CN110028467B - Synthesis and application of urushiol analogue - Google Patents

Synthesis and application of urushiol analogue Download PDF

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CN110028467B
CN110028467B CN201810028158.8A CN201810028158A CN110028467B CN 110028467 B CN110028467 B CN 110028467B CN 201810028158 A CN201810028158 A CN 201810028158A CN 110028467 B CN110028467 B CN 110028467B
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urushiol
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analogue
vegetable oil
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CN110028467A (en
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张爱东
段江
卫增峰
涂海洋
马健祥
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Central China Normal University
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Abstract

The invention discloses synthesis and application of urushiol analogues, and belongs to the field of high-molecular functional materials. The invention relates to a method for synthesizing urushiol analogues by using Mannich reaction and vegetable oil, which comprises the following steps of: (1) aminolysis is carried out on the vegetable oil by secondary diamine, and then Mannich reaction is carried out on the vegetable oil, pyrocatechol and formaldehyde, so as to obtain amide urushiol analogues; (2) catechol, formaldehyde and secondary amine containing hydroxyl are used as raw materials, a 3-substituted catechol intermediate containing hydroxyl is obtained through Mannich reaction, and then the intermediate and carboxylic acid from vegetable oil are subjected to esterification reaction to obtain the ester urushiol analogue. The synthetic method has the advantages of cheap and easily-obtained raw materials, short synthetic route, high atom economic efficiency, easy separation and purification of products and the like. The synthesized urushiol analogue is cured into a film under the irradiation of ultraviolet light, and the film has excellent adhesive force, flexibility, thermal stability and corrosion resistance.

Description

Synthesis and application of urushiol analogue
Technical Field
The invention relates to a synthetic method and application of urushiol analogues, and belongs to the field of high-molecular functional materials.
Background
Raw lacquer is a natural and renewable resin extracted from the sap of lacquer trees, has more than 7000 years of application history in China, and is widely applied to the painting and protection of artworks, daily utensils and the like. Raw lacquer films have excellent properties of durability, hardness, solvent resistance, adhesion, etc., for example, some of the antique lacquers have been stored for thousands of years (polymer. rev.,2013,53, 153-191). It has been found that urushiol is a key film-forming substance in raw lacquer, the main component of which is a mixture of catechol derivatives containing different olefin chains in the 3-position. The 3-position different olefins are long chain mono-, di-and trienes with chain lengths of C15-C17. The special structure can generate multiple forms of crosslinking, and endows the paint film with various excellent properties.
The natural raw lacquer is obtained by collecting lacquer tree juice, the source is limited, and the price is high; in addition, the curing conditions of the raw lacquer are harsh, proper humidity and temperature are needed, and the curing time is long (chem.Rev.2016,116, 2307-2413). In order to overcome the above disadvantages and realize low-cost application of raw lacquer, the research on synthesis of urushiol analogues through chemical methods has attracted extensive attention. In order to achieve or approach the excellent coating properties of natural raw lacquer, the main structural design of urushiol analogs should include the following aspects: (1) the polymer contains a catechol skeleton, allows urushiol analogues to perform oxidation or free radical polymerization, and endows the polymer with important properties such as excellent adhesion, stain resistance and the like; (2) contains different olefin chain structures as polymerizable functional groups, and generates a highly crosslinked network structure through polymerization to obtain a highly stable coating; (3) the lengths of the different olefin chains are close, giving the coating good flexibility. For example, Dawson et al used 2, 3-dimethoxybenzaldehyde (o-veratraldehyde) to add to Grignard reagent, dehydrate, and catalytically hydrogenate to obtain urushiol (J.Med.chem.,1971,14, 729-; kobayashi et al uses 3, 4-dihydroxy phenylethanol or p-hydroxybenzyl alcohol as raw material, and makes them undergo the process of esterification reaction with oleic acid, linoleic acid and linolenic acid to obtain urushiol analogue with 4-substituted unsaturated alkyl chain (chem.Letter.2000,29, 1214-1215; chem.Letter.2000,29,1122-1123), and Zhou et al uses tung oil as raw material, makes it undergo the process of ester exchange to obtain unsaturated carboxylic ester, and makes it undergo the process of Friedel-crafts alkylation reaction with pyrocatechol to obtain urushiol analogue (Industrial Crops and Products,2016,94, 424-430). Most of the synthetic methods have harsh reaction conditions, expensive raw materials and limited sources, and the practical low-cost application of artificially synthesized raw lacquer cannot be realized.
