A modified distiller's grains and its preparation method and application

Abstract

The present invention belongs to the field of composite material preparation, and particularly relates to a modified distillers' grains and its preparation method and application. The present invention selects the matching of coupling agents with different reactive groups and hyperbranched resins with different reactive end groups at the ends, and through the synergistic effect of the two, the surface of the distillers' grains powder is regulated and treated, solving the problems of poor interfacial compatibility between the distillers' grains powder and the biodegradable resin and the agglomeration of the distillers' grains powder due to strong hydrogen bond interaction, improving the compatibility and interfacial bonding strength between the distillers' grains powder and the biodegradable resin, and obtaining a fully biodegradable green composite material with excellent properties.

Description

Technical Field

[0001] The present invention belongs to the field of composite material preparation, and particularly relates to a modified distiller's grains and a preparation method and application thereof. Background Art

[0002] Green composite materials are a type of composite materials with renewable biomass resources as raw materials, and at least one of the component materials is obtained from natural resources and can be completely degraded. In recent years, with the increasing shortage of petrochemical polymer materials and their composite materials resources and the strengthening of environmental protection requirements, the demand for green environmental protection materials is also increasing. As a kind of green environmental protection material, biodegradable composite materials prepared with natural biomass fillers have received extensive attention in the market. In the past few years, researchers have successfully prepared green composite materials using various biomass fillers such as rice husk powder, bamboo powder, cellulose, and lignin. Biomass fillers have become one of the most popular fillers due to their rich sources and natural biodegradability.

[0003] Distiller's grains are solid waste obtained after wheat, sorghum and other grains are steamed, fermented, and distilled during the brewing process, and the output is huge. Distiller's grains have a high moisture content, high acidity, and are prone to decay and deterioration. Improper treatment will seriously pollute the ecological environment. Therefore, the reduction, harmlessness, and resource utilization of distiller's grains are imperative.

[0004] Research shows that distiller's grains contain rich hemicellulose and lignin, which can be used as biomass fillers to further reduce the cost of composite materials and have received continuous attention in recent years. In addition to cellulose and lignin, distiller's grains also contain rich nutrients and various active functional components, including alcohols, acids, aldehydes, esters, proteins, amino acids, active polypeptides, 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 distiller's grains to turn waste into treasure and realizing green circular development, it is urgent to carry out research on the high-value utilization of distiller's grains. Summary of the Invention

[0005] To solve the above problems, the present invention provides a preparation method of modified distiller's grains, and the steps include:

[0006] (1) Crushing, drying, grinding and sieving distiller's grains to obtain distiller's grains powder;

[0007] (2) Adding a coupling agent to the distiller's grains powder, heating and stirring to obtain coupling agent-treated distiller's grains;

[0008] (3) Adding a hyperbranched resin to the coupling agent-treated distiller's grains, heating and stirring for 5 - 45 min, and cooling to room temperature after the heating and stirring are completed to obtain modified distiller's grains.

[0009] Further, the drying temperature in step (1) is 80 - 120°C; the particle size of the distillers' grains powder is 100 - 2000 mesh.

[0010] Further, the coupling agent in step (2) is selected from at least one of silane coupling agents, aluminate coupling agents, and titanate coupling agents; the weight ratio of the distillers' grains powder to the coupling agent is 10:1 - 300:1.

[0011] Furthermore, the silane coupling agent is at least one of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane; the titanate coupling agent is isopropyltri(dioctylpyrophosphato)titanate.

[0012] Further, the hyperbranched resin in step (3) is selected from at least one of amino-terminated hyperbranched polyesters, carboxyl-terminated hyperbranched polyesters, hydroxyl-terminated hyperbranched polyesters, hyperbranched epoxy resins, hydroxyl-terminated hyperbranched polyamides, and amino-terminated hyperbranched polyamides; the weight ratio of the distillers' grains powder to the hyperbranched resin is 5:1 - 300:1.

[0013] The present invention also provides a fully biodegradable green composite material of distillers' grains, comprising 5 - 95 wt% of biodegradable polyester, 0.1 - 15 wt% of chain extender, 1 - 75 wt% of modified distillers' grains, 0.1 - 15 wt% of hydrolysis inhibitor, 0.1 - 5 wt% of heat stabilizer, and 0.1 - 7.5 wt% of lubricant; the modified distillers' grains are prepared by the above preparation method.

[0014] Further, the biodegradable polyester is selected from at least one of poly(butylene adipate-co-terephthalate), polylactic acid, poly(butylene succinate), poly(butylene succinate-co-adipate), poly(methyl acetyl carbonate), poly(glycolide), poly(ε-caprolactone), polyhydroxyalkanoates, polyhydroxybutyrate, polyhydroxyvalerate, poly(hydroxybutyrate-co-hydroxyvalerate); the chain extender is selected from at least one of epoxy compound chain extenders and styrene-methyl methacrylate copolymer chain extenders; the hydrolysis inhibitor is selected from at least one of carbodiimide compounds, isocyanate compounds, bisoxazoline compounds, and epoxy compounds; the heat stabilizer is selected from at least one of aromatic amine compounds, hindered phenol compounds, phosphite compounds, and thioester compounds; the lubricant is selected from at least one of long-chain carboxylic acids, amide waxes, carboxylic acid esters, carboxylates, and silicone resins.

[0015] The present invention also provides a preparation method of the above fully biodegradable green composite material of distillers' grains, the steps comprising: mixing the biodegradable polyester, chain extender, hydrolysis inhibitor, heat stabilizer, and lubricant to obtain a mixture of biodegradable polyester materials; mixing the mixture of biodegradable polyester materials and the modified distillers' grains, and drying thoroughly after mixing to obtain the fully biodegradable green composite material of distillers' grains.

[0016] The present invention also provides an application of the above-mentioned distillers' grains fully biodegradable green composite material as a blown film, injection molding, casting, rotational molding, 3D printing, extrusion, coating, spinning, thermoforming, and compression molding material.

[0017] The present invention has the following beneficial effects:

[0018] (1) The present invention provides a large-scale and high-value utilization of distillers' grains, a by-product of brewing. The present invention selects coupling agents with different reactive groups to chemically react with the reactive groups of distillers' grains, hyperbranched resin, and biodegradable resin; the present invention selects hyperbranched resins with different terminal reactive end groups to match different types of coupling agents. Through the synergistic effect of the coupling agent and the hyperbranched resin, the surface of the distillers' grains powder is modified and regulated, solving the problems of poor interfacial compatibility between the distillers' grains powder and the biodegradable resin and the strong hydrogen bond interaction between the distillers' grains powder molecules, which leads to agglomeration and poor performance, improving the compatibility and interfacial bonding strength between the distillers' grains and the biodegradable resin, and obtaining a biodegradable green composite material with excellent performance.

[0019] (2) The composite material provided by the present invention improves the filling amount of distillers' grains powder in the composite material while meeting the product standards and performance, expands the application fields of the distillers' grains biodegradable green composite material, and further speeds up the consumption of distillers' grains, avoiding resource waste and serious environmental pollution, bringing social benefits and ecological benefits while bringing certain economic benefits.

[0020] (3) The matrix resins used in the present invention are all fully biodegradable resins. The composite material obtained by adding distillers' grains as a green bio-based filler to the biodegradable resin is completely biodegradable within a certain environment and time, truly achieving the reduction, harmlessness, and resource utilization of distillers' grains.

[0021] (4) The processing technology of the total distillers' grains powder and the preparation technology of the green fully biodegradable composite material in the present invention are convenient and feasible, with high production efficiency and high economic benefits, and have great industrial application prospects. Detailed Embodiments

[0022] The various exemplary embodiments of the present invention will now be described in detail. Unless otherwise specified, the methods in the examples are all conventional methods, and the reagents used are all conventional commercially available reagents or reagents prepared by conventional methods. This detailed description should not be construed as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation embodiments of the present invention.

