Epoxy vegetable oil glass polymer material and preparation method thereof

Abstract

The present invention discloses a kind of epoxy vegetable oil glass polymer material and its preparation method, with epoxy vegetable oil, aldehyde compound containing phenolic hydroxyl group and / or carboxyl group, diamine as raw material, in the presence of catalyst, 130-200 ℃, react under nitrogen atmosphere to obtain. The present invention utilizes the difference in reactivity between functional groups and designs a novel method for preparing epoxy vegetable oil glass polymer material by solvent-free one-pot method. The preparation process does not require solvent, eliminates the tedious steps such as product purification and solvent treatment, and has the characteristics of high efficiency, low cost, and pollution-free. The preparation method has universality, and by selecting aldehyde-containing compounds and diamines of different structures, the structure and performance of epoxy vegetable oil glass polymer material can be regulated and controlled in a large range to meet the needs of different application fields. In addition, the preparation method provided by the present invention is simple to operate, does not need to use special instruments and equipment, is highly operable, and is economical.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to an epoxy vegetable oil glass polymer material and a preparation method thereof. Background Art

[0002] Epoxy resins are a class of thermosetting plastics with excellent dimensional stability, mechanical strength, heat resistance, and chemical resistance. They are widely used in adhesives, insulation materials, electronic packaging, and composite materials. However, the raw materials of traditional epoxy resins are derived from fossil resources, and their permanent cross-linked network structure makes them difficult to recycle after use. The development of epoxy resins faces the problems of resource depletion and environmental pollution. Therefore, the development of sustainable epoxy resins has become an urgent need. On the one hand, using renewable biomass as raw materials to prepare bio-based epoxy resins can solve the problem of epoxy resin's dependence on fossil resources. On the other hand, introducing dynamic covalent bonds into thermosetting epoxy resins to prepare epoxy glass polymers can make thermoplastic and recyclable epoxy resins by utilizing the exchange reaction of dynamic covalent bonds. Therefore, the development of bio-based epoxy glass polymer materials provides a way to simultaneously solve the resource crisis and environmental pollution problems faced by epoxy resins.

[0003] Epoxidized vegetable oils are a class of bio-based epoxy monomers prepared by epoxidizing double-bond vegetable oils. They can undergo curing reactions with carboxylic acids, anhydrides, amines, and phenolic compounds to produce bio-based epoxy resins. Introducing dynamic covalent bonds, such as imine bonds, disulfide bonds, or borate bonds, into epoxidized vegetable oil resins yields thermoplastically processable and easily recyclable bio-based epoxy glass polymers. Imine bonds have been widely used in epoxy glass polymers due to their ease of preparation, lack of catalysts for exchange, and controllable structure. Currently, there are two main methods for introducing imine bonds into epoxidized vegetable oil resins to produce epoxidized vegetable oil glass polymers. One involves first synthesizing a dynamic curing agent containing imine bonds and curing it with epoxidized vegetable oil to produce epoxidized vegetable oil glass polymers. The other involves reacting aldehyde-containing compounds with epoxidized vegetable oil to produce epoxidized vegetable oil polyaldehydes, which are then reacted with diamines in an aldehyde-amine condensation reaction to produce epoxidized vegetable oil glass polymers. However, these two methods involve many reaction steps and usually use solvents. The removal and residue of solvents will lead to problems such as increased costs and environmental pollution. Summary of the Invention

[0004] To address the above-mentioned technical problems, the first objective of the present invention is to provide a method for preparing an epoxidized vegetable oil-based glass polymer material, and the second objective is to provide the epoxidized vegetable oil-based glass polymer material prepared by this method. The present invention utilizes a solvent-free, one-pot melt polymerization process, which is simple, environmentally friendly, and economical. It allows for easy manipulation of the structure and properties of the vegetable oil-epoxidized glass polymer.

[0005] To achieve the above first purpose, the present invention is implemented through the following technical solution: a method for preparing an epoxy vegetable oil-based glass polymer material, characterized in that: epoxy vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and a diamine are used as raw materials, and are reacted at 130-200°C in a nitrogen atmosphere in the presence of a catalyst.

[0006] Since the epoxy bond of epoxidized vegetable oil has low activity in reacting with amino groups, while the reaction of amino groups with aldehyde groups and the reaction of another functional group (carboxyl group or phenolic hydroxyl group) of aldehyde compounds containing hydroxyl groups and / or carboxyl groups with epoxy bonds are all high, when the three substances are reacted in a one-pot method, the main reactions occur between the amino groups and aldehyde groups (forming imine bonds) and the reaction of another functional group (carboxyl group or phenolic hydroxyl group) with epoxy. Due to the strict control of the raw material ratio, the side reaction of the low-activity amino-epoxy reaction to form a permanent cross-linked structure can be basically ignored. Therefore, the successful preparation of epoxidized vegetable oil-based glass polymers can be achieved through a solvent-free one-pot method. This preparation method does not require solvents and has the characteristics of being green, environmentally friendly, and low-cost.

[0007] In the above solution, the epoxidized vegetable oil is any one or more of epoxidized soybean oil, epoxidized tung oil, and epoxidized linseed oil.

