A bio-based phenoloxy resin and its preparation method and application

Abstract

The present invention belongs to the technical field of phenoloxy resin process, and discloses a bio-based phenoloxy resin and its preparation method and application. The preparation process of the bio-based phenoloxy resin is as follows: heating the bio-based epoxy prepolymer, the bio-based chain extender and the solvent to 120-250°C, adding the catalyst after dissolving, reacting for 1-24 hours under nitrogen protection, cooling to 40-60°C, discharging, washing, filtering and vacuum drying, and obtaining a white powdery or flaky bio-based phenoloxy resin. The obtained bio-based phenoloxy resin has good mechanical strength, toughness, rigidity and thermal stability, which is similar to the performance of traditional petroleum-based phenoloxy resin, and even has improved tensile strength, and has good compatibility with petroleum-based epoxy resin. At the same time, it has excellent biodegradability and certain biocompatibility, and can be applied to bioengineering, medical field, food or drug packaging field, electronic computer field, adhesive field and metal anticorrosion field.

Description

Technical Field

[0001] The invention relates to the technical field of phenoloxy resin process, and in particular to a bio-based phenoloxy resin and a preparation method and application thereof. Background Art

[0002] Phenoxy resin, also known as phenoxy resin, is a linear thermoplastic resin with a structure highly similar to epoxy resin. It has a low epoxy group content and a high hydroxyl content, which provides the resin with strong adhesion to metal and other substrates, resulting in excellent adhesion. At the same time, due to the benzene ring and ether bond in the phenoloxy resin structure, the phenoloxy resin exhibits excellent mechanical strength, toughness, rigidity and low mold shrinkage.

[0003] Domestic and foreign researchers have also reported on the preparation of phenoloxy resins. Patent CN105985519B discloses a method for preparing phenoloxy resins, in which a high molecular weight phenoloxy resin is prepared by reacting bisphenol A and bisphenol A epoxy resin, and the glass transition temperature is 88°C and the tensile strength is 66MPa. Shih W C, Ma CCM reported a method for preparing phenoloxy resins by using aromatic dihydroxy compounds and bisphenol A epoxy resins (Journal of applied polymer science, 1999, 73 (12): 2369-2376.).

[0004] At present, phenolic resin has the problem of low softening point and tensile strength to be improved, which greatly limits the application of phenolic resin. At the same time, the use of bisphenol A not only poses a threat to human health, but also with the increasing environmental problems and the rapid consumption of petroleum raw materials, although petroleum compounds are widely available and have a stable supply, they are not sustainable. People have begun to explore natural biomaterials as renewable substitutes for petroleum compounds. Bio-based materials are a new type of materials, which are mainly obtained by physically and chemically modifying renewable substances extracted from natural substances such as plants and fungi. With the deepening of research, people have found a large number of naturally occurring aromatic and aliphatic compounds from cashew nut shell liquid (CNSL), lignin, tannin, palm oil and coconut shell tar (CST). Renewable resources generally need to be structurally modified before they can be used in the preparation of coating resins.

[0005] Bio-based materials are abundant in the world, widely available, cheap and easy to obtain. By chemically modifying bio-based materials, it is possible to design and retain degradable bio-based structures. At the same time, the reaction sites of bio-based materials can be used to react and introduce new functional groups, such as epoxy groups, carbon-carbon double bonds, etc., thereby preparing bio-based polyepoxides, bio-based polyolefins and other bio-based modified products, which is of great significance to the expansion of the application fields of renewable resources. Summary of the invention

[0006] The purpose of the present invention is to provide a bio-based phenoloxy resin and a preparation method and application thereof, so as to solve the problems existing in the prior art.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a method for preparing a bio-based phenoloxy resin, comprising the following steps:

[0009] (1) mixing a bio-based monomer A, dichloromethane, and a dichloromethane solution of a catalyst, and heating the mixture to obtain a bio-based epoxy prepolymer;

[0010] Alternatively, the bio-based monomer B, epichlorohydrin and a catalyst are mixed and reacted, and after the reaction is completed, a sodium hydroxide solution is added to react to obtain a bio-based epoxy prepolymer;

[0011] (2) The bio-based epoxy prepolymer, chain extender, and solvent are mixed, and a catalyst is added after heating to react to obtain a bio-based phenoloxy resin.