[0023] It should be understood that the terms described in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0024] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0025] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0026] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0027] Unless otherwise specified, the raw materials used in the examples are all commercially available products.

[0028] PBAT resin, TH801T, was purchased from Xinjiang Blueshirt Tunhe Technology Co., Ltd.;

[0029] PLA resin, LX175, was purchased from TotalEnergies Corbion;

[0030] PPC resin, T4, was purchased from Jiangsu Zhongke Jinlong Chemical Co., Ltd.;

[0031] PBS resin, FZ71PM, was purchased from PTT MCC Biochem Company Limited;

[0032] PBSA resin, FD92PB, was purchased from PTT MCC Biochem Company Limited;

[0033] PHBV resin, Y1000, was purchased from Ningbo Tian'an Biomaterials Co., Ltd.;

[0034] PGA resin, G 205S, was purchased from Evonik;

[0035] PCL resin, Esun 1000C, was purchased from Shenzhen Guanhua Weiye Co., Ltd.

[0036] Coupling agents γ-aminopropyltriethoxysilane (KH-550), (KH-560) and isopropyltri(dioctylpyrophosphate) titanate (NDZ-201) were all purchased from Nanjing Shuguang Chemical Group Co., Ltd.

[0037] Example 1:

[0038] Preparation of modified distiller's grains: (1) After the liquor distiller's grains were crushed, they were thoroughly washed in water, and after filtering the water, they were placed in a drying oven at 100 °C to dry the moisture; the dried distiller's grains were placed in a grinding machine and ground and sieved to a particle size of 1250 mesh to obtain distiller's grains powder; the above-mentioned distiller's grains powder was added to a high-speed mixer, the rotation speed was set at 1000 rad / min, and it was heated to 100 °C; under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%) : coupling agent (wt%) = 50:1, coupling agent KH560 was added while stirring, and after the addition was completed, the material temperature was controlled at 100 °C and stirred for 30 min to obtain KH560-treated distiller's grains powder. (2) Then, according to the weight ratio of distiller's grains powder (wt%) : hyperbranched resin (wt%) = 50:1, the hyperbranched polyester with terminal carboxyl groups Hyper C304 was added to the above-mentioned KH560-treated distiller's grains powder, the rotation speed of the high-speed mixer was set at 1000 rad / min, the material temperature was controlled at 100 °C, and it was stirred for 30 min; after completion, the heating was stopped after the reaction, and it was stirred at a low speed of 100 r / min and cooled to room temperature to obtain KH560 and Hyper C304 jointly modified distiller's grains 1#, which was reserved.

[0039] Preparation of distiller's grains fully biodegradable green composite material: (1) The biodegradable polyesters PBAT and PLA were respectively placed in a drying device for sufficient drying; the fully dried PBAT (53.9 wt%) and PLA (23.1 wt%), chain extender ADR 4468 (0.8 wt%), hydrolysis-resistant agent polymeric carbodiimide (1.6 wt%), heat stabilizer 1010 (0.2 wt%), heat stabilizer 168 (0.2 wt%), and lubricant erucamide (0.2 wt%) were weighed according to the above weight percentage ratios and added to a high-speed mixer. The temperature of the high-speed mixer was set at room temperature, the rotation speed was 1000 rad / min, and the mixing time was 10 min; to obtain mixture 1#. (2) The obtained mixture 1# and modified distillers grains 1# were respectively placed in the funnels of different loss-in-weight feeders, and the feeding parameters were set according to the ratio requirement of mixture 1# (wt%): modified distillers grains 1# (wt%) = 80:20. After extrusion, drawing, cooling, and pelletizing through a twin-screw extruder, the obtained pellets were fully dried to obtain distillers grains fully biodegradable green composite material 1#; during the processing, the temperature of the extruder was set at 180 °C, and the main machine rotation speed was 300 rpm.

[0040] Example 2:

[0041] Preparation of modified distillers grains: The same as in Example 1.

[0042] Preparation of distillers grains fully biodegradable green composite material: (1) The biodegradable polyesters PBAT and PLA were respectively placed in a drying device for full drying; After full drying, PBAT (47.04 wt%) and PLA (20.16 wt%), chain extender ADR 4468 (0.7 wt%), hydrolysis-resistant agent polymeric carbodiimide (1.4 wt%), heat stabilizer 1010 (0.2 wt%), heat stabilizer 168 (0.2 wt%), and lubricant erucamide (0.3 wt%) were weighed according to the above weight percentage ratios and added to a high-speed mixer. The temperature of the high-speed mixer was set at room temperature, the rotation speed was 1000 rad / min, and the mixing time was 10 min; to obtain mixture 2#. (2) The obtained mixture 2# and modified distillers grains 1# were respectively placed in the funnels of different loss-in-weight feeders, and the feeding parameters were set according to the ratio requirement of mixture 2# (wt%): modified distillers grains 1# (wt%) = 70:30. After extrusion, drawing, cooling, and pelletizing through a twin-screw extruder, the obtained pellets were fully dried to obtain distillers grains fully biodegradable green composite material 2#; during the processing, the temperature of the extruder was set at 180 °C, and the main machine rotation speed was 300 rpm.

[0043] Example 3:

[0044] Preparation of modified distillers grains: The same as in Example 1.

[0045] Preparation of fully biodegradable green composite from distillers' grains: (1) Place biodegradable polyesters PBAT and PLA in a drying equipment respectively for sufficient drying; place the sufficiently dried PBAT (40.18 wt%) and PLA (17.22 wt%), chain extender ADR 4468 (0.6 wt%), anti-hydrolysis polymeric carbodiimide (1.2 wt%), heat stabilizer 1010 (0.2 wt%), heat stabilizer 168 (0.2 wt%) and lubricant erucamide (0.4 wt%) into a high-speed mixer according to the above weight percentage ratios, set the temperature of the high-speed mixer to room temperature, the rotation speed to 1000 rad / min, and the mixing time to 10 min; obtain mixture 3#. (2) Place the obtained mixture 3# and modified distillers' grains 1# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 3# (wt%): modified distillers' grains 1# (wt%) = 60:40, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain fully biodegradable green composite 3# from distillers' grains; during the processing, set the extruder temperature to 180 °C and the main machine rotation speed to 300 rpm.

[0046] Example 4:

[0047] Preparation of modified distillers' grains: The same as Example 1.

[0048] Preparation of fully biodegradable green composite from distillers' grains: (1) Place biodegradable polyesters PBAT and PLA in a drying equipment respectively for sufficient drying; place the sufficiently dried PBAT (33.32 wt%) and PLA (14.28 wt%), chain extender ADR 4468 (0.5 wt%), anti-hydrolysis polymeric carbodiimide (1.0 wt%), heat stabilizer 1010 (0.2 wt%), heat stabilizer 168 (0.2 wt%) and lubricant erucamide (0.5 wt%) into a high-speed mixer according to the above weight percentage ratios, set the temperature of the high-speed mixer to room temperature, the rotation speed to 1000 rad / min, and the mixing time to 10 min; obtain mixture 4#. (2) Place the obtained mixture 4# and modified distillers' grains 1# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 4# (wt%): modified distillers' grains 1# (wt%) = 50:50, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain fully biodegradable green composite 4# from distillers' grains; during the processing, set the extruder temperature to 180 °C and the main machine rotation speed to 300 rpm.

[0049] Example 5:

[0050] Preparation of modified distiller's grains: (1) Treat the distiller's grains with a coupling agent in the same manner as in Example 1 to obtain distiller's grains powder treated with KH560. (2) Then, add hyperbranched polyester with terminal carboxyl groups Hyper C181 to the distiller's grains powder treated with the coupling agent KH560 according to the weight ratio of distiller's grains powder (wt%): hyperbranched resin (wt%) = 50:1. Set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C, and stir for 30 min. After completion, stop heating the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain jointly modified distiller's grains 2# with KH560 and Hyper C181, and set aside.

