CN114479034A - High-temperature-resistant ferulic acid-based unsaturated resin and preparation method thereof - Google Patents
High-temperature-resistant ferulic acid-based unsaturated resin 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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Abstract
The invention discloses a high-temperature-resistant ferulic acid group unsaturated resin and a preparation method thereof, relating to the technical field of high polymer materials. The invention firstly utilizes 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine and p-isocyanato-phenyl acrylic acid to modify ferulic acid to prepare modified ferulic acid with stronger oxidation resistance and low viscosity; then processing the modified ferulic acid by using an ultrasonic-assisted microwave swelling process to obtain ferulic acid-based unsaturated resin; and then, carrying out electric field induction assisted magnetron sputtering process treatment on the ferulic acid group unsaturated resin by utilizing copper cyanide, wherein the steric hindrance of the ferulic acid group unsaturated resin is small, and a benzimidazole compound and a metal phthalocyanine compound with multi-conjugate structures are more easily formed, so that the high-temperature resistant and corrosion resistant ferulic acid group unsaturated resin with strong high temperature resistance is prepared. The high-temperature resistant ferulic acid group unsaturated resin prepared by the invention has low viscosity and good oxidation resistance, high temperature resistance and corrosion resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to high-temperature-resistant ferulic acid-based unsaturated resin and a preparation method thereof.
Background
The unsaturated polyester resin, which is used as the resin with the largest usage amount of the reinforced fiber matrix, has good machinability, heat resistance, chemical corrosion resistance and excellent conductivity, is widely applied to the living fields of transportation, buildings, coatings, electronic and electric appliances and the like, and is an indispensable high polymer material.
The unsaturated polyester resin product sold in the market at present is mainly synthesized by petrochemical products, contains two main components of unsaturated polyester and diluent ethylene monomers, and the raw materials for industrially preparing the unsaturated polyester at present are usually synthesized by aromatic saturated dibasic acid/anhydride, saturated dibasic alcohol and unsaturated dibasic acid/anhydride, but the raw materials are mostly prepared by extracting petroleum resources. However, in recent years, the problems of large shortage of petroleum resources and environmental pollution have become serious, and the yield of unsaturated polyester resin products has been drastically reduced. The ferulic acid is widely available, renewable and high in safety and is explored by the industry and academia to prepare the unsaturated polyester resin, but the unsaturated polyester resin prepared from the ferulic acid has high viscosity and poor corrosion resistance, oxidation resistance and high temperature resistance, and the wide application of the ferulic acid in the field of high polymer materials is greatly limited.
The present invention focuses on such problems and solves them by preparing high temperature resistant ferulic acid based unsaturated resins.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant ferulic acid-based unsaturated resin and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the high-temperature-resistant ferulic acid-based unsaturated resin is prepared by the following steps of carrying out electric field induction assisted magnetron sputtering on modified ferulic acid by utilizing copper cyanide and then carrying out an electric treatment process to obtain the high-temperature-resistant ferulic acid-based unsaturated resin.
Further, the modified ferulic acid is prepared from 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine, p-isocyanate phenyl acrylic acid and ferulic acid.
Further, the high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following components in parts by weight: 50-60 parts of modified ferulic acid and 38-50 parts of copper cyanide.
Further, the preparation method of the high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following preparation steps:
(1) modifying ferulic acid by using 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine and p-isocyanato-phenyl acrylic acid to obtain modified ferulic acid;
(2) treating the modified ferulic acid by using an ultrasonic-assisted microwave swelling process to obtain ferulic acid-based unsaturated resin;
(3) the copper cyanide is used for carrying out electric field induction assisted magnetron sputtering technology on the ferulic acid group unsaturated resin to prepare the high-temperature resistant ferulic acid group unsaturated resin.
Further, the preparation method of the high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following preparation steps:
(1) placing the ferulic acid mixed solution in an oil bath pot at 70-80 ℃, dripping a p-isocyanate phenyl acrylic acid mixed solution with the mass of 0.8-1.2 times that of the ferulic acid mixed solution at 120-140 drops/min, stirring and refluxing for 3-4 h at 180-220 r/min, heating to 80-90 ℃ at 1-3 ℃/min, dripping 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine with the mass of 1.2-1.4 times that of the ferulic acid mixed solution at 60-80 drops/min, stirring and refluxing for 2-3 h at 160-180 r/min, naturally cooling to room temperature, placing in a rotary evaporator at 58-62 ℃, and rotationally steaming for 45-55 min at 120-160 r/min under the condition of 10-20 Pa to obtain modified ferulic acid;
(2) ultrasonically treating the modified ferulic acid mixed solution for 15-25 min at 20-30 kHz under the conditions of 2250-2350 MHz and 800-900W microwaves, naturally cooling to room temperature, putting into a rotary evaporator at 78-82 ℃, and rotationally evaporating for 45-55 min at 120-160 r/min under the condition of 10-20 Pa to obtain ferulic acid-based unsaturated resin;
(3) under the conditions of magnetron sputtering power of 60-80W and argon protection of 1-2 Pa, putting the ferulic acid group unsaturated resin into a magnetron sputtering device as a base material, and sputtering for 2-3 h by using a copper cyanide solution with the mass of 3-5 times of that of the ferulic acid group unsaturated resin as a target material to obtain the ferulic acid group unsaturated resin after magnetron sputtering; and under the conditions of 108-112 ℃, 10-14V, 8-12A and argon protection, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath for electric treatment for 28-32 min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin.
