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1、SC 水悬浮剂水悬浮剂描述:固体颗粒悬浮于水中 Description: Solid particles suspended in water 常见问题Issues悬浮物质与水之间存在密度差 Density difference between suspended matter and water 如果原药密度大于1克/毫升将形成沉淀 Will form sediment if density is 1 如果原药密度大于1克/毫升将漂浮 Will float if density is Dispersion - stabilization润湿润湿 分散分散 稳定性稳定性Issue during
2、 milling process砂磨过程中出现的问题砂磨过程中出现的问题During milling process fresh surface is generated砂磨过程中新的粒子表面产生Fresh surface is generally of non-polar nature en will cluster together rapidly新产生的非极性的表面通常是的自然对开很容易迅速聚集This could lead to increased viscosity and even mill blockage这可能导致粘度增加甚至阻碍砂磨进程To overcome mill blo
3、ckage a wetting agent is needed为了克服这一问题所以润湿剂润湿剂的加入是非常必要的To make an SC 水悬浮剂制备水悬浮剂制备 Preparation of small particles Preventing flocculation 絮凝的预防 Preventing sedimentationHow to prevent flocculation? 怎样预防絮凝的产生怎样预防絮凝的产生 Use of dispersants 分散剂的使用 Dispersant should be firmly locked on substrate Anchoring
4、锚固作用 Dispersant types: 分散剂种类 Anionic阴离子 Electrostatic stabilisation静电稳定作用CaDDBS / NaDDBS(十二烷基苯磺酸钙/钠)Fosfate esters (磷酸酯类) Non ionic非离子 Steric stabilisation 空间位阻稳定作用Alcohol etoxylates(乙氧基醇醚类)Polymeric dispersants(高分子表面活性剂) Mix of the two Electrosteric stabilisation混合静电/空间位阻Naphtalene condensate sulfo
5、nates (萘磺酸盐甲醛缩合物)Lignin sulfonates (木质素磺酸盐类)Electrostatic Stabilization静电排斥作用静电排斥作用+-+-+h+-+-+-+-+-+hGhGmaxElectrostatic静电学静电学Electrosteric静电空间静电空间GhGh 2d dMM h h G h d d2d dp p Monomer单体单体-Polymer高分子高分子Steric Stabilization空间位阻作用空间位阻作用空间位阻是由于非离子表里面活性剂和/或高分子表面活性剂提供的Steric barriers are produced by ads
6、orption of nonionic surfactants and/or polymeric surfactant由于链的不利交叉排斥和熵值作用对重大交叠的影响Repulsion is due to unfavourable mixing of the chains and entropic effects on significant overlapFunctions of surfactants表面活性剂的功能表面活性剂的功能 Wet 润湿 Disperse 分散Functions of surfactants表面活性剂的功能表面活性剂的功能 Wet 润湿作用 Dynamic mole
7、cules to wet surface during milling stage在砂磨期间动态分子润湿新鲜的表面 Smaller molecules 分子量较小 Negative regarding stability 对稳定性有负面影响 Disperse 分散作用 Larger molecules to stabilise suspended particles大分子对粒子提供稳定的悬浮支撑作用 Act slow 作用进程缓慢Size does matter 分子大小关系分子大小关系Dispersed Phase 分散内相CONVENTIONAL DISPERSANT 常规分散剂常规分散剂
8、POLYMERIC DISPERSANT 高分子分散剂高分子分散剂Dispersed Phase 分散内相2d dMM h h G h d d2d dp p Monomer单体单体-Polymer高分子高分子Steric Stabilization空间位阻作用空间位阻作用空间位阻是由于非离子表里面活性剂和/或高分子表面活性剂提供的Steric barriers are produced by adsorption of nonionic surfactants and/or polymeric surfactant由于链的不利混合排斥和熵值作用对重大交叠的影响Repulsion is due
9、to unfavourable mixing of the chains and entropic effects on significant overlapRheology profile wetting agent vs. polymeric dispersant 润湿剂与高分子分散剂流变性特征对比润湿剂与高分子分散剂流变性特征对比Wetting agent 润湿剂 Polymeric dispersant高分子分散剂 No shear effect polymeric dispersant flow curve: suspension is properly stabilized高分子
10、分散剂在剪切作用下的流变曲线无影响:悬浮液相对稳定 Wetting agent flow curve increases hugely at low shear: insufficient stabilisation润湿剂在低剪切作用下的流变曲线明显增大:不够稳定 If wetting agent is required, use at low possible concentration!如果润湿剂是必须添加的,尽可能在最低添加量下使用To make an SC 水悬浮剂制备水悬浮剂制备 Preparation of oil droplets in water Preventing coal
