聚氨酯泡沫是由含有羟基（-OH）的聚醚、聚酯多元醇与含有异氰酸酯基团（-NCO）的多异氰酸酯及助剂制备的合成树脂，其形态多样且用途广泛。在双碳理念的引领下，生物质基聚氨酯因原料可再生、绿色环保等优势，成为取代石油基原料合成聚氨酯泡沫的主要趋势。本研究选取来源广泛的木质素磺酸钠与棉花秸秆两种生物质资源为原料，利用直接液化技术合成生物质多元醇，然后以粉煤灰（Fly ash，FA）为成核剂，通过一次发泡工艺制备出微观结构可调、性能优良的生物质基聚氨酯泡沫。最后，引入绿色天然的植酸（Phytic acid，PA）对泡沫进行阻燃改性，提升其在实际应用中的耐火性。具体实验研究内容如下：

（1）木质素基聚氨酯泡沫的制备与性能研究。以木质素磺酸钠为原料，浓硫酸为催化剂，聚乙二醇和乙二醇为液化试剂，开展木质素基多元醇的制备研究。系统探究反应条件对木质素残渣率、羟值、酸值和黏度的影响，确定最佳液化工艺：液固比为14:1、聚乙二醇:乙二醇=4:1、温度为150°C、时间为1 h、浓硫酸含量为1.6%。在此条件下，制得了低残渣率（16.20%）、高羟值（496.04 mgKOH/g）且均一（PDI为1.18）的液化产物。随后，将其与多苯基多亚甲基多异氰酸酯（Polyphenylmethane polyisocyanate，PAPI）及助剂制成木质素基聚氨酯泡沫（LRPUs），研究了FA对其性能的影响。结果显示，当加入目数为100目、含量为8%的FA后，LRPU_8%FA的抗压强度为3096 kPa，导热系数为0.0215 W/(m·K)，实现了绿色制备，并提升了聚氨酯泡沫的机械性能和保温性能。

（2）棉秆基聚氨酯泡沫的制备与性能研究。本研究聚焦生物质的全组分利用，以棉秆粉末为原料，在浓硫酸催化下，用聚乙二醇/乙二醇进行液化，制备棉秆基多元醇。系统考察反应条件对残渣率、羟值、酸值和黏度的影响，确定最佳液化条件：液固比7:1、聚乙二醇:乙二醇=4:1、温度185°C、时间2 h、催化剂含量2.6%。在此条件下，制得了低残渣率（16.45%）、高羟值（391.5 mgKOH/g）且均一（PDI为1.2）的棉秆基多元醇。然后，采用了一次发泡法制备棉秆基聚氨酯泡沫(CSRPUs)，当加入目数为100目、含量为8%的FA后，CSRPU_8%FA的抗压强度为998.67 kPa，导热系数为0.0236 W/(m·K)，实现了生物质的全组分利用，并提升了材料的机械性能和保温性能。

（3）植酸改性生物质基聚氨酯泡沫的制备与阻燃性能研究。基于前期生物质多元醇的成功制备，本研究旨在提升聚氨酯泡沫的阻燃性能。通过合成PA-PAPI预聚体，并结合两种生物质多元醇，制备阻燃性生物质基聚氨酯泡沫（LRPU_8%FA-PAs和CSRPU_8%FA-PAs）。利用极限氧指数实验、水平燃烧测试和锥形量热测试，系统分析PA对两种泡沫的改性效果。研究发现，分别在204 g与186 g的两种生物质基聚氨酯体系中加入4 g的PA后，制得的LRPU_8%FA-PA4和CSRPU_8%FA-PA4阻燃性能提升：极限氧指数达到22.0%、22.4%；水平燃烧测试中，燃烧等级提升至HB；锥形量热测试中，LRPU_8%FA-Pas的THR下降了27.78%、TSP下降了33.87%，CSRPU_8%FA-PAs的THR下降了36.54%、TSP下降了34.72%。此外，两种泡沫的抗压强度分别为479.32 kPa、236.71 kPa，密度为106.93 kg/m³、74.55 kg/m³，导热系数为0.0192 W/(m·K)、0.0177 W/(m·K)，拓展了生物质基聚氨酯泡沫在阻燃领域的应用潜力。

Polyurethane foam is a synthetic resin prepared from polyether or polyester polyols containing hydroxyl groups (-OH), polyisocyanates containing isocyanate groups (-NCO), and additives. It has diverse forms and a wide range of applications. Under the guidance of the "dual carbon" concept, biomass-based polyurethane, with advantages such as renewable raw materials and environmental friendliness, has become the main trend to replace petroleum-based raw materials in the synthesis of polyurethane foam. In this study, two biomass resources with wide sources, namely sodium lignosulfonate and cotton straw, were selected as raw materials. Biomass polyols were synthesized using direct liquefaction technology, and then biomass-based polyurethane foams with adjustable microstructure and excellent performance were prepared through a one-step foaming process with fly ash (FA) as the nucleating agent. Finally, green and natural phytic acid (PA) is introduced to carry out flame-retardant modification on the foam, so as to improve its fire resistance in practical applications. The specific experimental research contents are as follows:

(1) Study on Preparation and Properties of Lignin-Based Polyurethane Foams. Using sodium lignosulfonate as the raw material, concentrated sulfuric acid as the catalyst, and polyethylene glycol and ethylene glycol as liquefaction reagents, the research on the preparation of lignin-based polyols was carried out. The effects of reaction conditions on the lignin residue rate, hydroxyl value, acid value and viscosity were systematically investigated, and the optimal liquefaction process was determined as follows: liquid-solid ratio of 14:1, polyethylene glycol:ethylene glycol = 4:1, temperature of 150°C, time of 1 h, and concentrated sulfuric acid content of 1.6%. Under these conditions, a liquefied product with a low residue rate (16.20%), a high hydroxyl value (496.04 mgKOH/g) and uniformity (with a PDI of 1.18) was obtained. Subsequently, it was mixed with polyphenylmethane polyisocyanate (PAPI) and additives to prepare lignin-based polyurethane foams (LRPUs), and the effect of FA on their properties was studied. The results showed that when FA with a mesh size of 100 and a content of 8% was added, the compressive strength of LRPU_8%FA reached 3096 kPa, and the thermal conductivity was 0.0215 W/(m·K). This not only realized green preparation but also improved the mechanical properties and thermal insulation performance of the polyurethane foam.

(2) Preparation and performance study of cotton straw-based polyurethane foams. Focusing on the full-component utilization of biomass, this study used cotton straw powder as the raw material, with concentrated sulfuric acid as the catalyst and polyethylene glycol/ethylene glycol as the liquefaction reagents to prepare cotton straw-based polyols. The effects of reaction conditions on the residue rate, hydroxyl value, acid value and viscosity were systematically investigated, and the optimal liquefaction conditions were determined as follows: liquid-solid ratio 7:1, polyethylene glycol:ethylene glycol = 4:1, temperature 185°C, time 2 h, and catalyst content 2.6%. Under these conditions, a cotton straw-based polyol with a low residue rate (16.45%), a high hydroxyl value (391.5 mgKOH/g) and uniformity (with a PDI of 1.2) was obtained. Then, the one-step foaming method was adopted to prepare cotton straw-based polyurethane foams (CSRPUs). When FA with a mesh size of 100 and a content of 8% was added, the compressive strength of CSRPU_8%FA was 998.67 kPa, and the thermal conductivity was 0.0236 W/(m·K). This realized the full-component utilization of biomass and improved the mechanical properties and thermal insulation performance of the material.

(3) Preparation and flame retardancy study of phytic acid-modified biomass-based polyurethane foams. Based on the successful preparation of biomass polyols in the early stage, this study aimed to improve the flame retardancy of polyurethane foams. Flame-retardant biomass-based polyurethane foams (LRPU_8%FA-PAs and CSRPU_8%FA-PAs) were prepared by synthesizing PA-PAPI prepolymers and combining them with the two types of biomass polyols. The modification effects of PA on the two foams were systematically analyzed using limiting oxygen index (LOI) test, horizontal burning test, and cone calorimeter test. The results showed that after adding 4 g of PA to 204 g and 186 g of the two biomass-based polyurethane systems respectively, the flame retardancy of the prepared LRPU_8%FA-PA4 and CSRPU_8%FA-PA4 was improved: the limiting oxygen indices reached 22.0% and 22.4% respectively; in the horizontal burning test, the burning grade was upgraded to HB; in the cone calorimeter test, the total heat release (THR) and total smoke production (TSP) of LRPU_8%FA-PAs decreased by 27.78% and 33.87% respectively, while those of CSRPU_8%FA-PAs decreased by 36.54% and 34.72% respectively. In addition, the compressive strengths of the two foams were 479.32 kPa and 236.71 kPa respectively, with densities of 106.93 kg/m³ and 74.55 kg/m³, and thermal conductivities of 0.0192 W/(m·K) and 0.0177 W/(m·K) respectively, which expanded the application potential of biomass-based polyurethane foams in the flame-retardant field.

[1]戚丁元.生物质基聚醚多元醇的制备及性能[D].吉林:长春工业大学,2020.

[2]2030年我国利用生物质能减碳将超9亿t [J] . 电力科技与环保, 2021, 37(05):21.