Further, the preparation method of the ferulic acid mixture in the step (1) is as follows: at the temperature of 25-26 ℃, mixing ferulic acid and dimethylformamide according to the mass ratio of 1: 2.5-1: 2.7, stirring at 240-260 r/min for 40-60 min to obtain ferulic acid mixed solution.
Further, the preparation method of the p-isocyanato phenyl acrylic acid mixed liquor in the step (1) is as follows: at the temperature of 25-26 ℃, mixing p-isocyanate phenyl acrylic acid, triethylamine and concentrated sulfuric acid with the mass fraction of 96-98% according to the mass ratio of 1: 1: 0.002 to 1: 1.1: 0.004, and stirring for 40-50 min at a speed of 180-220 r/min to obtain a p-isocyanate phenyl acrylic acid mixed solution.
Further, the preparation method of the modified ferulic acid mixture in the step (2) is as follows: at the temperature of 25-26 ℃, mixing the modified ferulic acid and benzene according to a mass ratio of 1: 0.6-1: 0.8, stirring for 10-20 min at 240-260 r/min to obtain a modified ferulic acid mixed solution.
Further, the preparation method of the copper cyanide solution in the step (3) is as follows: at the temperature of 25-26 ℃, copper cyanide and ethanol are mixed according to the mass ratio of 1: 3-1: 5, mixing, and stirring for 20-30 min at a speed of 180-220 r/min to obtain the copper cyanide solution.
Further, the anode electrode of the electrolytic cell in the step (3) is a copper electrode, the cathode electrode is a reticular glassy carbon electrode, and the polar distance is 4-4.5 cm.
Compared with the prior art, the invention has the following beneficial effects:
firstly, preparing modified ferulic acid by using 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine, p-isocyanate phenyl acrylic acid and ferulic acid; processing the modified ferulic acid by using an ultrasonic-assisted microwave swelling process to obtain ferulic acid-based unsaturated resin; and finally, carrying out electric field induction assisted magnetron sputtering technology on the ferulic acid group unsaturated resin by using copper cyanide to prepare the high-temperature resistant ferulic acid group unsaturated resin.
Firstly, preparing modified ferulic acid by using 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine, p-isocyanate phenyl acrylic acid and ferulic acid, performing alkylation reaction on carbon-carbon double bonds of the isocyanate phenyl acrylic acid and the ferulic acid to form covalent bond crosslinking, stably grafting the p-isocyanate phenyl acrylic acid on the ortho position of phenolic hydroxyl groups of the ferulic acid, and forming steric hindrance around the phenolic hydroxyl groups, so that hydrogen atoms of the phenolic hydroxyl groups are easy to fall off and are combined with free radicals to make the free radicals lose activity, and the antioxidant property of the modified ferulic acid is enhanced; the bromopropenyl of the 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine and the benzene ring of the ferulic acid are subjected to nucleophilic substitution reaction, the 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine is stably grafted on the ferulic acid by a covalent bond, the isocyanate group of the isocyanate group phenyl acrylic acid and the amino group of the p-phenylenediamine are reacted to form covalent bond crosslinking, a polyurea compound is generated, and the modified ferulic acid with a hyperbranched structure is formed, so that the viscosity of the high-temperature resistant ferulic acid group unsaturated resin is reduced.
