马来酸酐改性蓖麻油制备耐光性聚氨酯复鞣剂——乳液性能研究

用马来酸酐改性蓖麻油(MCO)合成了一系列不同组成的耐光性聚氨酯复鞣剂水乳液(MC-PUR),研究了复鞣剂中—COOH质量分数、n(NCO)/n(OH)、m(MCO)/m(PEG1000)对乳液电导率、黏度、临界聚沉值(CC.C)、耐酸稳定性的影响。结果表明,随—COOH质量分数从3%增大到7%,电导率从1 556μs/cm增大到3 435μs/cm,黏度先从168 mPa.s增大到224 mPa.s,后又降低到85 mPa.s,当w(—COOH)=5%时,黏度达到最大值;随n(NCO)/n(OH)从0.5增大到0.9,电导率从2 943μs/cm降到2 464μs/cm,黏度从428 m Pa.s降到224 mPa.s;随m(MCO)∶m(PEG1000)从1∶1增大到3∶0,黏度从224 mPa.s降到67 mPa.s;CC.C随—COOH质量分数增加和m(MCO)/m(PEG1000)增大而降低;耐酸稳定性结果证明,当w(—COOH)=3%~5%,m(MCO)∶m(PEG1000)=1∶1,n(NCO)/n(OH)=0.5~0.9时,MC-PUR适用于皮革复鞣工序。     

脂肪醇聚氧乙烯醚型阳离子聚氨酯表面活性剂的制备与性能

以异氟尔酮二异氰酸酯(IPDI)、N-甲基二乙醇胺(MDEA)、不同长链脂肪醇聚氧乙烯醚(AEO-2、AEO-5、AEO-9、O-2、O-5、O-10)为主要原料,合成了6个醇醚封端阳离子型聚氨酯高分子表面活性剂(PUS),并对产物进行了红外分析,考察了醇醚结构中烷基链长、环氧乙烷加合数、外加电解质对表面张力和临界胶束浓度的影响。结果表明:当脂肪醇聚氧乙烯醚为O-5时,其综合性能优异,溶液的临界胶束质量浓度(CMC)为32.947 mg/L,水溶液的表面张力(γCMC)最低可达34.142 mN/m。     

超高相对分子质量PA6冻胶的流变行为研究

以氯化钙为络合剂,将聚酰胺6(PA6)粉末与氯化钙溶解在甲酸/氯仿混合溶剂中制得冻胶样品,研究了PA6/氯化钙/甲酸冻胶体系的流变性能,以及温度、PA6的相对黏度、CaCl2与PA6的摩尔比和PA6的质量分数对冻胶的ηa-γ觶流变曲线、非牛顿指数和结构黏度指数的影响。结果表明:冻胶溶液属于宾汉流体,具有明显的非牛顿性;体系的表观黏度随着温度的升高而降低,随PA6的质量分数的升高、络合剂CaCl2与PA6的摩尔比的增大或PA6的相对黏度增大而增大;溶液的结构黏度指数随温度的升高而减少,随溶液PA6的相对黏度的升高或PA6的质量分数的升高而增大。     

乙二醇基纳米流体黏度的实验研究

实验研究了3种乙二醇基纳米流体（Al₂O₃-EG、ZnO-EG、CuO-EG）在不同质量分数（0.5%/3.0%/5.0%/7.0%）下的相对黏度随温度的变化规律,实验所用乙二醇基纳米流体采用两步法配制获得。结果表明：在30～60℃温度范围内乙二醇基纳米流体的相对黏度同温度之间并无较强的函数关系（单调递增或递减）;但在质量分数较高时,3种乙二醇基纳米流体的相对黏度随温度的变化会出现波动,且以非球形颗粒的ZnO乙二醇基纳米流体的波动最为显著;乙二醇基纳米流体的相对黏度均随纳米颗粒体积分数的增大而增大,其中CuO乙二醇基纳米流体相对黏度的增长速度最快,Al₂O₃乙二醇基纳米流体的增长速度最慢。最后比较分析了文献中相对黏度预测公式与本文实验数据的相符程度。     

乙二醇基纳米流体黏度的实验研究

实验研究了3种乙二醇基纳米流体(Al2O3-EG、ZnO-EG、CuO-EG)在不同质量分数(0.5%/3.0%/5.0%/7.0%)下的相对黏度随温度的变化规律,实验所用乙二醇基纳米流体采用两步法配制获得。结果表明:在30~60℃温度范围内乙二醇基纳米流体的相对黏度同温度之间并无较强的函数关系(单调递增或递减);但在质量分数较高时,3种乙二醇基纳米流体的相对黏度随温度的变化会出现波动,且以非球形颗粒的ZnO乙二醇基纳米流体的波动最为显著;乙二醇基纳米流体的相对黏度均随纳米颗粒体积分数的增大而增大,其中CuO乙二醇基纳米流体相对黏度的增长速度最快,Al2O3乙二醇基纳米流体的增长速度最慢。最后比较分析了文献中相对黏度预测公式与本文实验数据的相符程度。     

