Upgradable recyclable bio-based resin, method of making and use thereof
Patent Information
- Application Number
- CN202611020565.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-09
- Publication Date
- 2026-09-29
AI Technical Summary
[0005]解决的技术问题：为解决现有热固性树脂难以降解回收、热塑性树脂回收性能下降以及传统树脂原料过度依赖不可再生化石资源的问题，本发明提供一种可升级回收的生物基树脂及其制备方法和应用，该树脂在使用阶段能够保持传统热固性树脂的稳定高性能，在特定条件下又可解聚生成含有仲胺的升级回收单体，该单体能够进一步用于合成性能可调的新一代树脂材料，并且新一代树脂材料还可再次降解回收得到相同的升级回收单体，从而实现材料的高价值闭环循环
[0019]有益效果：本发明提供的可升级回收生物基树脂，在使用阶段能够保持与传统热固性树脂相当的稳定力学性能，如实施例中桐油基树脂的拉伸强度可达较高水平。在达到使用寿命后，通过动态酯键的可逆交换反应，该树脂能够在温和条件下高效解聚为含有仲胺的升级回收单体，该单体纯度高、结构明确，可直接用于制备新一代树脂。新一代树脂不仅保留了良好的热机械性能，其断裂伸长率较原始树脂还有显著提升，展示了性能升级的效果。更重要的是，该新一代树脂仍可通过动态氨酯键的交换反应再次解聚回收得到相同的仲胺单体，真正实现了从废料到高端材料的闭环循环。整个体系以可再生生物质（桐马酸酐、马来松香）为主要原料，减少了对化石资源的依赖，同时树脂在反复回收过程中无需额外添加复杂助剂，降解产物可重复利用，显著降低了长期使用的环境成本和资源消耗。与现有降级回收技术相比，本发明实现了性能维持甚至提升，与直接焚烧或填埋相比，大幅减少了碳排放和污染，体现出材料设计、降解回收与新树脂合成之间的协同增效，为高性能绿色复合材料、电子封装、粘合剂涂料及3D打印等领域提供了可持续的材料解决方案。
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Figure CN122832259A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of chemical synthesis technology, specifically relating to the field of polymer materials, and particularly to an upgradable and recyclable bio-based resin, its preparation method, and its application. Background Technology
[0002] Traditional thermosetting resins, such as epoxy resins and unsaturated polyesters, typically exhibit excellent mechanical properties, heat resistance, and dimensional stability due to their permanently cross-linked network structure, leading to their widespread application in composite materials, electronic packaging, and adhesives. However, this irreversible cross-linking structure makes them difficult to degrade or recycle after use, with landfilling or incineration being the primary disposal methods. This not only wastes resources but also imposes a severe environmental burden. In contrast, traditional thermoplastic resins can be physically recycled through melt processing. However, during each recycling process, the polymer chains often break due to thermomechanical degradation, resulting in a gradual decline in the material's mechanical properties and overall quality—a process known as downgraded recycling. Furthermore, the monomer raw materials for both thermosetting and thermoplastic resins are largely derived from non-renewable fossil resources such as petroleum and coal, further exacerbating human dependence on fossil fuels and carbon emissions.
[0003] In recent years, a new resource recycling concept known as upcycling has gradually gained attention. Unlike traditional downcycling, upcycling aims to transform waste polymer materials into products with superior performance, higher economic value, or entirely new functions through chemical decomposition, physical remodeling, or creative design at the molecular level. For example, using controlled chemical depolymerization methods, waste plastics can be precisely decomposed into virgin monomers or high-value-added intermediates. These products can then be repolymerized into new materials of comparable or even superior quality to the virgin materials, thus truly realizing a value leap from waste to premium. This approach not only reduces resource consumption and environmental pollution at the source but also has the potential to drive the entire industrial chain towards a high-value closed loop, becoming one of the key technological paths for building a circular economy and solving the plastic waste crisis. Of course, upcycling still faces many challenges in its practical promotion, such as cost control in the chemical depolymerization process, the establishment of a recycling system, and the sorting and pretreatment of different types of waste. However, these challenges cannot overshadow its core value: representing a sustainable future where resources move from linear consumption to closed-loop regeneration.