[3]Liu, Z-M., Yu, F., Fang, Gz. et al. Performance characterization of rigid polyurethane foam with refined alkali lignin and modified alkali lignin [J]. Journal of Forestry Research, 2009, 20:161-164.

[4]Faust S, Kaiser K, Wiedner K, et al. Comparison of different methods for determining lignin concentration and quality in herbaceous and woody plant residues [J]. Plant and Soil, 2018, 433(1):7-18.

[5]Shen C, Shao R, Wang W, et al. Progress of flame retardant research on flexible polyurethane foam [J]. European Polymer Journal, 2024, 220:113478.

[6]Chen G, Hu Z-Y, Chen N, et al. Phytic acid-based hybrid coating for improving the flame-retardancy of flexible polyurethane foam [J]. Materials Chemistry and Physics, 2024, 314:128842.

[7]Yin D, Zhai M, Wang X, et al. Fully bio-based thermoplastic polyurethane composites with enhanced flame retardancy via phytic acid integration [J]. Materials Today Communications, 2025, 45:112348.

[8]Chai H, Luo X, Gu X, et al. Multifunctional phytic acid/chitosan/polyvinyl acetate-coated polyurethane sponge with excellent flame retardancy [J]. Materials Letters, 2025, 394:138657.

[9]Zhang X, Wang Z, Ding S, et al. Fabrication of Flame-Retardant Ammonium Polyphosphate Modified Phytic Acid-Based Rigid Polyurethane Foam with Enhanced Mechanical Properties [J]. Polymers, 2024, 16(15):2229.

[10]Jiang Q, Li P, Liu Y, et al. Phytic Acid-Iron/Laponite Coatings for Enhanced Flame Retardancy, Antidripping and Mechanical Properties of Flexible Polyurethane Foam [J]. International Journal of Molecular Sciences, 2022, 23(16):9145.

[11]Bourguignon M, Thomassin J-M, Grignard B, et al. Fast and Facile One-Pot One-Step Preparation of Nonisocyanate Polyurethane Hydrogels in Water at Room Temperature [J]. ACS Sustainable Chemistry & Engineering, 2019, 7(14):12601-12610.

[12]Nazir M U, Mascolo R, Bouic P, et al. Upcycling leather waste: The effect of leather type and aspect ratio on the performance of thermoplastic polyurethane composites [J]. Sustainable Materials and Technologies, 2025, 43:e01221.

[13]Shi M, Wang X, Yang J. Development of lignin-based waterborne polyurethane materials for flame retardant leather application [J]. Polymer Bulletin, 2023, 80(5):5553-5571.

[14]Ustuntag S, Cakir N, Erdem A, et al. Production and Characterization of Flame Retardant Leather Waste Filled Thermoplastic Polyurethane [J]. ACS Omega, 2024, 9(8):9475-9485.

[15]Zhou Y, Zhang Q, Ma J, et al. Preparation of cationic waterborne polyurethane and its application in leather dyeing [J]. Polymer, 2024, 304:127099.

[16]Han Y, Hu J, Xin Z. Facile preparation of high solid content waterborne polyurethane and its application in leather surface finishing [J]. Progress in Organic Coatings, 2019, 130:8-16.

[17]Mistry M, Prajapati V, Dholakiya B Z. Redefining Construction: An In-Depth Review of Sustainable Polyurethane Applications [J]. Journal of Polymers and the Environment, 2024, 32(8):3448-3489.

[18]Nering K, Kowalska-Koczwara A. Determination of Vibroacoustic Parameters of Polyurethane Mats for Residential Building Purposes [J]. Polymers, 2022, 14(2):314.

[19]Wang X, Yin D, Chen Z, et al. An Innovative Approach of Using a Bio-Based Polyurethane Elastomer to Overcome the “Magic Triangle” in Tires [J]. Materials, 2025, 18(3):603.

[20]Gama N, Ferreira A, Barros-Timmons A. 3D Printed Thermoplastic Polyurethane Filled with Polyurethane Foams Residues [J]. Journal of Polymers and the Environment, 2020, 28(5):1560-1570.

[21]Gama N, Ferreira A, Barros-Timmons A. 3D printed cork/polyurethane composite foams [J]. Materials & Design, 2019, 179:107905.

[22]Kim N P. 3D-Printed Conductive Carbon-Infused Thermoplastic Polyurethane [J]. Polymers, 2020, 12(6):1224.

[23]Zhang J, Lv S, Zhao X, et al. Continuous Dynamic Chemistry Recombination for Fabricating Recyclable Hydrophilic Lubricating Zwitterionic Polyurethane [J]. ACS Sustainable Chemistry & Engineering, 2025, 13(8):3247-3257.

