过硫酸铵改性炭黑／天然胶乳复合材料的制备与性能研究

摘要：用过硫酸铵水溶液改性炭黑,制备亲水性炭黑悬浮液。采用乳液共混法,将制备的改性炭黑水溶液直接加入天然胶乳。结果表明：改性后炭黑表面亲水性含氧基团增多,粒径减小;与传统干法混炼炭黑,天然橡胶胶料相比,乳液共混改性炭黑／天然胶乳复合材料炭黑分散粒径小且分散均匀,复合材料拉伸强度和撕裂强度显著提高。     

对乙烯苯磺酸钠改性炭黑母炼胶的制备及性能

采用固相原位聚合接枝方法制备了对乙烯苯磺酸钠（NASS）改性的亲水性纳米炭黑。热重分析结果表明,NASS成功地接枝到炭黑表面,其接枝率为2．5％。水分散性测试结果表明,改性炭黑在水介质中分散稳定。扫描电子显微镜照片表明,改性炭黑以聚集体尺寸均匀分散于橡胶基体中。改性炭黑填充的天然胶乳硫化胶的物理性能有了较大幅度的提高,其中撕裂强度提高了160％。     

射流胶乳混合法天然橡胶复合材料的制备及性能研究

用射流胶乳混合法制备天然橡胶(NR)复合材料,并对复合材料性能进行研究。先用超声空化作用将炭黑团聚体破碎、切割、分散在水中制得炭黑悬浮液,然后在高速射流场中将炭黑微观分散到天然胶乳中制成NR复合材料。结果表明:与传统干法混炼工艺相比,射流胶乳混合工艺可以使炭黑更均匀地分散到NR基体中;射流胶乳混合工艺制备的复合材料硫化时间缩短,硫化程度增大,撕裂强度提高78%,回弹值提高20%,DIN磨耗量减小33%。     

纳米二氧化钛改性聚氨酯乳液性能初探

主要讨论了纳米二氧化钛对聚氨酯乳液的改性。首先讨论了在二氧化钛纳米分散液中制备聚氨酯乳液的可行性,分别制备了纳米二氧化钛改性的芳香族聚氨酯和脂肪族聚氨酯乳液,得到了稳定乳液。通过紫外光谱分析,发现脂肪族聚氨酯与纳米二氧化钛共聚乳液薄膜在紫外区域400-200nm区域出现很明显的吸收峰。纳米二氧化钛的加入使芳香族聚氨酯乳液胶膜的拉伸强度增强,断裂伸长率下降。此外,对试样进行了DSC分析,发现共聚物在136-145℃出现明显的新的吸热峰。     

改性纳米碳酸钙对天然胶乳胶膜性能的影响

研究改性纳米碳酸钙(表面处理剂由磷酸酯盐和多种化学助剂复合制成)对天然胶乳胶膜性能的影响。结果表明，改性纳米碳酸钙在橡胶基体中分散较均匀；加改性纳米碳酸钙的天然胶乳胶膜硬度略有提高，拉伸强度和拉断伸长率增大，耐热老化性能改善；改性纳米碳酸钙的最佳用量为3份。     

表面改性碳纳米管/天然橡胶复合材料的制备及性能研究

采用多巴胺对多壁碳纳米管(MWCNTs)进行非共价改性,得到多巴胺改性MWCNTs(简称PCNT)。将PCNT作为填料加入天然胶乳中制备PCNT/天然橡胶(NR)复合材料,并研究其性能。透射电子显微镜(TEM)分析结果表明MWCNTs经过多巴胺改性后在水中的分散效果明显改善。PCNT/NR复合材料的拉伸强度和撕裂强度明显提高,拉伸强度由22.7 MPa升至28.4 MPa,撕裂强度由26 kN·m^-1升至40 kN·m^-1。多巴胺用量适当的PCNT在NR基体中分散更均匀,填料与橡胶的相互作用较强,能够形成较好的填料网络结构,PCNT/NR复合材料的表面电阻显著降低。     

