【作者】 袁霞；

【导师】 房宽峻；

【作者基本信息】 江南大学 ， 纺织工程， 2007， 博士

【摘要】 炭黑是一种重要的化工原材料,广泛应用于橡胶、塑料、油墨、涂料等领域。本文研究了炭黑的分散性质,比较了两种制备超细炭黑水性分散体系的方法,并分析了超细炭黑水性体系的性质和染色性能,探讨了阳离子改性棉织物对炭黑染色性能的影响。从炭黑分散体系三部分（分散介质、添加剂和炭黑）作用的角度,初步研究了炭黑的分散性能。结果表明炭黑在弱极性（ε=4.9～13.3）或沉降因子低（C＜1.043）的介质中分散效果较好,添加剂会影响炭黑在介质中的分散,炭黑表面结构因液相氧化而改变,分散后的炭黑粒径随氧化程度的加剧而变大。采用分散剂直接分散法制备超细炭黑水性分散体系时,研究了低分子分散剂、高分子分散剂（羧甲基纤维素钠CMC和聚乙烯吡咯烷酮PVP）对炭黑的分散效果,并讨论了分散剂的混用。结果表明低分子分散剂中阴离子型能较好地分散炭黑,其中亚甲基二萘磺酸钠NNO最有效;CMC粘度影响对炭黑的分散,炭黑粒径随超声时间的延长而迅速降低至最小值160nm;过氧化氢高温处理有利于CMC分散炭黑;PVP分散后的炭黑粒径、Zeta电位绝对值随超声时间的延长也逐渐降低,但过氧化氢高温处理不利于PVP分散炭黑;非、阴离子型低分子分散剂混用时没有协同作用;在过氧化氢高温处理时,NNO与CMC有较好的混用性;另外NNO比聚氧乙烯辛基苯酚Tx能更有效地改善PVP对炭黑的分散效果;讨论了CMC、PVP包覆炭黑的分散效果。结果表明非溶剂用量影响CMC包覆后的炭黑粒径,包覆后的炭黑粒径较大、Zeta电位绝对值较高,离心稳定性较好;PVP交联包覆时,当引发剂用量＞1.6wt%时,炭黑粒径明显增加;在超声波处理时,PVP包覆分散和PVP直接分散的炭黑具有相似的粒径和Zeta电位,但前者的离心稳定性较好;然而PVP包覆后的炭黑在强烈超声时,会重新聚集成较大的附聚体,表明包覆的PVP交联层容易在炭黑表面剥落。分析了超细炭黑水性分散体系的性质,表明体系的表观粘度随NNO用量增加而略有增大,体系为剪切变稠型;体系的表观粘度也随炭黑用量增加而增大,当炭黑用量＜5wt%时,为剪切变稠型,而当炭黑用量为10 wt%时,则为明显的剪切变稀型;分散体系具有较好的离心稳定性,通过离心分级可获得不同粒径D₀（最小可达36.1nm）的炭黑分散液,都具有较好的静置稳定性（25℃和80℃）,D₀为90.5nm的炭黑具有很好的再分散性。研究了超细炭黑水性分散体系的染色性质。结果表明分散剂种类对棉织物K/S值影响较大,其中二丁基萘磺酸钠BX染色后的棉织物K/S值最高,炭黑上染率和织物K/S值随着分散剂（NNO、Tx）用量增加而明显降低;炭黑粒径对棉织物颜色性质影响较小,炭黑上染率随着炭黑用量增加而逐渐增加,但当CB＞8%owf时开始迅速下降;织物K/S值随炭黑用量变化的曲线类似于Langmuir型,染色后织物K/S值当炭黑为10%owf时达到最大,而皂洗后K/S值当炭黑为4%owf时达到最大;添加电解质NaCl对炭黑染色有一定的促染作用,粘合剂能明显提高棉织物K/S值,但并不能提高摩擦牢度。在阳离子改性棉织物的基础上,讨论了炭黑分散体系的染色性能。认为分散剂种类也影响炭黑对阳离子改性棉织物的染色,其中BX、Tx的染色效果较好;炭黑上染率和织物K/S值随分散剂（N-NO、Tx）用量增加而有所降低;炭黑粒径对阳离子改性棉织物的颜色性质影响较大;增加炭黑用量,则炭黑在阳离子棉织物上的上染率明显降低,当炭黑用量为2%owf时,达到最大色深值;添加电解质对阳离子棉织物染色的影响较小,可实现无盐染色;加入粘合剂降低了阳离子棉织物染色后的K/S值,但稍微提高了棉织物的干、湿摩擦牢度。探讨了超细炭黑染色阳离子改性棉织物的机理。阳离子改性棉织物提高了炭黑的染色效果,其中Tx分散体系染色后的效果改善最明显;超细炭黑与阳离子化棉纤维间有较强的亲和力,在很短的染色时间（5min）内,炭黑就能最大限度地吸附到棉纤维表面,随着染色时间的延长,炭黑粒子逐步向棉纤维表层内部孔隙或裂缝扩散。更多还原