[0012] Preferably, in the above-mentioned method for preparing a bio-based phenoloxy resin, the functionality of the carbon-carbon double bond of the bio-based monomer A in step (1) is ≥2, and the functionality of the hydroxyl and / or carboxyl group of the bio-based monomer B in step (1) is ≥2; the bio-based monomer A in step (1) is one or more of biseugenol, magnolol, rapeseed oil, and linseed oil; the bio-based monomer B in step (1) is one or more of isosorbide, salicylic acid, cardol, p-hydroxybenzoic acid, bisvanillin, magnolol, quinic acid, and castor oil.

[0013] Preferably, in the above-mentioned method for preparing a bio-based phenoloxy resin, the catalysts in step (1) and step (2) are independently meta-chloroperbenzoic acid, tertiary amines, imidazole compounds, quaternary ammonium salts, phosphides or alkali metals; the chain extender in step (2) is one or more of a bio-based monomer with a hydroxyl and / or carboxyl functionality ≥ 2, a petroleum-based bisphenol compound, and a dibasic acid; and the solvent in step (2) is one or more of tetrahydrofuran, an alcohol compound, an ether compound, a ketone compound, an ester compound, and an aromatic hydrocarbon compound.

[0014] Preferably, in the above-mentioned method for preparing a bio-based phenoloxy resin,

[0015] The heating temperature in step (1) is 40-60°C, and the heating time in step (1) is 12-24h; the reaction temperature in step (1) is 80-100°C, and the reaction time in step (1) is 2-8h; the reaction temperature of adding sodium hydroxide solution in step (1) is 20-25°C, and the reaction time of adding sodium hydroxide solution in step (1) is 1-24h;

[0016] The reaction temperature in step (2) is 120 to 250° C.; the reaction time in step (2) is 1 to 24 hours.

[0017] Preferably, in the above-mentioned method for preparing a bio-based phenoloxy resin, the mass volume ratio of the bio-based monomer A, dichloromethane, and the dichloromethane solution of the catalyst in the step (1) is 15-30 g: 50-150 mL: 60-100 mL, and the concentration of the dichloromethane solution of the catalyst is 1-3 mol / L; the mass volume ratio of the bio-based monomer B, epichlorohydrin, catalyst, and sodium hydroxide solution in the step (1) is 10-30 g: 60-150 g: 2-5 g: 50-150 mL; the mass volume ratio of the bio-based epoxy prepolymer, chain extender, solvent, and catalyst in the step (2) is 25-50 g: 8-30 g: 35-80 g: 0.01-0.2 g.

[0018] The present invention also provides a bio-based phenol-oxygen resin prepared by the above-mentioned method for preparing the bio-based phenol-oxygen resin.

[0019] The invention also provides an application of a bio-based phenoloxy resin as a thermoplastic resin.

[0020] The invention also provides an application of a bio-based phenoloxy resin in a two-component coating.

[0021] The invention also provides an application of a bio-based phenoloxy resin in an epoxy resin.

[0022] The invention also provides an application of a bio-based phenoloxy resin as a toughening resin.

[0023] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The bio-based monomer used in the present invention is a renewable material that is easy to obtain. The prepared bio-based phenol-oxygen resin has a high molecular weight, excellent mechanical strength, toughness, rigidity and thermal stability, and has strong adhesion to metal and other substrates. At the same time, its mold shrinkage rate is low, and it exhibits similar performance to traditional petroleum-based phenol-oxygen resins, and has improved tensile strength. Due to its excellent biodegradability and certain biocompatibility, it also greatly broadens the application field of bio-based phenol-oxygen resins.