“胶乳共混法”制备天然橡胶／二氧化硅纳米复合材料及其性能

采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）改性纳米二氧化硅（SiO2）,然后通过乳液聚合接枝上聚甲基丙烯酸甲酯（PMMA）,再将其与甲基丙烯酸甲酯（MMA）改性的天然胶乳,通过胶乳共混法制备天然橡胶／二氧化硅纳米复合材料,结果显示,纳米二氧化硅表面接枝上了PMMA,二氧化硅在橡胶基体中分散良好,粒径在60～100nm之间,得到的胶膜力学性能有很大的提高。     

改性纳米粘土/天然胶乳复合材料的制备与性能研究

研究表面改性剂对纳米粘土/天然胶乳复合材料性能的影响。结果表明:烷基表面活性剂对纳米粘土改性后,天然胶乳硫化胶膜老化前后的拉伸强度均明显提高,十六烷基三甲基溴化铵(CTAB)的改性效果最好,当改性纳米粘土用量为2份时,天然胶乳硫化胶膜的拉伸强度最高;CTAB改性纳米粘土能提高天然配合胶乳的保存稳定性、粘度和机械稳定性,并提高天然胶乳硫化胶膜的物理性能和耐热老化性能,补强效果明显。     

木质素基二氧化硅复合纳米颗粒的制备及在高密度聚乙烯中的应用

针对目前木质素基SiO₂复合纳米颗粒聚集严重及木质素负载量低,难以应用的现状,以碱木质素为主要原料,先通过磷酸化改性制备磷酸化碱木质素,再利用酸析共沉法将1.2份磷酸化碱木质素与1份纳米SiO₂(均为质量份)复合制备了木质素-SiO₂复合纳米颗粒,并探究复合颗粒对高密度聚乙烯(HDPE)力学性能的影响。FT-IR、XPS、TEM、TG和静态接触角测试结果表明,木质素主要以氢键作用与SiO₂结合;与原料二氧化硅相比,复合颗粒的粒径从25 nm增加到40 nm,聚集程度明显减弱;复合纳米颗粒中木质素占47%(质量分数);表面的疏水性增强,有利于复合颗粒在高密度聚乙烯中均匀分散,显著提高了HDPE的拉伸强度。与碱木质素/HDPE复合材料相比,木质素-SiO₂复合纳米颗粒/HDPE复合材料的拉伸强度和断裂拉伸率分别提高了48.68%和73.57%。     

原位法制备天然橡胶/二氧化硅纳米复合材料及其性能

采用原位生成共沉淀法制备天然橡胶/二氧化硅(NR/Si O2)纳米复合材料。先用乳化剂OP-10对硅溶胶进行处理,得到表面羟基比较少的硅溶胶,再与浓缩天然胶乳共混,原位生成纳米二氧化硅(n Si O2)制得NR/Si O2纳米复合材料。采用红外光谱仪、扫描电镜、橡胶拉伸测试机以及热重分析仪对不同Si O2含量的复合材料进行了表征。实验结果表明,干法混炼生成的Si O2粒径大且团聚严重,原位法生成的Si O2橡胶基体中分散更为均匀,平均粒径在50 nm左右;当Si O2为40份时,制得的复合材料力学性能最好,拉伸强度比纯的NR提高了67.8%,同时定伸应力也有明显提高。     

Rare earth compounds modified carbon black filled powdered natural rubber: Preparation,morphology and properties

Ten types of rare earth (RE) compounds modified carbon black (HAF‐RE) were prepared using chemical‐deposit method, then HAF‐RE were mixed with natural rubber latex to prepare HAF‐RE filled powdered natural rubber [P(NR/HAF‐RE)] by a carbon black/rubber latex coagulation method. It is found that most of the P(NR/HAF‐RE) vulcanizates showed better mechanical properties, especially higher tensile modulus, and tensile strength, compared with none‐rare earth modified carbon black filled powdered natural rubber [P(NR/HAF)]. Dysprosium (Dy) modified carbon black (HAF‐Dy) filled powdered natural rubber [P(NR/HAF‐Dy)] was chosen for intensive investigation because of its better comprehensive mechanical properties. It is found that the adding of Dy compounds could help to get smaller particles with narrower particle size distribution, and results from the SEM analysis show that carbon black has been dispersed in rubber matrix uniformly with diameter of 50–150 nm. The TEM analysis showed that Dy compounds could obviously reduce the aggregation of primary particles of carbon black, and promote the dispersion of carbon black in P(NR/HAF‐Dy) particles. © 2008 Wiley Periodicals, Inc. JAppl Polym Sci 2008     