Secondly, processing the modified ferulic acid by an ultrasonic-assisted microwave swelling process to obtain ferulic acid-based unsaturated resin, reducing methoxyl in the modified ferulic acid to form phenolic hydroxyl, esterifying the phenolic hydroxyl and carboxyl to form a polyester compound, forming an interpenetrating network structure with high crosslinking density by the polyester compound and a polyurea compound, and arranging ureido molecular chains in an oriented manner, so that bromine atoms of 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine are exposed on the surface of the interpenetrating network structure, and the interior of the modified ferulic acid is rapidly expanded, so that the steric hindrance around the ureido molecular chains is reduced; then, copper cyanide is used for carrying out electric field induction assisted magnetron sputtering on the ferulic acid group unsaturated resin to prepare the high-temperature resistant ferulic acid group unsaturated resin, a ureido molecular chain with smaller steric resistance in the ferulic acid group unsaturated resin is oxidized to generate a nitrogen center free radical, the nitrogen center free radical is easier to generate an internal amination reaction with a benzene ring, and a benzimidazole compound with a multi-conjugate structure is eliminated through addition, so that the high-temperature resistance of the high-temperature resistant ferulic acid group unsaturated resin is enhanced; copper cyanide dissociates copper ions and cyanide ions in ferulic acid group unsaturated resin, the cyanide ions substitute bromine atoms of the ferulic acid group unsaturated resin to form a phthalonitrile compound, cyano groups in the phthalonitrile compound polymerize to form a phthalocyanine group compound, the phthalocyanine group compound quickly captures free copper ions to form a stable coordination bond to form a photosensitive metal phthalocyanine group compound, and the corrosion resistance of the high-temperature resistant ferulic acid group unsaturated resin is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided to illustrate the method for testing each index of the high temperature resistant ferulic acid group unsaturated resin prepared in the following examples as follows:
viscosity: the viscosity of the high temperature resistant ferulic acid group unsaturated resin prepared by the same mass of the examples and the comparative examples is tested according to the GB/T7193.1 standard method.
High temperature resistance: the high temperature resistance of the high temperature resistant ferulic acid group unsaturated resin prepared by taking the same mass of the examples and the comparative example is determined by testing the glass transition temperature according to the GB/T19466 standard method.
Corrosion resistance: at 60 ℃, putting two parts of high-temperature resistant ferulic acid group unsaturated resin prepared in the embodiment and the comparative example with the same mass into a mould with the same length, width and thickness for curing for 14h, testing the tensile strength of one part of the cured high-temperature resistant ferulic acid group unsaturated resin according to the GB/T2568 standard method, putting the other part of the cured high-temperature resistant ferulic acid group unsaturated resin into a sulfuric acid solution with 10 mass percent of 10 mass times of the mass of the high-temperature resistant ferulic acid group unsaturated resin for soaking for 4 days, taking out, washing for 5 times by deionized water, putting into a 25 ℃ oven for baking for 12h to obtain the high-temperature resistant ferulic acid group unsaturated resin after acid etching, testing the tensile strength of the high-temperature resistant ferulic acid group unsaturated resin after acid etching according to the GB/T2568 standard method, and testing the corrosion rate (the tensile strength of the high-temperature resistant ferulic acid group unsaturated resin-the tensile strength of the high-temperature resistant ferulic acid group unsaturated resin after acid etching) to be 100%/the high-temperature resistant ferulic acid group unsaturated resin Tensile strength of the resin.
Oxidation resistance: at 60 ℃, putting two parts of high temperature resistant ferulic acid group unsaturated resin prepared in the embodiment and the comparative example with the same mass into a mould with the same length, width and thickness for curing for 14h, testing the tensile strength of one part of the cured high temperature resistant ferulic acid group unsaturated resin according to the GB/T2568 standard method, putting the other part of the cured high temperature resistant ferulic acid group unsaturated resin into a hydrogen peroxide solution with the mass fraction of 2 percent and the mass ratio of 10 times of that of the high temperature resistant ferulic acid group unsaturated resin at 45 ℃ for soaking for 72h, taking out, washing with deionized water for 5 times, putting into a baking oven with the temperature of 25 ℃ for 12h to obtain the oxidized high temperature resistant ferulic acid group unsaturated resin, testing the tensile strength of the oxidized high temperature resistant ferulic acid group unsaturated resin according to the GB/T2568 standard method, and testing the oxidation resistance (the tensile strength of the high temperature resistant ferulic acid group unsaturated resin-the tensile strength of the oxidized high temperature resistant ferulic acid group unsaturated resin) 100%/the high temperature resistant arabino unsaturated resin Tensile strength of the ferulic acid group unsaturated resin.
Example 1
A high-temperature resistant ferulic acid group unsaturated resin mainly comprises 50 parts of modified ferulic acid and 38 parts of copper cyanide in parts by weight.