[0025] (2) The molecular weight of the bio-based phenoloxy resin prepared by the present invention is 20,000 to 45,000 g / mol, the bio-based carbon content is 70 to 100%, the epoxy equivalent is 10,000 to 22,000 g / eq, and the hydroxyl equivalent is 250 to 370 g / eq; if the sodium hydroxide is added for reaction for more than 3 hours in the process of preparing the bio-based epoxy prepolymer of the present invention, there is a tendency for more side reactions; if the reaction temperature in the step of preparing the bio-based phenoloxy resin of the present invention is above 140°C, the reaction rate can be accelerated, and if the reaction temperature is below 180°C, the occurrence of side reactions can be effectively suppressed; in order to obtain a suitable bio-based phenoloxy resin, the reaction time can be appropriately selected by testing the molecular weight of the phenoloxy resin.

[0026] (3) The bio-based phenoloxy resin prepared by the present invention is a thermoplastic resin that can be used alone without a curing agent. A phenoloxy coating can be prepared by a solvent casting method, and can be applied to the fields of coils, cans, magnetic card coatings, and optical device substrates, such as color filter substrates, touch screen panel substrates, and solar cell substrates. At the same time, since the bio-based phenoloxy resin has a polyol structure, it is endowed with excellent gas barrier properties and can be well applied to the fields of food or drug packaging.

[0027] (4) The bio-based phenoloxy resin prepared by the present invention exhibits excellent toughness and can be used as a toughening resin. In practical applications, the bio-based phenoloxy resin is added as a modifier to the coating system to be modified for blending. When the addition amount of the bio-based phenoloxy resin is 5 to 10%, the toughening effect of the coating can be greatly improved. At the same time, since the bio-based phenoloxy resin has good compatibility with the petroleum-based epoxy resin, the addition of the bio-based phenoloxy resin can well solve the problem of insufficient toughness of the epoxy resin, and prepare an epoxy toughened coating.

[0028] (5) The bio-based phenoloxy resin prepared by the present invention can be cured with an isocyanate curing agent or an acid anhydride curing agent to obtain a phenoloxy coating. The bio-based phenoloxy resin has the characteristics of high molecular weight, and the prepared phenoloxy resin is a powder or flaky solid, which can be well used in powder coatings. At the same time, the cured bio-based phenoloxy resin not only has excellent adhesion, mechanical properties, strength, and toughness, but also its excellent heat resistance, chemical resistance and tensile strength can be well applied to the fields of electronic computers, pipeline transportation, packaging, and adhesives.

[0029] (6) The bio-based phenolic resin prepared by the present invention can be blended with other epoxy resins, modified epoxy resins or epoxy diluents, and then cured using an amine curing agent or an acid anhydride curing agent to obtain an epoxy coating. The bio-based phenolic resin is added to the epoxy resin to greatly improve the bonding strength between the coating and the substrate, and can be used in the field of metal corrosion protection. DETAILED DESCRIPTION

[0030] The present invention provides a method for preparing a bio-based phenoloxy resin, comprising the following steps:

[0031] (1) mixing a bio-based monomer A, dichloromethane, and a dichloromethane solution of a catalyst, and heating the mixture to obtain a bio-based epoxy prepolymer;

[0032] Alternatively, the bio-based monomer B, epichlorohydrin and a catalyst are mixed and reacted, and after the reaction is completed, a sodium hydroxide solution is added to carry out a ring-closing reaction to obtain a bio-based epoxy prepolymer;

[0033] (2) The bio-based epoxy prepolymer, chain extender, and solvent are mixed, and a catalyst is added after heating to react to obtain a bio-based phenoloxy resin.