[24]M’bengue M-S, Mesnard T, Chai F, et al. Evaluation of a Medical Grade Thermoplastic Polyurethane for the Manufacture of an Implantable Medical Device: The Impact of FDM 3D-Printing and Gamma Sterilization [J]. Pharmaceutics, 2023, 15(2):456.

[25]Horak Z, Dvorak K, Zarybnicka L, et al. Experimental Measurements of Mechanical Properties of PUR Foam Used for Testing Medical Devices and Instruments Depending on Temperature, Density and Strain Rate [J]. Materials, 2020, 13(20):4560.

[26]Jiang D, Wang Y, Li B, et al. Environmentally friendly alternative to polyester polyol by corn straw on preparation of rigid polyurethane composite [J]. Composites Communications, 2020, 17:109-114.

[27]Chang C, Liu L, Li P, et al. Preparation of flame retardant polyurethane foam from crude glycerol based liquefaction of wheat straw [J]. Industrial Crops and Products, 2021, 160:113098.

[28]Serrano L, Rincón E, García A, et al. Bio-Degradable Polyurethane Foams Produced by Liquefied Polyol from Wheat Straw Biomass [J]. Polymers, 2020, 12(11):2646.

[29]Malewska E, Kurańska M, Tenczyńska M, et al. Application of Modified Seed Oils of Selected Fruits in the Synthesis of Polyurethane Thermal Insulating Materials [J]. Materials, 2024, 17(1): 158.

[30] Ghasemlou M, Daver F, Ivanova E P, et al. Polyurethanes from seed oil-based polyols: A review of synthesis, mechanical and thermal properties [J]. Industrial Crops and Products, 2019, 142:111841.

[31]Darda A, Khatoon H, Siddiqi W A, et al. Polythiophene enveloped tungsten-oxide hybrid nanofillers dispersed oleo (Pithecellobium Dulce seed oil) polyurethane bi-functional nanocomposite coatings [J]. Progress in Organic Coatings, 2022, 172:107038.

[32]朱文波.车用大豆油聚氨酯多孔材料声学性能分析与优化[D].吉林:吉林大学,2019.

[33]Wang S, Liu W, Yang D, et al. Highly Resilient Lignin-Containing Polyurethane Foam [J]. Industrial & Engineering Chemistry Research, 2019, 58(1):496-504.

[34]Cao H, Liu R, Li B, et al. Biobased rigid polyurethane foam using gradient acid precipitated lignin from the black liquor: Revealing the relationship between lignin structural features and polyurethane performances [J]. Industrial Crops and Products, 2022, 177:114480.

[35]Mankar A R, Modak A, Pant K K. High yield synthesis of hexitols and ethylene glycol through one-pot hydrolytic hydrogenation of cellulose [J]. Fuel Processing Technology, 2021, 218:106847.

[36]Bayrakdar Ates E. Synthesis of Ni/Clinoptilolite catalyst by modified polyol method for upgrading of bio-oil produced from hazelnut husk pyrolysis [J]. Renewable Energy, 2023, 219:119560.

[37]Amran U A, Zakaria S, Chia C H, et al. Production of Liquefied Oil Palm Empty Fruit Bunch Based Polyols via Microwave Heating [J]. Energy & Fuels, 2017, 31(10):10975-10982.

[38]Erdem M, Akdogan E, Bekki A. Optimization and characterization studies on ecopolyol production from solvothermal acid-catalyzed liquefaction of sugar beet pulp using response surface methodology [J]. Biomass Conversion and Biorefinery, 2023, 13(8):6925-6940.

[39]Galhano Dos Santos R, Acero N F, Matos S, et al. One-Component Spray Polyurethane Foam from Liquefied Pinewood Polyols: Pursuing Eco-Friendly Materials [J]. Journal of Polymers and the Environment, 2018, 26(1):91-100.

[40]Chaudhary M L, Patel R, Gupta R K. Beyond isocyanates: Advances in non-isocyanate polyurethane chemistry and applications [J]. Polymer, 2025, 332:128553.

[41]Bukowczan A, Łukaszewska I, Pielichowski K. Thermal degradation of non-isocyanate polyurethanes [J]. Journal of Thermal Analysis and Calorimetry, 2024, 149(19):10885-10899.

[42]Seo W, Jung H, Hyun J, et al. Mechanical, morphological, and thermal properties of rigid polyurethane foams blown by distilled water [J]. Journal of Applied Polymer Science, 2003, 90(1):12-21.

[43]Wang H, Li T, Li J, et al. Structural engineering of polyurethanes for biomedical applications [J]. Progress in Polymer Science, 2024, 151:101803.

[44]Peyrton J, Avérous L. Structure-properties relationships of cellular materials from biobased polyurethane foams [J]. Materials Science and Engineering: R: Reports, 2021, 145:100608.

