US-20260125624-A1 - MODIFIED DISTILLER'S GRAINS, PREPARATION METHOD THEREOF, AND USE THEREOF

US20260125624A1US 20260125624 A1US20260125624 A1US 20260125624A1US-20260125624-A1

Abstract

A modified distiller's, a preparation method thereof, and a use thereof are provided, which relate to the field of composite material preparation. Coupling agents with different reactive groups and hyperbranched resins with different terminal reactive groups are used, and through synergistic effect of the coupling agent and the hyperbranched resin, the surface of distiller's grains powder is regulated. This approach solves problems of poor interfacial compatibility between the distiller's grains powder and the biodegradable resin, as well as agglomeration of the distiller's grains powder due to strong hydrogen bonding. As a result, the compatibility and interfacial bonding strength between the distiller's grains powder and the biodegradable resin are enhanced, leading to the production of a high-performance fully biodegradable green composite material.

Inventors

Chen Yu
Yaxi Liu
Juan Li
Haiyan Zhang
Zhangming Chen
Zunyi Yuan
Zhihao Chen
Yi Gao

Assignees

MOUTAI INSTITUTE

Dates

Publication Date: 20260507
Application Date: 20251003
Priority Date: 20241106

Claims (6)

1 . A preparation method of a modified distiller's grains, comprising the following steps: (1) crushing distiller's grains, followed by drying, grinding, and sieving to obtain distiller's grains powder; (2) adding a coupling agent to the distiller's grains powder, followed by heating and stirring to obtain coupling agent-treated distiller's grains; and (3) adding a hyperbranched resin to the coupling agent-treated distiller's grains, followed by heating, stirring for 5 minutes (min) to 45 min, and cooling to room temperature to obtain the modified distiller's grains; wherein a weight ratio of the distiller's grains powder to the coupling agent is (10:1) to (300:1), and the coupling agent is γ-aminopropyltriethoxysilane; and wherein a weight ratio of the distiller's grains powder to the hyperbranched resin is 50:1, and the hyperbranched resin is carboxyl-terminated hyperbranched polyester Hyper C304.
2 . The preparation method as claimed in claim 1 , wherein a drying temperature of the drying in the step (1) is 80° C. to 120° C., and a particle size of the distiller's grains powder is 100 mesh to 2,000 mesh.
3 . A distiller's grains-based fully biodegradable green composite material, wherein in terms of weight percent, a composition of the distiller's grain-based fully biodegradable green composite material comprises: 5 wt % to 95 wt % of biodegradable polyester, 0.1 wt % to 15 wt % of chain extender, 1 wt % to 75 wt % of the modified distiller's grains, 0.1 wt % to 5 wt % of anti-hydrolysis agent, 0.1 wt % to 5 wt % of thermal stabilizer, and 0.1 wt % to 7.5 wt % of lubricant; and the modified distiller's grains is prepared by the preparation method as claimed in claim 1 .
4 . The distiller's grains-based fully biodegradable green composite material as claimed in claim 3 , wherein the biodegradable polyester is at least one selected from the group consisting of poly(butylene adipate-co-terephthalate) (PBAT), polylactic acid (PLA), poly(butylene succinate) (PBS), poly(butylene succinate-co-butylene adipate) (PBSA), poly(propylene carbonate) (PPC), poly(glycolic acid) (PGA), poly(ε-caprolactone) (PCL), poly(hydroxyalkanoate) (PHA), poly(hydroxybutyrate) (PHB), poly(hydroxyvalerate) (PHV), and poly(hydroxybutyrate-co-hidroxyvalerate) (PHBV); the chain extender is at least one selected from the group consisting of an epoxy compound chain extender and a styrene-methyl acrylate copolymer chain extender; the anti-hydrolysis agent is at least one selected from the group consisting of a carbodiimide compound, an isocyanate compound, a bisoxazoline compound, and an epoxy compound; the thermal stabilizer is at least one selected from the group consisting of an aromatic amine compound, a hindered phenol compound, a phosphite compound, and a thioester compound; and the lubricant is at least one selected from the group consisting of a long-chain carboxylic acid, an amide wax, a carboxylic acid ester, a carboxylic acid salt, and an organosilicon resin.
5 . A preparation method of the distiller's grains-based fully biodegradable green composite material as claimed in claim 3 , comprising: mixing the biodegradable polyester, the chain extender, the anti-hydrolysis agent, the thermal stabilizer, and the lubricant to obtain a biodegradable polyester mixture; and mixing the biodegradable polyester mixture with the modified distiller's grains, followed by drying thoroughly to obtain the distiller's grains-based fully biodegradable green composite material.
6 . A use of the distiller's grains-based fully biodegradable green composite material as claimed in claim 3 as a material for blow molding, injection molding, cast film extrusion, rotational molding, three-dimensional (3D) printing, extrusion, coating, spinning, thermoforming, and compression molding.