[0051] Preparation of fully biodegradable green composite material from distiller's grains: Place the mixture 2# and the modified distiller's grains 2# in the funnels of different gravimetric feeders respectively. Set the feeding parameters according to the ratio of mixture 5# (wt%): modified distiller's grains 2# (wt%) = 70:30. Extrude, draw, cool, and pelletize through a twin-screw extruder. Then, fully dry the obtained pellets to obtain fully biodegradable green composite material 5# from distiller's grains. During the processing, set the temperature of the extruder at 180 °C and the main machine speed at 300 rpm.

[0052] Example 6:

[0053] Preparation of modified distiller's grains: (1) After crushing the liquor distiller's grains, wash them thoroughly in water, filter the water, and place them in a drying oven at 100 °C to dry the moisture. Place the fully dried liquor distiller's grains in a grinding machine, grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder. Add the above distiller's grains powder to a high-speed mixer, set the rotation speed at 1000 rad / min, and heat to 100 °C. Under high-speed stirring, add the coupling agent KH550 according to the weight ratio of distiller's grains powder (wt%): coupling agent (wt%) = 50:1. While stirring, control the material temperature at 100 °C after the addition and stir for 30 min to obtain distiller's grains powder treated with the coupling agent KH550. (2) Then, add hyperbranched epoxy resin Hyper E102 to the distiller's grains powder treated with the coupling agent KH550 according to the weight ratio of distiller's grains powder (wt%): hyperbranched resin (wt%) = 50:1. Set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C, and stir for 30 min. After completion, stop heating the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain jointly modified distiller's grains 3# with KH550 and Hyper E102, and set aside.

[0054] Preparation of fully biodegradable green composite material from distillers' grains: Place the mixture 2# and the modified distillers' grains 3# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 6# (wt%) : modified distillers' grains 3# (wt%) = 70 : 30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the fully biodegradable green composite material 6# from distillers' grains; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0055] Example 7:

[0056] Preparation of modified distillers' grains: (1) After crushing the liquor distillers' grains, wash them thoroughly in water, filter the water and place them in a drying oven at 100 °C to dry the moisture; place the fully dried liquor distillers' grains in a pulverizer and grind and sieve them to a particle size of 1250 mesh to obtain distillers' grains powder; add the above-mentioned distillers' grains powder to a high-speed mixer, set the rotation speed at 1000 rad / min and heat to 100 °C; under high-speed stirring, add the coupling agent NDZ-201 while stirring according to the weight ratio of distillers' grains powder (wt%) : coupling agent (wt%) = 50 : 1. After adding, control the material temperature at 100 °C and stir for 30 min to obtain the coupling agent NDZ-201-treated distillers' grains powder. (2) Then add the hyperbranched polyester with terminal carboxyl groups Hyper C304 to the coupling agent NDZ-201-treated distillers' grains powder according to the weight ratio of distillers' grains powder (wt%) : hyperbranched resin (wt%) = 50 : 1. Set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C and stir for 30 min; after completion, stop heating after the reaction, stir at a low speed of 100 r / min and cool to room temperature to obtain the combined modified distillers' grains 4# of NDZ-201 and HyperC304 for standby.

[0057] Preparation of fully biodegradable green composite material from distillers' grains: Place the mixture 2# and the modified distillers' grains 4# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 7# (wt%) : modified distillers' grains 4# (wt%) = 70 : 30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the fully biodegradable green composite material 7# from distillers' grains; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0058] Example 8:

[0059] Preparation of modified distillers' grains: (1) Treat the distillers' grains with coupling agent in the same way as in Example 7 to obtain the distillers' grains powder treated with NDZ-201. (2) Then, add Hyper C181 to the distillers' grains powder treated with the above coupling agent NDZ-201 according to the weight ratio of distillers' grains powder (wt%): hyperbranched resin (wt%) = 50:1. Set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C, and stir for 30 min. After completion, stop heating after the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain the jointly modified distillers' grains 5# with NDZ-201 and HyperC181, which is reserved for use.

[0060] Preparation of the fully biodegradable green composite material of distillers' grains: Place the mixture 2# and the modified distillers' grains 5# in the funnels of different automatic loss-in-weight feeders respectively. Set the feeding parameters according to the ratio requirement of mixture 8# (wt%): modified distillers' grains 5# (wt%) = 70:30. Extrude, draw, cool, and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the fully biodegradable green composite material 8# of distillers' grains. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0061] Example 9:

[0062] Preparation of modified distillers' grains with wine: (1) Treat the distillers' grains with coupling agent in the same way as in Example 6 to obtain the distillers' grains powder treated with KH550. (2) Then, add the hyperbranched polyester with terminal carboxyl groups Hyper C304 to the distillers' grains powder treated with the above coupling agent KH550 according to the weight ratio of distillers' grains powder (wt%): hyperbranched resin (wt%) = 50:1. Set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C, and stir for 30 min. After completion, stop heating after the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain the jointly modified distillers' grains 6# with KH550 and Hyper C304, which is reserved for use.

[0063] Preparation of the fully biodegradable green composite material of distillers' grains: Place the mixture 2# and the modified distillers' grains 6# in the funnels of different automatic loss-in-weight feeders respectively. Set the feeding parameters according to the ratio requirement of mixture 9# (wt%): modified distillers' grains 6# (wt%) = 70:30. Extrude, draw, cool, and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the fully biodegradable green composite material 9# of distillers' grains. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0064] Example 10:

[0065] Preparation of modified distillers' grains: (1) Treat the distillers' grains with coupling agent as in Example 6 to obtain distillers' grain powder treated with coupling agent KH550. (2) Then, according to the weight ratio of distillers' grain powder (wt%): hyperbranched resin (wt%) = 50:1, add terminal carboxyl hyperbranched polyester Hyper C181 to the distillers' grain powder treated with coupling agent KH550 above. Set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C, and stir for 30 min. After completion, stop heating after the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain the jointly modified distillers' grains 7# with KH550 and Hyper C181 for standby.

[0066] Preparation of fully biodegradable green composite material from distillers' grains: Place the mixture 2# and the modified distillers' grains 7# in the funnels of different automatic loss-in-weight feeders respectively. Set the feeding parameters according to the ratio requirement of mixture 2# (wt%): modified distillers' grains 7# (wt%) = 70:30. Extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the fully biodegradable green composite material 10# of distillers' grains. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0067] Example 11:

[0068] Preparation of modified distillers' grains: (1) Treat the distillers' grains with coupling agent: same as Example 1. (2) Treat the distillers' grains with hyperbranched resin: Then, according to the weight ratio of distillers' grain powder (wt%): hyperbranched resin (wt%) = 50:1, add terminal amino hyperbranched polyester Amine Functional Boltorn TM H40 to the distillers' grain powder treated with coupling agent KH560 above. Set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C, and stir for 30 min. After completion, stop heating after the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain the jointly modified distillers' grains 8# with KH560 and Amine Functional Boltorn TM H40 for standby.

[0069] Preparation of fully biodegradable green composite material from distillers' grains: Place the mixture 2# and the modified distillers' grains 8# in the funnels of different automatic loss-in-weight feeders respectively. Set the feeding parameters according to the ratio requirement of mixture 2# (wt%): modified distillers' grains 8# (wt%) = 70:30. Extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the fully biodegradable green composite material 11# of distillers' grains. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0070] Example 12:

[0071] Preparation of modified distiller's grains: (1) Treat the distiller's grains with a coupling agent in the same way as in Example 1 to obtain distiller's grains powder treated with KH560. (2) Then, according to the weight ratio of distiller's grains powder (wt%): hyperbranched resin (wt%) = 50:1, add hyperbranched polyester with terminal hydroxyl groups Boltorn TM Regular H40 into the distiller's grains powder treated with the above coupling agent KH560. Set the rotation speed of the high-speed mixer to 1000 rad / min, control the material temperature at 100 °C, and stir for 30 min. After completion, stop heating after the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain the combined modified distiller's grains 9# of KH560 and Boltorn TM Regular H40 for standby.