[0004] The key to achieving upgraded recycling lies in the collaborative innovation of materials science and manufacturing processes. At the materials design level, the core strategy is to develop polymer systems with controllable depolymerization capabilities, such as by introducing dynamic covalent bonds or specific breakable bonding units, while simultaneously utilizing bio-based raw materials as much as possible. This ensures that materials can be efficiently reduced to valuable chemicals or monomers after reaching their service life and maintain performance without degradation during multiple cycles. At the manufacturing and recycling process level, breakthroughs are needed in chemical recycling technologies such as efficient depolymerization and precise catalytic cracking, as well as the development of high-value physical reprocessing methods. This will systematically transform waste materials into high-quality raw materials that can be reused in production. These two levels of technological advancement complement each other: advanced materials design provides a feasible basis for recycling processes, while efficient and economical recycling processes allow the high performance and recyclability of the materials design to be truly realized. Only when breakthroughs are achieved and effectively integrated in both dimensions can upgraded recycling move from laboratory concepts to large-scale industrial applications, providing a practical solution to the increasingly serious problems of plastic pollution and resource depletion. Therefore, developing a novel bio-based resin that can maintain the stable and high performance of traditional thermosetting resins during its service life and can be upgraded and recycled under specific conditions has significant scientific research value and practical application value. Summary of the Invention
[0005] Technical problems solved: To address the issues of the difficulty in degrading and recycling existing thermosetting resins, the decline in the recycling performance of thermoplastic resins, and the over-reliance on non-renewable fossil resources for traditional resin raw materials, this invention provides an upgradable recyclable bio-based resin, its preparation method, and its applications. This resin can maintain the stable and high performance of traditional thermosetting resins during use, and under specific conditions, it can depolymerize to generate upgradable recyclable monomers containing secondary amines. These monomers can be further used to synthesize a new generation of resin materials with adjustable properties, and the new generation of resin materials can be degraded and recycled again to obtain the same upgradable recyclable monomers, thereby achieving a high-value closed-loop cycle of materials.
[0006] Technical solution: An upgradable and recyclable bio-based resin, with the chemical structure shown below:
[0007]
[0008] Where R1 is any one of the following groups:
[0009] .
[0010] The above-mentioned method for preparing the upgradable and recyclable bio-based resin includes: mixing a bio-based polyacid with 4,5-epoxytetrahydrophthalic acid diglycidyl ether at a molar ratio of 1:1; the epoxy ring-opening reaction temperature is 90-120℃, and the reaction time is 4-12 h, to obtain the upgradable and recyclable bio-based resin.
[0011] The aforementioned bio-based polyacids are tung oil anhydride or maleic rosin.
[0012] The application of the above-mentioned bio-based resin in upgrading and recycling includes the following recycling steps: placing the upgradable bio-based resin fragments in a mixed solution of a primary amine with a monofunctional group containing sodium methoxide and DMF, wherein the mass fraction of sodium methoxide is 0.1%-1% of the resin, the molar ratio of resin to primary amine is ≥1:2, the mass ratio of resin to DMF is 1:5, and degrading is carried out at 90-120 °C for 24-48 h to obtain a degradation solution.
[0013] The above method further includes: separating and purifying the degradation solution by dialysis to obtain an upgraded recovery monomer containing a secondary amine; the dialysis bag used in the dialysis method has a molecular weight cutoff greater than 400 Da.
[0014] The structure of the upgraded recovered monomer containing the secondary amine is shown below: R2 is any one of the following groups: , n=1-12.
[0015] The application of the bio-based resin in upgrading and recycling involves mixing the upgraded and recycled monomer containing secondary amine with diisocyanate at a molar ratio of 1:(1-1.5), dissolving it in 1,4-dioxane containing stannous octoate, and evaporating it at 40℃~60℃ for 6~12 h to obtain a new generation of recyclable bio-based resin material; wherein the mass fraction of stannous octoate is 0.1%~0.5% of the mass of the upgraded and recycled monomer containing secondary amine.
[0016] The structural formula of the above-mentioned new generation of recyclable bio-based resin materials is shown below: R3 is any one of the following groups: n = 1-12; wherein the diisocyanate group is any one of the following groups: , n=1-12.
[0017] A method for recycling the next-generation recyclable bio-based resin material, the method comprising: placing fragments of the next-generation recyclable bio-based resin material in a mixed solution of hexylamine and DMF, and degrading at 90℃~120℃ for 24~48h to obtain a degradation solution; the mass ratio of the next-generation recyclable bio-based resin material, hexylamine and DMF is 1:10:10; then separating and purifying the degradation solution by dialysis to obtain an upgraded recyclable monomer containing secondary amine; the dialysis bag used in the dialysis method has a molecular weight cutoff greater than 400 Da.
[0018] Applications of the upgradable and recyclable bio-based resin in the preparation of high-performance green composite materials, electronic packaging materials, adhesives and coatings, and 3D printing materials.