A preparation method of high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following preparation steps:
(1) at 25 ℃, ferulic acid and dimethylformamide are mixed according to the mass ratio of 1: 2.5, stirring at 240r/min for 40min to obtain ferulic acid mixed solution; at 25 ℃, p-isocyanate phenyl acrylic acid, triethylamine and concentrated sulfuric acid with the mass fraction of 96% are mixed according to the mass ratio of 1: 1: 0.002, stirring at 180r/min for 40min to obtain p-isocyanato phenyl acrylic acid mixed liquor; placing the ferulic acid mixed solution in a 70 ℃ oil bath pot, dripping 120 drops/min of p-isocyanate phenyl acrylic acid mixed solution with the mass 0.8 time of that of the ferulic acid mixed solution, stirring and refluxing for 3h at 180r/min, heating to 80 ℃ at 1 ℃/min, dripping 60 drops/min of 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine with the mass 1.2 times of that of the ferulic acid mixed solution, stirring and refluxing for 2h at 160r/min, naturally cooling to room temperature, placing in a 58 ℃ rotary evaporator, and rotationally evaporating for 45min at 120r/min under the condition of 10Pa to obtain modified ferulic acid;
(2) at the temperature of 25 ℃, mixing the modified ferulic acid and benzene according to the mass ratio of 1: 0.6, stirring for 10min at 240r/min to obtain a modified ferulic acid mixed solution; performing ultrasonic treatment on the modified ferulic acid mixed solution at 20kHz for 15min under 2250MHz and 800W microwave conditions, naturally cooling to room temperature, placing in a rotary evaporator at 78 ℃, and performing rotary evaporation at 120r/min for 45min under 10Pa to obtain ferulic acid group unsaturated resin;
(3) at 25 ℃, copper cyanide and ethanol are mixed according to a mass ratio of 1: 3, mixing and stirring at 180r/min for 20min to obtain a copper cyanide solution; under the protection conditions of magnetron sputtering power of 60W and 1Pa and argon gas, putting the ferulic acid group unsaturated resin into a magnetron sputtering device, and sputtering for 2h by using a copper cyanide solution with the mass of 3 times of that of the ferulic acid group unsaturated resin to obtain the ferulic acid group unsaturated resin after magnetron sputtering; under the conditions of 108 ℃, 10V, 8A and argon protection, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath with an anode electrode being a copper electrode and a cathode electrode being a reticular glassy carbon electrode and a polar distance of 4cm for electric treatment for 28min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin.
Example 2
A high-temperature resistant ferulic acid group unsaturated resin mainly comprises 55 parts of modified ferulic acid and 44 parts of copper cyanide in parts by weight.
A preparation method of high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following preparation steps:
(1) at 25.5 ℃, ferulic acid and dimethylformamide are mixed according to the mass ratio of 1: 2.6, mixing, and stirring for 50min at the speed of 250r/min to obtain ferulic acid mixed liquor; at 25.5 ℃, p-isocyanato phenyl acrylic acid, triethylamine and concentrated sulfuric acid with the mass fraction of 97 percent are mixed according to the mass ratio of 1: 1: 0.003 mixing, stirring for 45min at 200r/min to obtain a p-isocyanato phenyl acrylic acid mixed solution; placing the ferulic acid mixed solution in a 75 ℃ oil bath pot, dripping a p-isocyanate phenyl acrylic acid mixed solution with the mass 1 time of that of the ferulic acid mixed solution at a rate of 130 drops/min, stirring and refluxing for 3.5h at a rate of 200r/min, heating to 85 ℃ at a rate of 2 ℃/min, dripping 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine with the mass 1.3 times of that of the ferulic acid mixed solution at a rate of 70 drops/min, stirring and refluxing for 2.5h at a rate of 170r/min, naturally cooling to room temperature, placing in a 60 ℃ rotary evaporator, and rotationally evaporating for 50min at a rate of 140r/min under the condition of 15Pa to obtain modified ferulic acid;
(2) at the temperature of 25.5 ℃, mixing the modified ferulic acid and benzene according to the mass ratio of 1: 0.7, stirring for 15min at the speed of 250r/min to obtain a modified ferulic acid mixed solution; performing ultrasonic treatment on the modified ferulic acid mixed solution at 25kHz for 20min under the microwave condition of 2300MHz and 850W, naturally cooling to room temperature, placing in a rotary evaporator at 80 ℃, and performing rotary evaporation at 140r/min for 50min under the condition of 15Pa to obtain ferulic acid group unsaturated resin;
(3) at 25.5 ℃, copper cyanide and ethanol are mixed according to a mass ratio of 1: 4, mixing, and stirring at 200r/min for 25min to obtain a copper cyanide solution; under the protection conditions of magnetron sputtering power of 70W and 1.5Pa and argon gas, putting the ferulic acid group unsaturated resin into a magnetron sputtering device, and sputtering for 2.5h by using a copper cyanide solution 4 times the mass of the ferulic acid group unsaturated resin to obtain the ferulic acid group unsaturated resin after magnetron sputtering; under the conditions of 110 ℃, 12V, 10A and argon protection, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath with an anode electrode being a copper electrode, a cathode electrode being a reticular glassy carbon electrode and a polar distance of 4.25cm for electric treatment for 30min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin.