Therefore, the key to overcome these problems is to build a fast, low-cost method for synthesizing urushiol analogs, which is of great significance for the practical low-cost application of artificially synthesized raw lacquer.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art, provide a method for synthesizing urushiol analogue which is rapid, low in cost and easy to expand, and provide a method for ultraviolet curing paint film by urushiol analogue. The invention utilizes Mannich reaction and vegetable oil to synthesize urushiol analogues, and the specific method comprises the following steps: (1) aminolysis is carried out on the vegetable oil by using secondary diamine, and further Mannich reaction is carried out on the secondary diamine, catechol and formaldehyde to obtain the amide vegetable oil-based urushiol analogue; (2) pyrocatechol, formaldehyde and secondary amine are used as raw materials, a 3-substituted pyrocatechol intermediate is obtained through Mannich reaction, and then the intermediate and carboxylic acid from vegetable oil are subjected to esterification reaction to obtain the ester urushiol analogue. The obtained urushiol analogue has photocuring property similar to that of natural raw lacquer, and is cured to form a film under ultraviolet irradiation, and the generated paint film has excellent thermal stability, corrosion resistance and the like.
The purpose of the invention is realized by the following technical scheme:
a synthetic method of urushiol analogues is to synthesize urushiol analogues by using Mannich reaction and vegetable oil, wherein the urushiol analogues comprise amide urushiol analogues and ester urushiol analogues.
The synthesis method of the amide urushiol analogue comprises the following steps: (1) carrying out ammonolysis reaction on the vegetable oil and secondary diamine to obtain a vegetable oil ammonolysis product; (2) the aminolysis product of the vegetable oil is subjected to Mannich reaction with catechol and formaldehyde to obtain the amide urushiol analogue. The secondary diamine is preferably piperazine or N, N '-methyl ethylenediamine, correspondingly, the obtained vegetable oil ammonolysis product is vegetable oleoyl piperazine I-1 or N-methyl-N-vegetable oleamide-N' -methyl ethylenediamine I-2, the amide urushiol analogue is UA-1 or UA-2, and the reaction formula is as follows:
Figure BDA0001545632080000021
the vegetable oil is unsaturated carboxylic glyceride, including soybean oil, perilla oil, tung oil, cottonseed oil, etc., preferably soybean oil.
In the ammonolysis reaction in the step (1), the feeding molar ratio of the raw material vegetable oil to the secondary diamine is 1: 2-1: 10, preferably 1: 5; the reaction solvent used includes 1, 4-dioxane, nitromethane, N-dimethylformamide, pyridine, etc., preferably 1, 4-dioxane.
In the Mannich reaction in the step (2), the feeding molar ratio of catechol to formaldehyde to vegetable oil ammonolysis products is 1.0-1.5: 1:1, preferably 1:1: 1; the reaction solvent used includes water, methanol, tetrahydrofuran, acetonitrile, a mixture of water and methanol, etc., preferably water; the reaction temperature is 5-60 ℃, and preferably 40 ℃.
Step (2) is preferably: adding the vegetable oil ammonolysis product into a formaldehyde aqueous solution, and reacting for 0.5-2 h; then adding triethylamine, pyrocatechol and N2And reacting for 2-6 h in an atmosphere.
The synthesis method of the amide urushiol analogue further comprises a product purification step: extracting a product generated by 2-3 times of reaction by using n-hexane; combining the organic phases, washing with dilute alkali solution (pH 7.5-8), and anhydrous Na2SO4Drying and concentrating; adding a proper amount of n-pentane, dispersing, standing, separating, and retaining the lower-layer oily substance to obtain the target compound.
The synthesis method of the ester urushiol analogue comprises the following steps:
(1) using catechol, formaldehyde and secondary amine containing hydroxyl as raw materials, and obtaining a 3-substituted catechol intermediate containing hydroxyl through Mannich reaction; (2) and carrying out esterification reaction on the intermediate and the vegetable oil unsaturated fatty acid mixture to obtain the ester urushiol analogue. The hydroxyl-containing secondary amine is preferably N- (2-hydroxyethyl) piperazine or N-methylethanolamine, correspondingly, the obtained intermediate is I-3 or I-4, the ester urushiol analogue is UE-1 or UE-2, and the reaction formula is as follows:
Figure BDA0001545632080000031
the vegetable oil unsaturated fatty acid mixture is a long alkyl chain fatty carboxylic acid containing a plurality of unsaturated bonds, is obtained by hydrolyzing and acidifying vegetable oil (including soybean oil, perilla oil, cottonseed oil and the like, preferably soybean oil), and is preferably hydrolyzed by NaOH ethanol solution (90%).