[0019] Beneficial Effects: The upgradable recyclable bio-based resin provided by this invention maintains stable mechanical properties comparable to traditional thermosetting resins during its use phase. For example, the tensile strength of the tung oil-based resin in the embodiments can reach a high level. After reaching its service life, through a reversible exchange reaction of dynamic ester bonds, the resin can be efficiently depolymerized under mild conditions into upgradable recyclable monomers containing secondary amines. These monomers have high purity and well-defined structures and can be directly used to prepare next-generation resins. The next-generation resin not only retains good thermomechanical properties, but its elongation at break is also significantly improved compared to the original resin, demonstrating the effect of performance upgrade. More importantly, this next-generation resin can still be depolymerized again through a dynamic urethane bond exchange reaction to recover the same secondary amine monomers, truly realizing a closed-loop cycle from waste to high-end materials. The entire system uses renewable biomass (tung oil anhydride, maleic rosin) as the main raw material, reducing dependence on fossil resources. At the same time, the resin does not require the addition of complex additives during repeated recycling, and the degradation products can be reused, significantly reducing the environmental costs and resource consumption in the long term. Compared with existing degradation and recycling technologies, this invention achieves performance maintenance or even improvement. Compared with direct incineration or landfill, it significantly reduces carbon emissions and pollution, demonstrating the synergistic effect between material design, degradation and recycling and new resin synthesis. It provides sustainable material solutions for high-performance green composite materials, electronic packaging, adhesives and coatings and 3D printing. Attached Figure Description
[0020] Figure 1 This is the 1H NMR spectrum of tungmaric anhydride.
[0021] Figure 2 This is a picture of an upgradable and recyclable tung oil-based resin.
[0022] Figure 3 This refers to the upgrading and recycling process of tung oil-based resins that can be recycled.
[0023] Figure 4 The above is the 1H NMR spectrum of the upgraded recovered monomer containing secondary amines.
[0024] Figure 5 This is a picture of a new generation of recyclable tung oil-based resin.
[0025] Figure 6 This is a recycling process for a new generation of recyclable tung oil-based resins.
[0026] Figure 7 The image shows the 1H NMR spectrum of the upgraded and recovered monomer containing hydroxyl groups.
[0027] Figure 8 This image shows a new generation of non-recyclable tung oil-based resin and its recycling process.
[0028] Figure 9 This is a comparison chart of mechanical properties. Detailed Implementation
[0029] Example 1
[0030] 3.8 g of tung oil anhydride and 3 g of 4,5-epoxytetrahydrophthalic acid diglycidyl ether were mixed and subjected to an epoxy ring-opening reaction at 90 °C for 6 h in an oven to prepare a bio-based resin that can be upgraded and recycled. 6 g of the bio-based resin fragments were placed in a mixed solution containing 0.03 g sodium methoxide, 12 g of hexylamine, and 30 g of DMF, and degraded at 120 °C for 24 h. Under the action of heat and a catalyst, the dynamic ester bonds in the network underwent a large-scale exchange reaction, leading to network depolymerization. The degradation solution was then separated and purified by dialysis (dialysis bag with a permeation molecular weight of 500) to obtain the upgraded and recycled monomer containing secondary amines.
[0031] Example 2
[0032] Two g of the monomer containing secondary amine recovered in Example 1 was dissolved with 0.75 g of isophorone diisocyanate in 5 mL of 1,4-dioxane containing 0.005 g of stannous octoate. The mixture was then evaporated in an oven at 40 °C for 12 h to obtain a new generation of recyclable tung oil-based resin. 0.5 g of fragments of this new generation of recyclable tung oil-based resin were placed in a mixed solution of 3 g hexylamine and 3 g DMF and degraded at 120 °C for 24 h. Under heat, the dynamic urethane bonds in the network underwent a large-scale exchange reaction, leading to network depolymerization. The degradation solution was then separated and purified by dialysis (dialysis bag with a molecular weight cutoff of 500 Da) to regenerate the upgraded recovered monomer containing secondary amine.
[0033] Example 3
[0034] Six g of upgradable tung oil-based resin fragments were placed in a mixed solution of 12 g serine alcohol and 30 g DMF containing 0.03 g sodium methoxide and degraded at 120 °C for 24 h. Under the action of heat and catalyst, the dynamic ester bonds in the network underwent a large-scale exchange reaction, leading to network depolymerization. The degradation solution was then separated and purified by dialysis (dialysis bag with a molecular weight cutoff of 500 Da) to obtain hydroxyl-containing monomers. Two g of the hydroxyl-containing monomers recovered in Example 1 were dissolved with 0.75 g isophorone diisocyanate in 5 ml of 1,4-dioxane containing 0.005 g stannous octoate and evaporated in an oven at 40 °C for 12 h to obtain a new generation of tung oil-based resin. 0.5 g of the new generation of tung oil-based resin fragments were placed in a mixed solution of 3 g hexylamine and 3 g DMF and degraded at 120 °C for 24 h. Since this material is obtained by the reaction of diisocyanate and hydroxyl groups, it does not have a degradable trisubstituted urea structure, and the material cannot be chemically recycled.