一步法制备铜导热油纳米流体的导热系数与黏度

为研究Cu纳米颗粒对VP-1导热油导热系数和黏度的影响,基于两相法一步制备十二烷基硫醇表面修饰的Cu/VP-1导热油纳米流体,研究30—130℃下不同质量分数纳米流体的导热系数和黏度变化规律。实验结果表明：添加分散剂可以改善纳米流体稳定性。在30—130℃纳米流体导热系数随温度、质量分数的增加而增大;黏度随温度升高呈指数降低,质量分数越高,黏度下降越缓慢。通过计算纳米流体在不同体积分数下的黏度和导热系数理论模型,对实验结果进行验证。Prasher模型能够准确预测纳米流体的导热系数,而现有的黏度模型不适用于Cu/VP-1导热油纳米流体,在修正现有的黏度模型基础上,提出新的黏度计算公式。     

磁力搅拌下离子液体AlCl_3/Et_3NHCl恒电流法电沉积铝

磁力搅拌下,在1.75AlCl3/Et3NHCl离子液体中不锈钢电极片上利用恒电流法电沉积制备金属铝。研究发现,AlCl3/Et3NHCl离子液体的黏度随温度的升高而减小,lnμ与T-1符合线性关系;AlCl3/Et3NHCl离子液体的电导率随温度的升高而增大,符合Arrhenius公式。磁力搅拌下恒电流法电沉积铝实验结果表明,转速低于700 r/min时电流效率和沉积速率随着转速的增大而升高,沉积物表面形貌逐渐平整致密,颗粒细化。温度70℃、电流密度22 mA/cm2、转速700 r/min、电沉积90 min下,沉积铝的表面形貌相对比较平整致密,电流效率达到78%,沉积铝的纯度（质量分数）达到97%。     

脂肪醇族酰基受体对酶法拆分扁桃酸对映体的影响

利用脂肪酶拆分手性酸是目前研究的热点及难点,脂肪醇作为手性拆分中的酰基受体,对选择性具有较大的影响。探究了不同碳链长度的脂肪醇作为酰基受体对扁桃酸对映体的拆分的影响,选取了不同的脂肪醇与扁桃酸在异丙醚中进行酯化反应。结果表明,随着脂肪醇链长增加,选择性呈降低趋势,转化率呈升高趋势。其中中链脂肪醇(碳原子数5～8个的脂肪醇)相比短链脂肪醇(碳原子数小于等于4个的脂肪醇)选择性差别并不大,而转化率明显提升;长链脂肪醇(碳原子数大于等于9个的脂肪醇)选择性较差。在对中链脂肪醇进一步探究中发现,正戊醇作为酰基受体优于其他中链脂肪醇,继而考察了各条件对反应的影响,得到在反应温度30℃,摇床转速200 r/min,加酶量200 mg,底物物质的量之比1:4和反应时间5 h的条件下,扁桃酸戊酯过量值(eep)可以达到70.09%,外消旋转化率达到23.40%。     

干法纺丝用聚间苯二甲酰间苯二胺溶液的流变性能

研究了聚间苯二甲酰间苯二胺溶液的固体质量分数、相对分子质量、温度对溶液流变性能的影响。结果表明:聚间苯二甲酰间苯二胺溶液的流变性能受溶液固体质量分数、相对分子质量、温度的影响明显,聚合物相对分子质量增大、溶液固体质量分数增加均使溶液表观黏度增大,温度升高使溶液表观黏度减小,溶液表观黏度随剪切速率的变化幅度较小。试验结果表明:适合干法纺丝的聚间苯二甲酰间苯二胺溶液的固体质量分数为31%³5%,特性黏度为1.6 dL/g左右,纺丝时原液温度范围为5035%,特性黏度为1.6 dL/g左右,纺丝时原液温度范围为50¹20℃。     