[45]Du X, Wu S, Li P. Catalytic hydrogenolysis lignin to obtain phenols: A review of selective cleavage of ether bonds [J]. BioResources, 2023, 18(2):4231.

[46]Li J, Li Q, Steinberg C E W, et al. Reaction of Substituted Phenols with Lignin Char: Dual Oxidative and Reductive Pathways Depending on Substituents and Conditions [J]. Environmental Science & Technology, 2020, 54(24):15811-15820.

[47]Cai C, Hirth k, Gleisner R, et al. Maleic acid as a dicarboxylic acid hydrotrope for sustainable fractionation of wood at atmospheric pressure and≤ 100 °C: mode and utility of lignin esterification [J]. Green Chemistry, 2020, 22(5):1605-1617.

[48]Aro T, Fatehi P. Production and application of lignosulfonates and sulfonated lignin [J]. ChemSusChem, 2017, 10(9):1861-1877.

[49]Singh M, Lee S C, Won K. Lignin phenolation by graft copolymerization to boost its reactivity [J]. International Journal of Biological Macromolecules, 2024, 266:131258.

[50]Rath S, Pradhan D, Du H, et al. Transforming lignin into value-added products: Perspectives on lignin chemistry, lignin-based biocomposites, and pathways for augmenting ligninolytic enzyme production [J]. Advanced Composites and Hybrid Materials, 2024, 7(1):27.

[51]Lima García J, Pans G, PHANOPOULOS C. Use of lignin in polyurethane-based structural wood adhesives [J]. The Journal of Adhesion, 2018, 94(10):814-828.

[52]Ma X, Chen J, Zhu J, Yan N. Lignin‐based polyurethane: recent advances and future perspectives [J]. Macromolecular rapid communications, 2021, 42(3):2000492.

[53]Wu Z, Zhang X, Kang S, et al. Preparation of biodegradable recycled fiber composite film using lignin-based polyurethane emulsion as strength agent [J]. Industrial Crops and Products, 2023, 197:116512.

[54]Xu J, Xu J J, Lin Q, et al. Lignin-incorporated nanogel serving as an antioxidant biomaterial for wound healing [J]. ACS Applied Bio Materials, 2020, 4(1):3-13.

[55]Jędrzejczak P, Collins M N, Jesionowski T, et al. The role of lignin and lignin-based materials in sustainable construction–a comprehensive review [J]. International Journal of Biological Macromolecules, 2021, 187:624-650.

[56]Zhu S, Chen K, Xu J, et al. Bio-based polyurethane foam preparation employing lignin from corn stalk enzymatic hydrolysis residues [J]. RSC advances, 2018, 8(28):15754-15761.

[57]Lai Y, Qian Y, Yang D, et al. Preparation and performance of lignin-based waterborne polyurethane emulsion [J]. Industrial Crops and Products, 2021, 170:113739.

[58]Zhang X, Jeremic D, Kim Y, et al. Effects of Surface Functionalization of Lignin on Synthesis and Properties of Rigid Bio-Based Polyurethanes Foams [J]. Polymers, 2018, 10(7):706.

[59]Quinsaat J E Q, Feghali E, Van De Pas D J, et al. Preparation of Mechanically Robust Bio-Based Polyurethane Foams Using Depolymerized Native Lignin [J]. ACS Applied Polymer Materials, 2021, 3(11):5845-5856.

[60]Quinsaat J E Q, Feghali E, Van De Pas D J, et al. Preparation of Biobased Nonisocyanate Polyurethane/Epoxy Thermoset Materials Using Depolymerized Native Lignin [J]. Biomacromolecules, 2022, 23(11):4562-4573.

[61]Sternberg J, Pilla S. Chemical recycling of a lignin-based non-isocyanate polyurethane foam [J]. Nature Sustainability, 2023, 6(3):316-324.

[62]Li J, Xu X, Ma X, et al. Antimicrobial Nonisocyanate Polyurethane Foam Derived from Lignin for Wound Healing [J]. ACS Applied Bio Materials, 2024, 7(2):1301-1310.

[63]陈秋玲, 李如燕, 孙可伟, 等. 利用麦秆制聚氨酯多元醇研究 [J]. 高分子通报, 2009(11):37-42.

[64]袁东方,张玉苍.物理发泡水稻秸秆基聚氨酯泡沫研究 [J]. 生物质化学工程, 2020, 54(02):33-39.

[65]付文星, 王敦, 王万雨, 等. 水稻秸秆基聚氨酯泡沫制备工艺改进及性能表征 [J]. 生物质化学工程, 2017, 51(02):31-36.