In the Mannich reaction in the step (1) for synthesizing the ester urushiol analogue, the feeding molar ratio of catechol, formaldehyde and secondary amine is 1.0-1.5: 1:1, preferably 1:1: 1; the reaction solvent used includes water, methanol, tetrahydrofuran, acetonitrile, a mixture of water and methanol, etc., preferably water; the reaction temperature is 10-60 ℃, and preferably 40 ℃.
Among them, step (1) is preferably: firstly, adding secondary amine into a formaldehyde water solution, and reacting for 0.5-2 h; then adding catechol, N2Reacting for 2-6 h in an atmosphere; adding dilute acid, adjusting the pH of the solution to 1-3, extracting with ethyl acetate or diethyl ether for 2-3 times, and keeping the water phase; and adding a dilute alkali solution, adjusting the pH value of the solution to 8-9, extracting for 3-5 times by using ethyl acetate, combining organic phases, drying, and desolventizing to obtain an intermediate.
The esterification reaction in the step (2) is carried out by adopting 1-10 times of equivalent of 4- (N, N-dimethylamino) pyridine (DMAP) and equivalent of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC-HCl). In the esterification reaction, the reaction solvent used includes tetrahydrofuran, acetonitrile, 1, 4-dioxane, etc., preferably 1, 4-dioxane; the reaction temperature is 40-80 ℃, and preferably 60 ℃; the reaction time is 8-12 h.
The synthesized urushiol analogue is used as a film forming substance, and a urushiol analogue photocuring film forming method is established, is used for curing and forming a film under ultraviolet irradiation, and comprises the following steps: preparing a xylene solution (with the solid content of 20-50%) from the urushiol analog, coating the xylene solution on the surface of a base material such as glass, a copper sheet, stainless steel and the like, and irradiating the xylene solution for 60-300 seconds under ultraviolet light to obtain a paint film. Wherein the thickness of the coating film is 1-50 μm; the ultraviolet light source adopts a high-pressure mercury lamp, the power is 2kW, the wavelength is 365nm, and the irradiation distance is 10 cm.
Compared with the prior art, the invention has the following advantages and effects:
the invention adopts cheap and easily obtained secondary diamine and vegetable oil as raw materials, and the amide urushiol analogue is synthesized through ammonolysis and Mannich reaction; mannich reaction and esterification reaction are adopted to obtain the ester urushiol analogue. The urushiol analogue has short synthetic route, high atom economic efficiency and easy separation and purification of products. The urushiol analogue can be cured into a film under the ultraviolet irradiation condition, and the film has excellent adhesive force, flexibility, thermal stability and corrosion resistance, and has similar properties with natural urushiol.
Drawings
FIG. 1 is a scanning electron micrograph of the surface and cross-section of a UV-curable film of urushiol analogs UA-1 and UE-1 of example 6; wherein A, B is a surface topography map of the UA-1 and UE-1 photocuring films, and C, D is a cross-sectional topography map of the UA-1 and UE-1 photocuring films.
FIG. 2 is a thermogravimetric analysis graph of UV-cured films of urushiol analogs UA-1(A) and UE-1(B) of example 6.
FIG. 3 is a graph of electrochemical polarization curves for the blank copper sheet (a) and the copper sheet modified with urushiol analog UA-1(b) and UE-1(c) photocured films of example 7.
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
EXAMPLE 1 Synthesis of intermediates I-1 and I-2
Synthesis of N-vegetable oleoyl piperazine (I-1): a250 mL round bottom flask was charged with soybean oil (26.4g, ca. 0.03mol), anhydrous piperazine (25.8g, 0.3mol), and 100mL of 1, 4-dioxane, dissolved by stirring, heated, refluxed for 24h, and checked for the end of the reaction by TLC. Removing the solvent 1.4-dioxane under reduced pressure, adding a proper amount of ethyl acetate to dissolve and disperse, washing for 3-4 times with salt water, removing the residual piperazine and glycerol generated in the reaction, drying the organic phase, concentrating to obtain light yellow oily substance, adding a proper amount of methanol to stir and disperse, standing and layering, taking supernatant, and concentrating to obtain an intermediate I-1 with the yield of 80%.