水性紫外光固化合成革用聚氨酯丙烯酸酯树脂的合成及性能研究

采用聚丁二醇(PBG)、2,4-甲苯二异氰酸酯、二羟甲基丙酸(DMPA)和丙烯酸羟乙酯合成了紫外光固化水性聚氨酯丙烯酸酯树脂,利用FT-IR对树脂进行了表征,探讨了树脂亲水基团含量和中和度对乳液性能的影响,分析表征了固化膜的基本性能。结果表明:乳液的粒径随着—COOH含量的提高而下降,乳液的分散性、稳定性及黏度随—COOH含量增加而增大;乳液黏度在中和度为90%时达到最高6.222 mPa.s,粒径达到最小59.8 nm。固化膜的吸水率随—COOH含量的增加而上升,固化膜对PVC板具有很好的附着力,其铅笔硬度随着DMPA/PBG比例的增加而上升。     

Effects of molecular weight distribution and branching on rheological properties of polyolefin melts

The objective of this work was to determine the relationships among molecular and melt parameters of polyolefins. The polyolefins studied are polypropylene, poly-1-butene, poly-1-hexene, poly-1-dodecene, these have regularly spaced short-chain branches. Conclusions from previous work, as well as some new data, on polyethylene are given. As the molecular weight increases, the critical shear rate decreases but the melt viscosity and non-Newtonian ratio increase. As the molecular weight distribution broadens, the critical shear rate decreases, whereas the normal forces and the non-Newtonian ratio increase. Increasing the number of short-chain branches increases the energy of activation and the melt viscosity but decreases the non-Newtonian ratio. As the length of the short-chain branches increases, the non-Newtonian ratio increases, but the melt viscosity, critical shear rate, and energy of activation decrease. Increasing the number of long-chain branches decreases the non-Newtonian ratio, but the normal forces and the melt viscosity increase. Such information allows the polymer chemist to design a polyolefin molecule having the critical melt properties required for a given production technique.     

All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM₉ whose POEM content = 51 wt% shows 2 × 10⁻⁵ S/cm at 30 °C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte.     

长碳链二元酸酯的合成及其物化性能

以杂多酸为催化剂、不同链长的二元酸为原料,合成了系列长碳链二元酸二元酯,考察了影响合成反应的因素及碳链长度对合成酯物化性能的影响. 结果表明,在回流温度160℃、醇/酸摩尔比3:1、催化剂用量为总质量1%、反应时间120 min、带水剂用量为总质量10%的条件下,酯化率达98%以上. 合成的酯具有良好的物化性能,其倾点最低为-74℃,闪点最高为258℃,粘度指数最大为187,优于现有商业化酯类润滑油基础油,达到现有航空润滑油基础油的标准. 随着碳链增长,合成酯粘度增大,增加醇碳链长度对粘度的影响大于增加酸碳链长度的影响.     

扩链改性对聚对苯二甲酸乙二酯挤出吹膜成型的影响

通过添加多官能团环氧扩链剂对聚对苯二甲酸乙二酯(PET)进行扩链改性,然后用改性PET进行吹膜成型,研究了扩链剂含量对PET特性黏度、膜泡稳定性及薄膜力学性能和透明度的影响。结果表明,扩链剂的添加显著提升了PET的特性黏度;随着扩链剂含量的增加,薄膜膜泡稳定性以及表面质量、最大吹胀比、拉伸强度得到显著改善,断裂伸长率呈先增大后减小的趋势。当扩链剂质量分数为0.7%时,PET的特性黏度由纯PET的0.71 d L/g上升至0.94 d L/g,最大吹胀比则由1.9提高至4.5,横纵向拉伸强度分别为61.7 MPa和64.4 MPa,横纵向断裂伸长率达到最高,分别为12%和12.45%,较扩链剂质量分数为0.2%时提高了105.5%以及125.1%,而透光率仅下降1.4%,得到了性能较优的吹塑薄膜制品。     

Sizes of long-chain branches in a high-pressure low-density polyethylene as a function of molecular weight

The mean length and the indices of long-chain branches (LCBs) of a high-pressure lowdensity polyethylene (HPLDPE) as a function of molecular weight have been determined for its molecular-weight-tractionated parts by the ¹³C-NMR analysis and the viscosity measurements. The mean LCB length of the fractions was of the order of 200–300 carbons in length. The size of LCBs increases with increasing molecular weight, but the size of LCBs relative to the overall macromolecular size decreases with increasing molecular weight. The LCB sizes as a function of molecular weight determined for the fractions of one parent HPLDPE are in good agreement with those previously reported for HPLDPE whole polymers.     