Example 3
A high-temperature resistant ferulic acid group unsaturated resin mainly comprises 60 parts of modified ferulic acid and 50 parts of copper cyanide in parts by weight.
A preparation method of high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following preparation steps:
(1) at 26 ℃, ferulic acid and dimethylformamide are mixed according to the mass ratio of 1: 2.7, stirring for 60min at the speed of 260r/min to obtain ferulic acid mixed liquor; at 26 ℃, p-isocyanate phenyl acrylic acid, triethylamine and concentrated sulfuric acid with the mass fraction of 98 percent are mixed according to the mass ratio of 1: 1.1: 0.004, stirring for 50min at the speed of 220r/min to obtain a p-isocyanate phenyl acrylic acid mixed solution; placing the ferulic acid mixed solution in an oil bath pot at 80 ℃, dripping a p-isocyanate phenyl acrylic acid mixed solution with the mass of 1.2 times of that of the ferulic acid mixed solution at 140 drops/min, stirring and refluxing for 4h at 220r/min, heating to 90 ℃ at 3 ℃/min, dripping 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine with the mass of 1.4 times of that of the ferulic acid mixed solution at 80 drops/min, stirring and refluxing for 3h at 180r/min, naturally cooling to room temperature, placing in a rotary evaporator at 62 ℃, and rotationally evaporating for 55min at 160r/min under the condition of 20Pa to obtain modified ferulic acid;
(2) at 26 ℃, mixing the modified ferulic acid and benzene according to a mass ratio of 1: 0.8, stirring for 20min at the speed of 260r/min to obtain a modified ferulic acid mixed solution; ultrasonically treating the modified ferulic acid mixed solution at 30kHz for 25min under the conditions of 2350MHz and 900W microwaves, naturally cooling to room temperature, putting into a rotary evaporator at 82 ℃, and rotationally evaporating at 160r/min for 55min under the condition of 20Pa to obtain ferulic acid-based unsaturated resin;
(3) at 26 ℃, copper cyanide and ethanol are mixed according to a mass ratio of 1: 5, mixing, and stirring for 30min at 220r/min to obtain a copper cyanide solution; under the protection of magnetron sputtering power of 80W and 2Pa and argon, putting the ferulic acid group unsaturated resin into a magnetron sputtering device, and sputtering for 3h by using a copper cyanide solution with the mass of 5 times of that of the ferulic acid group unsaturated resin to obtain the ferulic acid group unsaturated resin after magnetron sputtering; under the protection conditions of 112 ℃, 14V, 12A and argon, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath with an anode electrode being a copper electrode and a cathode electrode being a reticular glassy carbon electrode and a polar distance of 4.5cm for carrying out electric treatment for 32min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin.
Comparative example 1
A high temperature resistant ferulic acid group unsaturated resin mainly comprises 55 parts of ferulic acid and 44 parts of copper cyanide by weight.
A preparation method of high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following preparation steps:
(1) at the temperature of 25.5 ℃, ferulic acid and benzene are mixed according to the mass ratio of 1: 0.7, stirring for 15min at the speed of 250r/min to obtain ferulic acid mixed liquor; performing ultrasonic treatment on the ferulic acid mixed solution at 25kHz for 20min under the microwave condition of 2300MHz and 850W, naturally cooling to room temperature, placing in a rotary evaporator at 80 ℃, and performing rotary evaporation at 140r/min for 50min under the condition of 15Pa to obtain ferulic acid group unsaturated resin;
(2) at 25.5 ℃, copper cyanide and ethanol are mixed according to a mass ratio of 1: 4, mixing, and stirring at 200r/min for 25min to obtain a copper cyanide solution; under the protection conditions of magnetron sputtering power of 70W and 1.5Pa and argon gas, putting the ferulic acid group unsaturated resin into a magnetron sputtering device, and sputtering for 2.5h by using a copper cyanide solution 4 times the mass of the ferulic acid group unsaturated resin to obtain the ferulic acid group unsaturated resin after magnetron sputtering; under the conditions of 110 ℃, 12V, 10A and argon protection, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath with an anode electrode being a copper electrode, a cathode electrode being a reticular glassy carbon electrode and a polar distance of 4.25cm for electric treatment for 30min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin.