Synthesis of N-methyl-N-vegetable oleoyl-N' -methylethylenediamine (I-2): soybean oil (26.4g, about 0.03mol), N' -dimethylethylenediamine (26.4g, 0.3mol) and 100mL of 1, 4-dioxane were added to a 250mL round-bottomed flask, and dissolved by stirring, heated, refluxed for 24 hours, and the end point of the reaction was checked by TLC. Removing the solvent 1.4-dioxane under reduced pressure, adding a proper amount of ethyl acetate to dissolve and disperse, washing for 3-4 times by using salt water, removing the residual N, N' -dimethylethylenediamine and glycerin generated by the reaction, drying the organic phase, concentrating to obtain light yellow oily matter, adding a proper amount of methanol to stir and disperse, standing and layering, taking supernatant, and concentrating to obtain an intermediate I-2 with the yield of 71%.
I-1：1H NMR(600MHz,CDCl3)δ5.44–5.24(m,3H),3.61(s,2H),3.46(s,2H),2.98–2.68(m,5H),2.52(s,1H),2.33(dd,J＝15.3,7.4Hz,2H),2.13–1.93(m,4H),1.62(s,2H),1.48–1.15(m,14H),0.89(d,J＝5.0Hz,3H).ESI-MS(M+)350.42,348.16,346.78,324.19 (calculated 350.33,348.31,346.30,324.31).
I-2：1H NMR(600MHz,CDCl3)δ5.43–5.29(m,3H),3.75–3.37(m,5H),3.01(dd,J＝36.3,21.5Hz,2H),2.79(s,3H),2.48(d,J＝5.9Hz,1H),2.34(dd,J＝18.3,10.7Hz,4H),2.16–1.95(m,5H),1.62(d,J＝5.4Hz,2H),1.47–1.23(m,14H),0.89(t,J＝18Hz,3H).ESI-MS(M+)366.38,364.26,362.78,340.62 (calculated 366.36,364.35,362.33,340.36).
EXAMPLE 2 Synthesis of amide urushiol analogs UA-1 and UA-2
Synthesis of amide urushiol analog UA-1: adding the intermediate I-1(17.4g, about 0.05mol), formaldehyde (0.05mol, 37 wt% aqueous solution) and 50mL of distilled water into a 250mL round-bottom flask, and stirring at room temperature for 0.5-1 h; triethylamine (0.5g, 5mmol), catechol (5.5g, 0.05mol), N were added2The reaction was continued for 4h at 40 ℃ under ambient and the end of the reaction was monitored by TLC. After the reaction is finished, n-hexane is used for extracting the product for 2-3 times, organic phases are combined, and the organic phases are washed by dilute NaOH solution (pH is 7.5-8) and anhydrous Na2SO4Drying and concentrating to obtain yellow oily matter; adding 50mL of n-pentane, dispersing, standing, separating, and obtaining lower-layer oily matter, namely the amide urushiol analogue UA-1 with the yield of 60%.1H NMR(400MHz,CDCl3)δ9.33(s,1H),6.86(d,J＝7.9Hz,1H),6.71(t,J＝7.8Hz,1H),6.53(d,J＝7.5Hz,1H),5.35(dd,J＝12.2,6.3Hz,5H),3.73(s,2H),3.53(s,2H),3.30(dd,J＝7.1,5.5Hz,1H),2.77(t,J＝6.5Hz,2H),2.63–2.49(m,4H),2.36–2.30(m,2H),2.08–2.00(m,5H),1.63(d,J＝6.5Hz,4H),1.25(s,17H),0.89(dd,J＝8.5,4.6Hz,4H).ESI-MS(M+)472.13,470.35,468.38,446.79 (calculated 472.36,472.35,468.34,446.35).
