改性菜籽油/蒙脱土纳米复合加脂剂的合成及性能研究
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摘要
加脂剂是重要的皮革化学品之一，在赋予皮革良好性能的同时，由于其与皮革纤维之间的结合牢度比较低，在受热过程中极易迁移至皮革表面，直接成为燃料，从而提高了皮革的易燃性。因此，阻燃性已经成为高层建筑内装潢、飞机和汽车内装饰、办公家具制造、森林防火装备制造用皮革的要求之一。传统的阻燃皮革以外加含卤素阻燃剂为主，但卤素作为阻燃剂燃烧时会产生大量烟雾并释放有毒、腐蚀性的卤化氢气体，对人体和环境造成严重的危害。因此绿色环保型阻燃剂的研究备受研究者的关注。由于石油资源的有限性带来的能源危机以及使用过程中造成的环境污染，迫使人们以天然油脂替代石油作为化工原料进行深度加工；另一方面，我国是世界油料大国，天然油脂成为制备加脂剂的最主要原材料。菜籽油是制革工业中最早使用且沿用至今的植物油基加脂剂原料之一。
本课题以廉价的菜籽油为原料，将其与乙二胺进行部分酰胺化反应，适当降低碳链长度，同时引进-OH，然后通过丙烯酸引入-COOH，再加入亚硫酸氢钠对菜籽油进行亚硫酸化改性，制得改性菜籽油（MRO）加脂剂；通过超声波法将钠基蒙脱土引入改性菜籽油中。分别采用季铵盐、脂肪酸、鞣性离子、硅烷偶联剂对蒙脱土（MMT）进行改性，制备了季铵盐改性蒙脱土（季铵盐-MMT）、脂肪酸改性蒙脱土（脂肪酸-MMT）、鞣性离子改性蒙脱土（鞣性离子-MMT）、硅烷偶联剂改性蒙脱土（硅烷偶联剂-MMT）；采用XRD、FT-IR及TGA对改性蒙脱土进行了表征。进而将不同类型的改性蒙脱土分别通过原位法引入改性菜籽油加脂剂的合成中，对制得的纳米复合加脂剂各项稳定性进行了检测，采用FT-IR、XRD、TGA、DLS对纳米复合加脂剂进行了表征；将纳米复合加脂剂分别应用于山羊皮服装革加脂工艺中，对加脂后革样的物理机械性能、柔软度和加脂后废液进行了检测，并通过垂直燃烧对革样的阻燃性能进行了测定，采用SEM与EDS对加脂后革样进行了表征。将改性菜籽油加脂剂与植物油、矿物油等复配制备复合加脂剂，将其与国外同类产品的应用性能进行对比。
通过单因素试验、正交试验对改性菜籽油的最优工艺进行了优化，最优制备条件为：菜籽油用量为1mol，乙二胺用量为0.6mol，丙烯酸用量为2.6mol，氧化铝用量为0.12mol，亚硫酸氢钠用量为2.88mol。FT-IR、UV结果表明：成功制备了改性菜籽油加脂剂。应用结果表明：MRO加脂剂具有更好的吸收效果，能赋予革样更好的柔软性、丰满性及弹性，加脂后革样的物理机械性能与同类商业产品相当。
通过均匀试验、单因素试验和正交试验优化了超声法制备改性菜籽油/钠基蒙脱土纳米复合加脂剂（MRO/Na-MMT）的最优条件为：超声功率700W（50g），超声总时间35min，超声间隔时间2s/1s，蒙脱土用量7%。FT-IR、TEM及XRD结果表明：改性菜籽油能够顺利进入蒙脱土层间，制备了插层型纳米复合材料；随着蒙脱土用量的增加，纳米复合材料中蒙脱土的层间距先增加后降低。应用结果表明：与MRO加脂后革样相比较，蒙脱土的加入能够有效提高革样的阻燃性、抗张强度和撕裂强度，降低革样的塑性；采用MRO/Na-MMT加脂后革样的抗张强度、撕裂强度、弹性、柔软性及丰满性均优于同类商业产品加脂后革样。
对于不同链长的季铵盐-MMT，经FT-IR、XRD及TGA分析结果表明：季铵盐能够进入蒙脱土层间，成功改性蒙脱土。将季铵盐-MMT通过原位法引入改性菜籽油加脂剂中，XRD与FT-IR结果表明：成功制备了改性菜籽油/季铵盐改性蒙脱土纳米复合加脂剂（MRO/季铵盐-MMT），当引入适量季铵盐-MMT，纳米复合加脂剂中蒙脱土片层以剥离的形态存在。应用结果表明：与MRO加脂后革样相比，使用MRO/季铵盐-MMT加脂后革样的柔软度、物理机械性能和阻燃性均有所提高；当烷基链长相等时，含单链和三链烷基链的季铵盐所制得的纳米复合加脂剂阻燃效果均优于双链季铵盐制得的纳米复合加脂剂；当烷基取代数相等时，季铵盐中烷基链长越短，阻燃效果越好；其中改性菜籽油/三辛基甲基氯化铵改性蒙脱土纳米复合加脂剂（MRO/T811-MMT）加脂后革样的综合性能最优。
对于不同种类的脂肪酸-MMT，经FT-IR、XRD及TGA分析结果表明：各种脂肪酸均能进入蒙脱土层间，成功改性蒙脱土。将油酸改性蒙脱土、芥酸改性蒙脱土和肉豆蔻酸改性蒙脱土通过原位法分别引入改性菜籽油中，能够成功制备纳米复合加脂剂；然而将硬脂酸改性蒙脱土、棕榈酸改性蒙脱土、月桂酸改性蒙脱土通过原位法分别引入改性菜籽油中时，无法获得稳定的纳米复合加脂剂。应用结果表明：与MRO加脂后革样相比，采用稳定的改性菜籽油/脂肪酸-蒙脱土纳米复合加脂剂（MRO/脂肪酸-MMT）加脂后革样的柔软度、机械性能均有不同程度提高；革样阻燃性能随着蒙脱土用量的增加而增强，其中改性菜籽油/油酸-蒙脱土纳米复合加脂剂加脂后革样的综合性能最优。
对于鞣性离子-MMT，经FT-IR、XRD及TGA分析结果表明：Cr~(3+)、Al~(3+)、Fe~(3+)、Zr~(4+)与钠基蒙脱土反应的最佳pH分别为3.5、4.5、7.0、2.0，在最优pH条件下，各种离子改性蒙脱土的层间距分别为1.55nm、1.54nm、1.53nm、1.43nm。将鞣性离子-MMT通过原位法引入改性菜籽油中，XRD、FT-IR及TGA结果表明：成功制备了改性菜籽油/鞣性离子-蒙脱土纳米复合加脂剂（MRO/鞣性离子-MMT）；采用不同用量铝离子改性蒙脱土（Al-MMT）制备纳米复合加脂剂时，蒙脱土片层均以剥离的形态存在；改性菜籽油/铝离子-蒙脱土纳米复合加脂剂（MRO/Al-MMT）的热稳定性最好。应用结果表明：与MRO加脂后革样相比，改性菜籽油/鞣性离子-蒙脱土纳米复合加脂剂加脂后革样的柔软度、物理机械性能、阻燃性能均有所提高。