Comparative example 2
Comparative example 2 was formulated in the same manner as in example 2. The preparation method of the high-temperature resistant ferulic acid group unsaturated resin is different from the preparation method of the example 2 only in the difference of the step (1), and the step (1) is modified as follows: at 25.5 ℃, ferulic acid and dimethylformamide are mixed according to the mass ratio of 1: 2.6, mixing, and stirring for 50min at the speed of 250r/min to obtain ferulic acid mixed liquor; at 25.5 ℃, p-isocyanato phenyl acrylic acid, triethylamine and concentrated sulfuric acid with the mass fraction of 97 percent are mixed according to the mass ratio of 1: 1: 0.003 mixing, stirring for 45min at 200r/min to obtain a p-isocyanato phenyl acrylic acid mixed solution; placing the ferulic acid mixed solution in a 75 ℃ oil bath pot, dripping a p-isocyanate phenyl acrylic acid mixed solution with the mass of 1 time of the ferulic acid mixed solution at a rate of 130 drops/min, stirring and refluxing for 3.5h at a rate of 200r/min, naturally cooling to room temperature, placing in a rotary evaporator at 60 ℃, and rotationally evaporating for 50min at a rate of 140r/min under the condition of 15Pa to obtain the modified ferulic acid. The rest of the preparation steps are the same as example 2.
Comparative example 3
A high-temperature resistant ferulic acid group unsaturated resin mainly comprises 55 parts of modified ferulic acid and 44 parts of copper cyanide in parts by weight.
A preparation method of high-temperature resistant ferulic acid group unsaturated resin mainly comprises the following preparation steps:
(1) at 25.5 ℃, ferulic acid and dimethylformamide are mixed according to the mass ratio of 1: 2.6, mixing, and stirring for 50min at the speed of 250r/min to obtain ferulic acid mixed liquor; at 25.5 ℃, p-isocyanato phenyl acrylic acid, triethylamine and concentrated sulfuric acid with the mass fraction of 97 percent are mixed according to the mass ratio of 1: 1: 0.003 mixing, stirring for 45min at 200r/min to obtain a p-isocyanato phenyl acrylic acid mixed solution; placing the ferulic acid mixed solution in a 75 ℃ oil bath pot, dripping a p-isocyanate phenyl acrylic acid mixed solution with the mass 1 time of that of the ferulic acid mixed solution at a rate of 130 drops/min, stirring and refluxing for 3.5h at a rate of 200r/min, heating to 85 ℃ at a rate of 2 ℃/min, dripping 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine with the mass 1.3 times of that of the ferulic acid mixed solution at a rate of 70 drops/min, stirring and refluxing for 2.5h at a rate of 170r/min, naturally cooling to room temperature, placing in a 60 ℃ rotary evaporator, and rotationally evaporating for 50min at a rate of 140r/min under the condition of 15Pa to obtain modified ferulic acid;
(2) at 25.5 ℃, copper cyanide and ethanol are mixed according to a mass ratio of 1: 4, mixing, and stirring at 200r/min for 25min to obtain a copper cyanide solution; under the protection conditions of magnetron sputtering power of 70W and 1.5Pa and argon gas, putting the ferulic acid group unsaturated resin into a magnetron sputtering device, and sputtering for 2.5h by using a copper cyanide solution 4 times the mass of the ferulic acid group unsaturated resin to obtain the ferulic acid group unsaturated resin after magnetron sputtering; under the conditions of 110 ℃, 12V, 10A and argon protection, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath with an anode electrode being a copper electrode, a cathode electrode being a reticular glassy carbon electrode and a polar distance of 4.25cm for electric treatment for 30min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin.
Comparative example 4
The formulation composition of comparative example 4 mainly included: 55 parts of modified ferulic acid. The preparation method of the high-temperature resistant ferulic acid group unsaturated resin is only different from the preparation method of the example 2 in the step (3), and the step (3) is modified as follows: under the conditions of 110 ℃, 12V, 10A and argon protection, the ferulic acid group unsaturated resin is put into an electrolytic bath with a positive electrode of a copper electrode and a negative electrode of a reticular glassy carbon electrode and a polar distance of 4.25cm for electric treatment for 30min, and is naturally cooled to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin. The rest of the preparation steps are the same as example 2.
Comparative example 5
Comparative example 5 was formulated as in example 2. The preparation method of the high-temperature resistant ferulic acid group unsaturated resin is only different from the preparation method of the example 2 in the step (3), and the step (3) is modified as follows: at 25.5 ℃, copper cyanide and ethanol are mixed according to a mass ratio of 1: 4, mixing, and stirring at 200r/min for 25min to obtain a copper cyanide solution; under the conditions of magnetron sputtering power of 70W and 1.5Pa and argon protection, the ferulic acid group unsaturated resin is put into a magnetron sputtering device, and copper cyanide solution with the mass 4 times of that of the ferulic acid group unsaturated resin is used for sputtering for 2.5h to obtain the high-temperature resistant ferulic acid group unsaturated resin. The rest of the preparation steps are the same as example 2.