Synthesis of amide urushiol analog UA-2: adding intermediate I-2(17.5g, about 0.05mol), formaldehyde (0.05mol, 37 wt% aqueous solution) and 50mL of distilled water into a 250mL round-bottom flask, and stirring at room temperature for 0.5-1 h; triethylamine (0.5g, 5mmol), catechol (5.5g, 0.05mol), N were added2The reaction was continued for 4h at 40 ℃ under ambient and the end of the reaction was monitored by TLC. After the reaction is finished, n-hexane is used for extracting the product for 2-3 times, organic phases are combined, and the organic phases are washed by dilute NaOH solution (pH is 7.5-8) and anhydrous Na2SO4Drying and concentrating to obtain yellow oily matter; adding 50mL of n-pentane, dispersing, standing, separating, and obtaining lower-layer oily matter, namely the amide urushiol analogue UA-2 with the yield of 56%.1H NMR(400MHz,CDCl3)δ6.90(d,J＝5.9Hz,1H),6.77(dd,J＝13.8,6.5Hz,1H),6.66(d,J＝7.9Hz,1H),5.54(s,1H),5.44–5.31(m,5H),2.99(d,J＝26.3Hz,5H),2.86–2.73(m,7H),2.18(t,J＝7.6Hz,3H),2.05(s,5H),1.62(s,3H),1.26(d,J＝6.7Hz,17H),0.88(s,3H).ESI-MS(M+)488.43,486.45,484.29,448.27 (calculated 488.36,486.35,484.37,448.37).
EXAMPLE 3 Synthesis of intermediates I-3 and I-4
Synthesizing a hydroxyl-containing 3-substituted catechol intermediate I-3: a250 mL round-bottom flask was charged with N- (2-hydroxyethyl) piperazine (6.50g, 0.05mol), formaldehyde solution (37 wt%, 0.05mol), 60mL distilled water, stirred at 25 ℃ for 1h, added with catechol solid (5.50g, 0.05mol), N2The temperature is raised to 40 ℃ under the atmosphere, the reaction is continued for 2h, and the end point of the reaction is monitored by TLC. Adding diluted hydrochloric acid (1mol/L) into the reaction solution, adjusting the pH value of the reaction solution to about 2, extracting and recovering the catechol raw material by using ethyl acetate, and keeping the water phase. Adding 2.0M NaOH solution to adjust the pH value of the water phase to about 8, extracting for 3-5 times by 100mL ethyl acetate, combining organic phases and anhydrous Na2SO4Drying, desolventizing to obtain intermediate I-3, and collectingThe rate was 81%.
Intermediate I-3:1H NMR(600MHz,CD3OD)δ6.71(d,J＝7.8Hz,1H),6.59(t,J＝7.7Hz,1H),6.48(d,J＝7.5Hz,1H),3.65(t,J＝5.9Hz,2H),3.61(s,2H),2.51(t,J＝5.9Hz,10H).13c NMR (151MHz, DMSO). delta.140.1(s), 139.9(s),116.8(s),114.8(s),114.1(s),109.7(s),55.1(s),54.8(s),53.6(s). HRMS (ESI-TOF):253.1555 (calculated [ C.sub.M. ], DMSO). delta.140.1(s), 139.9(s),116.8(s),114.8(s)13H20N2O3+H+]253.1547)。
Synthesizing a hydroxyl-containing 3-substituted catechol intermediate I-4: adding N-methylethanolamine (3.75g, 0.05mol), formaldehyde solution (37%, 0.05mol) and 60mL of distilled water into a 250mL round-bottom flask, stirring at 25 ℃ for 30 min-1 h, adding catechol solid (5.50g, 0.05mol) and N2The temperature is raised to 40 ℃ under the atmosphere, the reaction is continued for 2h, and the end point of the reaction is monitored by TLC. Adding diluted hydrochloric acid (1mol/L) into the reaction solution, adjusting the pH value of the reaction solution to about 2, extracting and recovering ethyl acetate to obtain catechol raw material, and retaining a water phase. Adding 2.0M NaOH solution to adjust the pH value of the water phase to about 8, extracting for 3-5 times by 100mL ethyl acetate, combining organic phases and anhydrous Na2SO4Drying and desolventizing to obtain the intermediate I-4 with the yield of 78 percent.
