基于鞣制废革屑的生物基皮革填料的制备及性能

采用双氧水对非铬金属鞣制废革屑进行了催化氧化,制得降解产物(DCH),然后采用双醛海藻酸钠(DSA)对DCH进行改性,获得生物基皮革填料(BDH).采用FTIR、GPC、XPS和Zeta电位分析仪对DCH和BDH的结构和性质进行了表征.结果表明,DSA对DCH成功进行了改性,BDH的重均相对分子质量可由DCH的3900...     

苯乙烯-alt-马来酸酐共聚物的合成及其复鞣填充作用

采用溶液聚合的方法制备了系列相对分子质量(简称分子量,下同)不同的苯乙烯-alt-马来酸酐共聚物(SMA),并通过FTIR、1HNMR、13CNMR对产物结构进行了表征,通过DSC对其热性能进行了分析。考察了分子量大小对其在皮革中复鞣填充作用的影响。结果表明,分子量是影响SMA复鞣填充作用的重要因素,随聚合物分子量的增加,处理革的抗张强度降低、撕裂强度增加、部位差降低率增大。当SMA的Mn为6 620时,处理革的撕裂强度、抗张强度和部位差降低率分别为18.325 N/mm、9.519 N/mm2和7.44%,当SMA的Mn为59 058时,处理革的撕裂强度、抗张强度和部位差率降低率分别为20.577 N/mm、5.539 N/mm2和44.98%。     

一种阳离子型合成鞣剂的制备及其鞣革性能

在丙酮和水为混合溶剂的介质中,以三聚氯氰和3-二甲氨基丙胺为原料合成N,N’-2-(4,6-二氯-1,3,5-三嗪基-2-氨基)-二甲基丙胺（TAMP）,通过FT-IR和1H-NMR对合成产物结构进行表征。以脱灰软化的绵羊皮为鞣制实验材料对象,采用坯革的收缩温度及其感官状态为指标,通过单因素实验法确定适宜鞣制工艺条件为：鞣剂用量20%（以灰皮重量计）,鞣制过程采用25℃、35℃和45℃阶梯控温模式进行,各温度模式阶段鞣制时间依次为1h、1.5h和3 h;在鞣制坯革的染整实验中,借助于染料的上染率以及坯革色泽干湿擦坚牢度评价TAMP鞣革对染料吸收结合性能的影响。实验结果表明：TAMP初鞣的坯革收缩温度可达71.6℃,粒面洁白细腻;染色加油处理的初鞣坯革撕裂强度为71.33N/mm,拉伸强度为34.00N/mm2,染料上染率为96.8%,色泽干/湿擦坚牢度为2.0-4.0级,坯革上述物性指标均优于F-90鞣剂的应用性能。该实验研究对制革无铬鞣剂的开发与应用提供了一条新颖的技术思路和途径。     

P（POSS-IA）纳米复合材料的制备及其鞣制性能

以八乙烯基笼型倍半硅氧烷（POSS-Vi）和衣康酸（IA）为原料，通过自由基聚合制得聚（笼型倍半硅氧烷-衣康酸）〔P（POSS-IA）〕纳米复合材料。通过FT-IR、1H-NMR、XRD、TEM对其结构进行了表征，POSS-Vi均匀分散在聚合物基体中，直径在50nm左右。将P（POSS-IA）应用于坯革鞣制工序中，与聚（衣康酸）〔P（IA）〕、聚（丙烯酸）〔P（AA）〕、聚（笼型倍半硅氧烷-丙烯酸）〔P（POSS-AA）〕、聚（甲基丙烯酸）〔P（MAA）〕、聚（笼型倍半硅氧烷-甲基丙烯酸）〔P（POSS-MAA）〕鞣制坯革进行了性能对比。结果表明，P（POSS-IA）鞣制坯革具有较高的收缩温度，达到68.2 ℃；P（POSS-MAA）鞣制坯革增厚率最大，可达到53.3%；P（POSS-AA）鞣制坯革的抗张强度和撕裂强度最高，分别达到31.6 MPa、59.3 N/mm。坯革的SEM和EDS结果表明，P（POSS-IA）纳米复合材料在鞣制坯革中分散更均匀。     

共改性煤粉增强丁苯橡胶的硫化、力学和热稳定性能研究

将硅烷偶联剂KH⁃560和硫化促进剂CZ共改性煤粉（Coal）作为增强填料加入到丁苯橡胶（SBR）中制备改性SBR/ Coal复合材料,通过设置不同的共改性Coal的添加量,寻找KH⁃560、CZ共改性Coal增强丁苯橡胶的最佳实验配比。结果表明,KH⁃560的最佳添加量为Coal质量的5 %,此时SBR/ Coal⁃KH560复合材料的力学性能最佳; KH⁃560和CZ改性Coal可以明显减少Coal团聚现象,在丁苯橡胶中均匀分散。当Coal⁃KH560⁃CZ添加量为40 %时,与纯SBR相比,拉伸强度由1.66 MPa升高至2.9 MPa,断裂伸长率由295 %升高至390 %,撕裂强度由7.1 N/mm增加至11.6 N/mm,复合材料的力学性能和热稳定性能得到改善,加工性能也得到较大提升。     