[0072] Preparation of the fully biodegradable green composite material of distiller's grains: Place the mixture 2# and the modified distiller's grains 9# in the funnels of different automatic loss-in-weight feeders respectively. Set the feeding parameters according to the ratio of the mixture 2# (wt%): the modified distiller's grains 9# (wt%) = 70:30. Extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the fully biodegradable green composite material 12# of distiller's grains. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0073] Example 13:

[0074] Preparation of modified distiller's grains: (1) After crushing the liquor distiller's grains, wash them thoroughly in water, filter the water and place them in a drying oven at 80 °C to dry the moisture. Place the fully dried liquor distiller's grains in a grinder and grind and sieve them to a particle size of 100 mesh to obtain distiller's grains powder. Add the above distiller's grains powder to a high-speed mixer, set the rotation speed to 2000 rad / min, and heat to 90 °C. Under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%): coupling agent (wt%) = 100:1, add the coupling agent KH560 while stirring. After the addition is completed, control the material temperature at 90 °C and stir for 5 min to obtain the distiller's grains powder treated with the coupling agent KH560. (2) Then, according to the weight ratio of distiller's grains powder (wt%): hyperbranched resin (wt%) = 25:1, add hyperbranched polyester with terminal hydroxyl groups Hyper H304 to the distiller's grains powder treated with the above coupling agent KH560. Set the rotation speed of the high-speed mixer to 100 rad / min, control the material temperature at 90 °C, and stir for 45 min. After completion, stop heating after the reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain the combined modified distiller's grains 10# of KH560 and Hyper H304 for standby.

[0075] Preparation of fully biodegradable green composite material from distiller's grains: Mixing material 2# and modified distiller's grains 11# are respectively placed in the funnels of different loss-in-weight feeders. The feeding parameters are set according to the ratio of Mixing material 2# (wt%) : modified distiller's grains 11# (wt%) = 70 : 30. After extrusion, drawing, cooling and granulation by a twin-screw extruder, the obtained pellets are fully dried to obtain the fully biodegradable green composite material 13# of distiller's grains. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0076] Example 14:

[0077] Preparation of modified distiller's grains: (1) After the white spirit distiller's grains are crushed, they are fully washed in water, and after filtering the water, they are placed in a drying oven at 120 °C to dry the moisture. The fully dried white spirit distiller's grains are ground and sieved in a grinder to a particle size of 2000 mesh to obtain distiller's grains powder. The above-mentioned distiller's grains powder is added to a high-speed mixer, the rotation speed is set at 100 rad / min, and it is heated to 110 °C. Under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%) : coupling agent (wt%) = 25 : 1, the coupling agent NDZ-201 is added while stirring. After the addition is completed, the material temperature is controlled at 110 °C and stirred for 45 min to obtain the distiller's grains powder treated with the coupling agent NDZ-201. (2) Then, according to the weight ratio of distiller's grains powder (wt%) : hyperbranched resin (wt%) = 100 : 1, hyperbranched epoxy resin Hyper E102 is added to the distiller's grains powder treated with the coupling agent NDZ-201. The rotation speed of the high-speed mixer is set at 2000 rad / min, the material temperature is controlled at 110 °C, and stirred for 5 min. After completion, the heating is stopped after the reaction, and it is stirred at a low speed of 100 r / min and cooled to room temperature to obtain the jointly modified distiller's grains 11# of NDZ-201 and HyperH304 for standby.

[0078] Preparation of fully biodegradable green composite material from distiller's grains: Mixing material 2# and modified distiller's grains 11# are respectively placed in the funnels of different loss-in-weight feeders. The feeding parameters are set according to the ratio of Mixing material 2# (wt%) : modified distiller's grains 11# (wt%) = 70 : 30. After extrusion, drawing, cooling and granulation by a twin-screw extruder, the obtained pellets are fully dried to obtain the fully biodegradable green composite material 14# of distiller's grains. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0079] Example 15:

[0080] Preparation of modified distiller's grains: The only difference from Example 1 is that the distiller's grains used in this example are beer distiller's grains, and the rest of the products and processes used are the same as those in Example 1 to obtain the modified distiller's grains 12#.

[0081] Preparation of lees fully biodegradable green composite material: Mixing material 2# and modified lees 12# are respectively placed in the funnels of different loss-in-weight feeders. The feeding parameters are set according to the ratio requirement of mixing material 2# (wt%) : modified lees 12# (wt%) = 70 : 30. After extrusion, drawing, cooling and pelletizing by a twin-screw extruder, the obtained pellets are fully dried to obtain the lees fully biodegradable green composite material 15#. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0082] Example 16:

[0083] Preparation of modified lees: The only difference from Example 1 is that the lees used in this example is yellow rice wine lees, and the rest of the products and processes used are the same as those in Example 1, to obtain modified lees 13#.

[0084] Preparation of lees fully biodegradable green composite material: Mixing material 2# and modified lees 13# are respectively placed in the funnels of different loss-in-weight feeders. The feeding parameters are set according to the ratio requirement of mixing material 2# (wt%) : modified lees 13# (wt%) = 70 : 30. After extrusion, drawing, cooling and pelletizing by a twin-screw extruder, the obtained pellets are fully dried to obtain the lees fully biodegradable green composite material 16#. During the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0085] Example 17:

[0086] Preparation of modified lees: The same as Example 1, to obtain modified lees 1#, for standby.

[0087] Preparation of lees fully biodegradable green composite material: (1) Place the biodegradable polyester PPC in a drying equipment for full drying; PPC (67.6 wt%) after full drying, chain extender 4468 (0.7 wt%), hydrolysis-resistant monomeric carbodiimide (1.0 wt%), heat stabilizer 1076 (0.2 wt%), heat stabilizer 168 (0.2 wt%), and lubricant palmitic acid (0.3 wt%) were weighed according to the above weight percentage ratios and added to a high-speed mixer. The temperature of the high-speed mixer was set at room temperature, the rotation speed was 1000 rad / min, and the mixing time was 10 min; mixture 5# was obtained. (2) The obtained mixture 5# and modified distillers grains 1# were respectively placed in the funnels of different loss-in-weight feeders. The feeding parameters were set according to the ratio requirement of mixture 5# (wt%): modified distillers grains 1# (wt%) = 70:30. After extrusion, stringing, cooling, and pelletizing through a twin-screw extruder, the obtained pellets were fully dried to obtain distillers grains fully biodegradable green composite material 17#; during the processing, the temperature of the extruder was set at 180 °C, and the main machine rotation speed was 300 rpm.

[0088] Example 18:

[0089] Preparation of modified distillers grains: The same as Example 1, modified distillers grains 1# was obtained and reserved.

[0090] Preparation of distillers grains fully biodegradable green composite material: (1) The biodegradable polyester PBS was placed in a drying equipment for full drying; the fully dried PBS (67.6 wt%), chain extender Bio-Master TM HPC-3510P (0.7 wt%), hydrolysis-resistant monomeric carbodiimide (1.0 wt%), heat stabilizer 330 (0.2 wt%), heat stabilizer 636 (0.2 wt%), and lubricant montanic acid (0.3 wt%) were weighed according to the above weight percentage ratios and added to a high-speed mixer. The temperature of the high-speed mixer was set at room temperature, the rotation speed was 1000 rad / min, and the mixing time was 10 min; mixture 6# was obtained. (2) The obtained mixture 6# and modified distillers grains 1# were respectively placed in the funnels of different loss-in-weight feeders. The feeding parameters were set according to the ratio requirement of mixture 6# (wt%): modified distillers grains 1# (wt%) = 70:30. After extrusion, stringing, cooling, and pelletizing through a twin-screw extruder, the obtained pellets were fully dried to obtain distillers grains fully biodegradable green composite material 18#; during the processing, the temperature of the extruder was set at 135 °C, and the main machine rotation speed was 300 rpm.

