The development and preparation of the benzoxazine can promote the development of bio-based materials, has important significance for promoting the sustainable development of the fields of whole high polymer materials and the like, is a bio-based, green and environment-friendly product, and has double effects of saving petroleum resources and protecting the environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows the NMR spectrum of a chrysin-furfuryl amino benzoxazine precursor prepared in example 1 of the present invention 1 H-NMR；
FIG. 2 is an infrared spectrum of a chrysin-furfuryl amino benzoxazine precursor prepared in example 1 of the present invention;
FIG. 3 shows the NMR spectrum of the scutellarein-furfuryl amino benzoxazine precursor prepared in example 2 of the present invention 1 H-NMR；
Fig. 4 is an infrared spectrum of the scutellarein-furfuryl amino benzoxazine precursor prepared in example 2 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to provide the technical solution of the present invention,
the technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a bio-based benzoxazine precursor having a structure as shown in formula (I):
wherein R is 1 Selected from H, C 6 H 5 、CH 3 OC 6 H 5 、
Any one of (1), R 2 Selected from H, OH, CH 3 O、CH 3 OC 6 H 5 And
any one of (1), R 3 Selected from H, OH and CH 3 Any one of O and R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
In some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein R is 1 Selected from H, R 2 Is selected from CH 3 OC 6 H 5 ，R 3 Selected from H and/or CH 3 O and R are selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
In some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein when R is 1 Selected from H, R 2 Is selected from
R 3 Selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 5 And C 6 H 13 Any one of them.
In some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein when R is 1 Selected from H, R 2 Is selected from
R 3 Is selected from CH 3 O and R are selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
In some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein R is 1 Is selected from C 6 H 5 ，R 2 Selected from H, R 3 Selected from H and/or OH, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
In some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein R is 1 Is selected from
R 2 Selected from H, R 3 Selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H l1 、C 6 H 5 And C 6 H 13 Any one of them.
In some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein R is 1 Is selected from
R 2 Selected from H, R 3 Selected from OH, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 、C 6 H 13 Any one of the above;
in some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein R is 1 Is selected from
And/or
Any one of (1), R 2 Selected from H, R 3 Is selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 1l 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
In some more specific embodiments, the bio-based benzoxazine precursor has the structure shown in formula (I):
wherein R is 1 Is selected from C 6 H 5 、CH 3 OC 6 H 5 、
Any one of (1), R 2 Selected from OH, R 3 Is selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
Another aspect of the embodiments of the present invention also provides a preparation method of the aforementioned bio-based benzoxazine precursor, which includes:
the method comprises the following steps of enabling a mixed reaction system containing natural flavonoid compounds, monoamine and formaldehyde to carry out Mannich reaction, and preparing the biobased benzoxazine precursor.
In some more specific embodiments, the method for preparing the bio-based benzoxazine precursor specifically comprises the following steps: the mixed reaction system containing natural flavonoid compounds, monoamine and formaldehyde is subjected to Mannich reaction at 50-70 ℃ for 36-72 h to prepare the bio-based benzoxazine precursor.
Further, the natural flavonoid compound includes any one or a combination of two or more of chrysin, genistein (or genistein), apigenin, biochanin a (biochanin a), tectoridin, baicalein, scutellarein, luteolin, diosmetin, galangin, kaempferide, kaempferol, quercetin, and isorhamnetin, and is not limited thereto.
Further, the monoamine has a structure as shown in formula (II):
R-NH 2
(II)
wherein R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 And is not limited thereto.
Further, the monoamine includes any one or a combination of two or more of ethylamine, propylamine, butylamine, pentylamine, hexylamine, aniline, and furfuramine, and is not limited thereto.
Still further, the monoamine includes aniline and/or furfuryl amine, and is not limited thereto.
Furthermore, the molar ratio of the natural flavonoid compound, the monoamine and the formaldehyde is 1: 2-6: 8-24.
In some preferred embodiments, the chrysin-pentylamino benzoxazine precursor prepared from chrysin and pentylamine and the scutellarein-furfurylamino benzoxazine precursor prepared from scutellarein and furfurylamino have high reactivity and high yield (82.7% and 83.6%, respectively).