[0034] In the present invention, the specific process of mixing the bio-based monomer A, dichloromethane and the dichloromethane solution of the catalyst in step (1) is: firstly mix the bio-based monomer A with dichloromethane, add the dichloromethane solution of the catalyst dropwise after dissolving, and then introduce nitrogen; the temperature of mixing the bio-based monomer A with dichloromethane is preferably -5 to 5°C, more preferably -5, -4, -3, -2, 0, 2, 4 or 5°C, and more preferably -2, 0 or 2°C.

[0035] In the present invention, the heating temperature in the step (1) is preferably 40-60°C, more preferably 40, 42, 45, 48, 50, 53, 55, 57 or 60°C, and more preferably 40°C; the heating time in the step (1) is preferably 12-24h, more preferably 12, 14, 16, 18, 20, 22 or 24h, and more preferably 22 or 24h.

[0036] In the present invention, the specific process of mixing the bio-based monomer B, epichlorohydrin and the catalyst in step (1) is as follows: the bio-based monomer B and epichlorohydrin are mixed and then heated to 80-100° C., and the catalyst is added after the mixture is dissolved.

[0037] In the present invention, the reaction temperature in step (1) is preferably 80-100°C, more preferably 80, 83, 85, 88, 90, 92, 95, 98 or 100°C, more preferably 80°C; the reaction time in step (1) is preferably 2-8h, more preferably 2, 3, 4, 5, 6, 7 or 8h, more preferably 5 or 6h; the temperature of the ring-closing reaction in step (1) is preferably 20-25°C, more preferably 20, 21, 22, 23, 24 or 25°C, more preferably 22 or 23°C; the ring-closing reaction time in step (1) is preferably 1-24h, more preferably 1, 2, 3, 4, 8, 10, 14, 15, 18, 20 or 24h, more preferably 1, 2 or 3h.

[0038] In the present invention, before obtaining the bio-based epoxy prepolymer in step (1), the process further comprises: extracting, drying, and removing the solvent by rotary evaporation.

[0039] In the present invention, the functionality of the carbon-carbon double bond of the bio-based monomer A in step (1) is preferably ≥2, and the functionality of the hydroxyl and / or carboxyl groups of the bio-based monomer B in step (1) is preferably ≥2, and the functionality of the hydroxyl and / or carboxyl groups ≥2 means that the functionality of the hydroxyl or carboxyl groups is ≥2, or the sum of the functionalities of the hydroxyl and carboxyl groups is ≥2; the bio-based monomer A in step (1) is preferably one or more of biseugenol, magnolol, rapeseed oil, and linseed oil, and is further preferably one or more of biseugenol, magnolol, and rapeseed oil, and is more preferably biseugenol; the bio-based monomer B in step (1) is preferably one or more of isosorbide, salicylic acid, cardol, p-hydroxybenzoic acid, vanillin, honokiol, quinic acid, and castor oil, and is further preferably one or more of cardol, p-hydroxybenzoic acid, vanillin, and honokiol, and is more preferably one or two of cardol and p-hydroxybenzoic acid.

[0040] In the present invention, the catalyst in step (1) is preferably meta-chloroperbenzoic acid, tertiary amines, imidazole compounds, quaternary ammonium salts, phosphides or alkali metals, further preferably meta-chloroperbenzoic acid or quaternary ammonium salts, more preferably quaternary ammonium salts, the quaternary ammonium salts are preferably tetraethylammonium bromide, tetrabutylammonium bromide, triethylbenzylammonium bromide, benzyltriethylammonium chloride or tetrapropylammonium chloride, further preferably tetraethylammonium bromide, tetrabutylammonium bromide or triethylbenzylammonium bromide, more preferably tetraethylammonium bromide or tetrabutylammonium bromide.