[66]Chen W, Zhang Q, Lin X, et al. The degradation and repolymerization analysis on solvolysis liquefaction of corn stalk [J]. Polymers, 2020, 12(10):2337.

[67]Zhang Q, Chen W, Qu G, et al. Liquefaction of peanut shells with cation exchange resin and sulfuric acid as dual catalyst for the subsequent synthesis of rigid polyurethane foam [J]. Polymers, 2019, 11(6):993.

[68]Zhang Q, Lin X, Chen W, et al. Modification of rigid polyurethane foams with the addition of nano-SiO2 or lignocellulosic biomass [J]. Polymers, 2020, 12(1):107.

[69]刘利威，常春，戚小各等.甘油制备及其在生物质基聚氨酯泡沫塑料合成中的应用研究进展[J].化工新型材料, 2020, 48(01):237-241.

[70]Mapossa A B, Dos Anjos E G R, Sundararaj U. Boosting Flame Retardancy of Polypropylene/Calcium Carbonate Composites with Inorganic Flame Retardants [J]. Materials, 2024, 17(18):4553.

[71]Bevington C, Williams A J, Guider C, et al. Development of a Flame Retardant and an Organohalogen Flame Retardant Chemical Inventory [J]. Scientific Data, 2022, 9(1):295.

[72]Ma L, Song Q, Dong F, et al. Effect of Organic–Inorganic Mixed Intumescent Flame Retardants on Fire-Retardant Coatings [J]. Coatings, 2024, 14(8):1034.

[73]Tirri T, Aubert M, Aziz H, et al. Sulfenamides in synergistic combination with halogen free flame retardants in polypropylene [J]. Polymer Degradation and Stability, 2019, 164:75-89.

[74]Wu M, Emmerich L, Kurkowiak K, et al. Combined treatment of wood with thermosetting resins and phosphorous flame retardants [J]. European Journal of Wood and Wood Products, 2024, 82(1):167-174.

[75]Deng C, Ji Y, Zhu M, et al. Preparation of Organic-Inorganic Phosphorus-Nitrogen-Based Flame Retardants and Their Application to Plywood [J]. Polymers, 2023, 15(14):3112.

[76]Yu M, Dai Z, He M, et al. A phosphorus/silicon hybrid curing agent for epoxy resin: Synergistically enhanced thermal resistance, flame retardancy, and toughness [J]. Chemical Engineering Journal, 2025, 519:164924.

[77]Hewitt F, Rhebat D E, Witkowski A, et al. An experimental and numerical model for the release of acetone from decomposing EVA containing aluminium, magnesium or calcium hydroxide fire retardants [J]. Polymer Degradation and Stability, 2016, 127:65-78.

[78]Zhou F, Zhang T, Zou B, et al. Synthesis of a novel liquid phosphorus-containing flame retardant for flexible polyurethane foam: Combustion behaviors and thermal properties [J]. Polymer Degradation and Stability, 2020, 171:109029.

[79]Zhang S, Chu F, Xu Z, et al. The improvement of fire safety performance of flexible polyurethane foam by Highly-efficient P-N-S elemental hybrid synergistic flame retardant [J]. Journal of Colloid and Interface Science, 2022, 606:768-783.

[80]Zhao D, Li L, Xie Y-H, et al. Functionalized Soybean Oil as a Bio-based Flame Retardant for Poly(lactic acid): Role of Phosphorus Content [J]. ACS Applied Polymer Materials, 2024, 6(11):6517-6529.

[81]Zhu Z-M, Wang L-X, Lin X-B, DONG L-P. Synthesis of a novel phosphorus-nitrogen flame retardant and its application in epoxy resin [J]. Polymer Degradation and Stability, 2019, 169:108981.

[82]Lu W, Ye J, Zhu L, et al. Intumescent Flame Retardant Mechanism of Lignosulfonate as a Char Forming Agent in Rigid Polyurethane Foam [J]. Polymers, 2021, 13(10):1585.

[83]Zhao K, Xu W, Song L, et al. Synergistic effects between boron phosphate and microencapsulated ammonium polyphosphate in flame‐retardant thermoplastic polyurethane composites [J]. Polymers for Advanced Technologies, 2012, 23(5):894-900.

[84]Lu W, Li Q, Zhang Y, et al. Lignosulfonate/APP IFR and its flame retardancy in lignosulfonate-based rigid polyurethane foams [J]. Journal of Wood Science, 2018, 64(3):287-293.

[85]Zhang L, Zhang M, Zhou Y, et al. The study of mechanical behavior and flame retardancy of castor oil phosphate-based rigid polyurethane foam composites containing expanded graphite and triethyl phosphate [J]. Polymer Degradation and Stability, 2013, 98(12):2784-2794.