[0091] Example 19:

[0092] Preparation of modified distillers grains: The same as Example 1, modified distillers grains 1# was obtained and reserved.

[0093] Preparation of fully biodegradable green composite material from distillers' grains: (1) Place the biodegradable polyester PHBV in a drying equipment for sufficient drying; After sufficient drying, PHBV (68.3 wt%), chain extender 4400 (0.7 wt%), hydrolysis-resistant monomeric carbodiimide (0.1 wt%), heat stabilizer 1098 (0.2 wt%), heat stabilizer 168 (0.2 wt%), and lubricant pentaerythritol stearate (0.3 wt%) are weighed according to the above weight percentage and added to a high-speed mixer. Set the temperature of the high-speed mixer to room temperature, the rotation speed to 1000 rad / min, and the mixing time to 10 min; Obtain mixture 6#. (2) Place the obtained mixture 6# and modified distillers' grains 1# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 6# (wt%) : modified distillers' grains 1# (wt%) = 65 : 35, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain fully biodegradable green composite material 19# of distillers' grains; During the processing, the temperature of the extruder is set to 200 °C and the main machine rotation speed is 300 rpm.

[0094] Example 20:

[0095] Preparation of modified distillers' grains: The same as Example 1, obtain modified distillers' grains 1# for standby.

[0096] Preparation of fully biodegradable green composite material from distillers' grains: (1) Place the biodegradable polyester PGA in a drying equipment for sufficient drying; After sufficient drying, PGA (85 wt%), chain extender 4440 (5.05 wt%), hydrolysis-resistant monomeric carbodiimide (3.3 wt%), heat stabilizer 245 (1 wt%), heat stabilizer 626 (0.55 wt%), and lubricant zinc stearate (0.1 wt%) are weighed according to the above weight percentage and added to a high-speed mixer. Set the temperature of the high-speed mixer to room temperature, the rotation speed to 100 rad / min, and the mixing time to 15 min; Obtain mixture 6#. (2) Place the obtained mixture 6# and modified distillers' grains 1# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 6# (wt%) : modified distillers' grains 1# (wt%) = 95 : 5, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain fully biodegradable green composite material 20# of distillers' grains; During the processing, the temperature of the extruder is set to 250 °C and the main machine rotation speed is 100 rpm.

[0097] Example 21:

[0098] Preparation of modified distillers' grains: The same as Example 1, obtain modified distillers' grains 1# for standby.

[0099] Preparation of fully biodegradable green composite material from distillers' grains: (1) Place biodegradable polyester PCL in a drying equipment for sufficient drying; After sufficient drying, weigh PCL (25 wt%), chain extender Eco-Batch TM ECO-1120 (2.3 wt%), anti-hydrolysis monomeric carbodiimide (5.05 wt%), heat stabilizer DPT (0.05 wt%), heat stabilizer 1790 (0.05 wt%), and lubricant polysiloxane (2.55 wt%) according to the above weight percentage ratios, add them to a high-speed mixer, set the temperature of the high-speed mixer to room temperature, the rotation speed to 2000 rad / min, and the mixing time to 5 min; Obtain mixture 6#. (2) Place the obtained mixture 6# and modified distillers' grains 1# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 6# (wt%): modified distillers' grains 1# (wt%) = 35:65, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain fully biodegradable green composite material 21# of distillers' grains; During the processing, the temperature of the extruder is set to 100 °C and the main machine rotation speed is 400 rpm.

[0100] Example 22:

[0101] Preparation of modified distillers' grains: The same as Example 1, obtain modified distillers' grains 1#, and reserve for use.

[0102] Preparation of fully biodegradable green composite material from distillers' grains: (1) Place biodegradable polyester PBAT in a drying equipment for sufficient drying; After sufficient drying, weigh PBAT (55 wt%), chain extender Bio-Master TM SG-20 (10 wt%), anti-hydrolysis polymeric carbodiimide (10 wt%), heat stabilizer 5067 (1.5 wt%), heat stabilizer 168 (1.5 wt%), and lubricant stearic acid (5 wt%) according to the above weight percentage ratios, add them to a high-speed mixer, set the temperature of the high-speed mixer to room temperature, the rotation speed to 1050 rad / min, and the mixing time to 10 min; Obtain mixture 10#. (2) Place the obtained mixture 10# and modified distillers' grains 1# in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 10# (wt%): modified distillers' grains 1# (wt%) = 83:17, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain fully biodegradable green composite material 22# of distillers' grains; During the processing, the temperature of the extruder is set to 180 °C and the main machine rotation speed is 250 rpm.

[0103] Comparative Example 1:

[0104] The biodegradable polyesters PBAT and PLA were respectively placed in a drying device for sufficient drying; the sufficiently dried PBAT (68.04 wt%), PLA (0.7 wt%), chain extender ADR 4468 (0.8 wt%), anti-hydrolysis agent polymeric carbodiimide (1.4 wt%), heat stabilizer 1010 (0.2 wt%), heat stabilizer 168 (0.2 wt%), and lubricant erucamide (0.3 wt%) were weighed according to the above weight percentage ratios and then added to a high-speed mixer. The temperature of the high-speed mixer was set at room temperature, the rotation speed was 1000 rad / min, and the mixing time was 10 min; a mixed material was obtained. The above-obtained mixed material was placed in the hopper of an automatic loss-in-weight feeder, the feeding parameters were set, and the material required for Comparative Example 1 was prepared by a co-rotating twin-screw extruder. After extrusion, stringing, cooling, and pelletizing by the twin-screw extruder, the obtained pellets were then sufficiently dried to obtain the material required for Comparative Example 1, which was marked as Composite Material A. During the processing, the temperature of the extruder was set at 180 °C, and the main machine rotation speed was 300 rpm.

[0105] Comparative Example 2:

[0106] Preparation of modified distiller's grains: After the liquor distiller's grains were pulverized, they were thoroughly washed in water, and after filtering the water, they were placed in a drying oven at 100 °C to dry the moisture; the dried distiller's grains were placed in a pulverizer and ground and sieved to a particle size of 1250 mesh to obtain distiller's grains powder, which was marked as modified distiller's grains B.

[0107] Preparation of composite material: (1) The same as in Example 2, a mixed material 2# was obtained. (2) The mixed material 2# and the modified distiller's grains B were respectively placed in the hoppers of different automatic loss-in-weight feeders, and the feeding parameters were set according to the ratio requirement of mixed material 2# (wt%): modified distiller's grains B (wt%) = 70:30. After extrusion, stringing, cooling, and pelletizing by the twin-screw extruder, the obtained pellets were then sufficiently dried to obtain Composite Material B; during the processing, the temperature of the extruder was set at 180 °C, and the main machine rotation speed was 300 rpm.

[0108] Comparative Example 3:

[0109] Preparation of modified distiller's grains: After crushing the distiller's grains from white liquor, wash them thoroughly in water, filter the water, and then place them in a drying oven at 100 °C to dry the moisture; place the dried distiller's grains in a pulverizer, grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%) : coupling agent (wt%) = 25 : 1, add coupling agent KH560 while stirring. After the addition is completed, control the material temperature at 100 °C and stir for 30 min. After completing the post-reaction, stop heating, stir at a low speed of 100 r / min, and cool to room temperature to obtain KH560-treated distiller's grains powder, marked as modified distiller's grains C.

[0110] Preparation of composite material: (1) The same as in Example 2 to obtain mixture 2#. (2) Place mixture 2# and modified distiller's grains C in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains C (wt%) = 70 : 30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain composite material C; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0111] Comparative Example 4:

[0112] Preparation of modified distiller's grains: After crushing the distiller's grains from white liquor, wash them thoroughly in water, filter the water, and then place them in a drying oven at 100 °C to dry the moisture; place the dried distiller's grains in a pulverizer, grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%) : coupling agent (wt%) = 25 : 1, add coupling agent KH550 while stirring. After the addition is completed, control the material temperature at 100 °C and stir for 30 min. After completing the post-reaction, stop heating, stir at a low speed of 100 r / min, and cool to room temperature to obtain KH550-treated distiller's grains powder, marked as modified distiller's grains D.