[0041] In the present invention, the mass volume ratio of the bio-based monomer A, dichloromethane, and the dichloromethane solution of the catalyst in step (1) is preferably 15-30 g: 50-150 mL: 60-100 mL, more preferably 16-28 g: 60-135 mL: 65-95 mL, and more preferably 17 g: 110 mL: 85 mL; the concentration of the dichloromethane solution of the catalyst is preferably 1-3 mol / L, more preferably 1, 1.5 , 2, 2.5 or 3 mol / L, more preferably 2 or 2.5 mol / L; in the step (1), the mass volume ratio of the bio-based monomer B, epichlorohydrin, catalyst and sodium hydroxide solution is preferably 10-30g:60-150g:2-5g:50-150mL, more preferably 12-27g:63-135g:2.5-4.5g:65-135mL, more preferably 20g:90g:3g:100mL.

[0042] In the present invention, the specific process of mixing the bio-based epoxy prepolymer, the chain extender and the solvent in step (2) is as follows: after mixing the bio-based epoxy prepolymer with part of the solvent, heating to 100-130° C., and then adding the chain extender; after the catalyst reaction is completed, adding the remaining solvent and continuing the reaction for 1-2 hours.

[0043] In the present invention, after adding the catalyst in step (2), the step further includes: introducing nitrogen.

[0044] In the present invention, after the remaining solvent is added in step (2) and the reaction is continued, the process further comprises: cooling the temperature to 40-60° C., discharging the material, and then washing, filtering, and vacuum drying to obtain a bio-based phenoloxy resin; the mass ratio of the remaining solvent to the bio-based epoxy prepolymer is 1:1.

[0045] In the present invention, the reaction temperature in step (2) is preferably 120-250°C, more preferably 120, 140, 160, 180, 200, 220 or 250°C, more preferably 140, 160 or 180°C; the reaction time in step (2) is preferably 1-24h, more preferably 1, 4, 8, 10, 14, 15, 18, 20 or 24h, more preferably 10 or 14h.

[0046] In the present invention, the chain extender in step (2) is preferably one or more of a bio-based monomer having a hydroxyl and / or carboxyl functionality of ≥2, a petroleum-based bisphenol compound, and a dibasic acid, and is further preferably one or two of a bio-based monomer having a hydroxyl and / or carboxyl functionality of ≥2 and a petroleum-based bisphenol compound, and is more preferably a bio-based monomer having a hydroxyl and / or carboxyl functionality of ≥2. The bio-based monomer having a hydroxyl and / or carboxyl functionality of ≥2 is preferably vanillyl alcohol, isosorbide, salicylic acid, p-hydroxybenzoic acid, 2,5-furandicarboxylic acid, cardol, succinic acid, glycerol, sorbitol, aspartic acid, gluconic acid or xylitol, and is further preferably isosorbide, salicylic acid, p-hydroxybenzoic acid, succinic acid or glycerol, and is more preferably isosorbide or salicylic acid.

[0047] In the present invention, the solvent in step (2) is preferably one or more of tetrahydrofuran, alcohol compounds, ether compounds, ketone compounds, ester compounds, and aromatic hydrocarbon compounds, further preferably one or more of tetrahydrofuran, alcohol compounds, ether compounds, and ketone compounds, more preferably one or more of tetrahydrofuran, alcohol compounds, and ether compounds; the ether compound is preferably propylene glycol methyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, or diethylene glycol dimethyl ether, further preferably propylene glycol methyl ether or diethylene glycol dimethyl ether, more preferably propylene glycol methyl ether.

[0048] In the present invention, the catalyst in step (2) is preferably a tertiary amine, an imidazole compound, a quaternary ammonium salt, a phosphide or an alkali metal, more preferably an imidazole compound or a quaternary ammonium salt, more preferably a quaternary ammonium salt; the imidazole compound is preferably 2-methylimidazole or 2-ethyl-4-methylimidazole; the quaternary ammonium salt is preferably bis(triphenylphosphine)ammonium chloride or tetraethylammonium hydroxide.