[0008] In the above scheme: the aldehyde compound containing phenolic hydroxyl group and / or carboxyl group is any one of vanillin, 4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 2-carboxybenzaldehyde and 3-carboxybenzaldehyde.

[0009] In the above scheme, the aldehyde compound containing phenolic hydroxyl and / or carboxyl groups and the epoxy vegetable oil are added according to the molar ratio of phenolic hydroxyl and / or carboxyl groups to epoxy groups of 0.5:1.0-1.0:1.0.

[0010] In the above scheme, the diamine is any one of decanediamine, dimeramine, p-phenylenediamine, diphenylmethanediamine, isophoronediamine, and dicyclohexylmethanediamine.

[0011] In the above scheme, the aldehyde compound containing phenolic hydroxyl group and / or carboxyl group and the diamine are added according to the aldehyde group / amino group molar ratio of 1:1.

[0012] In the above scheme: the catalyst is any one of 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole and 4-dimethylaminopyridine.

[0013] In the above scheme, the amount of the catalyst is 0.01-1% of the total mass of the epoxy vegetable oil, the aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and the diamine.

[0014] In the above scheme: reaction time is 1-12h.

[0015] An epoxy vegetable oil glass polymer material prepared by the preparation method of the epoxy vegetable oil glass polymer material.

[0016] Beneficial Effects: This invention utilizes the differences in reactivity between functional groups to design a novel, solvent-free, one-pot method for preparing epoxy vegetable oil-based glass polymers. This preparation process requires no solvent, eliminating tedious steps such as product purification and solvent treatment, resulting in high efficiency, low cost, and a pollution-free environment. This preparation method is universally applicable, and by selecting aldehyde-containing compounds and diamines of varying structures, the structure and properties of epoxy vegetable oil-based glass polymers can be tailored over a wide range to meet the needs of diverse applications. Furthermore, the preparation method provided by this invention is simple to operate, requiring no specialized equipment, and is highly operational and cost-effective. DETAILED DESCRIPTION

[0017] The present invention will be further described below with reference to the embodiments.

[0018] Example 1

[0019] Epoxidized soybean oil, vanillin and decanediamine were added to a reaction flask at a phenolic hydroxyl group / epoxy group molar ratio of 0.7:1 and an aldehyde group / amino group molar ratio of 1:1. Epoxidized vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and a catalyst 1-methylimidazole (0.1% of the total mass of the diamine) were added, and the mixture was reacted at 130°C under a nitrogen atmosphere for 12 hours to obtain an epoxidized vegetable oil-based glass polymer material.

[0020] Performance Testing

[0021] The obtained epoxy vegetable oil-based glass polymer was hot-pressed at 160°C and 10 MPa for 10 minutes using a molding method to obtain an epoxy vegetable oil-based glass polymer sheet. The tensile strength of the epoxy vegetable oil-based glass polymer was measured according to GB1040-92 standard to be 4.7±0.6 MPa, and the elongation at break was 117±7%; the gel fraction was measured using N,N-dimethylformamide to be 90.5%.

[0022] Example 2

[0023] Epoxidized linseed oil, 4-hydroxybenzaldehyde and p-phenylenediamine were added to a reaction flask at a phenolic hydroxyl group / epoxy group molar ratio of 0.5:1 and an aldehyde group / amino group molar ratio of 1:1. Epoxidized vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups and a catalyst 1,2-dimethylimidazole (0.01% of the total mass of the diamine) were added, and the mixture was reacted at 150° C. under a nitrogen atmosphere for 10 hours to obtain an epoxy vegetable oil-based glass polymer material.

[0024] Performance Testing

[0025] The obtained epoxy vegetable oil-based glass polymer was hot-pressed at 160°C and 10 MPa for 10 minutes using a molding method to obtain an epoxy vegetable oil-based glass polymer sheet. The tensile strength of the epoxy vegetable oil-based glass polymer was measured according to GB1040-92 standard to be 25.3±0.2 MPa, and the elongation at break was 12±3%; the gel fraction was measured using N,N-dimethylformamide to be 93.4%.

[0026] Example 3

[0027] Epoxidized tung oil, 3-carboxybenzaldehyde, and diphenylmethanediamine were added to a reaction flask at a carboxyl / epoxy molar ratio of 1:1 and an aldehyde / amino molar ratio of 1:1. Epoxidized vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and a catalyst 4-dimethylaminopyridine (1% of the total mass of the diamine) were also added. The mixture was reacted at 200° C. under a nitrogen atmosphere for 1 hour to obtain an epoxy vegetable oil-based glass polymer material.

[0028] Performance Testing

[0029] The obtained epoxy vegetable oil-based glass polymer was hot-pressed at 160°C and 10 MPa for 10 minutes using a molding method to obtain an epoxy vegetable oil-based glass polymer sheet. The tensile strength of the epoxy vegetable oil-based glass polymer was measured according to GB1040-92 standard to be 38.7±0.5 MPa, and the elongation at break was 8±2%; the gel fraction was measured using N,N-dimethylformamide to be 95.4%.