Intermediate I-4:1H NMR(600MHz,DMSO-d6)δ7.38(s,2H),6.65(d,J＝7.7Hz,1H),6.54(t,J＝7.6Hz,1H),6.49(d,J＝7.2Hz,1H),3.65(s,2H),3.56(t,J＝5.8Hz,2H),2.54(t,J＝5.8Hz,2H),2.22(s,3H).13c NMR (151MHz, DMSO-d6) delta 141.7(s),141.4(s),119.2(s),115.5(s),114.7(s),111.1(s),56.2(s),54.9(s),54.4(s) HRMS (ESI-TOF):198.1134 (calculated [ C.sub.M. ]10H15NO3+H+]197.1132)。
Example 4 preparation of Soybean oleic acid
A250 mL round-bottom flask was charged with 17.6g soybean oil (ca. 0.02mol), 100mL NaOH in 90% ethanol (NaOH 10.0g, 0.025mol), and the mixture was stirred in a nitrogen atmosphere2Heating and refluxing for 6h under protection. Cooling to room temperature, distilling under reduced pressure to remove ethanol, and adding concentrated hydrochloric acid (37%) to adjust the pH value of the system to about 2-3. Adding 100mL of petroleum ether to extract oleic acid obtained by hydrolysis, washing the petroleum ether phase with 100mL of brine for 2-3 times, removing salt and hydrolyzingProduced glycerol; organic phase anhydrous Na2SO4Drying and desolventizing to obtain the soybean oleic acid.
The oleic acid of the soybean oil is obtained,1H NMR(600MHz,CDCl3)δ9.94(s,3H),5.36(dd,J＝13.2,6.2Hz,3H),2.78(dd,J＝17.2,11.1Hz,1H),2.35(t,J＝7.3Hz,2H),2.21–1.93(m,5H),1.63(d,J＝6.6Hz,2H),1.29(d,J＝37.2Hz,16H),0.93(dt,J＝12.6,6.8Hz,3H).13C NMR(151MHz,cdcl3) δ 179.99(s),177.27(s),130.13(s),129.94(s),127.90(d, J ═ 25.2Hz),33.96(s),31.64(d, J ═ 57.4Hz), 30.38-28.56 (m),27.13(s),25.55(s),24.58(s),22.55(d, J ═ 16.4Hz),20.71(s),13.99(s), GC/MS, gas chromatography retention time: 11.27min,11.99min,12.35min,12.54min, ms spectrum: 256.32(11.27min, palmitic acid), 282.27(11.99min, oleic acid), 280.16(12.35min, linoleic acid), 278.41(12.54min, linolenic acid), composition (GC/MS): 15.90% (palmitic acid), 9.12% (oleic acid), 64.39% (linoleic acid), 9.59% (linolenic acid).
Example 5 Synthesis of ester urushiol analogs UE-1 and UE-2
Synthesizing ester urushiol analogue UE-1: soybean oleic acid (5.48g, 0.02mol) and 100mL of 1, 4-dioxane were added to a 250mL round bottom flask, 4- (N, N-dimethylamino) pyridine (0.25g, 2mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC-HCl, 3.8g, 0.02mol) were added under ice bath, the mixture was stirred at room temperature for 0.5 to 1 hour, I-3(5.08g, 0.02mol) was added, the reaction was continued at 60 ℃ for 8 hours, and the reaction end point was monitored by TLC. After the reaction is finished, the 1, 4-dioxane is removed by reduced pressure distillation, 100mL of ethyl acetate is added to dissolve and disperse the distillation residue, and 100mL of sodium chloride is used for washing the ethyl acetate phase for 2-3 times, and anhydrous Na2SO4Drying, desolventizing, adding a proper amount of n-pentane, dispersing, standing, separating, and keeping a lower-layer oily substance, namely urushiol analogue UE-1, with the yield of 80%.
Ester urushiol analog UE-1:1H NMR(400MHz,CDCl3)δ6.84(dd,J＝8.0,1.2Hz,1H),6.69(t,J＝7.8Hz,1H),6.53(d,J＝7.4Hz,1H),5.35(dd,J＝12.5,6.0Hz,4H),4.25–4.16(m,2H),3.72(s,2H),2.73(dt,J＝11.6,6.2Hz,10H),2.30(t,J＝7.6Hz,3H),2.05(dd,J＝13.5,6.6Hz,5H),1.62(d,J＝6.9Hz,2H),1.28(dd,J＝13.5,6.2Hz,28H),0.89–0.79(m,3H).ESI-MS(M+)530.13,528.25,526.07,490.19 (calculated 530.30,528.39,526.38,490.38).