Another aspect of the embodiments of the present invention also provides a use of the aforementioned bio-based benzoxazine precursor in the preparation of a polybenzoxazine resin.
Another aspect of the embodiments of the present invention also provides a method for preparing a polybenzoxazine resin, which includes:
providing the aforementioned bio-based benzoxazine precursor;
and heating and reacting the bio-based benzoxazine precursor at the temperature of 140-170 ℃ for 6-12 h to prepare the polybenzoxazine resin.
In some preferred embodiments, the prepared tectoridin-furfuryl amine based polybenzoxazine resin and genistein-ethylamino based polybenzoxazine resin respectively have 96% and 97% of bacteriostasis rate on escherichia coli, 94% and 95% of killing rate on navicula and 91% and 92% of killing rate on triangle alga.
Another aspect of an embodiment of the present invention also provides a polybenzoxazine resin prepared by the foregoing method.
Further, the bacteriostasis rate of the polybenzoxazine resin to escherichia coli is 91-97%.
Further, the killing rate of the polybenzoxazine resin to navicula is 90-95%.
Another aspect of the embodiments of the present invention also provides a use of the aforementioned bio-based benzoxazine precursor or polybenzoxazine resin in preparing a marine antibacterial and/or antifouling paint or a marine antibacterial and/or antifouling coating.
The application adopts a flavonoid compound different from naringenin, namely the flavonoid compound containing conjugated double bonds, and the benzoxazine polymer based on the compound has excellent antibacterial and seaweed killing performances. Simultaneously, this patent provides a biobased benzoxazine precursor, can solidify under the lower temperature to have excellent thermodynamic properties and antibiotic and kill performances such as marine alga and anti-soil, can develop and be used as marine anti-soil polybenzoxazine resin coating, therefore this type of benzoxazine resin has very huge application potential in marine anti-soil coating field.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Dissolving 1mol of chrysin, 1mol of furfuryl amine and 10mol of formaldehyde aqueous solution in 200mL of chloroform, reacting for 36h at 70 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing and drying to obtain a chrysin-furfuryl amino benzoxazine precursor with the yield of 79.5 percent and nuclear magnetic resonance hydrogen spectrum 1 H-NMR is shown in figure 1, and each peak on the figure corresponds to a hydrogen atom on the structure of the chrysin-furfuryl amino benzoxazine precursor one by one. Similarly, the infrared spectrum FT-IR is shown in figure 2, and absorption vibration peaks on the figure completely correspond to the chrysin-furfuryl amino benzoxazine precursor structure.
And (3) carrying out step heating on the chrysin-furfurylaminobenzoxazine precursor in a forced air oven (at the temperature of 140-170 ℃ and the heating rate of 10 ℃/2 h), and finally curing at the temperature of 170 ℃ to obtain the chrysin-furfurylaminobenzoxazine resin. The vitrification transition of the resulting cured product was 260 ℃ T d10 The temperature is 445 ℃, the bacteriostasis rate on escherichia coli is 95%, the killing rate on navicula is 90%, and the killing rate on triangle alga is 92%.
Example 2
Dissolving 1mol of scutellarein, 3mol of furfuryl amine and 24mol of formaldehyde aqueous solution in 300mL of dioxane, reacting at 60 ℃ for 72 hours, performing reduced pressure rotary evaporation to remove the solvent, washing with water and drying to obtain the scutellarein-furfuryl amine benzoxazine precursor, wherein the yield is 83.6 percent, and the nuclear magnetic resonance hydrogen spectrum of the precursor is 1 H-NMR is shown in figure 3, each peak on the figure is in one-to-one correspondence with a hydrogen atom on the structure of the scutellarein-furfuryl amine benzoxazine precursor, and similarly, an infrared spectrum FT-IR is shown in figure 4, and absorption vibration peaks on the figure are in complete correspondence with the structure of the scutellarein-furfuryl amine benzoxazine precursor. The scutellarein-furfuryl amino benzoxazine precursor has a structure shown as the following formula:
and (3) carrying out step heating on the scutellarein-furfurylaminobenzoxazine precursor in a forced air oven (140-170 ℃, the heating rate is 5 ℃/2 h), and finally curing to 170 ℃ to obtain the scutellarein-furfurylaminobenzoxazine resin. The resulting cured product had a glass transition of 358 ℃ T d10 467 deg.C, 94% of Escherichia coli, 96% of Navicula algae, and 91% of triangular algae. Meanwhile, the prepared scutellarein-furfuryl amino benzoxazine precursor is defoamed in a vacuum oven at 90 ℃, then is uniformly coated on a 304 stainless steel plate through a coating machine for a polybenzoxazine resin coating test, and the antifouling performance (water, seawater, crude oil/water mixture) and the high-temperature resistant impregnation performance (40-100 ℃) of the coating are tested according to NACE TM-01-74 and ASTM C868. Experiments show that the coating has excellent anti-fouling performance and high-temperature-resistant impregnation performance, and can be used for preparing a polybenzoxazine resin coating with marine anti-fouling performance.