Description

CROSS-REFERENCE TO RELATED APPLICATION This application claims priority to Chinese Patent Application No. 202411574583.9, filed on Nov. 6, 2024, which is herein incorporated by reference in its entirety. TECHNICAL FIELD The disclosure relates to the field of composite material preparation, and more particularly to a modified distiller's grains, a preparation method thereof, and a use thereof. BACKGROUND Green composite materials are a category of composite materials that use renewable biomass resources as raw materials, and at least one of constituent materials is derived from natural resources and is capable of complete biodegradation. In recent years, with the increasing scarcity of petrochemical polymer materials and their composite resources and the growing environmental protection requirements, the demand for green and environmentally friendly materials has been growing. Biodegradable composite materials prepared with natural biomass fillers, as a type of green and environmentally friendly material, attract widespread market attention. Over the past few years, researchers have successfully prepared green composite materials by using a variety of the biomass fillers, such as rice husk powder, bamboo powder, cellulose, lignin, etc. Owing to their abundant availability and natural biodegradability, the biomass fillers have become one of the most popular types of fillers. Distiller's grains are solid waste products obtained from a brewing process after cereals such as wheat and sorghum have been steamed, fermented, and distilled to extract alcoholic beverages. They are generated in substantial quantities. The distiller's grains exhibit high moisture content, significant acidity, and are prone to spoilage and decomposition. Inappropriate handling may lead to severe ecological and environmental pollution. Therefore, it is necessary to implement treatment processes aimed at reduction, detoxification, and resource recovery of the distiller's grains. Studies have shown that the distiller's grains contain abundant hemicellulose and lignin, which can be used as biomass fillers to further reduce the cost of the composite materials and have received sustained attention in recent years. In addition to cellulose and lignin, the distiller's grains also contain a wealth of nutrients and various active functional components, including alcohols, acids, aldehydes, esters, proteins, amino acids, bioactive peptides, functional oligosaccharides, antioxidant phenols, and flavonoids, which have high utilization value and great development potential and are an important resource. Promoting the resource utilization of the distiller's grains to turn waste into treasure and achieve green circular development, and conducting research on the high-value utilization of the distiller's grains is urgent. SUMMARY To solve the above problems, an embodiment the disclosure provides a preparation method of a modified distiller's grains, including the following steps: (1) crushing distiller's grains, followed by drying, grinding, and sieving to obtain distiller's grains powder;(2) adding a coupling agent to the distiller's grains powder, followed by heating and stirring to obtain coupling agent-treated distiller's grains; and(3) adding a hyperbranched resin to the coupling agent-treated distiller's grains, followed by heating, stirring for 5 minutes (min) to 45 min, and cooling to room temperature to obtain the modified distiller's grains. In an embodiment, a drying temperature of the drying in the step (1) is 80° C. to 120° C., and a particle size of the distiller's grains powder is 100 mesh to 2,000 mesh. In an embodiment, the coupling agent in the step (2) is at least one selected from the group consisting of a silane coupling agent, an aluminum stearate coupling agent, and a titanate coupling agent, and a weight ratio of the distiller's grains powder to the coupling agent is (10:1) to (300:1). Furthermore, in an embodiment, the silane coupling agent is at least one selected from the group consisting of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane; and the titanate coupling agent is isopropyl tri(dioctylpyrophosphate) titanate. In an embodiment, the hyperbranched resin in the step (3) is at least one selected from the group consisting of amino-terminated hyperbranched polyester, carboxyl-terminated hyperbranched polyester, hydroxyl-terminated hyperbranched polyester, hyperbranched epoxy resin, hydroxyl-terminated hyperbranched polyamide, and amino-terminated hyperbranched polyamide, and a weight ratio of the distiller's grains powder to the hyperbranched resin is (5:1) to (300:1). Another embodiment of the disclosure provides a distiller's grains-based fully biodegradable green composite material. In terms of weight percent (wt %), a composition of the distiller's grain-based fully biodegradable green composite material includes: 5 wt % to 95 wt % of biodegradable polyester, 0.1 wt % to 15 wt % of chain extender, 1 wt