Phase diagram of α-sulfonate methyl esters derived from palm stearin/alcohol/water systems

Phase diagrams of α-sulfonate methyl ester derived from palm stearin (α-SMEPS)/alcohol/water systems were mapped at 30±0.1°C. Two main regions—an isotropic and a lamellar liquid crystalline—were the focal points in this system. An increase in alcohol chain length decreased the isotropic region and increased the lamellar liquid crystal region. In the isotropic region, self-assembly of α-SMEPS at different alcohol chain lengths was determined by using conductivity and viscosity measurements. The phase boundaries of micelle to bicontinuous structure and bicontinuous structure to inverse micelle transitions in the isotropic regions are proposed from these analytical methods. The increase in alcohol chain length shifted the micelle ⇆ bicontinuous structure to the water-rich corner, and the bicontinuous structure ⇆ inverse micelle transition moved toward the alcohol-rich corner.     

反应性乳化剂的制备及其在纯丙乳液聚合中的应用

将马来酸酐分别与苯甲醇、正辛醇、十二醇、十四醇和脂肪醇聚氧乙烯醚AEO-7通过酯化、中和反应生成相应的产物,依次记为ME-B,ME-8,ME-12,ME-14和M-AEO-7,测试并对比了各产物乳化力和临界胶束浓度的大小。结果表明ME-12和M-AEO-7的综合性能较佳。采用红外光谱对2者的结构进行表征。分别将十二烷基硫酸钠SDS、ME-12和M-AEO-7用于纯丙乳液聚合中,发现采用自制的反应性乳化剂所得乳液的聚合稳定性和乳胶膜的耐水性比SDS有所提高。将ME-12分别和AEO-3(AEO-5或AEO-7)以1∶1或1∶1.5质量比复配使用,仅在m∶m=1∶1.5时乳液的耐电解质稳定性才较好,而ME-12 AEO-7单独采用M-AEO-7即能得到耐电解质性能极佳的聚合物乳液。     

Aggregation of unsaturated long-chain fatty alcohols in nonaqueous systems

Aggregation and related phenomena in nonaqueous binary and ternary solutions containing unsaturated long-chain fatty alcohol amphiphiles have been studied. Six C₁₈ fatty alcohols were studied—oleyl alcohol (9Z-octadecen-1-ol), elaidyl alcohol (9E-octadecen-1-ol), linoleyl alcohol (9Z, 12Z-octadecadien-1-ol), elaidolinoleyl alcohol (9E, 12E-octadecadien-1-ol), linolenyl alcohol (9Z, 12Z, 15Z-octadecatrien-1-ol) and elaidolinolenyl alcohol (9E, 12E, 15E-octadecatrien-1-ol). Equivalent conductivity and photon correlation spectroscopy confirmed that unsaturated long-chain fatty alcohols form large and polydisperse aggregates in methanol. Critical micelle concentration (CMC) results showed that the degree of unsaturation and configuration of the double bonds in the fatty alcohol significantly influences aggregation. Aggregation of oleyl alcohol in a series of straight and branched medium-chainlength (C₃-C₈) alkanol solvents was studied. For shorter-chained alkanols (C₁-C₄), decreasing solvent dielectric constant decreases the CMC; however, for longer-chained alkanols (C₄-C₈), no significant effects occurred on the CMC. The effect of solubilized soybean oil on the viscosity of long-chain fatty alcohol/methanol solutions was also analyzed. Relative viscosity results were consistent with those expected for microemulsions. Although preliminary in nature, these results generally support the notion that soybean oil is solubilized by incorporation into large soybean oil-in-fatty alcohol aggregates in methanol solvent, resembling a nonaqueous detergentless microemulsion. Presented at the 67th Colloid and Surface Science Symposium, Toronto, Canada, June 20–23, 1993.     

磺基甜菜碱型两性离子表面活性剂的相行为研究

采用自制的4种磺基甜菜碱,运用多种方法对4种磺基甜菜碱/短链醇/正癸烷/NaCl/水形成的微乳液体系相行为进行了研究,并考察了温度、磺基甜菜碱的分子结构、短链醇浓度及其分子结构等对微乳液相行为的影响。实验表明:温度越高,中相微乳液形成的中相体积越大;SB9体系形成中相微乳液时,所需要的最小w(醇)为2%,最大醇宽为12%;SB12体系形成中相微乳液时所需要的最小w(醇)为4%,最大醇宽8%;随着磺基甜菜碱烷基碳数的增加,微乳区面积增大,增溶能力降低;最佳增容参数SP*和表面活性剂在油相和水相的平均溶解度SO.W均随短链醇碳链的增加而增加;平衡界面膜上的表面活性剂和醇在整个微乳液体系中所占的质量分数C S,C A,短链醇平衡界面膜所占的质量比AS,短链醇在油水相中的平均溶解度AO.W,均随短链醇碳链的增加而减小;w(醇)的增加使得微乳液体系发生由WinsorⅠ→WinsorⅢ→WinsorⅡ型的相态变化。