自交联型改性苯丙乳液的制备及其用于防水涂料的性能研究

以丙烯酸（AA）、丙烯酸丁酯（ BA）和苯乙烯（St）为基础单体,通过调控功能单体甲基丙烯酸缩水甘油酯（ GMA）的用量制备了一种自交联型改性苯丙乳液（ PGSA）对乳液粒径大小与分布、形态与形貌以及乳液涂膜吸水性能进行了表征。以 PGSA乳液为液料辅以无,机水泥等填料制备了双组分聚合物水泥防水涂料,对其抗渗及力学性能进行了研究。结果表明：当 GMA用量为 7%时（以单体 AA、BA和 St的总质量计）,PGSA乳液的粒径为 210 nm、粒径分布（PDI）为 0. 17~0. 21,且放置 6个月后乳液的粒径及分布基本保持不变。此外,随着 GMA用量的增加, PGSA乳液涂膜的吸水率呈下降趋势。 PGSA基防水涂料的抗渗性、抗拉强度及断裂伸长率都符合 GB/T 23445—2009《聚合物水泥防水涂料》标准的要求,应用前景广阔。     

白炭黑/炭黑并用对轮胎胎面胶性能的影响

研究了白炭黑175Gr分别与4种炭黑并用对轮胎胎面胶加工性能、物理机械性能和动态物理机械性能的影响。研究表明,随着炭黑粒径的增大和结构度的提高,白炭黑175Gr/炭黑填充的胶料正硫化时间都缩短;白炭黑175Gr/炭黑N234并用时,其胶料拉伸强度和拉断伸长率都最高;白炭黑175Gr分别与炭黑N220和炭黑N550并用时,两种胶料的回弹性和压缩疲劳性都较好;白炭黑175Gr/炭黑N220并用后,其胶料的Payne效应较小,滞后损耗因子最低。     

超声波湿法混炼炭黑/天然橡胶复合材料的性能研究

利用超声波的乳化均质作用,将经水湿润的炭黑与稀释的天然胶乳混合均匀,然后采用蒸发成膜法和胶凝成膜法制备胶膜(炭黑/天然橡胶复合材料),探究制膜方法及超声波处理时间和功率对胶膜性能的影响。结果表明:蒸发成膜法成膜时间过长,打开的炭黑二次结构重新团聚,胶膜中炭黑分散性差,胶膜的拉伸强度较小,而胶凝成膜法稳定性更高,胶膜中炭黑分散性好;超声波处理时间为90 s、功率为840~960 W时,超声波的乳化均质效果最好,炭黑二次结构打开程度更高,此时采用胶凝成膜法制备胶膜,成膜速度快,炭黑来不及团聚,胶膜中炭黑分散性较好和结合橡胶较多,胶膜的拉伸强度较大。     

羟基硅油改性水性聚氨酯的制备与性能研究

以羟基硅油（PDMS）、二苯基甲烷二异氰酸酯（MDI）、聚醚多元醇为主要原料,合成了有机硅改性的水性聚氨酯（WPU）材料,探讨了PDMS用量对WPU乳液和胶膜性能的影响,并采用FT—IR和DSC对其进行了表征。结果表明,随着PDMS加入量的增加,乳液粒径增大,粘度升高,胶膜的吸水率降低,力学性能和热稳定性提高。当PDMS质量分数为11．8％时,制备的有机硅改性聚氨酯材料性能最佳,其吸水率下降至5．6％,拉伸强度达到14．74MPa,断裂伸长率为462％,胶膜的初始分解温度提高了36℃。     

The effect of pressure on carbon black/elastomer powders. IV. Comparison of press-cured powders containing vulcanizing agents with mill-mixed compounds