【Abstract】 Carbon black （CB） is one of the most important chemical materials. It is widely used in rubber, plastics, printing ink, coating and the other fields. The dispersing performances of CB particles were discussed and two preparing methods of waterborne dispersions of ultrafine CB particles were compared. The performances and dyeing properties of waterborne dispersions were also analyzed. And the effects of cotton modified with a cationic reagent on the dyeing properties of ultrafine CB dispersions by an exhaustion process were investigated in this paper.From the point of the action of three parts （dispersing media, addition and CB particles） in CB dispersions, the dispersing performances of CB particles were discussed. The results showed that the dispersing effect was better when CB particles were dispersed in media either with lower polar which the dielectric constantεof the liquid is at the range of 4.9～13.3 or with smaller sedimentation factor C which C is below 1.043. Addition would influence CB particles to disperse in media. Moreover the CB particle size became larger with the extent of oxidation because the surface structure of CB was changed by the liquid oxidation.The effects of small molecular dispersants, polymer dispersants （sodium carboxymethyl cellulose （CMC） and poly （vinyl pyrrolidone） （PVP）） on dispersing CB particles directly were studied. And the mixtures of two dispersants used to disperse were also discussed. The results showed that anionic dispersant with small molecular weight could disperse CB particles effectively, and among these sodium methylenedinaphthalene disulphonate （NNO） was the most effective agent in dispersing CB particles. CMC with different viscosity was able to affect the degree of dispersing CB particles in aqueous media. CB particle size obviously decreased with increasing ultrasonic time and arrived at minimum about 160nm. Oxidation with hydrogen peroxide was beneficial to preparing for waterborne ultrafine carbon black dispersion. The particle size and the absolute value of Zeta potential of CB particles dispersed by PVP decreased with increasing ultrasonic time. However oxidation with hydrogen peroxide was not in favor of dispersing CB particles. It seemed that the mixture of nonionic and anionic dispersant had not sympathetic effect on dispersing CB particles. The CB dispersion properties dispersed by the mixture of CMC and NNO were superior when the dispersion was oxidized with hydrogen peroxide at high temperature. And the dispersing efficiency of PVP can be more effectively promoted by adding NNO than polyoxyethylenated octylphenol （Tx）.The dispersion properties were also discussed when CB particles were encapsulated by CMC or PVP. The results showed that the amount of nonsolvent affected the CB particle size. The particle size and the absolute value of Zeta potential of CMC-encapsulated CB particles were larger and the dispersion had better centrifugal stability. However when the amount of initiator was larger than 1.6wt%, the CB particle size was obviously increased which CB particles was covered by PVP. Moreover, when CB dispersions were treated by ultrasonic, the particle size and Zeta potential of PVP-encapsulated CB particles were similar to those of PVP-adsorbed, but the former had better centrifugal stability. Nevertheless the PVP-encapsulated layer can be destroyed by long-time ultrasonic treatment and the dispersed CB particles can congregate with each other again.The properties of waterborne dispersions of ultrafine CB particles were analyzed. The results showed that the apparent viscosity of dispersions increased with the increasing amount of NNO and the rheological property of CB dispersions was pseudo-plastic behavior which the apparent viscosity of system became thicker with the increasing shear rate. And the apparent viscosity increased with the increasing amount of CB particles. When the amount of CB particles is below 5 wt %, the apparent viscosity of CB dispersions became thicker with the increasing shear rate. While the amount of CB particles is 10 wt %, the apparent viscosity of CB dispersions became thinner with the increasing shear rate. The waterborne dispersions of ultrafine CB particles had good centrifugal stability. CB dispersions with various particles size D₀ can achieve by centrifugal method, which the minimum D₀ was 36.1nm. All of the CB dispersions had good stability under gravity at 25℃and 80℃. CB dispersions which D₀ was 90.5nm had good re-dispersing properties.The dyeing properties of waterborne dispersions of ultrafine CB particles were investigated. The results showed that the various dispersants affected the K/S value of dyed cotton fabrics. Among these cotton fabrics dyed with sodium dibutylnaphthalene sulphonate （BX） dispersions had the highest K/S value. CB uptake and colour yield on cotton obviously decreased with the increasing amount of dispersant NNO or Tx used in waterborne dispersions. The CB particle size has a little effect on the dyeing properties of cotton fabrics. CB uptake increased with the increasing amount of CB particles, however it decreased when the amount of CB particles was above 8%owf. The curves of the color strength changed by the amount of CB particles were similar to the Langmuir type. The K/S value of dyed fabrics arrived at the maximum when the amount of CB particles was 10%owf, while the K/S value of fabrics after washed with soap reached to the maximum when CB particles was 4%owf. Adding electrolyte NaCl to CB dispersions favored the CB particles adsorption. Adding binder can obviously improve the color strength of dyed fabrics, but can not improve the rubbing colorfastness.On the basis of cotton fabrics modified with a cationic reagent, the dyeing properties of CB dispersions were discussed. The results showed that the various dispersants also affected the dyeing properties of cationised cotton fabrics. Among these the cationised cotton dyed with BX or Tx dispersions had higher K/S value. CB uptake and the K/S value of cationised cotton obviously decreased with the increasing amount of dispersants NNO or Tx. However the CB particle size affected the dyeing properties of cationised cotton obviously. CB uptake on cationised cotton decreased with the increasing amount of CB particles. When the CB concentration was 2%owf,. the largest color strength of cationised cotton was obtained. Adding electrolyte to CB dispersions had little effect on the dyeing properties of cationised cotton. And it was feasible to dye without electrolyte. Adding binder reduced the K/S value of cationised cotton, while it improved the dryfastness and wetfastness properties.The mechanism of cationised cotton dyed by an exhaustion process using waterborne ultrafine CB dispersions was investigated. Cotton modified with a cationic reagent enhanced the dyeing properties of waterborne CB dispersions and the improvement of cotton dyed by Tx dispersions was the best of all. There were higher affinity existed between ultrafine CB particles and cationised cotton. CB particles can quickly adsorb on the surface of cationised cotton fibers within 5 mins and diffuse into the inner pores and cracks on the surface layer of cationised cotton step by step.更多还原