[0049] In the present invention, the mass ratio of the bio-based epoxy prepolymer, chain extender, solvent and catalyst in the step (2) is preferably 25-50g: 8-30g: 35-80g: 0.01-0.2g, more preferably 22-47g: 10-28g: 37-70g: 0.05-0.17g, and more preferably 32g: 15g: 40g: 0.1g.

[0050] The present invention also provides a bio-based phenol-oxygen resin prepared by the above-mentioned method for preparing the bio-based phenol-oxygen resin.

[0051] The present invention also provides an application of a bio-based phenoloxy resin as a thermoplastic resin; the method for applying the bio-based phenoloxy resin as a thermoplastic resin is: dissolving the bio-based phenoloxy resin in a solvent, and preparing a phenoloxy coating after coating; the solvent is propylene glycol methyl ether, diethylene glycol dimethyl ether, toluene or acetone; the phenoloxy coating is used in the field of optical device substrates, and the field of optical device substrates includes color filter substrates, touch screen panel substrates or solar cell substrates.

[0052] The present invention also provides an application of a bio-based phenoloxy resin in a two-component coating; the method for applying the bio-based phenoloxy resin in the two-component coating is: using an isocyanate or anhydride curing agent to cure the bio-based phenoloxy resin to prepare a phenoloxy coating; the phenoloxy coating is used for the coating of powder coatings.

[0053] The present invention also provides an application of a bio-based phenoloxy resin in an epoxy resin; the method for applying the bio-based phenoloxy resin in the epoxy resin is: the bio-based phenoloxy resin is blended with other epoxy resins, modified epoxy resins or epoxy diluents, and after mixing, an amine curing agent or an acid anhydride curing agent is added for curing to prepare an epoxy coating; the epoxy coating is applied to the field of metal corrosion protection.

[0054] The present invention also provides an application of a bio-based phenoloxy resin as a toughening resin; the method for applying the bio-based phenoloxy resin as a toughening resin is: mixing the bio-based phenoloxy resin with a resin, wherein the mass of the bio-based phenoloxy resin is 5 to 10% of the total mass of the resin.

[0055] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0056] Example 1

[0057] 20g of magnolol and 100ml of dichloromethane were added to a 500ml reactor equipped with a stirring device and a thermometer. After mixing evenly at 0°C, 80ml of a dichloromethane solution of meta-chloroperbenzoic acid (2.5mol / L) was added dropwise to the reactor. After 20 minutes of dropwise addition, nitrogen was introduced, the temperature was raised to 40°C, and the reaction was carried out under nitrogen protection for 24 hours. After extraction, drying, and solvent removal by rotary evaporation, the bio-based epoxy prepolymer EP-1 was obtained.

[0058] Example 2

[0059] 20 g of divanillin and 65 g of epichlorohydrin were added to a 500 ml reactor equipped with a stirring device and a thermometer, the reaction system temperature was heated to 80°C, 3 g of tetrabutylammonium bromide was added, and the reaction was kept at 80°C for 2 hours, then cooled to room temperature, 100 ml of sodium hydroxide solution was added, and the reaction was continued for 1 hour. After extraction, drying, and solvent removal by rotary evaporation, the bio-based epoxy prepolymer EP-2 was obtained.

[0060] Example 3

[0061] Add 30g of bio-based epoxy prepolymer EP-1 and 10g of propylene glycol methyl ether into a 250ml reactor equipped with a stirring device and a thermometer, heat the reaction system to 100°C, add 10g of isosorbide, raise the temperature to 140°C, add 0.1g of bis(triphenylphosphine)ammonium chloride, introduce nitrogen, and keep the reaction at 140°C under nitrogen protection for 4h, then add 30g of propylene glycol methyl ether, continue the reaction for 2h, then cool to 60°C to discharge, wash with water, filter, and vacuum dry to obtain a white powdery bio-based phenoloxy resin BPO-1.

