Bio-based monomer and manufacturing method thereof

Abstract

This disclosure provides a bio-based monomer having a structure as shown in formula (1), formula (2), or formula (3), where each symbol in formula (1), formula (2), or formula (3) is as defined in the specification. The bio-based monomer of this disclosure is prepared from a bio-based diol with high rigidity, high thermal stability, and biodegradability, and can be successfully epoxidized, thereby enabling its use in the preparation of biopolymer materials with good mechanical strength.

Claims

1. A biomass-based monomer having a structure as shown in formula (1), formula (2), or formula (3): wherein A1 and A2 are each independently a hydrogen atom, an aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, or a structure as shown in formula (4); A3 and A4 are each independently a hydrogen atom, the aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, or a structure as shown in formula (4); A5 and A6 are each independently a hydrogen atom, the aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, or a structure as shown in formula (4): FE - Formula (4); wherein, E is a straight-chain or branched carbonyl group of C3-C20, and F is an aromatic hydrocarbon; wherein at least one of A1 and A2 has an unsaturated olefin bond, at least one of A3 and A4 has the unsaturated olefin bond, and at least one of A5 and A6 has the unsaturated olefin bond.

2. The biomass monomer as claimed in claim 1, wherein A1 and A2 are each independently the aromatic hydrocarbon or a straight-chain or branched hydrocarbon of C10-C30, A3 and A4 are each independently the aromatic hydrocarbon or a straight-chain or branched hydrocarbon of C10-C30, and A5 and A6 are each independently the aromatic hydrocarbon or a straight-chain or branched hydrocarbon of C10-C30.

3. The biomass monomer as claimed in claim 1, wherein at least one of A1 and A2 has the structure shown in formula (4), at least one of A3 and A4 has the structure shown in formula (4), and at least one of A5 and A6 has the structure shown in formula (4).

4. A method for preparing a biomass-based monomer, comprising: providing a first reaction solution comprising a dihydrohexitol, a sulfonic acid compound, and a first solvent; performing a first polymerization reaction on the first reaction solution and an alkaline solution at a first polymerization temperature to form a first polymer solution, wherein the first polymerization temperature is 0°C to 35°C; and performing a second polymerization reaction on the first polymer solution and a phenol solution at a second polymerization temperature to form a biomass-based monomer solution, wherein the second polymerization temperature is 80°C to 160°C; wherein the biomass-based monomer solution comprises a biomass-based monomer having a structure as shown in formula (1), formula (2), or formula (3): A1 and A2 are each independently selected from a group consisting of a hydrogen atom, an aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, and a structure shown in formula (4); A3 and A4 are each independently selected from the group consisting of a hydrogen atom, the aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, and the structure shown in formula (4); A5 and A6 are each independently selected from the group consisting of a hydrogen atom, the aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, and the structure shown in formula (4); at least one of A1 and A2 is an aromatic hydrocarbon; at least one of A3 and A4 is an aromatic hydrocarbon; at least one of A5 and A6 is an aromatic hydrocarbon: FE - Formula (4); where E is a carbonyl group of C3-C20 straight-chain or branched, and F is an aromatic hydrocarbon.

5. The method for preparing the biomass monomer as described in claim 4, wherein the dihydrohexitol is isosorbide, isomannitol, isoidolitinol, or a combination thereof.

6. The method for preparing the biomass monomer as claimed in claim 4, wherein the sulfonic acid compound is benzenesulfonate chloride, mesitylenesulfonate chloride, 4-toluenesulfonate chloride, 4-ethylbenzenesulfonate chloride, or a combination thereof.

7. The method for preparing the biomass monomer as claimed in claim 4, wherein the phenol solution comprises a phenol, which is an alkylresorcinol, cashew phenol, ascorbic acid, eugenol, vanillin, or a combination thereof.

8. A method for preparing a biomass-based monomer, comprising: providing a reaction solution comprising a dihydrohexitol, a carboxylic acid, and a solvent; performing a prepolymerization reaction with a thionyl chloride solution at a prepolymerization reaction temperature to form a prepolymer solution, wherein the prepolymerization reaction temperature is 70°C to 130°C; and performing a polymerization reaction with a phenol solution at a polymerization reaction temperature to form a biomass-based monomer solution, wherein the polymerization reaction temperature is 0°C to 35°C; wherein the biomass-based monomer solution comprises a biomass-based monomer having a structure as shown in formula (1), formula (2), or formula (3): A1 and A2 are each independently selected from a group consisting of a hydrogen atom, an aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, and a structure shown in formula (4); A3 and A4 are each independently selected from the group consisting of a hydrogen atom, the aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, and a structure shown in formula (4); A5 and A6 are each independently selected from the group consisting of a hydrogen atom, the aromatic hydrocarbon, a straight-chain or branched hydrocarbon of C10-C30, and a structure shown in formula (4); at least one of A1 and A2 is a structure shown in formula (4); at least one of A3 and A4 is a structure shown in formula (4); at least one of A5 and A6 is a structure shown in formula (4): FE - Formula (4); where E is a straight-chain or branched carbonyl group of C3-C20, and F is an aromatic hydrocarbon.

9. The method for preparing the biomass monomer as described in claim 8, wherein the dihydrohexitol is isosorbide, isomannitol, isoidutol, or a combination thereof.

10. The method for preparing the biomass monomer as described in claim 8, wherein the carboxylic acid is malonic acid, succinic acid, glutaric acid, or a combination thereof.

11. The method for preparing the biomass monomer as claimed in claim 8, wherein the phenol solution comprises a phenol, which is an alkylresorcinol, cashew phenol, ascorbic acid, eugenol, vanillin, or a combination thereof.

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