[0113] Preparation of composite material: (1) The same as in Example 2 to obtain mixture 2#. (2) Place mixture 2# and modified distiller's grains D in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains D (wt%) = 70 : 30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain composite material D; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0114] Comparative Example 5:

[0115] Preparation of modified distiller's grains: After crushing the distiller's grains from liquor production, wash them thoroughly in water, filter the water, and then dry the moisture in a drying oven at 100 °C; place the dried distiller's grains in a grinding machine and grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, add coupling agent NDZ-201 while stirring according to the weight ratio of distiller's grains powder (wt%) : coupling agent (wt%) = 25:1. After the addition is completed, control the material temperature at 100 °C and stir for 30 min. After the post-reaction is completed, stop heating, stir at a low speed of 100 r / min, and cool to room temperature to obtain KH550-treated distiller's grains powder, marked as modified distiller's grains E.

[0116] Preparation of composite material: (1) The same as in Example 2 to obtain mixture 2#. (2) Place mixture 2# and modified distiller's grains E in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains E (wt%) = 70:30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain composite material E; during the processing, the temperature of the extruder is set at 180 °C and the main machine rotation speed is 300 rpm.

[0117] Comparative Example 6:

[0118] Preparation of modified distiller's grains: After crushing the distiller's grains from liquor production, wash them thoroughly in water, filter the water, and then dry the moisture in a drying oven at 100 °C; place the dried distiller's grains in a grinding machine and grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, add hyperbranched resin while stirring according to the weight ratio of distiller's grains powder (wt%) : hyperbranched resin (wt%) = 25:1. Add carboxyl-terminated hyperbranched polyester Hyper C304 while stirring. After the addition is completed, control the material temperature at 100 °C and stir for 30 min. After the post-reaction is completed, stop heating, stir at a low speed of 100 r / min, and cool to room temperature to obtain Hyper C304-treated distiller's grains powder, marked as modified distiller's grains F.

[0119] Preparation of composite material: (1) The same as in Example 2 to obtain mixture 2#. (2) Place mixture 2# and modified distiller's grains F in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains F (wt%) = 70:30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain composite material F; during the processing, the temperature of the extruder is set at 180 °C and the main machine rotation speed is 300 rpm.

[0120] Comparative Example 7:

[0121] Preparation of modified distiller's grains: After crushing the distiller's grains from Chinese liquor, wash them thoroughly in water, filter the water, and then dry the moisture in a drying oven at 100 °C; place the dried distiller's grains in a grinder, grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%) : hyperbranched resin (wt%) = 25:1, add hyperbranched epoxy resin Hyper E102 while stirring, after the addition, control the material temperature at 100 °C, stir for 30 min, stop heating after completing the post-reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain Hyper E102-treated distiller's grains powder, marked as modified distiller's grains G.

[0122] Preparation of composite material: (1) Similar to Example 2, obtain mixture 2#. (2) Place mixture 2# and modified distiller's grains G in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains G (wt%) = 70:30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain composite material G; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0123] Comparative Example 8:

[0124] Preparation of modified distiller's grains: After crushing the distiller's grains from Chinese liquor, wash them thoroughly in water, filter the water, and then dry the moisture in a drying oven at 100 °C; place the dried distiller's grains in a grinder, grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%) : hyperbranched resin (wt%) = 25:1, add terminal carboxyl hyperbranched polyester Hyper C181 while stirring, after the addition, control the material temperature at 100 °C, stir for 30 min, stop heating after completing the post-reaction, stir at a low speed of 100 r / min, and cool to room temperature to obtain Hyper C181-treated distiller's grains powder, marked as modified distiller's grains H.

[0125] Preparation of composite material: (1) Similar to Example 2, obtain mixture 2#. (2) Place mixture 2# and modified distiller's grains H in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains H (wt%) = 70:30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain composite material H; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0126] Comparative Example 9:

[0127] Preparation of modified distiller's grains: After crushing the liquor distiller's grains, wash them thoroughly in water, filter the water, and place them in a drying oven at 100 °C to dry the moisture; place the dried distiller's grains in a grinding machine and grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%): hyperbranched resin (wt%) = 25:1, add the amino-terminated hyperbranched polyester AmineFunctional Boltorn TM H40 while stirring. After the addition, control the material temperature at 100 °C and stir for 30 min. After completing the post-reaction, stop heating, stir at a low speed of 100 r / min, and cool to room temperature to obtain Amine Functional Boltorn TM H40-treated distiller's grains powder, marked as modified distiller's grains I.

[0128] Preparation of composite material: (1) The same as in Example 2 to obtain mixture 2#. (2) Place mixture 2# and modified distiller's grains I in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%): modified distiller's grains I (wt%) = 70:30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain composite material I; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0129] Comparative Example 10:

[0130] Preparation of modified distiller's grains: After crushing the liquor distiller's grains, wash them thoroughly in water, filter the water, and place them in a drying oven at 100 °C to dry the moisture; place the dried distiller's grains in a grinding machine and grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above-mentioned distiller's grains powder to a high-speed mixer, set the rotation speed to 1000 rad / min, and heat to 100 °C; under high-speed stirring, according to the weight ratio of distiller's grains powder (wt%): hyperbranched resin (wt%) = 25:1, add the hydroxyl-terminated hyperbranched polyester Boltorn TM Regular H40 while stirring. After the addition, control the material temperature at 100 °C and stir for 30 min. After completing the post-reaction, stop heating, stir at a low speed of 100 r / min, and cool to room temperature to obtain Boltorn TM Regular H40-treated distiller's grains powder, marked as modified distiller's grains J.

[0131] Preparation of composite material: (1) The same as in Example 2, to obtain the mixture 2#. (2) Place the mixture 2# and the modified distiller's grains J in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains J (wt%) = 70 : 30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the composite material J; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0132] Comparative Example 11:

[0133] Preparation of modified distiller's grains: (1) After crushing the liquor distiller's grains, wash them thoroughly in water, filter the water and place them in a drying oven at 100 °C to dry the moisture; place the fully dried liquor distiller's grains in a pulverizer and grind and sieve them to a particle size of 1250 mesh to obtain distiller's grains powder; add the above distiller's grains powder to a high-speed mixer, set the rotation speed at 1000 rad / min and heat to 100 °C; under high-speed stirring, add the hyperbranched polyester with terminal carboxyl groups Hyper C304 while stirring according to the weight ratio of distiller's grains powder (wt%) : hyperbranched resin (wt%) = 50 : 1. After the addition, control the material temperature at 100 °C and stir for 30 min to obtain the modified distiller's grains powder of hyperbranched polyester with terminal carboxyl groups Hyper C304. (2) Then add the coupling agent KH560 to the above-mentioned modified distiller's grains powder of hyperbranched polyester with terminal carboxyl groups Hyper C304, set the rotation speed of the high-speed mixer at 1000 rad / min, control the material temperature at 100 °C and stir for 30 min; after completion, stop heating the reaction, stir at a low speed of 100 r / min and cool to room temperature to obtain the jointly modified distiller's grains of HyperC304 and KH560, marked as modified distiller's grains K, for standby.

[0134] Preparation of composite material: (1) The same as in Example 2, to obtain the mixture 2#. (2) Place the mixture 2# and the modified distiller's grains I in the funnels of different loss-in-weight feeders respectively, set the feeding parameters according to the ratio requirement of mixture 2# (wt%) : modified distiller's grains J (wt%) = 70 : 30, extrude, draw, cool and pelletize through a twin-screw extruder, and then fully dry the obtained pellets to obtain the composite material K; during the processing, the temperature of the extruder is set at 180 °C and the main machine speed is 300 rpm.