[0062] Example 4

[0063] 30g of bio-based epoxy prepolymer EP-1 and 10g of propylene glycol methyl ether were added to a 250ml reactor equipped with a stirring device and a thermometer, the reaction system was heated to 100°C, 10g of 2,5-furandicarboxylic acid was added, the temperature was raised to 140°C, 0.1g of bis(triphenylphosphine)ammonium chloride was added, nitrogen was introduced, and the reaction was kept warm at 140°C under nitrogen protection for 4h, 30g of propylene glycol methyl ether was added, the reaction was continued for 2h, and then the temperature was lowered to 60°C for discharge. After washing, filtering and vacuum drying, a white flaky bio-based phenoloxy resin BPO-2 was obtained.

[0064] Example 5

[0065] Add 30g of epoxy prepolymer EP-1 and 10g of propylene glycol methyl ether into a 250ml reactor equipped with a stirring device and a thermometer, heat the reaction system to 120°C, add 10g of vanillin, raise the temperature to 160°C, add 0.1g of 2-ethyl-4-methylimidazole, introduce nitrogen, and keep the reaction at 160°C under nitrogen protection for 2h, then add 30g of propylene glycol methyl ether, continue the reaction for 1h, then cool to 60°C and discharge the material. After washing, filtering and vacuum drying, a white flaky bio-based phenoloxy resin BPO-3 is obtained.

[0066] Example 6

[0067] 30g of epoxy prepolymer EP-2 and 10g of propylene glycol methyl ether were added to a 250ml reactor equipped with a stirring device and a thermometer, the reaction system was heated to 120°C, 10g of p-hydroxybenzoic acid was added, the temperature was raised to 160°C, 0.1g of 2-ethyl-4-methylimidazole was added, nitrogen was introduced, and the reaction was kept warm at 160°C under nitrogen protection for 2h, 30g of propylene glycol methyl ether was added and the reaction was continued for 1h, then the temperature was lowered to 60°C and the material was discharged. After washing with water, filtering and vacuum drying, a white flaky bio-based phenoloxy resin BPO-4 was obtained.

[0068] Example 7

[0069] Add 30g of epoxy prepolymer EP-2 and 8g of propylene glycol methyl ether into a 250ml reactor equipped with a stirring device and a thermometer, heat the reaction system to 100°C, add 8g of succinic acid, raise the temperature to 140°C, add 0.1g of bis(triphenylphosphine)ammonium chloride, introduce nitrogen, and keep the reaction at 140°C under nitrogen protection for 4h, then add 30g of propylene glycol methyl ether, continue the reaction for 2h, then cool to 60°C to discharge the material, wash with water, filter, and vacuum dry to obtain a white powdery bio-based phenoloxy resin BPO-5.

[0070] Example 8

[0071] 65.0 parts by mass of bisphenol A epoxy resin (epoxy equivalent is 227 g / eq), 8.0 parts by mass of bio-based phenoloxy resin BPO-3 prepared in Example 5, and 27.0 parts by mass of 4,4'-diaminodiphenylmethane are mixed and coated. The curing conditions are as follows: curing at 80°C for 2 hours, then heating to 150°C for 2 hours to obtain an epoxy toughened coating.

[0072] Example 9

[0073] 60.0 parts by mass of bisphenol A epoxy resin (epoxy equivalent is 196 g / eq), 10.0 parts by mass of the bio-based phenoloxy resin BPO-4 prepared in Example 6 above, and 30.0 parts by mass of hexahydrophthalic anhydride are mixed and coated. The curing conditions are curing at 80°C for 2 hours, then heating to 150°C for curing for 2 hours to obtain an epoxy toughened coating.

[0074] Example 10

[0075] The above bio-based phenol-oxygen resins BPO-1, BPO-2, BPO-3, BPO-4 and BPO-5 were tested for molecular weight, glass transition temperature, tensile strength, flexural strength and mold shrinkage, and the test results are shown in Table 1. From the results in Table 1, it can be seen that the bio-based phenol-oxygen resin BPO-3 has a glass transition temperature of 98.7°C, a tensile strength of 76.3MPa, a flexural strength of 97MPa, a mold shrinkage of 0.003cm / cm, good transparency and no yellowing, and has the conditions to be a renewable substitute for bisphenol A phenol-oxygen resin.