Example 3
Dissolving 1mol of tectoridin, 3mol of furfuryl amine and 16mol of formaldehyde aqueous solution in 300mL of dioxane, reacting for 56h at 60 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing and drying to obtain an tectoridin-furfuryl benzoxazine precursor with the yield of 69.8%, wherein the tectoridin-furfuryl benzoxazine precursor has the following structure:
and (3) carrying out step heating (140-170 ℃, the heating rate is 5 ℃/2 h) on the tectoridin-furfuryl benzoxazine precursor in a forced air oven, and finally curing at 170 ℃ to obtain the tectoridin-furfuryl polybenzoxazine resin. The vitrification transition of the resulting cured product was 350 ℃ C.T d10 At 475 ℃, the bacteriostasis rate to colibacillus is 96 percent, the killing rate to navicula is 94 percent, and the killing rate to triangle algae is 91 percent. Meanwhile, the prepared tectoridin-furfuryl amino benzoxazine precursor is uniformly coated on a 304 stainless steel plate through a coating machine after being defoamed at 90 ℃ in a vacuum oven for performance test of the polybenzoxazine resin coating, and the solvent resistance (water, seawater, crude oil/water mixture) and the high-temperature resistant dipping performance (40-100 ℃) of the coating are tested according to NACE TM-01-74 and ASTM C868. Experiments show that the coating has good anti-fouling performance and high-temperature-resistant impregnation performance, and can be used for preparing a polybenzoxazine resin coating with marine anti-fouling performance.
Example 4
Dissolving 1mol of chrysin, 3mol of pentylamine and 12mol of formaldehyde aqueous solution in 200mL of chloroform, reacting for 40h at 50 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing and drying to obtain a chrysin-pentylamine benzoxazine precursor with a yield of 82.7%, wherein the chrysin-pentylamine benzoxazine precursor has a structure shown in the following formula:
and (3) carrying out step heating (140 ℃/1h, 150 ℃/2h, 160 ℃/2h and 170 ℃/2 h) on the chrysin-pentylamine benzoxazine precursor in a forced air oven, and finally curing at 170 ℃ to obtain the chrysin-pentylamine polybenzoxazine resin. Obtained byThe glass transition of the cured product of (2) is 254 ℃, T d10 At 436 ℃, the bacteriostasis rate to escherichia coli is 96 percent, the killing rate to navicula is 93 percent, and the killing rate to triangle algae is 91 percent.
Example 5
Dissolving 1mol of genistein, 3mol of ethylamine and 20mol of formaldehyde aqueous solution in 250mL of chloroform, reacting for 48h at 65 ℃, removing the solvent by reduced pressure rotary evaporation, washing with water and drying to obtain a genistein-ethylamino benzoxazine precursor with the yield of 78.2%, wherein the structure of the genistein-ethylamino benzoxazine precursor is shown as the following formula:
and (3) carrying out step heating (140 ℃/2h, 150 ℃/2h, 160 ℃/2h and 170 ℃/2 h) on the genistein-ethylamino benzoxazine precursor in a blast oven, and finally curing at 170 ℃ to obtain the genistein-ethylamino polybenzoxazine resin. The vitrification transition of the resulting cured product was 324 ℃ T d10 At 457 ℃, the bacteriostasis rate to escherichia coli is 97 percent, the killing rate to navicula is 95 percent, and the killing rate to triangle algae is 92 percent.