采用不同种类的硅烷偶联剂对蒙脱土进行改性，结果表明：γ-（甲基丙烯酰氧）丙基三甲氧基硅烷（KH570）、g-氨丙基三甲氧基硅烷（KH551）、3-哌嗪基丙基甲基二甲氧基硅烷（KH108）与γ-氨丙基三乙氧基硅烷（KH550）均能成功插层到蒙脱土层间；但是KH560、十六烷基三甲氧基硅烷、N-十二烷基三甲氧基硅烷及A-151未能顺利进入蒙脱土层间进行改性。将硅烷偶联剂-MMT通过原位法引入改性菜籽油中，XRD、FT-IR及TGA结果表明：成功制备了改性菜籽油/硅烷偶联剂-蒙脱土纳米复合加脂剂（MRO/硅烷偶联剂-MMT）；当硅烷偶联剂-MMT用量小于2%时，MRO/硅烷偶联剂-MMT中蒙脱土片层均以剥离的形态存在；应用结果表明：与MRO加脂后革样相比，MRO/硅烷偶联剂-MMT加脂后革样的柔软度、物理机械性能、阻燃性能均有所提高，其中改性菜籽油/g-氨丙基三甲氧基硅烷改性蒙脱土纳米复合加脂剂（MRO/KH551-MMT）加脂后革样的综合性能最优。SEM及EDS结果表明：蒙脱土片层能够有效地渗透到革样的内部，均匀地分散到胶原纤维之间，不改变原纤维的三股螺旋结构，使胶原纤维的分散程度有所增加。
将改性菜籽油加脂剂与动物油、矿物油等复配制备复合加脂剂，应用结果表明：复合加脂剂能提高革样的柔软性、丰满性等，且其抗张强度、撕裂强度和断裂伸长率等均与同类商业产品接近。通过对工业化原料进行工艺调整，该改性菜籽油复合加脂剂已投入工业化生产，且市场反映效果良好。
本文通过改性菜籽油制备功能性皮革加脂剂，能够满足皮革工业发展需要，提高菜籽油在皮革工业中的使用价值。将传统制革工业与新兴纳米技术结合起来，分别将不同类型改性蒙脱土引入制备阻燃型改性菜籽油/蒙脱土纳米复合加脂剂，不仅能够满足人们日常生活的需要、拓展皮革的用途，也对无卤阻燃型皮革化学品的开发和皮革工业的可持续发展具有重要意义。
Fatliquoring agent is one of the important leather chemicals with widelyapplications in leather industry, and can endow the leather with goodperformances. However, it can migrate easily to the surface of leather to becomefuel due to the low fixation between fatliquoring agent and collagen fibers. Thusit improves the flammability. Therefore, flame retardance has become one of therequirements of leather used in decorating of high building, aircraft and car,manufacturing of office furniture, fire-prevention equipment in forest. Thetraditional flame retardant leather is obtained through adding halogen-containingflame retardants. But the halogen could release a lot of smoke and toxic,corrosive hydrogen halide when flaming which could cause serious harm tohumans and environment. Therefore, green flame retardant has attracted muchconcern. The energy crisis caused by the limitation of non-renewable petroleumresource and environmental pollution during using force people to replacepetroleum with natural oils to process in-depth as chemical raw materials. On theother hand, our country has become a global oil country. Natural oils become themain raw material to prepare fatliquoring agent. Rapeseed oil is one of rawmaterials to prepare vegetable oil-based fatliquoring agent which is earliest usedand still in used.
In our research, modified rapeseed oil (MRO) was prepared by usingrapeseed oil, ethylene diamine, acrylic acid and sodium bisulfite as raw material.Then modified rapeseed oil/Na-montmorillonite was prepared by ultrasonicmethod. On the other hand, modified montmorillonite was prepared usingquaternary ammonium salt (fatty acid, tanning ion or silane coupling agents) asmodifiers. Modified montmorillonite was characterized by XRD, FT-IR andTGA. Then modified rapeseed oil/modified montmorillonite by quaternary ammonium salt (fatty