Comparative example 6
The formulation composition of comparative example 6 mainly included: 55 parts of modified ferulic acid and 44 parts of copper powder. The preparation method of the high-temperature resistant ferulic acid group unsaturated resin is only different from the preparation method of the example 2 in the step (3), and the step (3) is modified as follows: under the conditions of magnetron sputtering power of 70W and protection of 1.5Pa and argon, putting the ferulic acid group unsaturated resin into a magnetron sputtering device, and sputtering for 2.5h by using copper powder 4 times the mass of the ferulic acid group unsaturated resin to obtain the ferulic acid group unsaturated resin after magnetron sputtering; under the conditions of 110 ℃, 12V, 10A and argon protection, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath with an anode electrode being a copper electrode, a cathode electrode being a reticular glassy carbon electrode and a polar distance of 4.25cm for electric treatment for 30min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin. The rest of the preparation steps are the same as example 2.
Examples of effects
The following table 1 shows the analysis results of the viscosity, high temperature resistance, oxidation resistance and corrosion resistance of the high temperature resistant ferulic acid based unsaturated resin prepared by the examples 1 to 3 and the comparative examples 1 to 6 of the present invention.
TABLE 1
From table 1, it can be seen that the high temperature resistant ferulic acid group unsaturated resin prepared in examples 1, 2 and 3 has low viscosity absorption and good oxidation resistance, high temperature resistance and corrosion resistance; from the comparison of experimental data of examples 1, 2 and 3 and comparative examples 1 and 2, it can be found that 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine and isocyanate group phenyl acrylic acid modified ferulic acid are used for forming a polyurea compound with a hyperbranched structure, and after an ultrasonic-assisted microwave swelling process, a copper cyanide is used for performing an electric field induction-assisted magnetron sputtering process, so that a metal phthalocyanine-based compound and a benzimidazole compound are more easily formed, and the prepared high-temperature resistant ferulic acid group unsaturated resin has low viscosity and strong oxidation resistance, high temperature resistance and corrosion resistance; only by using isocyanate group phenyl acrylic acid modified ferulic acid, a polyurea compound cannot be formed, and after the ultrasonic-assisted microwave swelling process, an electric field induction-assisted magnetron sputtering process is carried out by using copper cyanide, so that a metal phthalocyanine compound and a benzimidazole compound are more easily formed, and the prepared high-temperature resistant ferulic acid group unsaturated resin is weaker in high-temperature resistance and corrosion resistance; from the experimental data of the examples 1, 2 and 3 and the comparative example 3, it can be found that the benzimidazole compound can not be formed by using the copper cyanide to perform the electric field induction assisted magnetron sputtering process on the modified ferulic acid, and the high-temperature resistant ferulic acid group unsaturated resin prepared by the method has weaker high-temperature resistance; from the experimental data of examples 1, 2, 3 and comparative example 4, it can be found that the prepared high-temperature resistant ferulic acid group unsaturated resin has weaker corrosion resistance because the ferulic acid group unsaturated resin is only subjected to the electric field induction treatment and cannot form a metal phthalocyanine group compound; from the experimental data of examples 1, 2 and 3 and comparative example 5, it can be found that the metal phthalocyanine-based compound and the benzimidazole compound cannot be formed by performing magnetron sputtering treatment on the ferulic acid-based unsaturated resin only by using copper cyanide, and the prepared high-temperature resistant ferulic acid-based unsaturated resin has weak high-temperature resistance and corrosion resistance; from the experimental data of examples 1, 2, 3 and comparative example 6, it can be found that the magnetron sputtering treatment of ferulic acid group unsaturated resin by copper powder can not form metal phthalocyanine group compound and benzimidazole compound, and the prepared high temperature resistant ferulic acid group unsaturated resin has weak high temperature resistance and corrosion resistance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The high-temperature-resistant ferulic acid group unsaturated resin is characterized by being prepared by carrying out electric field induction assisted magnetron sputtering on modified ferulic acid by utilizing copper cyanide and then carrying out an electrical treatment process.
2. The high temperature resistant ferulic acid based unsaturated resin of claim 1, wherein the modified ferulic acid is prepared from 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine, p-isocyanato-phenyl acrylic acid and ferulic acid.
3. The high temperature resistant ferulic acid group unsaturated resin of claim 2, which mainly comprises, by weight: 50-60 parts of modified ferulic acid and 38-50 parts of copper cyanide.