11、escence Preventing sedimentation 沉淀的预防Stokes law 斯托克斯定律斯托克斯定律 Vs = velocity of settling /creaming粒子沉降速度,cm/s; = viscosity 水悬浮剂粘度,Pa.S;g = gravity 重力加速度, cm/s;r = radius of sphere 分散介质粒子直径,cm; = density difference sphere & continuous phase 分散粒子的密度与水的密度差Vs=-92gr2Stokes law 斯托克斯定律斯托克斯定律 Vs=-92gr2No sed
12、imentation if density of suspended matter and water phase are equal如果悬浮介质和水相之间没有密度差,沉淀问题就不可能发生固相/液相密度差=0Stokes law 斯托克斯定律斯托克斯定律 Vs=-92gr2The smaller the particle size, the lesser sedimentation粒径越小沉淀越慢Note this a square function值得注意的是称将速度与粒径的平方正相关10 times the particle size is 100 times faster sedimen
13、tation10倍的粒径大小差异将导致100倍的沉降速度差别粒径大小Stokes law 斯托克斯定律斯托克斯定律 Vs=-92gr2Increased viscosity will reduce sedimentation提高粘度有利于减少沉降However viscosity cannot be increased infinitely然而粘度不可能被无限制的增加Need of shear thinning rheology modifier需要使界面内剪切力变小的流体改性物Xanthan or Kelzan Gum provides this effect黄原胶可以提供这种作用体系粘度R
14、heology profile Kelzan gum黄原胶的流变学特征黄原胶的流变学特征粘度转速SC 水悬浮剂水悬浮剂General formula:一般配方组成 成份 用量Suspended phase分散相40%Dispersant分散剂4%Wetting agent润湿剂 0.5%Glycerine 防冻剂5.2%Anti foam 消泡剂0.1%Preservative防腐剂 0.1%Kelzan gum增稠剂 0.1%Water水50%Issue: long term stability and emulsion stability upon dilution 问题:经时稳定性和乳液
15、的稀释稳定性Croda SC recommendation英国禾大公司在水悬浮剂方面的核心产品英国禾大公司在水悬浮剂方面的核心产品Dispersants:分散剂Atlox 4913 羧酸盐枝接物Atlox Metasperse 100L 羧酸盐修饰物Atlox Metasperse 500L 羧酸盐修饰物Co dispersant/wetting agent:助分散剂/润湿剂Atlas G-5000 高分子嵌段共聚物Atlas G-5002L 高分子前段共聚物Atlox 4894 高分子前段共聚物Traditional wetting agent: 传统润湿剂Synperonic A7 聚氧乙
16、烯醇醚Further guidelines 使用说明使用说明Dispersant level 10% of dispersed phase 分散剂的用量通常是分散内相的10%30 % dispersed phase 30%的分散内向3% total surfactants 需要3%的总的分散剂Ratio dispersant/co-dispersant: 2:1分散剂和助分散剂的比例为2:12% Atlox 4913 分散剂1% Atlox 4894 助分散剂With traditional wetting agent: 配以传统的润湿剂2% Atlox 4913 分散剂1% Atlas G-
17、5002L 助分散剂Minimum amount Synperonic A7 最小量的润湿剂With traditional wetting agent传统的润湿剂用量的确定传统的润湿剂用量的确定Optimum approach:最理想的途径三元复配组合12 34 5 67 8 9 1011 12 13 14 1516 17 18 19 20 2122 23 24 25 26 27 2829 30 31 32 33 34 35 36 3738 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 5657 58 59 60 61 62 63 64
18、 65 66 67Dispersant 分散剂Co-dispersant 助分散剂Wetting agent 润湿剂Performance criteria:评估标准评估标准Milling efficiency 砂磨的效率Storage stability 储存稳定性Crystal growth; part II结晶增结晶增长长 Particle Size Distribution 0.01 0.1 1 10 100 1000 3000 Particle Size (m)0 1 2 3 4 5 6 7 Volume (%)20477-89-1a 2.5% SC 4913 fridge 7 da
19、ys, 24 August 2007 10:49:0220477-89-1b 2nd repeat 2.5% SC with 4913 oven 7 days, 24 August 2007 10:05:50 Particle Size Distribution 0.01 0.1 1 10 100 1000 3000 Particle Size (m)0 1 2 3 4 5 6 7 8 Volume (%)20477-89-2a 2.5% SC 4913+A3 fridge 7 days, 24 August 2007 14:20:2320477-89-2b repeat 2.5% SC 49
20、13 + A3 oven 7 days, 24 August 2007 10:12:12PolymericDispersant高分子分散剂Polymeric plus monomeric Dispersant高分子/单体分散剂Crystal growth; part II结晶增结晶增长长 Effect of surfactant micelles 表面活性剂胶体束的作用油滴油滴oil droplets固体颗粒固体颗粒solid particlesCrystal growth; part II结晶增结晶增长长Avoid micelle forming surfactants 避免使用产生胶体束的表面活性剂Monomeric surfactants form relatively easy micelles 单体表面活性剂相对容易形成胶体束Polymeric surfactants do not form micelles 高分子表面活性剂不会形成胶体束33 结束语结束语