acid, tanning ion or silane coupling agents) nanocompositefatliquoring agent were synthesized by in-situ method. The stabilities ofnanocomposite fatliquoring agent were investigated and nanocompositefatliquoring agents were characterized using XRD, FT-IR, TGA and SEM, andapplied in fatliquoring process of goatskin garment leather. Physical andmechanical properties, flexibility and flame retardant property of leather usingnanocomposite as fatliquoring agent and the waste liquid after fatliquoringprocess were discussed. SEM and EDS were used to characterize the leather afterfatliquoring. At last, composite fatliquoring agent was prepared through mixingmodified rapeseed oil, vegetable oil and mineral oil. The performances ofleathers fatliquored by our product and similar foreign products as fatliquoringagent were compared.
Synthetic process of modified rapeseed oil was optimized throughorthogonal experiment and single factor experiment. The optimal preparationconditions were: dosage of rapeseed oil was1mol, dosage of ethylene diaminewas0.6mol, dosage of acrylic acid was2.6mol, dosage of aluminum oxide was0.12mol, and dosage of sodium hydrogen sulfite was2.88mol. The FT-IR andUV results show that the modified rapeseed oil fatliquoring agent was preparedsuccessfully. Then MRO was applied in leather fatliquoring process. Comparedwith commercial product, the application results show that MRO has goodabsorption effect and could endow leather with better flexibility, fullness,flexibility.
The optimum preparation condition of modified rapeseedoil/montmorillonite (MRO/Na-MMT) was investigated through the single factorexperiment and the orthogonal experiment. The optimal conditions were:ultrasonic power was700W (50g), total ultrasonic time was35min, ultrasonicinterval time was2s/1s, and dosage of montmorillonite was7%. FT-IR, TEM andXRD results show that the modified rapeseed oil could smoothly into theinterlayer of montmorillonite and intercalation nano-meter composite wasobtained. Interlamellar spacing of MMT in nanocomposite increased and thendecreased. The modified rapeseed oil, MRO/Na-MMT and commercial productfatliquoring separately applied in leather fatliquoring process. The applicationresults show that MRO/MMT could improve the flame retardancy effectively, tensile strength and tear strength of leather and reduce plastic of crust leathercompared with MRO. Tensile strength, tear strength, flexibility, softness andfullness of leather fatliquoried by MRO/Na-MMT were better than that of leatherfatliquored with commercial product.