[86]Yang R, Wang B, Han X, et al. Synthesis and characterization of flame retardant rigid polyurethane foam based on a reactive flame retardant containing phosphazene and cyclophosphonate [J]. Polymer Degradation and Stability, 2017, 144:62-69.

[87]ZemłA M, Prociak A, Michałowski S, et al. Thermal Insulating Rigid Polyurethane Foams with Bio-Polyol from Rapeseed Oil Modified by Phosphorus Additive and Reactive Flame Retardants [J]. International Journal of Molecular Sciences, 2022, 23(20):12386.

[88]Li D, Liu L, Zhang Z, et al. An urethane-based phosphonate ester for improving flame retardancy and smoke suppression of thermoplastic polyurethane [J]. Polymer Degradation and Stability, 2021, 188:109568.

[89]Liu J, Liu Y, Hou Z, et al. One-Step Synthesis of Waterborne Epoxidized Lignin Nanoparticles with High Epoxy Value and Stability for High-Strength Adhesives [J]. ACS Sustainable Chemistry & Engineering, 2024, 12(42):15376-15386.

[90]Giannì P, Lange H, Crestini C. Functionalized Organosolv Lignins Suitable for Modifications of Hard Surfaces [J]. ACS Sustainable Chemistry & Engineering, 2020, 8(20):7628-7638.

[91]Bension Y, Kurnaz L B, Ge T, et al. Mechanically Tunable and Reconstructable Lignin Thermosets via “Click” Chemistry and Surface Functionalization [J]. Macromolecules, 2023, 56(7):2831-2840.

[92]Zare M, Figueiredo P, Lahtinen M H, et al. Interfacial Properties of Surface-Modified Lignin Nanoparticles [J]. Langmuir, 2025.

[93]Du X, Wu S. Effect of lignin modification on the selectivity of pyrolysis products from softwood kraft lignin [J]. Journal of Analytical and Applied Pyrolysis, 2024, 179:106517.

[94]Ren Y, Cao H, Xu H, et al. Improved aging properties of bio-bitumen coating sheets by using modified lignin [J]. Journal of Environmental Management, 2020, 274:111178.

[95]Pishva P, Li J, Xie R, et al. Nonthermal hydrogen plasma-enabled ambient, fast lignin hydrogenolysis to valuable chemicals and bio-oils [J]. Chemical Engineering Journal, 2024, 501:157776.

[96]Ma C, Kumagai S, Watanabe A, et al. Thermal and catalytic fast hydropyrolysis of lignin: Optimization for selective production of aromatics using high-pressure tandem μ-reactor – gas chromatography/mass spectrometry [J]. Chemical Engineering Journal, 2024, 479:147524.

[97]Song K, Li Y, Nie M, et al. Rigid polyurethane foams reinforced with ultrafine powder from automotive shredder residue [J]. Journal of Vinyl and Additive Technology, 2021, 27(3):508-518.

[98]Alves L R P S T, Alves M D T C, Honorio L M C, et al. Polyurethane/Vermiculite Foam Composite as Sustainable Material for Vertical Flame Retardant [J]. Polymers, 2022, 14(18):3777.

[99]Barczewski M, Kurańska M, Sałasińska K, et al. Comprehensive Analysis of the Influence of Expanded Vermiculite on the Foaming Process and Selected Properties of Composite Rigid Polyurethane Foams [J]. 2022, 14(22):4967.

[100]Rabello L G, Carlos Da Conceição Ribeiro R. A novel vermiculite/ vegetable polyurethane resin-composite for thermal insulation eco-brick production [J]. Composites Part B: Engineering, 2021, 221:109035.

[101]Kim H M, Park J, Huang Z M, et al. Carbon Nanotubes Embedded Shape Memory Polyurethane Foams [J]. Macromolecular Research, 2019, 27(9):919-925.

[102]Pilch-Pitera B, Czachor D, Kowalczyk K, et al. Conductive polyurethane-based powder clear coatings modified with carbon nanotubes [J]. Progress in Organic Coatings, 2019, 137:105367.

[103]Lederer J, Trinkel V, Fellner J. Wide-scale utilization of MSWI fly ashes in cement production and its impact on average heavy metal contents in cements: The case of Austria [J]. Waste Management, 2017, 60:247-258.

[104]Rutkowska G, Chalecki M, Żółtowski M. Fly Ash from Thermal Conversion of Sludge as a Cement Substitute in Concrete Manufacturing [J]. 2021, 13(8):4182.

[105]Kalinowska-Wichrowska K, Pawluczuk E, Bołtryk M, et al. The Performance of Concrete Made with Secondary Products-Recycled Coarse Aggregates, Recycled Cement Mortar, and Fly Ash–Slag Mix [J]. 2022, 15(4):1438.