Example 6
Dissolving 1mol of apigenin, 4mol of aniline and 24mol of formaldehyde aqueous solution in 300mL of dioxane, reacting for 65 hours at 65 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing and drying to obtain an apigenin-anilino benzoxazine precursor, wherein the yield is 73.8%, and the structure of the apigenin-anilino benzoxazine precursor is shown as the following formula:
and (3) carrying out step heating (140-170 ℃ and the heating rate of 5 ℃/2 h) on the apigenin-anilino benzoxazine precursor in a forced air oven, and finally curing at 170 ℃ to obtain the apigenin-anilino benzoxazine resin. Vitrification conversion of the resulting cured product365℃，T d10 469 ℃, the bacteriostasis rate to escherichia coli is 92%, the killing rate to navicula is 93%, and the killing rate to triangle algae is 91%.
Example 7
Dissolving 1mol of genistein, 4mol of aniline and 14mol of formaldehyde aqueous solution in 300mL of dioxane, reacting for 42h at 70 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing and drying to obtain a genistein-anilino benzoxazine precursor with the yield of 65.8%, wherein the structure of the genistein-anilino benzoxazine precursor is shown as the following formula:
and (3) carrying out step heating (140-170 ℃ and the heating rate of 5 ℃/2 h) on the genistein-anilino benzoxazine precursor in a blast oven, and finally curing at 170 ℃ to obtain the genistein-anilino polybenzoxazine resin. The resulting cured product had a glass transition of 366 ℃ T d10 At 473 ℃, the bacteriostasis rate to escherichia coli is 91%, the killing rate to navicula is 92%, and the killing rate to triangle algae is 91%.
Example 8
Dissolving 1mol of diosmetin, 3mol of furfuryl amine and 20mol of formaldehyde aqueous solution in 300mL of dioxane, reacting for 36h at 70 ℃, decompressing, rotating and evaporating to remove the solvent, washing for 3 times with hot water, and drying in vacuum to obtain a diosmetin-furfuryl benzoxazine precursor, wherein the yield is 78.3%, and the diosmetin-furfuryl benzoxazine precursor has a structure shown in the following formula:
and (3) carrying out step heating on the diosmetin-furfuryl amine benzoxazine precursor in a blast oven (at the temperature of 140-170 ℃, the heating rate is 5 ℃/2 h), and finally curing at the temperature of 170 ℃ to obtain diosmetin-furfuryl amine polybenzoxazine resin. The vitrification transition of the cured product obtained is 372 ℃ C.T d10 At 464 ℃, the bacteriostasis rate to escherichia coli is 92 percent, the killing rate to navicula is 93 percent, and the killing rate to triangle algae is 91 percent.
Example 9
Dissolving 1mol of kaempferol, 3mol of butylamine and 20mol of formaldehyde aqueous solution in 300mL of dioxane, reacting for 28h at 70 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing and drying to obtain a kaempferol-butylamine-based benzoxazine precursor, wherein the yield is 71.2%, and the kaempferol-butylamine-based benzoxazine precursor has a structure shown in the following formula:
and (3) carrying out step heating (140 ℃/2h, 150 ℃/2h, 160 ℃/2h and 170 ℃/2 h) on the kaempferol-butylamine-based benzoxazine precursor in a blast oven, and finally curing at 170 ℃ to obtain the kaempferol-butylamine-based benzoxazine resin. The vitrification transition of the resulting cured product was 345 ℃ C. d10 At 462 ℃, the bacteriostasis rate to escherichia coli is 92 percent, the killing rate to navicula is 91 percent, and the killing rate to triangle algae is 90 percent. Meanwhile, the prepared kaempferol-butylamine benzoxazine precursor is uniformly coated on a 304 stainless steel plate through a film coating machine after debubbling at 90 ℃ in a vacuum oven for performance test of the polybenzoxazine resin coating, and the solvent resistance (water, seawater, crude oil/water mixture) and high temperature resistant dipping performance (40-100 ℃) of the coating are tested according to NACETM-01-74 and ASTMC 868. Experiments show that the coating has outstanding anti-fouling performance and high-temperature-resistant impregnation performance and can be used for preparing a polybenzoxazine resin coating with marine anti-fouling performance.