Modified montmorillonite using quaternary ammonium salt with differentchain length as modifiers were prepared. FT-IR, XRD, TGA results show thatquaternary ammonium salt could enter into the interlayer of montmorillonite andmodify montmorillonite successfully. The modified montmorillonite byquaternary ammonium was introduced into the modified rapeseed oil by in-situmethod. FT-IR and XRD results show that MRO/quaternary ammoniumsalt-MMT nanocomposite fatliquoring agent was prepared successfully andlayers of MMT were existed in the form of stripping. Application results indicatethat softness, physical mechanical properties and flame retardant performance ofleather fatliquored by MRO/quaternary ammonium salt-MMT were improvedcomparing with that of leather fatliquored by MRO. The flame retardancy ofnanocomposite fatliquoring agent containing modified MMT by single-chain andthree-chain quaternary ammoniums were both better than that of nanocompositefatliquoring agent containing modified MMT by double-chain quaternaryammonium when the length of alkyl chains were equal. As the substitutionnumber of alkyl were equal, the flame retardancy was better with increasing thelength of alkyl in quaternary ammonium salt. Among them, the comprehensiveperformance of leather farliquored by MRO/trioctylphosphine methylammonium chloride-MMT nanocomposite fatliquoring agent was optimal.
Modified MMT by a variety of fatty acid were prepared. FT-IR, XRD, TGAresults show that a serious of fatty acid could enter the interlayer of MMT andMMT was modified successfully. The nanocomposite fatliquoring agent wasobtained through introducing the modified MMT by a serious of fatty acid intomodified rapeseed oil by in-situ method. Stable nanocomposite fatliquoringagent containing stearic acid-MMT, cetylic acid-MMT or lauric acid-MMT couldnot be obtained. Application results show that softness, physical and mechanicalproperties of leather fatliquored by MRO/fatty acid-MMT were improvedcomparing with that of leather fatliquored by MRO. And flame retardancy ofleather was increased with increasing amount of MMT. Among them, the comprehensive performance of leather farliquored by MRO/oleic acid-MMTnanocomposite fatliquoring agent was optimal.
Modified MMT by tanning ions was characterized by FT-IR, XRD andTGA. The result indicates that the best pH for reaction between Cr~(3+)、Al~(3+)、Fe~(3+)、Zr~(4+)and Na-montmorillonite were3.5,4.5,7.0,2.0, respectively. The interlayerspacing of various ions-MMT was1.55nm,1.54nm,1.53nm,1.43nm,respectively. The modified MMT by tanning ions were introduced into modifiedrapeseed oil by in-situ method. The results of FT-IR, XRD and TGA show thatMRO/tanning ions-MMT nanocomposite fatliquoring agent were preparedsuccessfully. Layers of MMT were existed in the form of stripping whendifferent amount of Al ion were utilized to prepare nanocomposite fatliquoringagent and the thermal stability of MRO/Al-MMT nanocomposite fatliquoringagent was the highest. Softness, physical and mechanical properties and flameretardant performance of leather fatliquored by MRO/tanning ions-MMT wereimproved compared with that of leather fatliquored by MRO.
Different kinds of silane coupling agent were used to modify MMT. Theresults show that KH570，KH551，KH108and KH550could enter the interlayerof MMT. However, hexadecyltrimethoxysilane, dodecyltrimethoxysilane,KH560and A-151could not enter the interlayer of MMT. The silane couplingagent-MMT was introduced into the modified rapeseed oil by in-situ method.The results of FT-IR, XRD and TGA show that MRO/silane couplingagent-MMT nanocomposite fatliquoring agent was obtained successfully. Layersof MMT were existed in the form of stripping when the amount of silanecoupling agent-MMT was lower than2%. Application results show that softness,physical and mechanical properties and flame retardancty of leather fatliquoredby MRO/silane coupling agent-MMT were improved compared with that ofleather fatliquored by MRO. Among them, the comprehensive performance ofleather fatliquored by MRO/KH551-MMT nanocomposite fatliquoring agentwas optimal. The results of SEM and EDS show that the layers of MMT couldpenetrate effectively into or disperse uniformly into the collagen fiber withoutany changes on structure of fibers which make the loose of collagen fiberincreased.
Composite fatliquoring agent was prepared through mixing MRO and vegetable oil, mineral oil. Application results show that softness and fullness offatliquored leather could be improved. Tensile strength, tear strength andelongation at break of leather were approximate to that of leather farliquored bysimilar commercial products. The MRO composite fatliquoring agent has alreadyput into industrial production through adjustment on process and raw materialand market effect is good.