[0135] In practical applications, when the fully biodegradable green composite material prepared by the present invention is used for film products, the film strength plays an important role in the packaging or handling of commercial goods. It ensures the integrity and usability of the film and has strong guiding significance for various commercial applications. The object of the present invention is to provide a low-cost fully biodegradable green composite material with good mechanical properties. Therefore, a universal material testing machine was used to conduct tensile tests on all film samples to verify their mechanical properties. At the same time, the water vapor transmission rate of the film was tested to verify its barrier properties. The composite materials obtained from Examples 1-22 and Comparative Examples 1-11 in the present invention were made into films for testing in the GB / T 35795-2017 standard, and their performance tests are listed in Table 1.

[0136] Table 1 Performance test results of Examples 1-22 and Comparative Examples 1-11

[0137]

[0138]

[0139]

[0140] (1) Analysis of the test results of Comparative Example 1 and Examples 1-4:

[0141] Comparative Example 1 is a resin material without adding distillers grains. It can be seen from Comparative Example 1 and Examples 1-4 that the tensile strength first increases and then decreases with the increase of the content of modified distillers grains. Among them, in Example 2, when the content of modified distillers grains is 30wt%, the tensile strength reaches the maximum value. Compared with Comparative Example 1, the transverse and longitudinal tensile strengths in Example 2 are increased by 142.3% and 151.16% respectively; the elongation at break also first increases and then decreases with the increase of the content of modified distillers grains. The reason for the increase in the elongation at break is that during the modification and blending of distillers grains powder, the coupling agent and hyperbranched resin act as compatibilizers to increase the molecular chain length between the distillers grains powder and the biodegradable resin matrix, thus forming a flexible interface and improving the elongation at break of the composite material. When the content of distillers grains powder is too high, the elongation at break may decrease due to poor dispersion of agglomerated distillers grains powder; the water vapor transmission rate first decreases and then increases with the increase of the content of modified distillers grains, and reaches the minimum value in Example 2; the following conclusions can be drawn from this: ① Modified distillers grains will improve the tensile strength of the composite material, but when the content of modified distillers grains is 40% and 50%, the tensile strength begins to show a downward trend. The increase in tensile strength is because the distillers grains powder improves the interfacial strength with the biodegradable resin under the combined modification of the coupling agent and hyperbranched polyester, thus increasing the strength; the reason for the decrease in strength when continuing to increase the content of distillers grains powder may be related to the partial agglomeration and uneven dispersion of too much distillers grains powder in the biodegradable polyester. However, even so, the tensile strengths of the composite materials obtained with 40wt% (Example 3) and 50wt% (Example 3) modified distillers grains content are higher than that of Comparative Example 1. Under the condition of meeting the use and strength requirements of the product, the content of distillers grains powder can be increased to 50wt%, which provides data support for the large-scale and rapid consumption of distillers grains. ② The increase in modified distillers grains will increase the elongation at break of the composite material, but too high a content of distillers grains powder is not conducive to the elongation at break, which limits the places that require a higher elongation at break. ③ The water absorption rate will increase when the content of distillers grains powder is high (50wt%), which is because the distillers grains powder is more hydrophilic than the resin.

[0142] (2) Analysis of the test results of Comparative Example 2 and Example 2:

[0143] The distillers grains added in Comparative Example 2 were not treated with a coupling agent and hyperbranched resin. The distillers grains powder in Example 2 was treated with a combination of the coupling agent KH560 and the carboxyl-terminated hyperbranched polyester Hyper C304. It can be seen from the test data that the transverse and longitudinal tensile strengths of Example 2 are increased by 82% and 74.9% respectively compared with Comparative Example 2, and the transverse and longitudinal fracture productivities are increased by 71.7% and 73.9% respectively; the water absorption rate decreased from 931.8 g / (m 2 ·24h) to 377.6 g / (m 2· (24 h). It can be concluded that the joint treatment of distillers' grains with coupling agent KH560 and carboxyl-terminated hyperbranched polyester plays a positive role in improving the properties of the composite material.

[0144] (3) Comparative analysis of the test of treating distillers' grains by the combined treatment of coupling agent and hyperbranched resin and treating distillers' grains with only coupling agent or only hyperbranched resin:

[0145] In Comparative Examples 3-5, only coupling agent was used to treat the distillers' grains powder without using hyperbranched resin. In Comparative Example 3, only coupling agent KH560 was used for treatment, and comparative analysis was made with Examples 2, 5, 11, and 12; in Comparative Example 4, only coupling agent KH550 was used for treatment, and comparative analysis was made with Examples 6, 9, and 10; in Comparative Example 5, only coupling agent NDZ-201 was used for treatment, and comparative analysis was made with Examples 7 and 8.

[0146] In Comparative Examples 6-10, only hyperbranched resin was used to treat the distillers' grains powder without using coupling agent. In Comparative Example 6, only carboxyl-terminated hyperbranched polyester Hyper C304 was used for treatment, and comparative analysis was made with Examples 2, 7, and 9; in Comparative Example 7, only hyperbranched epoxy Hyper E102 was used for treatment and comparative analysis was made with Example 6; in Comparative Example 8, only carboxyl-terminated hyperbranched polyester Hyper C181 was used for treatment, and comparative analysis was made with Examples 5, 8, and 10; in Comparative Example 9, only amino-terminated hyperbranched polyester Amine Functional Boltorn TM H40 was used for treatment and comparative analysis was made with Example 11; in Comparative Example 10, only hydroxyl-terminated hyperbranched polyester Boltorn TM Regular H40 was used for treatment and comparative analysis was made with Example 12.

[0147] From the test data of the above examples and comparative examples, the following conclusions can be drawn:

[0148] ① The properties of the biodegradable polyester filled with the distillers' grains powder treated with only coupling agent or only hyperbranched resin are lower than those of the composite material obtained by the joint treatment of coupling agent and hyperbranched resin for the distillers' grains powder; ② It can be concluded from Comparative Examples 3-5 that among coupling agents KH550, KH560H, and NDZ-201, the effect of KH560H is better than the other two. ③ It can be concluded from Comparative Examples 6-9 that among carboxyl hyperbranched polyester Hyper C304, hyperbranched epoxy Hyper E102, carboxyl-terminated hyperbranched polyester Hyper C181, amino-terminated hyperbranched polyester Amine Functional Boltorn TM H40 and hydroxyl-terminated hyperbranched polyester Boltorn TMAmong Regular H40, the treatment with hyperbranched polyester with terminal carboxyl groups Hyper C304 is superior to the other four. However, the performance differences of the biodegradable composites obtained by treating distiller's grains with these five hyperbranched resins are not significant. This is because distiller's grains powder not only contains a large number of hydroxyl groups, but also rich active functional components, including alcohols, acids, aldehydes, esters, proteins, amino acids, active polypeptides, functional oligosaccharides, antioxidant phenols and flavonoids. These active components can react well with the terminal amino groups, terminal hydroxyl groups, terminal carboxyl groups and epoxy groups of the hyperbranched resins, so that the hyperbranched resins with different terminal group types, distiller's grains powder and biodegradable resins have good compatibility, increasing their interfacial strength and improving the performance.