[106]Li J, Sun Z, Wang L, et al. Properties and mechanism of high-magnesium nickel slag-fly ash based geopolymer activated by phosphoric acid [J]. Construction and Building Materials, 2022, 345:128256.

[107]Kuźnia M, Zygmunt-Kowalska B, Szajding A, et al. Comparative Study on Selected Properties of Modified Polyurethane Foam with Fly Ash [J]. Materials, 2022, 23(17):9725.

[108]Kuźnia M, Magiera A, Zygmunt-Kowalska B, et al. Fly Ash as an Eco-Friendly Filler for Rigid Polyurethane Foams Modification [J]. Materials, 2021, 14(21):6604.

[109]刘波.基于餐饮废弃油和水稻秸秆制备聚氨酯泡沫的研究[D].湖南:湖南农业大学,2017.

[110]Wang Y-Y, Charles E. W, Charles M. C, et al. Lignin-Based Polyurethanes from Unmodified Kraft Lignin Fractionated by Sequential Precipitation [J]. Ragauskas ACS Applied Polymer Materials, 2019, 1(7):1672-1679.

[111]Chen W, Zhang Q, Lin X, et al. The degradation and repolymerization analysis on solvolysis liquefaction of corn stalk [J]. Polymers, 2020, 12(10):2337.

[112]杨京京, 王明娟, 宁克伟, 等. 不同亏缺灌溉对石河子垦区棉花主栽品种生长发育及产量形成的影响 [J]. 作物杂志, 2025, 1-13.

[113]Velmourougane K, Manikandan A, Blaise D, et al. Cotton Stalk Compost as a Substitution to Farmyard Manure Along with Mineral Fertilizers and Microbials Enhanced Bt Cotton Productivity and Fibre Quality in Rainfed Vertisols [J]. Waste and Biomass Valorization, 2022, 13(6): 2847-2860.

[114]An X, Wu Z, Qin H, et al. Integrated co-pyrolysis and coating for the synthesis of a new coated biochar-based fertilizer with enhanced slow-release performance [J]. Journal of Cleaner Production, 2021, 283:124642.

[115]Wzorek M, Junga R, Yilmaz E, et al. Combustion behavior and mechanical properties of pellets derived from blends of animal manure and lignocellulosic biomass [J]. Journal of Environmental Management, 2021, 290:112487.

[116]Miron J, Ben-Ghedalia D. Digestibility by sheep of direct cut alfalfa silage made with ozonated cotton stalks [J]. Animal Feed Science and Technology, 1997, 67(4):311-317.

[117]Chen H, Sun Q, Tian C, et al. Assessment of the Nutrient Value and In Vitro Rumen Fermentation Characteristics of Garlic Peel, Sweet Potato Vine, and Cotton Straw [J]. 2024, 10(9):464.

[118]Worku L A, Bachheti A, Bachheti R K, et al. Agricultural Residues as Raw Materials for Pulp and Paper Production: Overview and Applications on Membrane Fabrication [J]. 2023, 13(2):228.

[119]Adel A M, Ahmed E O, Ibrahim M M, et al. Microfibrillated cellulose from agricultural residues. Part II: Strategic evaluation and market analysis for MFCE30 [J]. Industrial Crops and Products, 2016, 93:175-185.

[120]Cai C, Wang Z, Ma L, et al. Cotton stalk valorization towards bio-based materials, chemicals, and biofuels: A review [J]. Renewable and Sustainable Energy Reviews, 2024, 202:114651.

[121]Song X, Zhang S, Wu Y, Cao Z. Investigation on the properties of the bio-briquette fuel prepared from hydrothermal pretreated cotton stalk and wood sawdust [J]. Renewable Energy, 2020, 151:184-191.

[122]Zhang G, Zhang Q, Wu Y, et al. Effect of auxiliary blowing agents on properties of rigid polyurethane foams based on liquefied products from peanut shell [J]. Journal of Applied Polymer Science, 2017, 134(48):45582.

[123]Hadała B, Zygmunt-Kowalska B, Kuźnia M, et al. Thermal insulation properties of rigid polyurethane foam modified with fly ash- a comparative study [J]. Thermochimica Acta, 2024, 731:179659.

[124]李捍东.基于不同基材聚氨酯泡沫的阻燃特性研究[D].辽宁:沈阳航空航天大学,2022.

[125]史亚楠.生物基阻燃剂的合成及其对聚氨酯的改性研究[D].河北:河北科技大学,2023.

[126]邢硕.新型磷氮硼协效阻燃剂构筑及在软质聚氨酯泡沫中的应用研究[D].北京:北京化工大学,2023.