In this paper, functional leather fatliquoring agent was prepared usingmodified rapeseed oil as raw material, which could achieve the developmentneeds of the leather industry and improve the value in use of rapeseed oil inleather industry. The combination of traditional leather industry with theemerging nanotechnology and introduction of different modified montmorilloniteinto flame retardant modified rapeseed oil/MMT nanocomposite fatliquoringagent can not only satisfy the needs of people's daily life, expand leatherapplication, but also has an important significance to development ofhalogen-free flame retardant leather chemical and sustainable development ofleather industry.
本课题以廉价的菜籽油为原料，将其与乙二胺进行部分酰胺化反应，适当降低碳链长度，同时引进-OH，然后通过丙烯酸引入-COOH，再加入亚硫酸氢钠对菜籽油进行亚硫酸化改性，制得改性菜籽油（MRO）加脂剂；通过超声波法将钠基蒙脱土引入改性菜籽油中。分别采用季铵盐、脂肪酸、鞣性离子、硅烷偶联剂对蒙脱土（MMT）进行改性，制备了季铵盐改性蒙脱土（季铵盐-MMT）、脂肪酸改性蒙脱土（脂肪酸-MMT）、鞣性离子改性蒙脱土（鞣性离子-MMT）、硅烷偶联剂改性蒙脱土（硅烷偶联剂-MMT）；采用XRD、FT-IR及TGA对改性蒙脱土进行了表征。进而将不同类型的改性蒙脱土分别通过原位法引入改性菜籽油加脂剂的合成中，对制得的纳米复合加脂剂各项稳定性进行了检测，采用FT-IR、XRD、TGA、DLS对纳米复合加脂剂进行了表征；将纳米复合加脂剂分别应用于山羊皮服装革加脂工艺中，对加脂后革样的物理机械性能、柔软度和加脂后废液进行了检测，并通过垂直燃烧对革样的阻燃性能进行了测定，采用SEM与EDS对加脂后革样进行了表征。将改性菜籽油加脂剂与植物油、矿物油等复配制备复合加脂剂，将其与国外同类产品的应用性能进行对比。
通过单因素试验、正交试验对改性菜籽油的最优工艺进行了优化，最优制备条件为：菜籽油用量为1mol，乙二胺用量为0.6mol，丙烯酸用量为2.6mol，氧化铝用量为0.12mol，亚硫酸氢钠用量为2.88mol。FT-IR、UV结果表明：成功制备了改性菜籽油加脂剂。应用结果表明：MRO加脂剂具有更好的吸收效果，能赋予革样更好的柔软性、丰满性及弹性，加脂后革样的物理机械性能与同类商业产品相当。
通过均匀试验、单因素试验和正交试验优化了超声法制备改性菜籽油/钠基蒙脱土纳米复合加脂剂（MRO/Na-MMT）的最优条件为：超声功率700W（50g），超声总时间35min，超声间隔时间2s/1s，蒙脱土用量7%。FT-IR、TEM及XRD结果表明：改性菜籽油能够顺利进入蒙脱土层间，制备了插层型纳米复合材料；随着蒙脱土用量的增加，纳米复合材料中蒙脱土的层间距先增加后降低。应用结果表明：与MRO加脂后革样相比较，蒙脱土的加入能够有效提高革样的阻燃性、抗张强度和撕裂强度，降低革样的塑性；采用MRO/Na-MMT加脂后革样的抗张强度、撕裂强度、弹性、柔软性及丰满性均优于同类商业产品加脂后革样。
对于不同链长的季铵盐-MMT，经FT-IR、XRD及TGA分析结果表明：季铵盐能够进入蒙脱土层间，成功改性蒙脱土。将季铵盐-MMT通过原位法引入改性菜籽油加脂剂中，XRD与FT-IR结果表明：成功制备了改性菜籽油/季铵盐改性蒙脱土纳米复合加脂剂（MRO/季铵盐-MMT），当引入适量季铵盐-MMT，纳米复合加脂剂中蒙脱土片层以剥离的形态存在。应用结果表明：与MRO加脂后革样相比，使用MRO/季铵盐-MMT加脂后革样的柔软度、物理机械性能和阻燃性均有所提高；当烷基链长相等时，含单链和三链烷基链的季铵盐所制得的纳米复合加脂剂阻燃效果均优于双链季铵盐制得的纳米复合加脂剂；当烷基取代数相等时，季铵盐中烷基链长越短，阻燃效果越好；其中改性菜籽油/三辛基甲基氯化铵改性蒙脱土纳米复合加脂剂（MRO/T811-MMT）加脂后革样的综合性能最优。
对于不同种类的脂肪酸-MMT，经FT-IR、XRD及TGA分析结果表明：各种脂肪酸均能进入蒙脱土层间，成功改性蒙脱土。将油酸改性蒙脱土、芥酸改性蒙脱土和肉豆蔻酸改性蒙脱土通过原位法分别引入改性菜籽油中，能够成功制备纳米复合加脂剂；然而将硬脂酸改性蒙脱土、棕榈酸改性蒙脱土、月桂酸改性蒙脱土通过原位法分别引入改性菜籽油中时，无法获得稳定的纳米复合加脂剂。应用结果表明：与MRO加脂后革样相比，采用稳定的改性菜籽油/脂肪酸-蒙脱土纳米复合加脂剂（MRO/脂肪酸-MMT）加脂后革样的柔软度、机械性能均有不同程度提高；革样阻燃性能随着蒙脱土用量的增加而增强，其中改性菜籽油/油酸-蒙脱土纳米复合加脂剂加脂后革样的综合性能最优。