蓖麻油改性两性聚氨酯复鞣剂的制备及应用

以异氟尔酮二异氰酸酯和聚四氢呋喃二醚醇为原料、2,2-二羟甲基丙酸为阴离子扩链剂、N-甲基二乙醇胺为阳离子扩链剂,制备了两性聚氨酯乳液,接着使用蓖麻油改性两性聚氨酯得到产物(COWPU)。通过FTIR对其进行了表征,采用纳米粒度及zeta电位仪对COWPU乳液的粒径及等电点进行了测试,采用TG对COWPU膜进行了热性能测试。随后将其用于有机无铬鞣剂TWS鞣制绵羊皮服装白湿革的复鞣工序。结果表明,COWPU已成功制备,具有显著的两性特征(等电点为6.29)和良好的生物降解性[5日生化需氧量(BOD5)与化学需氧量(COD)的比值为0.37],经COWPU复鞣后的坯革的撕裂强度为43.15 N/mm,抗张强度为9.99 MPa,均优于市售两性丙烯酸复鞣剂复鞣后的坯革。此外,COWPU还对坯革有一定的柔顺作用,有望实现复鞣-加脂一体工艺。     

LDH@MMT/MZBMSO的制备及其在皮革中的阻燃性能

采用水热法在蒙脱土（MMT）表面原位生长层状双氢氧化物（LDH），获得了层状双氢氧化物@蒙脱土（LDH@MMT）。通过XRD、SEM、FTIR对LDH@MMT进行了表征。结果表明，LDH和MMT通过氢键复合在一起，呈花状结构。将其引入花椒籽油（ZBMSO）中制得层状双氢氧化物@蒙脱土/改性花椒籽油（LDH@MMT/MZBMSO），TEM结果表明：LDH@MMT均匀分散在MZBMSO中。将其应用于皮革加脂工艺，结果表明：与MZBMSO加脂坯革相比，当LDH@MMT的质量占ZBMSO的12%时，LDH@MMT/MZBMSO加脂坯革阻燃性能明显提高，加脂坯革氧指数由22.8%提升至28.3%，有焰燃烧时间由87 s减少到43 s，热释放速率降低了43.6%，总热释放速率降低了73.6%，产烟速率降低了63.5%；LDH@MMT包裹在坯革纤维表面，形成的“曲折路径”可减缓热量及烟气的释放，燃烧后在纤维表面形成致密碳层进一步阻隔坯革燃烧过程中释放的热量、烟气，并隔绝氧气，从而提升了加脂坯革的阻燃抑烟性能。     

改性凹凸棒石及硅灰石填充PTFE的摩擦性能研究

采用硅烷偶联剂（KH550）及十六烷基三甲基溴化铵（CTAB）对凹凸棒石粉体进行改性，并将改性前后的凹凸棒石粉体与硅灰石复合填充至聚四氟乙烯（PTFE），制备PTFE复合材料。采用傅里叶红外光谱仪（FTIR）、扫描电子显微镜（SEM）、邵氏硬度计、环块摩擦磨损试验机、万能试验机对改性凹凸棒石粉体的理化性能及复合材料摩擦学性能进行表征。结果表明：凹凸棒石及硅灰石的加入可以降低复合材料的磨损率。经CTAB改性的凹凸棒石与硅灰石填充至PTFE，复合材料的邵氏硬度增至70，磨损率降至1.54×10-6 mm3/（N·m），压缩性能提高40%左右。对凹凸棒石进行表面改性，可提高粉体与PTFE基体的界面结合，从而改善复合材料摩擦学性能和力学性能。     

含氨基和羧基POSS/聚合物复合材料鞣制性能

以笼型八乙烯基倍半硅氧烷(POSS-Vi)、丙烯酰胺(AM)和甲基丙烯酸(MAA)为原料,通过自由基聚合法制备含氨基、羧基的POSS/聚合物复合材料P(POSS-AM-MAA)。采用FTIR、XRD、TEM等对P(POSS-AM-MAA)的结构和形貌进行表征。结果表明：复合材料P(POSS-AM-MAA)是具有立方笼型结构的POSS外围被聚合物链段包覆的材料。将复合材料P(POSS-AM-MAA)配合占酸皮重的4%戊二醛应用于山羊酸皮鞣制工艺中,考察了氨基含量、相对分子质量(简称分子量)大小、复合材料用量等对坯革性能的影响。结果表明：当复合材料P(POSS-AM-MAA)中氨基含量为433 μmol/g、数均分子量为27237,其用量为酸皮重的8%,结合pH为8.5时,结合鞣坯革收缩温度为83.7 ℃,增厚率为107.3%,相较于单独戊二醛鞣制坯革均有所提高;结合鞣坯革中的游离甲醛含量为28.3 mg/kg;结合鞣坯革的抗张强度为16.5 MPa,断裂伸长率为109.5%,撕裂强度为58.8N/mm,与戊二醛鞣制坯革相当。     