Example 10
Dissolving 1mol of kaempferol, 3mol of furfuryl amine and 16mol of formaldehyde aqueous solution in 300mL of dioxane, reacting for 30h at 68 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing and drying to obtain a kaempferol-furfuryl amino benzoxazine precursor with the yield of 75.3%, wherein the kaempferol-furfuryl amino benzoxazine precursor has the following structure:
and (2) carrying out step heating on the kaempferol-furfurylaminobenzoxazine precursor in a forced air oven (at the temperature of 140-170 ℃, at the heating rate of 5 ℃/2 h), and finally curing at the temperature of 170 ℃ to obtain the kaempferol-furfurylaminobenzoxazine resin. The vitrification transition of the resulting cured product was 335 ℃ T d10 468 ℃, the bacteriostasis rate to colibacillus is 92 percent, the killing rate to navicula is 92 percent, and the killing rate to triangle algae is 90 percent. Meanwhile, the prepared kaempferol-furfuryl amino benzoxazine precursor is uniformly coated on a 304 stainless steel plate through a film coating machine after debubbling at 90 ℃ in a vacuum oven for performance test of the polybenzoxazine resin coating, and the solvent resistance (water, seawater, crude oil/water mixture) and high temperature resistant impregnation (40-100 ℃) of the coating are tested according to NACE TM-01-74 and ASTM C868. Experiments show that the coating has excellent anti-fouling performance and high-temperature-resistant impregnation performance, and can be used for preparing a polybenzoxazine resin coating with marine anti-fouling performance.
Example 11
Dissolving 1mol of quercetin, 5mol of propylamine and 36mol of formaldehyde aqueous solution in 250mL of dioxane, reacting for 42h at 70 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing with a water-methanol (10%) solution, and drying to obtain a quercetin-propylamino benzoxazine precursor, wherein the yield is 64.8%, and the structure of the quercetin-propylamino benzoxazine precursor is shown as the following formula:
and (3) carrying out step heating (140 ℃/2h, 150 ℃/2h, 160 ℃/2h and 170 ℃/2 h) on the quercetin-propylamine benzoxazine precursor in a blast oven, and finally curing at 170 ℃ to obtain the quercetin-propylamine benzoxazine resin. The vitrification transition of the cured product obtained is 322 ℃ T d10 At 438 deg.C, the bacteriostasis rate to colibacillus is 94%, and the killing rate to navicula algae93 percent and the killing rate to the triangle alga is 91 percent. Meanwhile, the prepared quercetin-propylamino benzoxazine precursor is uniformly coated on a 304 stainless steel plate through a film coating machine after being defoamed at 90 ℃ in a vacuum oven, is used for the performance test of a polybenzoxazine resin coating, and tests the solvent resistance (water, seawater, crude oil/water mixture) and the high-temperature resistant dipping performance (40-100 ℃) of the coating according to NACE TM-01-74 and ASTM C868. Experiments show that the coating has good anti-fouling performance and high-temperature-resistant impregnation performance, and can be used for preparing a polybenzoxazine resin coating with marine anti-fouling performance.
Example 12
Dissolving 1mol of isorhamnetin, 6mol of furfuryl amine and 24mol of formaldehyde aqueous solution in 250mL of dioxane, reacting for 72 hours at 70 ℃, performing reduced pressure rotary evaporation to remove the solvent, washing with a water-methanol (10%) solution, and drying to obtain an isorhamnetin-furfuryl amine benzoxazine precursor with a yield of 68.5%, wherein the isorhamnetin-furfuryl amine benzoxazine precursor has a structure shown in the following formula:
carrying out step heating (140-170 ℃, the heating rate is 5 ℃/2 h) on the isorhamnetin-furfuryl amino benzoxazine precursor in a forced air oven, and finally curing to 170 ℃ to obtain the isorhamnetin-furfuryl amino benzoxazine resin. The resulting cured product had a glass transition of 358 ℃ T d10 The temperature is 465 ℃, the bacteriostasis rate on colibacillus is 91 percent, the killing rate on navicula is 92 percent, and the killing rate on triangle alga is 91 percent. Meanwhile, the prepared isorhamnetin-furfuryl amine benzoxazine precursor is uniformly coated on a 304 stainless steel plate through a coating machine after being de-bubbled at 90 ℃ in a vacuum oven for performance test of the polybenzoxazine resin coating, and the solvent resistance (water, seawater, crude oil/water mixture) and the high temperature resistant dipping performance (40-100 ℃) of the coating are tested according to NACE TM-01-74 and ASTM C868. Experiments show that the coating has good anti-fouling performance and high-temperature-resistant dipping performance, and can be used for preparing polyphenyl with marine anti-fouling performanceAn oxazine resin coating.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A bio-based benzoxazine precursor, characterized in that it has the structure shown in formula (I):