对于鞣性离子-MMT，经FT-IR、XRD及TGA分析结果表明：Cr~(3+)、Al~(3+)、Fe~(3+)、Zr~(4+)与钠基蒙脱土反应的最佳pH分别为3.5、4.5、7.0、2.0，在最优pH条件下，各种离子改性蒙脱土的层间距分别为1.55nm、1.54nm、1.53nm、1.43nm。将鞣性离子-MMT通过原位法引入改性菜籽油中，XRD、FT-IR及TGA结果表明：成功制备了改性菜籽油/鞣性离子-蒙脱土纳米复合加脂剂（MRO/鞣性离子-MMT）；采用不同用量铝离子改性蒙脱土（Al-MMT）制备纳米复合加脂剂时，蒙脱土片层均以剥离的形态存在；改性菜籽油/铝离子-蒙脱土纳米复合加脂剂（MRO/Al-MMT）的热稳定性最好。应用结果表明：与MRO加脂后革样相比，改性菜籽油/鞣性离子-蒙脱土纳米复合加脂剂加脂后革样的柔软度、物理机械性能、阻燃性能均有所提高。
采用不同种类的硅烷偶联剂对蒙脱土进行改性，结果表明：γ-（甲基丙烯酰氧）丙基三甲氧基硅烷（KH570）、g-氨丙基三甲氧基硅烷（KH551）、3-哌嗪基丙基甲基二甲氧基硅烷（KH108）与γ-氨丙基三乙氧基硅烷（KH550）均能成功插层到蒙脱土层间；但是KH560、十六烷基三甲氧基硅烷、N-十二烷基三甲氧基硅烷及A-151未能顺利进入蒙脱土层间进行改性。将硅烷偶联剂-MMT通过原位法引入改性菜籽油中，XRD、FT-IR及TGA结果表明：成功制备了改性菜籽油/硅烷偶联剂-蒙脱土纳米复合加脂剂（MRO/硅烷偶联剂-MMT）；当硅烷偶联剂-MMT用量小于2%时，MRO/硅烷偶联剂-MMT中蒙脱土片层均以剥离的形态存在；应用结果表明：与MRO加脂后革样相比，MRO/硅烷偶联剂-MMT加脂后革样的柔软度、物理机械性能、阻燃性能均有所提高，其中改性菜籽油/g-氨丙基三甲氧基硅烷改性蒙脱土纳米复合加脂剂（MRO/KH551-MMT）加脂后革样的综合性能最优。SEM及EDS结果表明：蒙脱土片层能够有效地渗透到革样的内部，均匀地分散到胶原纤维之间，不改变原纤维的三股螺旋结构，使胶原纤维的分散程度有所增加。
将改性菜籽油加脂剂与动物油、矿物油等复配制备复合加脂剂，应用结果表明：复合加脂剂能提高革样的柔软性、丰满性等，且其抗张强度、撕裂强度和断裂伸长率等均与同类商业产品接近。通过对工业化原料进行工艺调整，该改性菜籽油复合加脂剂已投入工业化生产，且市场反映效果良好。
本文通过改性菜籽油制备功能性皮革加脂剂，能够满足皮革工业发展需要，提高菜籽油在皮革工业中的使用价值。将传统制革工业与新兴纳米技术结合起来，分别将不同类型改性蒙脱土引入制备阻燃型改性菜籽油/蒙脱土纳米复合加脂剂，不仅能够满足人们日常生活的需要、拓展皮革的用途，也对无卤阻燃型皮革化学品的开发和皮革工业的可持续发展具有重要意义。
Fatliquoring agent is one of the important leather chemicals with widelyapplications in leather industry, and can endow the leather with goodperformances. However, it can migrate easily to the surface of leather to becomefuel due to the low fixation between fatliquoring agent and collagen fibers. Thusit improves the flammability. Therefore, flame retardance has become one of therequirements of leather used in decorating of high building, aircraft and car,manufacturing of office furniture, fire-prevention equipment in forest. Thetraditional flame retardant leather is obtained through adding halogen-containingflame retardants. But the halogen could release a lot of smoke and toxic,corrosive hydrogen halide when flaming which could cause serious harm tohumans and environment. Therefore, green flame retardant has attracted muchconcern. The energy crisis caused by the limitation of non-renewable petroleumresource and environmental pollution during using force people to replacepetroleum with natural oils to process in-depth as chemical raw materials. On theother hand, our country has become a global oil country. Natural oils become themain raw material to prepare fatliquoring agent. Rapeseed oil is one of rawmaterials to prepare vegetable oil-based fatliquoring agent which is earliest usedand still in used.