[0030] Example 4

[0031] Epoxidized soybean oil, 2-carboxylbenzaldehyde and diamine were added to a reaction flask at a carboxyl / epoxy molar ratio of 0.8:1 and an aldehyde / amino molar ratio of 1:1. Epoxidized vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and a catalyst 2-methylimidazole (0.5% of the total mass of the diamine) were added, and the mixture was reacted at 170°C under a nitrogen atmosphere for 5 hours to obtain an epoxidized vegetable oil-based glass polymer material.

[0032] Performance Testing

[0033] The obtained epoxy vegetable oil-based glass polymer was hot-pressed at 160°C and 10 MPa for 10 minutes using a molding method to obtain an epoxy vegetable oil-based glass polymer sheet. The tensile strength of the epoxy vegetable oil-based glass polymer was measured according to GB1040-92 standard to be 15.5±2.3 MPa, and the elongation at break was 185±12%; the gel fraction was measured using N,N-dimethylformamide to be 93.8%.

[0034] Example 5

[0035] Epoxidized tung oil, 4-hydroxybenzaldehyde, and dicyclohexylmethanediamine were added to a reaction flask at a phenolic hydroxyl group / epoxy group molar ratio of 0.6:1 and an aldehyde group / amino group molar ratio of 1:1. Epoxidized vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and a catalyst 1,2-dimethylimidazole (0.3% of the total mass of the diamine) were added, and the mixture was reacted at 180° C. under a nitrogen atmosphere for 3 hours to obtain an epoxy vegetable oil-based glass polymer material.

[0036] Performance Testing

[0037] The obtained epoxy vegetable oil-based glass polymer was hot-pressed at 160°C and 10 MPa for 10 minutes using a molding method to obtain an epoxy vegetable oil-based glass polymer sheet. The tensile strength of the epoxy vegetable oil-based glass polymer was measured according to GB1040-92 standard to be 37.6±1.9 MPa, and the elongation at break was 9±3%; the gel fraction was measured using N,N-dimethylformamide to be 85.7%.

[0038] Example 6

[0039] Epoxidized linseed oil, 3-hydroxybenzaldehyde, and isophorone diamine were added to a reaction flask at a phenolic hydroxyl group / epoxy group molar ratio of 0.8:1 and an aldehyde group / amino group molar ratio of 1:1. Epoxidized vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and a catalyst 4-dimethylaminopyridine (0.05% by weight of the total mass of the diamine) were added, and the mixture was reacted at 140° C. under a nitrogen atmosphere for 10 hours to obtain an epoxy vegetable oil-based glass polymer material.

[0040] Performance Testing

[0041] The obtained epoxy vegetable oil-based glass polymer was hot-pressed at 160°C and 10 MPa for 10 minutes using a molding method to obtain an epoxy vegetable oil-based glass polymer sheet. The tensile strength of the epoxy vegetable oil-based glass polymer was measured according to GB1040-92 standard to be 25.3±0.2 MPa, and the elongation at break was 12±3%; the gel fraction was measured using N,N-dimethylformamide to be 93.4%.

[0042] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an epoxy vegetable oil glass polymer material, characterized by: The method uses epoxy vegetable oil, an aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups, and a diamine as raw materials, and reacts at 130-200° C. in a nitrogen atmosphere in the presence of a catalyst. The aldehyde compound containing phenolic hydroxyl groups and carboxyl groups and the epoxy vegetable oil are added at a molar ratio of phenolic hydroxyl groups to carboxyl groups to epoxy groups of 0.5:1.0-1.0:1.0, and the aldehyde compound containing phenolic hydroxyl groups and / or carboxyl groups and the diamine are added at a molar ratio of aldehyde groups to amino groups of 1:

1.

2. The method for preparing the epoxy vegetable oil glass polymer material according to claim 1, characterized in that: The epoxidized vegetable oil is any one or more of epoxidized soybean oil, epoxidized tung oil and epoxidized linseed oil.

3. The method for preparing the epoxy vegetable oil glass polymer material according to claim 2, characterized in that: The aldehyde compound containing phenolic hydroxyl group and / or carboxyl group is any one of vanillin, 4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 2-carboxybenzaldehyde and 3-carboxybenzaldehyde.

4. The method for preparing the epoxy vegetable oil-based glass polymer material according to any one of claims 1 to 3, characterized in that: The diamine is any one of decanediamine, dimeramine, p-phenylenediamine, diphenylmethanediamine, isophoronediamine, and dicyclohexylmethanediamine.

5. The method for preparing the epoxy vegetable oil glass polymer material according to claim 4, characterized in that: The catalyst is any one of 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole and 4-dimethylaminopyridine.

6. The method for preparing the epoxy vegetable oil glass polymer material according to claim 5, characterized in that: The amount of the catalyst used is 0.01-1% of the total mass of the epoxy vegetable oil, the aldehyde compound containing phenolic hydroxyl and / or carboxyl groups and the diamine.

7. The method for preparing the epoxy vegetable oil glass polymer material according to claim 1, characterized in that: Reaction time 1-12h.

8. An epoxy vegetable oil-based glass polymer material prepared by the method for preparing an epoxy vegetable oil-based glass polymer material according to any one of claims 1 to 7.