[0076] Table 1 Performance test results of bio-based phenoloxy resin

[0077]

[0078]

[0079] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a bio-based phenoloxy resin, characterized in that: The following steps are involved: (1) mixing a bio-based monomer A, dichloromethane, and a dichloromethane solution of a catalyst, and heating to obtain a bio-based epoxy prepolymer; wherein the catalyst in step (1) is m-chloroperbenzoic acid; Alternatively, the bio-based monomer B, epichlorohydrin and a catalyst are mixed and reacted, and after the reaction is completed, a sodium hydroxide solution is added to react to obtain a bio-based epoxy prepolymer; (2) mixing a bio-based epoxy prepolymer, a chain extender, and a solvent, and adding a catalyst after heating to obtain a bio-based phenoloxy resin; The bio-based monomer A in step (1) is one or more of biseugenol and magnolol; the bio-based monomer B in step (1) is one or more of isosorbide, salicylic acid, cardol, p-hydroxybenzoic acid, bisvanillin, magnolol, and quinic acid; The chain extender in step (2) is one or more of a bio-based monomer, a petroleum-based bisphenol compound, and a dibasic acid having a hydroxyl and / or carboxyl functionality of ≥2; The bio-based monomer with hydroxyl and / or carboxyl functionality ≥ 2 is vanillyl alcohol, isosorbide, salicylic acid, p-hydroxybenzoic acid, 2,5-furandicarboxylic acid, cardol, succinic acid, glycerol, sorbitol, aspartic acid, gluconic acid or xylitol.

2. The method for preparing a bio-based phenoloxy resin according to claim 1, characterized in that: The catalyst in step (2) is a tertiary amine, an imidazole compound, a quaternary ammonium salt, a phosphide or an alkali metal; the solvent in step (2) is one or more of an alcohol compound, an ether compound, a ketone compound, an ester compound, and an aromatic hydrocarbon compound.

3. The method for preparing the bio-based phenoloxy resin according to claim 2, characterized in that: The heating temperature in step (1) is 40-60° C., and the heating time in step (1) is 12-24 hours; the reaction temperature in step (1) is 80-100° C., and the reaction time in step (1) is 2-8 hours; the reaction temperature of adding sodium hydroxide solution in step (1) is 20-25° C., and the reaction time of adding sodium hydroxide solution in step (1) is 1-24 hours; The reaction temperature in step (2) is 120-250° C.; the reaction time in step (2) is 1-24 h.

4. The method for preparing the bio-based phenoloxy resin according to claim 3, characterized in that: In step (1), the mass volume ratio of bio-based monomer A, dichloromethane, and dichloromethane solution of the catalyst is 15-30 g: 50-150 mL: 60-100 mL, and the concentration of the dichloromethane solution of the catalyst is 1-3 mol / L; the mass volume ratio of bio-based monomer B, epichlorohydrin, catalyst, and sodium hydroxide solution in step (1) is 10-30 g: 60-150 g: 2-5 g: 50-150 mL; the mass volume ratio of bio-based epoxy prepolymer, chain extender, solvent, and catalyst in step (2) is 25-50 g: 8-30 g: 35-80 g: 0.01-0.2 g.

5. The bio-based phenoloxy resin prepared by the method for preparing the bio-based phenoloxy resin according to any one of claims 1 to 4.

6. Use of the bio-based phenoloxy resin according to claim 5 as a thermoplastic resin.

7. Use of the bio-based phenoloxy resin according to claim 5 in a two-component coating.

8. Use of the bio-based phenoloxy resin according to claim 5 in epoxy resin.

9. Use of the bio-based phenoloxy resin according to claim 5 as a toughening resin.

Images