In our research, modified rapeseed oil (MRO) was prepared by usingrapeseed oil, ethylene diamine, acrylic acid and sodium bisulfite as raw material.Then modified rapeseed oil/Na-montmorillonite was prepared by ultrasonicmethod. On the other hand, modified montmorillonite was prepared usingquaternary ammonium salt (fatty acid, tanning ion or silane coupling agents) asmodifiers. Modified montmorillonite was characterized by XRD, FT-IR andTGA. Then modified rapeseed oil/modified montmorillonite by quaternary ammonium salt (fatty acid, tanning ion or silane coupling agents) nanocompositefatliquoring agent were synthesized by in-situ method. The stabilities ofnanocomposite fatliquoring agent were investigated and nanocompositefatliquoring agents were characterized using XRD, FT-IR, TGA and SEM, andapplied in fatliquoring process of goatskin garment leather. Physical andmechanical properties, flexibility and flame retardant property of leather usingnanocomposite as fatliquoring agent and the waste liquid after fatliquoringprocess were discussed. SEM and EDS were used to characterize the leather afterfatliquoring. At last, composite fatliquoring agent was prepared through mixingmodified rapeseed oil, vegetable oil and mineral oil. The performances ofleathers fatliquored by our product and similar foreign products as fatliquoringagent were compared.
Synthetic process of modified rapeseed oil was optimized throughorthogonal experiment and single factor experiment. The optimal preparationconditions were: dosage of rapeseed oil was1mol, dosage of ethylene diaminewas0.6mol, dosage of acrylic acid was2.6mol, dosage of aluminum oxide was0.12mol, and dosage of sodium hydrogen sulfite was2.88mol. The FT-IR andUV results show that the modified rapeseed oil fatliquoring agent was preparedsuccessfully. Then MRO was applied in leather fatliquoring process. Comparedwith commercial product, the application results show that MRO has goodabsorption effect and could endow leather with better flexibility, fullness,flexibility.
The optimum preparation condition of modified rapeseedoil/montmorillonite (MRO/Na-MMT) was investigated through the single factorexperiment and the orthogonal experiment. The optimal conditions were:ultrasonic power was700W (50g), total ultrasonic time was35min, ultrasonicinterval time was2s/1s, and dosage of montmorillonite was7%. FT-IR, TEM andXRD results show that the modified rapeseed oil could smoothly into theinterlayer of montmorillonite and intercalation nano-meter composite wasobtained. Interlamellar spacing of MMT in nanocomposite increased and thendecreased. The modified rapeseed oil, MRO/Na-MMT and commercial productfatliquoring separately applied in leather fatliquoring process. The applicationresults show that MRO/MMT could improve the flame retardancy effectively, tensile strength and tear strength of leather and reduce plastic of crust leathercompared with MRO. Tensile strength, tear strength, flexibility, softness andfullness of leather fatliquoried by MRO/Na-MMT were better than that of leatherfatliquored with commercial product.