wherein R is 1 Selected from H, C 6 H 5 、CH 3 OC 6 H 5 、
Any one of (1), R 2 Selected from H, OH, CH 3 O、CH 3 OC 6 H 5 And
any one of (1), R 3 Selected from H, OH and CH 3 Any one of O and R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
2. The bio-based benzoxazine precursor according to claim 1, wherein:
when R is 1 Selected from H, R 2 Is selected from CH 3 OC 6 H 5 ，R 3 Selected from H and/or CH 3 O and R are selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of the above;
and/or when R 1 Selected from H, R 2 Is selected from
R 3 Selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 5 And C 6 H 13 Any one of the above;
and/or when R 1 Selected from H, R 2 Is selected from
R 3 Is selected from CH 3 O, R are selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of the above;
and/or when R 2 Selected from H, R 1 Is selected from C 6 H 5 ，R 3 Selected from H and/or OH, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 、C 6 H 13 Any one of the above;
and/or when R 2 Selected from H, R 1 Is selected from
R 3 Is selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 5 、C 6 H 13 Any one of the above;
and/or when R 2 Selected from H, R 1 Is selected from
R 3 Selected from OH, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 、C 6 H 13 Any one of the above;
and/or when R 2 Selected from H, R 1 Is selected from
And/or
R 3 Is selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 、C 6 H 13 Any one of the above;
and/or when R 2 Selected from OH, R 1 Is selected from C 6 H 5 、CH 3 OC 6 H 5 、
Any one of (1), R 3 Selected from H, R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of them.
3. The method for producing a biobased benzoxazine precursor according to claim 1 or 2, characterized by comprising:
the method comprises the following steps of enabling a mixed reaction system containing natural flavonoid compounds, monoamine and formaldehyde to carry out Mannich reaction, and preparing the biobased benzoxazine precursor.
4. The method according to claim 3, comprising in particular: the mixed reaction system containing natural flavonoid compounds, monoamine and formaldehyde is subjected to Mannich reaction at 50-70 ℃ for 36-72 h to prepare the bio-based benzoxazine precursor.
5. The production method according to claim 3, characterized in that: the natural flavonoid compound comprises one or more of chrysin, genistein, apigenin, biochanin A, tectoridin, baicalein, scutellarein, luteolin, diosmetin, galangin, kaempferide, kaempferol, quercetin and isorhamnetin;
and/or the monoamine has a structure as shown in formula (II):
R-NH 2
(II)
wherein R is selected from C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 5 H 5 O、C 6 H 5 And C 6 H 13 Any one of the above;
and/or the monoamine comprises any one or the combination of more than two of ethylamine, propylamine, butylamine, pentylamine, hexylamine, aniline and furfurylamine; preferably, the monoamine comprises aniline and/or furfuryl amine.
6. The production method according to claim 3, characterized in that: the mol ratio of the natural flavonoid compound, the monoamine and the formaldehyde is 1: 2-6: 8-24.
7. Use of the bio-based benzoxazine precursor according to claim 1 or 2 in the preparation of a polybenzoxazine resin.
8. A method for preparing a polybenzoxazine resin, which is characterized by comprising the following steps:
providing a biobased benzoxazine precursor according to claim 1 or 2;
and heating and reacting the bio-based benzoxazine precursor at the temperature of 140-170 ℃ for 6-12 h to prepare the polybenzoxazine resin.
9. A polybenzoxazine resin prepared by the method of claim 8;
preferably, the bacteriostasis rate of the polybenzoxazine resin to escherichia coli is 91-97%;
preferably, the killing rate of the polybenzoxazine resin to navicula is 90-95%.
10. Use of the bio-based benzoxazine precursor according to claim 1 or 2 or the polybenzoxazine resin according to claim 9 for the preparation of a marine antibacterial and/or antifouling coating or a marine antibacterial and/or antifouling coating.
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