4. A preparation method of high temperature resistant ferulic acid group unsaturated resin is characterized by mainly comprising the following preparation steps:
(1) modifying ferulic acid by using 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine and p-isocyanato-phenyl acrylic acid to obtain modified ferulic acid;
(2) treating the modified ferulic acid by using an ultrasonic-assisted microwave swelling process to obtain ferulic acid-based unsaturated resin;
(3) the copper cyanide is used for carrying out electric field induction assisted magnetron sputtering technology on the ferulic acid group unsaturated resin to prepare the high-temperature resistant ferulic acid group unsaturated resin.
5. The method for preparing high temperature resistant ferulic acid group unsaturated resin according to claim 4, wherein the method for preparing high temperature resistant ferulic acid group unsaturated resin mainly comprises the following steps:
(1) placing the ferulic acid mixed solution in an oil bath pot at 70-80 ℃, dripping a p-isocyanate phenyl acrylic acid mixed solution with the mass of 0.8-1.2 times that of the ferulic acid mixed solution at 120-140 drops/min, stirring and refluxing for 3-4 h at 180-220 r/min, heating to 80-90 ℃ at 1-3 ℃/min, dripping 2-bromopropenyl-5, 6-dibromo-p-phenylenediamine with the mass of 1.2-1.4 times that of the ferulic acid mixed solution at 60-80 drops/min, stirring and refluxing for 2-3 h at 160-180 r/min, naturally cooling to room temperature, placing in a rotary evaporator at 58-62 ℃, and rotationally steaming for 45-55 min at 120-160 r/min under the condition of 10-20 Pa to obtain modified ferulic acid;
(2) ultrasonically treating the modified ferulic acid mixed solution for 15-25 min at 20-30 kHz under the conditions of 2250-2350 MHz and 800-900W microwaves, naturally cooling to room temperature, putting into a rotary evaporator at 78-82 ℃, and rotationally evaporating for 45-55 min at 120-160 r/min under the condition of 10-20 Pa to obtain ferulic acid-based unsaturated resin;
(3) under the conditions of magnetron sputtering power of 60-80W and argon protection of 1-2 Pa, putting the ferulic acid group unsaturated resin into a magnetron sputtering device as a base material, and sputtering for 2-3 h by using a copper cyanide solution with the mass of 3-5 times of that of the ferulic acid group unsaturated resin as a target material to obtain the ferulic acid group unsaturated resin after magnetron sputtering; and under the conditions of 108-112 ℃, 10-14V, 8-12A and argon protection, placing the ferulic acid group unsaturated resin subjected to magnetron sputtering into an electrolytic bath for electric treatment for 28-32 min, and naturally cooling to room temperature to obtain the high-temperature resistant ferulic acid group unsaturated resin.
6. The method for preparing the high temperature resistant ferulic acid group unsaturated resin according to claim 5, wherein the method for preparing the ferulic acid mixture in step (1) is as follows: at the temperature of 25-26 ℃, mixing ferulic acid and dimethylformamide according to the mass ratio of 1: 2.5-1: 2.7, stirring at 240-260 r/min for 40-60 min to obtain ferulic acid mixed solution.
7. The method for preparing high temperature resistant ferulic acid group unsaturated resin of claim 6, wherein the method for preparing the p-isocyanate phenyl acrylic acid mixed solution of step (1) is as follows: at the temperature of 25-26 ℃, mixing p-isocyanate phenyl acrylic acid, triethylamine and concentrated sulfuric acid with the mass fraction of 96-98% according to the mass ratio of 1: 1: 0.002 to 1: 1.1: 0.004, and stirring for 40-50 min at a speed of 180-220 r/min to obtain a p-isocyanate phenyl acrylic acid mixed solution.
8. The method for preparing the high temperature resistant ferulic acid based unsaturated resin according to claim 7, wherein the method for preparing the modified ferulic acid based mixed solution in the step (2) comprises the following steps: at the temperature of 25-26 ℃, mixing the modified ferulic acid and benzene according to a mass ratio of 1: 0.6-1: 0.8, and stirring for 10-20 min at 240-260 r/min to obtain a modified ferulic acid mixed solution.
9. The method for preparing high temperature resistant ferulic acid group unsaturated resin according to claim 8, wherein the copper cyanide solution of step (3) is prepared as follows: at the temperature of 25-26 ℃, copper cyanide and ethanol are mixed according to the mass ratio of 1: 3-1: 5, mixing, and stirring at 180-220 r/min for 20-30 min to obtain the copper cyanide solution.
10. The method for preparing high temperature resistant ferulic acid group unsaturated resin of claim 9, wherein the anode electrode of the electrolytic cell in step (3) is copper electrode, the cathode electrode is reticular glassy carbon electrode, and the polar distance is 4-4.5 cm.
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