Modified montmorillonite using quaternary ammonium salt with differentchain length as modifiers were prepared. FT-IR, XRD, TGA results show thatquaternary ammonium salt could enter into the interlayer of montmorillonite andmodify montmorillonite successfully. The modified montmorillonite byquaternary ammonium was introduced into the modified rapeseed oil by in-situmethod. FT-IR and XRD results show that MRO/quaternary ammoniumsalt-MMT nanocomposite fatliquoring agent was prepared successfully andlayers of MMT were existed in the form of stripping. Application results indicatethat softness, physical mechanical properties and flame retardant performance ofleather fatliquored by MRO/quaternary ammonium salt-MMT were improvedcomparing with that of leather fatliquored by MRO. The flame retardancy ofnanocomposite fatliquoring agent containing modified MMT by single-chain andthree-chain quaternary ammoniums were both better than that of nanocompositefatliquoring agent containing modified MMT by double-chain quaternaryammonium when the length of alkyl chains were equal. As the substitutionnumber of alkyl were equal, the flame retardancy was better with increasing thelength of alkyl in quaternary ammonium salt. Among them, the comprehensiveperformance of leather farliquored by MRO/trioctylphosphine methylammonium chloride-MMT nanocomposite fatliquoring agent was optimal.
Modified MMT by a variety of fatty acid were prepared. FT-IR, XRD, TGAresults show that a serious of fatty acid could enter the interlayer of MMT andMMT was modified successfully. The nanocomposite fatliquoring agent wasobtained through introducing the modified MMT by a serious of fatty acid intomodified rapeseed oil by in-situ method. Stable nanocomposite fatliquoringagent containing stearic acid-MMT, cetylic acid-MMT or lauric acid-MMT couldnot be obtained. Application results show that softness, physical and mechanicalproperties of leather fatliquored by MRO/fatty acid-MMT were improvedcomparing with that of leather fatliquored by MRO. And flame retardancy ofleather was increased with increasing amount of MMT. Among them, the comprehensive performance of leather farliquored by MRO/oleic acid-MMTnanocomposite fatliquoring agent was optimal.
Modified MMT by tanning ions was characterized by FT-IR, XRD andTGA. The result indicates that the best pH for reaction between Cr~(3+)、Al~(3+)、Fe~(3+)、Zr~(4+)and Na-montmorillonite were3.5,4.5,7.0,2.0, respectively. The interlayerspacing of various ions-MMT was1.55nm,1.54nm,1.53nm,1.43nm,respectively. The modified MMT by tanning ions were introduced into modifiedrapeseed oil by in-situ method. The results of FT-IR, XRD and TGA show thatMRO/tanning ions-MMT nanocomposite fatliquoring agent were preparedsuccessfully. Layers of MMT were existed in the form of stripping whendifferent amount of Al ion were utilized to prepare nanocomposite fatliquoringagent and the thermal stability of MRO/Al-MMT nanocomposite fatliquoringagent was the highest. Softness, physical and mechanical properties and flameretardant performance of leather fatliquored by MRO/tanning ions-MMT wereimproved compared with that of leather fatliquored by MRO.
Different kinds of silane coupling agent were used to modify MMT. Theresults show that KH570，KH551，KH108and KH550could enter the interlayerof MMT. However, hexadecyltrimethoxysilane, dodecyltrimethoxysilane,KH560and A-151could not enter the interlayer of MMT. The silane couplingagent-MMT was introduced into the modified rapeseed oil by in-situ method.The results of FT-IR, XRD and TGA show that MRO/silane couplingagent-MMT nanocomposite fatliquoring agent was obtained successfully. Layersof MMT were existed in the form of stripping when the amount of silanecoupling agent-MMT was lower than2%. Application results show that softness,physical and mechanical properties and flame retardancty of leather fatliquoredby MRO/silane coupling agent-MMT were improved compared with that ofleather fatliquored by MRO. Among them, the comprehensive performance ofleather fatliquored by MRO/KH551-MMT nanocomposite fatliquoring agentwas optimal. The results of SEM and EDS show that the layers of MMT couldpenetrate effectively into or disperse uniformly into the collagen fiber withoutany changes on structure of fibers which make the loose of collagen fiberincreased.
Composite fatliquoring agent was prepared through mixing MRO and vegetable oil, mineral oil. Application results show that softness and fullness offatliquored leather could be improved. Tensile strength, tear strength andelongation at break of leather were approximate to that of leather farliquored bysimilar commercial products. The MRO composite fatliquoring agent has alreadyput into industrial production through adjustment on process and raw materialand market effect is good.
In this paper, functional leather fatliquoring agent was prepared usingmodified rapeseed oil as raw material, which could achieve the developmentneeds of the leather industry and improve the value in use of rapeseed oil inleather industry. The combination of traditional leather industry with theemerging nanotechnology and introduction of different modified montmorilloniteinto flame retardant modified rapeseed oil/MMT nanocomposite fatliquoringagent can not only satisfy the needs of people's daily life, expand leatherapplication, but also has an important significance to development ofhalogen-free flame retardant leather chemical and sustainable development ofleather industry.
引文
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