Synthesizing ester urushiol analogue UE-2: soybean oleic acid (5.48g, 0.02mol) and 100mL of 1, 4-dioxane were added to a 250mL round bottom flask, 4- (N, N-dimethylamino) pyridine (0.25g, 2mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC-HCl, 3.8g, 0.02mol) were added under ice bath, the mixture was stirred at room temperature for 0.5 to 1 hour, I-4(3.94g, 0.02mol) was added, the reaction was continued at 60 ℃ for 8 hours, and the reaction end point was monitored by TLC. After the reaction is finished, the 1, 4-dioxane is removed by reduced pressure distillation, 100mL of ethyl acetate is added to dissolve and disperse the distillation residue, and 100mL of sodium chloride is used for washing the ethyl acetate phase for 2-3 times, and anhydrous Na2SO4Drying, desolventizing, adding a proper amount of n-pentane, dispersing, standing, separating liquid, and keeping a lower-layer oily substance, namely the urushiol analogue UE-2, with the yield of 78%.
Ester urushiol analog UE-2:1H NMR(400MHz,CDCl3)δ6.84(d,J＝7.9Hz,1H),6.69(t,J＝7.8Hz,1H),6.52(d,J＝7.5Hz,1H),5.45–5.27(m,2H),4.24(t,J＝5.3Hz,2H),3.74(s,2H),2.77(t,J＝5.3Hz,3H),2.36(d,J＝8.4Hz,5H),2.17–1.92(m,5H),1.62(d,J＝6.8Hz,2H),1.28(d,J＝22.6Hz,15H),0.92–0.84(m,2H).ESI-MS(M+)461.27,459.22,457.09,435.30 (calculated 461.35,459.33,457.32,435.33).
EXAMPLE 6 Photocurable and coating Properties of urushiol analog coatings
Mixing urushiol analogs (UA-1 and UE-1) with xylene respectively to prepare a solution with the mass fraction of 50%, uniformly coating the solution on a clean glass plate or a clean copper sheet, and testing the thickness of a paint film to be 40 mu m (a coating thickness gauge EC-700) after a solvent is volatilized; and irradiating for 180 seconds under ultraviolet light (the ultraviolet light source adopts a high-pressure mercury lamp, the power is 2kW, the wavelength is 365nm, and the irradiation distance is 10cm), so as to obtain the urushiol analogue ultraviolet curing film. Paint film property tests include hardness (pencil hardness test method), gel fraction (gel fraction ═ m'/m)0 X 100% (m' denotes the mass of the membrane dried after extraction with xylene, m0Initial mass of the membrane), thermal stability (thermogravimetric analysis, N2Atmosphere, temperature range: room temperature to 600 ℃, and fast temperature riseThe rate is 10 ℃/min), the appearance analysis of the paint film and the like.
The coating film begins to turn brown and become sticky in about 20 seconds under the irradiation of ultraviolet light, the hardness of the coating film is 4B in about 1min, the hardness is 2H after 3min, and the hardness is still 2H after 5 min. And (3) by SEM analysis (figure 1) of the coating film, the surface shows uniform micro-wrinkle appearance, and the cross section shows non-porous and uniform appearance. The gel fraction of the paint film increased with the increase of the light time, reaching 99.9% in about 3min (as shown in Table 1). After the UV irradiation is carried out for 3min, the gel rate of the cured films of the urushiol analogue UA-1 and the UE-1 is more than 99.9 percent. The thermal weight loss at 600 ℃ for the photocured UA-1 and UE-1 films was 54.2% and 59.5%, respectively (fig. 2). The synthetic urushiol analogs were shown to have similar photocuring properties to natural urushiol (ACS appl. mater. interfaces 2011,3, 482-.
TABLE 1 gelation Rate (%) of urushiol analog films as a function of time of illumination
Figure BDA0001545632080000081
EXAMPLE 7 anticorrosive Properties of photo-cured film of urushiol analog
Soaking the polished and cleaned copper sheet in urushiol analogue UA-1 and UE-1 ethanol solution (10mg/mL) for 30min, taking out, drying in the air, wherein the thickness of a paint film is 1 mu m, and irradiating for 3min under ultraviolet light (an ultraviolet light source adopts a high-pressure mercury lamp, the power is 2kW, the wavelength is 365nm, and the irradiation distance is 10cm) to obtain the copper sheet coated with the UA-1 and UE-1 photocuring film, and testing the corrosion behavior of the copper sheet in 3.5 wt% NaCl solution by adopting an electrochemical polarization method.