SBR latex was compounded with six different types of carbon black (SRF, FEF, HAF, SAF, HEB, and HCC-I) and vulcanization ingredients in aqueous dispersion by means of a dispersing agent. The particle size of the carbon black agglomerates in aqueous dispersion was estimated from turbidity and light scattering measurements. It was found that the size of the aggregates is by far larger than the average particle size of the SBR-latex used. The latex mixture containing carbon black and vulcanization ingredients was spray-dried to a fine-sized powder of an average particle size of 0.25 mm; this powder was subsequently vulcanized without the action of shear forces at a pressure of 200 bar. It was the aim of this study to answer the question whether latex-stage compounded vulcanizates can be reinforced without applying shear forces, if only the distribution of the carbon black in the compound is sufficiently good. The tensile strength was used for judging reinforcement; the quality of the carbon black dispersion was estimated by means of the Cabot rating method. The carbon black dispersion in the compounded powders proved to be excellent with fine-sized carbon blacks and was in the order of A 1 and B 2 of the Cabot scale. Scanning electron micrographs of the fracture zones and transmission electron micrographs on ultrathin cuts showed, however, differences in the microdispersion of the carbon blacks between powder-and mill-mixed compounds. A comparison of the mechanical properties of powder-and mill-mixed compounds yielded partially comparable tensile values for the powder compounds up to 20 MN/m², but strikingly high hardness, elongation set and a pronounced stress-softening after repeated deformation (Mullins-effect).     

稀土掺杂炭黑填充型粉末天然橡胶（I）制备与粒径分布

利用稀土（Ln）可与有机高分子化合物发生作用的性质。用稀土盐和炭黑以液相化学沉积法制备了稀土化合物掺杂炭黑（HAF—Ln）,以增加炭黑粒子的表面活性,并将其与天然胶乳（NRL）共混,采用凝聚共沉法制备稀土掺杂炭黑填充型粉末天然橡胶[P（NR／HAF—Ln）]。透射电镜（TEM）、傅立叶转换红外光谱（FTIR）、等离子发射光谱（ICP）分析表明,稀土可全部沉积到炭黑粒子表面;稀土可有效减少炭黑粒子的团聚,促进炭黑在水中的稳定分散。稀土的加入可提高NR胶乳与乳化炭黑构成的粉末体系的成粉率。     

Reinforcement of natural rubber latex film by ultrafine calcium carbonate

Using ultrafine calcium carbonate to reinforce natural rubber latex film, the effect of its content on latex properties such as surface tension, viscosity, mechanical stability, and heat stability and the physical properties of latex film before and after aging such as tear strength, modulus, and tensile strength were investigated. The results showed that the surface tension of natural rubber latex reinforced by ultrafine calcium carbonate only changed slightly; when the content of calcium carbonate was less than 20%, the change of viscosity was not obvious, but when the content was greater than 20%, the viscosity significantly lowered. Ultrafine calcium carbonate could effectively improve the tear strength, tensile strength, and modulus of the natural rubber latex film. The modulus increased with the increment of the calcium carbonate. When the content of calcium carbonate was less than 15%, the tear strength and tensile strength increased with the increments of calcium carbonate, but when the content was greater than 15%, the above‐mentioned properties decreased with the increment of calcium carbonate. By comprehensive consideration, the best reinforcing effect was obtained at a content of 15% ultrafine calcium carbonate. The particle diameters of calcium carbonate and their distribution in the calcium carbonate emulsion and in the rubber film were analyzed with SEM and a laser particle size tester, which showed that the distribution of calcium carbonate in the latex film was even and that it could effectively reinforce natural rubber latex film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 982–985, 2003     

黏土/天然橡胶纳米复合材料的制备及性能

利用乳液插层法制备了黏土／天然橡胶纳米复合材料,研究了该复合材料的力学性能、应力应变行为、耐磨性、气体阻隔性和耐老化性能。结果表明,黏土／天然橡胶纳米复合材料与高耐磨炭黑(N330)、白炭黑增强橡胶相比,邵尔A型硬度、定伸应力和撕裂强度较高,拉伸强度相当。黏土、N330以及白炭黑对天然橡胶的拉伸结晶有影响,填料用量对材料拉伸强度的影响存在最佳值。黏土／天然橡胶纳米复合材料具有良好的耐磨性、气体阻隔性和耐老化性能。