阳离子角蛋白絮凝回收利用废水中的皮革助剂

通过在角蛋白分子上引入季铵基制得一种阳离子角蛋白。将该阳离子角蛋白对几种常见的皮革助剂进行絮凝处理,考察其絮凝性能,同时,对絮凝得到的絮体进行适当处理,用于皮革填充,对回收利用的可行性进行初步探讨。该絮凝剂对染料的絮凝效果较好,脱色率可达到90%以上。絮体用于皮革填充,填充后皮革增厚率达15.12%,抗张强度从15.81 MPa提高到16.40 MPa,填充后坯革的断裂伸长率在较理想的范围,柔软度从5提升到8,丰满度从5提升到9,表现了理想的填充效果。     

Mechanical and thermal properties of ABS and leather waste composites

To determine the possibility of using leather waste as reinforcing filler in the thermoplastic polymer composite, acrylonitrile–butadiene–styrene (ABS) as the matrix and leather buffing powder as reinforcing filler were used to prepare a particulate reinforced composite to determine testing data for the physical, mechanical, and thermal properties of the composites, according to the filler loading in respect to thermoplastic polymer. The ABS and leather powder composites were prepared by the extrusion of ABS with 2.5, 5, 7.5, 10, 12.5, and 15 wt % of leather powder in corotating twin screw extruder. The extruded strands were cut into pellets and injection molded to make specimens. These specimens were tested for physicomechanical properties like tensile and flexural strengths, tensile and flexural modulus, Izod and charpy impact strength, abrasion resistance, Rockwell hardness, density, Heat deflection temperature (HDT) and Vicat softening point (VSP), water absorption, and thermal degradation analysis. The incorporation of leather waste powder does not affect the tensile, flexural strengths, Izod impact strength, abrasion resistance, Rockwell hardness, density, HDT and VSP values drastically. However, the tensile modulus, tensile elongation, and charpy impact strength values are reduced significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3062–3066, 2006     

Preparation of flame‐retardant leather pretreated with pyrovatex CP

Resistance to burning is one of the most useful properties that can be imparted to leather. Pyrovatex CP is rich in phosphorus and nitrogen and has been successfully used as a flame‐retardant agent in the presence of etherified methylolated melamine (EMM). The effects of a finishing formulation containing Pyrovatex CP and EMM on the flame retardancy and other properties of modified leather have been studied under different conditions. The synergistic effect of the N/P ratio has been thoroughly investigated through the estimation of the nitrogen and phosphorus contents, and their impact on the flame retardancy, tensile strength, and elongation at break of the treated leather has been studied. An investigation of the different factors has led to the following conclusions: (1) the P and N percentages increase with increasing curing temperature and time, (2) increases in the Pyrovatex CP and EMM concentrations are accompanied by an enhancement of the P and N percentages, and (3) all samples exhibit loss in their tensile properties but within an acceptable range (20%). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

纳米SiOx改性天然胶乳用表面处理剂的选择

分别以丙二醇、一缩二乙二醇、丙三醇处理纳米SiOx，研究了纳米SiOx在天然乳胶及PVA复合天然乳胶体系中的均匀分散技术；性能测试结果及SEM照片表明：①采用多羟基有机化合物作为表面处理剂，可以使纳米SiOx在胶膜中分散均匀．并有效防止其在体系中的聚集。②多数试样的拉伸强度和撕裂强度均高于添加常规补强剂（白炭黑或炭黑）的试样。③采用一缩二乙二醇作为纳米SiOx表面处理剂的天然乳胶膜，其拉伸强度为59．44MPa，撕裂强度为27．66N／mm，综合力学性能最优，分别比添加白炭黑的试样提高了44．6％和33．2％。     

Curing of crust leather by ultraviolet radiation with urethane acrylate: Role of pigment