[0149] (4) Analysis of test results of treating distiller's grains powder with different types of coupling agents and hyperbranched resins combined:

[0150] ① In Examples 2, 7 and 9, the hyperbranched resin is hyperbranched polyester with terminal carboxyl groups Hyper C304. The difference is that the coupling agent used in Example 2 is KH560, the coupling agent used in Example 7 is NDZ-201, and the coupling agent used in Example 9 is KH550. It can be seen from the performance test results that the performance of Example 2 using KH560 and hyperbranched polyester with terminal carboxyl groups Hyper C304 is superior to the other two. The amino group of coupling agent KH550, the epoxy group of KH560, and the hydroxyl group of NDZ-201 react with the terminal carboxyl groups of the hyperbranched polyester respectively. Among them, the amino group and the carboxyl group undergo an acid-base neutralization reaction. The oxygen in the carboxyl group induces an electron-withdrawing effect, weakening the electronegativity of the oxygen of -OH in the carboxyl group and the binding ability to H, and the carboxyl group and the amino group undergo a dehydration reaction; the carboxyl group, as a nucleophile, attacks the ring group, causing its ring opening and undergoing a nucleophilic addition reaction. The epoxy group and the carboxyl group form an ester bond, which has a strong chemical binding force. Since the activation index of KH560 is higher, the reaction product is relatively stable, and it itself has a long alkyl chain, so the crosslinking degree of the modified distiller's grains powder with the hyperbranched resin and the biodegradable resin is slightly larger and the interfacial compatibility is better. Therefore, the modification effect is superior to that of the biodegradable composites obtained by modifying distiller's grains with KH550 and NDZ-201 combined with hyperbranched resin respectively. This result is consistent with the conclusion obtained in ② of the above analysis (3). Similarly, the experimental conclusions obtained in Examples 5, 8 and 10 are the same as the above. It can be concluded that KH560 is preferred among the three coupling agents.

[0151] ② The coupling agents in Examples 2, 5, 11 and 12 are all KH560. The difference lies in the types of hyperbranched resins used. Example 2 uses hyperbranched polyester with terminal carboxyl groups Hyper C304, Example 5 uses hyperbranched polyester with terminal carboxyl groups Hyper C181, and Example 11 uses hyperbranched polyester with terminal amino groups Amine Functional Boltorn TMH40, Example 12: Hydroxyl-terminated hyperbranched polyester Boltorn TM Regular H40. From the performance tests of these four examples, it can be seen that Example 2 using carboxyl-terminated hyperbranched polyester Hyper C304 has the best performance. The same conclusion was also drawn in Examples 6, 9, and 10. This result is consistent with the conclusion obtained in ③ of the above analysis (3). It can be concluded that the hyperbranched resin preferably uses carboxyl-terminated hyperbranched polyester Hyper C304.

[0152] (5) Analysis of the test results of Example 2 and Comparative Example 11:

[0153] In Example 2, the treatment sequence of distiller's grains was to first treat with a coupling agent and then with a hyperbranched resin; while in Comparative Example 11, the treatment sequence of distiller's grains was opposite to that in Example 2. It can be seen that the performance of Comparative Example 11 is significantly lower than that of Example 2. In the present invention, the treatment process of distiller's grains powder follows the principle of first treating with a coupling agent and then with a hyperbranched resin because the coupling agent has a lower viscosity and surface tension and stronger wetting ability, and can quickly spread on the surface of the distiller's grains powder, so that the surface of the distiller's grains powder is wetted by the silane coupling agent and evenly distributed on the surface of the treated distiller's grains powder, thereby improving the compatibility and dispersibility between the component materials. When the surface of the distiller's grains powder is infiltrated, the groups on the coupling agent molecule diffuse towards the surfaces with similar polarities respectively. In Example 2, in the coupling agent KH560, one end of the alkoxy group hydrolyzes to form silanol groups, which are oriented towards the surface of the distiller's grains powder containing a large amount of hydroxyl groups and undergo hydrolysis polycondensation reactions with the hydroxyl groups on the surface; the organic groups are oriented towards the surfaces of the hyperbranched resin and the biodegradable resin, and chemical reactions occur during the processing, thus completing the coupling process of the distiller's grains powder, the hyperbranched resin, and the biodegradable resin.

[0154] In summary, in the present invention, the decoupling agent molecules used have both organic groups that are pro-hyperbranched resin and biodegradable resin matrix materials, and groups that are pro-vinasse powder materials. Among them, the organic groups have a great influence on the performance of the product. Only when the organic groups can react with the corresponding hyperbranched resin and biodegradable resin matrix materials can the performance of the composite material be improved. The present invention selects three different types of coupling agents, namely, γ-glycidyloxypropyltrimethoxysilane (KH560) with an epoxy reaction group at the end, γ-aminopropyltriethoxysilane (KH-550) with an amino reaction group at the end, and isopropyl tri(dioctylpyrophosphate acyloxy) titanate (NDZ-201) with a hydroxyl reaction group at the end. These reaction groups can react chemically with the reaction groups carried by vinasse, hyperbranched resins with different end groups, and biodegradable resins. In the selection of hyperbranched resins, the present invention selects amino-terminated hyperbranched polyesters, carboxyl-terminated hyperbranched polyesters, hydroxyl-terminated hyperbranched polyesters and hyperbranched epoxy resins according to the different terminal reaction end groups of the hyperbranched resins, so as to match different types of coupling agents and biodegradable resins, and finally obtains a biodegradable green composite material with excellent performance, and at the same time, on the premise of meeting the product standards and performance, it is expected to increase the content of vinasse powder in the composite material, thereby accelerating the consumption of vinasse powder. Among the embodiments 1-22 of the present invention, embodiment 2 has the best comprehensive performance and is the optimal implementation scheme.

[0155] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing modified distiller's grains, characterized in that the steps include: (1) crushing and drying the vinasse, grinding and sieving to obtain vinasse powder; (2) adding a coupling agent to the vinasse powder, heating and stirring, and obtaining coupling agent treated vinasse; (3) adding a hyperbranched resin to the coupling agent treated distiller's grains, heating and stirring for 5 to 45 minutes, and cooling to room temperature after the heating and stirring are completed to obtain modified distiller's grains; The weight ratio of the vinasse powder to the coupling agent is 10:1 to 300:1; the coupling agent is γ-aminopropyltriethoxysilane; The weight ratio of the vinasse powder to the hyperbranched resin is 50:1; the hyperbranched resin is the carboxyl-terminated hyperbranched polyester HyperC304.

2. The preparation method according to claim 1, characterized in that: The drying temperature in step (1) is 80-120° C.; the particle size of the vinasse powder is 100-2000 mesh.

3. A green composite material made of fully biodegradable lees, characterized in that: The ingredients include 5-95wt% of biodegradable polyester, 0.1-15wt% of chain extender, 1-75wt% of modified wine lees, 0.1-15wt% of anti-hydrolysis agent, 0.1-5wt% of heat stabilizer and 0.1-7.5wt% of lubricant; the modified wine lees is prepared by any preparation method of claims 1-2.

4. The vinasse fully biodegradable green composite material according to claim 3, characterized in that: The biodegradable polyester is selected from at least one of polybutylene adipate / terephthalate copolyester, polylactic acid, polybutylene succinate, polybutylene succinate / adipate, polymethyl vinyl carbonate, polyglycolide, polyε-caprolactone, polyhydroxyalkanoate, polyhydroxybutyrate, polyhydroxyvalerate, and polyhydroxybutyrate / valerate; the chain extender is selected from at least one of epoxy compound chain extenders and styrene-methylacrylate copolymer chain extenders; the anti-hydrolysis agent is selected from at least one of carbodiimide compounds, isocyanate compounds, bisoxazoline compounds, and epoxy compounds; the heat stabilizer is selected from at least one of aromatic amine compounds, hindered phenol compounds, phosphite compounds, and thioester compounds; the lubricant is selected from at least one of long-chain carboxylic acids, amide waxes, carboxylates, carboxylates, and silicone resins.

5. The method for preparing the green composite material of vinasse biodegradable according to claim 3, characterized in that the steps include: The biodegradable polyester, chain extender, anti-hydrolysis agent, heat stabilizer and lubricant are mixed to obtain a biodegradable polyester material mixture; the biodegradable polyester material mixture is mixed with modified wine lees, and the mixture is fully dried to obtain a wine lees fully biodegradable green composite material.

6. Application of the fully biodegradable green composite material of distiller's grains as claimed in claim 3 as a material for film blowing, injection molding, casting, rotational molding, 3D printing, extrusion, coating, spinning, vacuum forming and molding.

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