Electrochemical polarization of parameters such as corrosion potential (E)corr) Corrosion current (i)corr) And the like are obtained from Tafel curves, wherein the corrosion inhibition ratio (IE) and the Corrosion Rate (CR) are calculated by the following formulas:
Figure BDA0001545632080000091
Figure BDA0001545632080000092
in the formula i0Corrosion current of blank copper sheet, icorrCorrosion current of the copper sheet coated with the photocuring film; for copper, the constant K is 3.27 × 10-3mm/(μA·cm·a)，ρ＝8.96×103kg/m3，Ew31.77; wherein, muA is microampere of current unit, cm is centimeter of length unit, and a is year of time unit.
The electrochemical polarization data measured are shown in table 2 and fig. 3:
TABLE 2 corrosion data for the blank and finished copper sheets in 3.5 wt% NaCl solution (temperature 25. + -. 1 ℃ C.).
Figure BDA0001545632080000093
As can be seen from FIG. 3 and Table 2, the copper sheets coated with the urushiol analogues UA-1 and the UE-1 photo-cured film have greatly inhibited corrosion, show a corrosion inhibition rate of 99.3% or more, and the corrosion rate is reduced from 0.2840mm/a to about 0.0020 mm/a.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A method for synthesizing urushiol analogues is characterized by comprising the following steps: the method comprises the following steps of (1) utilizing Mannich reaction and vegetable oil to synthesize urushiol analogues, wherein the urushiol analogues comprise amide urushiol analogues and ester urushiol analogues;
the synthesis method of the amide urushiol analogue comprises the following steps:
(1) carrying out ammonolysis reaction on the vegetable oil and the dibasic secondary amine to obtain a vegetable oil ammonolysis product; the dibasic secondary amine is piperazine or N, N' -methyl ethylenediamine;
(2) the aminolysis product of vegetable oil is subjected to Mannich reaction with catechol and formaldehyde to obtain an amide urushiol analogue;
the synthesis method of the ester urushiol analogue comprises the following steps:
(1) using catechol, formaldehyde and secondary amine containing hydroxyl as raw materials, and obtaining a 3-substituted catechol intermediate containing hydroxyl through Mannich reaction; the secondary amine containing hydroxyl is N- (2-hydroxyethyl) piperazine or N-methylethanolamine;
(2) and carrying out esterification reaction on the intermediate and vegetable oil unsaturated fatty acid to obtain the ester urushiol analogue.
2. The method of synthesis according to claim 1, characterized in that: the synthetic method of the amide urushiol analogue comprises the step of synthesizing the amide urushiol analogue, wherein the vegetable oil is soybean oil, perilla oil, tung oil or cottonseed oil.
3. The method of synthesis according to claim 1, characterized in that: in the ammonolysis reaction in the step (1), the feeding molar ratio of the vegetable oil to the binary secondary amine is 1: 2-1: 10; the adopted reaction solvent is 1, 4-dioxane, nitromethane, N-dimethylformamide or pyridine.
4. The method of synthesis according to claim 2, characterized in that: in the Mannich reaction in the step (2), the feeding molar ratio of catechol, formaldehyde and vegetable oil ammonolysis products is 1.0-1.5: 1: 1; the adopted reaction solvent is water, methanol, tetrahydrofuran, acetonitrile or a mixture of water and methanol; the reaction temperature is 5-60 ℃.
5. The method of synthesis according to claim 1, characterized in that: in the Mannich reaction in the step (1), the feeding molar ratio of catechol, formaldehyde and secondary amine is 1.0-1.5: 1: 1; the adopted reaction solvent is water, methanol, tetrahydrofuran, acetonitrile or a mixture of water and methanol; the reaction temperature is 10-60 ℃.
6. The method of synthesis according to claim 1, characterized in that: the ester urushiol analogue synthesis method comprises the steps that 4- (N, N-dimethylamino) pyridine and 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride are adopted in esterification reaction in the step (2); in the esterification reaction, the adopted reaction solvent is tetrahydrofuran, acetonitrile or 1, 4-dioxane; the reaction temperature is 40-80 ℃; the reaction time is 8-12 h.
7. A method for photocuring lacquer phenol analogue into film, which is characterized by comprising the following steps: the method comprises the following steps: the urushiol analog prepared by the method according to any one of claims 1 to 6, wherein the urushiol analog is prepared into a xylene solution, and the xylene solution is coated on the surface of the substrate and cured under the irradiation of ultraviolet light for 60 to 300 seconds.
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