Eight different formulations were developed with four diacrylate reactive monomers such as tripropylene glycol diacrylate (TPGDA), 1,4‐butanediol diacrylate (BDDA), 1,6‐hexanediol diacrylate (HDDA), and 2‐ethylene glycol dimethacrylate (EGDMA) and aromatic urethane diacrylate (M1100) in order to modify the crust leather surface. To study the effect of pigment on the performance of ultraviolet (UV)‐cured leather surface, 1% pigment (congored) was incorporated in the formulations. Irgacure 369 (2%) was also used in the formulation as photoinitiator. The gel content, tensile strength, elongation at break, and pendulum hardness of UV‐cured thin films with and without pigment was studied. The films without pigment produced better properties. Among all the diluents, BDDA‐containing films showed the best performance. Different properties of UV‐coated leather surface such as pendulum hardness, tensile strength, elongation, gloss (at 20° and 60°), adhesion, and abrasion were studied. Effect of gloss on simulating weathering was also performed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 692–697, 2002     

Biodegradability and mechanical properties of agro‐flour–filled polybutylene succinate biocomposites

The objective of this study was the production of rice husk flour (RHF) and wood flour (WF) filled polybutylene succinate (PBS) biocomposites as alternatives to cellulosic material filled conventional plastic (polyolefins) composites. PBS is one of the biodegradable polymers, made from the condensation reaction of 1,4‐butanediol and succinic acid that can be naturally degraded in the natural environment. We compared the mechanical properties between conventional plastics and agro‐flour–filled PBS biocomposites. We evaluated the biodegradability and mechanical properties of agro‐flour–filled PBS biocomposites according to the content and filler particle size of agro‐flour. As the agro‐flour loading was increased, the tensile and impact strength of the biocomposites decreased. As the filler particle size decreased, the tensile strength of the biocomposites increased but the impact strength decreased. The addition of agro‐flour to PBS produced a more rapid decrease in the tensile strength, notched Izod impact strength, and percentage weight loss of the biocomposites during the natural soil burial test. These results support the application of biocomposites as environmentally friendly materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1513–1521, 2005     

A comparative study of aging characteristics and thermal stability of oil palm ash,silica, and carbon black filled natural rubber vulcanizates

Filler‐filled natural rubber (NR) vulcanizates were prepared by conventional laboratory‐sized two roll mills and cured using sulfuric system. The effect of thermal aging on physical properties and thermogravimetric analysis (TGA) of oil palm ash (OPA) and commercial fillers (i.e., silica vulkasil C and carbon black N330)‐filled NR vulcanizates at respective optimum loading and equal loading were studied. Before aging, the OPA‐filled vulcanizates showed comparable optimum strength as carbon black‐filled vulcanizates. The hardening of aged filler‐filled NR vulcanizates happened after aging, thereby tensile strength and elongation at break reduced while the modulus increased. Fifty phr carbon black‐filled vulcanizates showed better retention in tensile properties as compared to silica (10 phr) and OPA (1 phr). This was attributed to the addition of different filler loading and this finding was further explained when equal loading of filler‐filled vulcanizates was studied. Fourier transform infra‐red analysis showed chemical structure had changed and tensile fractured surface exhibited smooth appearance due to the deterioration in tensile properties after aging. TGA also denoted the thermal stability was depending on the amount of filler loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4474–4481, 2013     

Surface modification of natural leather using diffuse ambient air plasma

The aim of this work was to activate the surface of dyed natural leather using a diffuse ambient air plasma treatment. The plasma was generated by the so-called diffuse coplanar surface barrier discharge (DCSBD). It was observed that a 10 s plasma treatment time is enough to decrease the water contact angle from 85° to 45°. Improvement of wettability is important for gluing of dyed leather and better adhesion of glue to leather parts. XPS study indicated that the percentage of oxygen-containing bonds responsible for hydrophilicity is significantly increased by the plasma treatment. Influence of the plasma treatment on mechanical properties of dyed leather was evaluated using tensile strength measurement and no significant changes in the surface morphology and mechanical properties were observed. The results indicate that the DCSBD technique can provide high throughput, technical simplicity and economy required by the leather industry.     

Vulcanization characteristics and mechanical properties of natural rubber–scrap rubber compositions filled with leather particles

Scrap rubber recycling combined with waste leather particles in natural rubber compounds has been studied. The effect of leather and scrap rubber loading on vulcanization characteristics of natural rubber compounds has been evaluated. The presence of leather was found to reduce the scorch time and increase the maximum and minimum torque. While reversion was not observed in the absence of leather at 150 °C, it was more prominent when leather was incorporated. Mechanical properties such as tensile strength, elongation at break, tear strength, modulus and hardness were found to increase on increasing the scrap rubber loading in the absence of leather. Compounds containing leather exhibited higher tensile strength, modulus, hardness and tear strength values but the modulus and hardness values were found to decrease as the scrap rubber loading increased. All the vulcanizates exhibited only limited swelling in different media as the swelling of one phase of the composite was found to be restricted by the other phase. Copyright © 2004 Society of Chemical Industry