[0035] Example 4
[0036] 4 g of maleic rosin was mixed with 3 g of 4,5-epoxytetrahydrophthalic acid diglycidyl ether and subjected to an epoxy ring-opening reaction at 90 °C for 6 h in an oven to prepare a recyclable rosin-based resin. 6 g of the recyclable bio-based resin fragments were placed in a mixed solution containing 0.3 g sodium methoxide, 12 g of hexylamine, and 30 g of DMF, and degraded at 120 °C for 24 h. Under the action of heat and a catalyst, the dynamic ester bonds in the network underwent a large-scale exchange reaction, leading to network depolymerization. The degradation solution was then separated and purified by dialysis (with a molecular weight cutoff of 500 Da in the dialysis bag) to obtain a recyclable monomer containing a secondary amine.
[0037] Depend on Figure 9 It can be seen that the recyclable tung oil-based resin obtained in Example 1 has the highest tensile strength, and the new generation of recyclable tung oil-based resin obtained in Example 2 has a higher elongation at break than the new generation of non-recyclable tung oil-based resin obtained in Example 3.
Claims
1. A bio-based resin that is upgradable and recyclable, characterized in that, The chemical structure is shown below: Where R1 is any one of the following groups: 。 2. The method for preparing the upgradable and recyclable bio-based resin according to claim 1, characterized in that, The preparation method includes: mixing a bio-based polyacid with 4,5-epoxytetrahydrophthalic acid diglycidyl ether at a molar ratio of 1:1; the epoxy ring-opening reaction temperature is 90-120 °C, and the reaction time is 4-12 h, to obtain the upgradable and recyclable bio-based resin.
3. The preparation method according to claim 2, characterized in that, The bio-based polyacid is tung oil anhydride or maleic rosin.
4. The application of the bio-based resin according to claim 1 in upgrading and recycling, characterized in that, The recycling steps include: placing the upgradable recyclable bio-based resin fragments into a mixed solution of a primary amine with a monofunctional group containing sodium methoxide and DMF, wherein the mass fraction of sodium methoxide is 0.1%-1% of the resin, the molar ratio of resin to primary amine is ≥1:2, the mass ratio of resin to DMF is 1:5, and degrading is carried out at 90-120 °C for 24-48 h to obtain a degradation solution.
5. The application of the bio-based resin according to claim 4 in upgrading and recycling, characterized in that, The method further includes: separating and purifying the degradation solution by dialysis to obtain an upgraded recovery monomer containing a secondary amine; the dialysis bag used in the dialysis method has a molecular weight cutoff greater than 400 Da.
6. The application of the bio-based resin according to claim 5 in upgrading and recycling, characterized in that, The structure of the upgraded recovered monomer containing the secondary amine is shown below: R2 is any one of the following groups: , n=1-12.
7. The application of the bio-based resin of claim 1 in upgrading and recycling, characterized in that, The upgraded and recycled monomer containing secondary amine is mixed with diisocyanate at a molar ratio of 1:(1-1.5), dissolved in 1,4-dioxane containing stannous octoate, and evaporated at 40℃~60℃ for 6~12 h to obtain a new generation of recyclable bio-based resin material; wherein the mass fraction of stannous octoate is 0.1%~0.5% of the mass of the upgraded and recycled monomer containing secondary amine.
8. The application of the bio-based resin according to claim 7 in upgrading and recycling, characterized in that, The structural formula of the new generation of recyclable bio-based resin material is shown below: R3 is any one of the following groups: n = 1-12; wherein the diisocyanate group is any one of the following groups: , n=1-12.
9. A method for recycling the new generation of recyclable bio-based resin material as described in claim 8, characterized in that, The method includes: placing fragments of the new generation of recyclable bio-based resin material in a mixed solution of hexylamine and DMF, and degrading them at 90℃~120℃ for 24~48 h to obtain a degradation solution; the mass ratio of the new generation of recyclable bio-based resin material, hexylamine and DMF is 1:10:10; then separating and purifying the degradation solution by dialysis to obtain upgraded recyclable monomers containing secondary amines; the dialysis bag used in the dialysis method has a molecular weight cutoff greater than 400 Da.
10. The application of the upgradable and recyclable bio-based resin of claim 1 in the preparation of high-performance green composite materials, electronic packaging materials, adhesives and coatings, and 3D printing materials.