包禮SCformulations水懸浮劑

1、SC formulations Suspension Concentrates論壇（第十屆山東省農(nóng)藥信息交流會(huì)）1SC 水懸浮劑描述：固體顆粒懸浮于水中 Description: Solid particles suspended in water 常見問題Issues懸浮物質(zhì)與水之間存在密度差 Density difference between suspended matter and water如果原藥密度大于1克/毫升將形成沉淀 Will form sediment if density is 1如果原藥密度大于1克/毫升將漂浮 Will float if density is Ca.

2、i. large大粒徑4How to prevent Oswald ripening怎樣預(yù)防奧氏熟化的發(fā)生較窄的粒徑分布范圍 Narrow particle size distribution還有其他的訣竅 There are other tricks: Very limited amount of diluted oil in aqueous phase 將一定量的油稀釋到水相中 5To make an SC 水懸浮劑制備Preparation of small particles 小粒子的制備Preventing flocculationPreventing sedimentation6T

3、o make an SC 水懸浮劑制備Preparation of small particles 小粒子的制備Small suspended particles are prepared by milling process 通過砂磨設(shè)備獲得較小粒徑Processing conditions are important 生產(chǎn)工藝條件很重要7To make an SC 水懸浮劑制備Preparation of small particles 小粒子的制備8Milling砂磨Wetting - Dispersion - stabilization潤(rùn)濕 分散 穩(wěn)定性9Issue during mi

4、lling process砂磨過程中出現(xiàn)的問題During milling process fresh surface is generated砂磨過程中新的粒子表面產(chǎn)生Fresh surface is generally of non-polar nature en will cluster together rapidly新產(chǎn)生的非極性的表面通常是的自然對(duì)開很容易迅速聚集This could lead to increased viscosity and even mill blockage這可能導(dǎo)致粘度增加甚至阻礙砂磨進(jìn)程To overcome mill blockage a wetti

5、ng agent is needed為了克服這一問題所以潤(rùn)濕劑的加入是非常必要的10To make an SC 水懸浮劑制備Preparation of small particlesPreventing flocculation 絮凝的預(yù)防Preventing sedimentation11How to prevent flocculation? 怎樣預(yù)防絮凝的產(chǎn)生Use of dispersants 分散劑的使用Dispersant should be firmly locked on substrateAnchoring 錨固作用Dispersant types: 分散劑種類Anioni

6、c陰離子 Electrostatic stabilisation靜電穩(wěn)定作用CaDDBS / NaDDBS（十二烷基苯磺酸鈣/鈉）Fosfate esters （磷酸酯類）Non ionic非離子 Steric stabilisation 空間位阻穩(wěn)定作用Alcohol etoxylates（乙氧基醇醚類）Polymeric dispersants（高分子表面活性劑）Mix of the two Electrosteric stabilisation混合靜電/空間位阻Naphtalene condensate sulfonates (萘磺酸鹽甲醛縮合物)Lignin sulfonates （木

7、質(zhì)素磺酸鹽類）12Electrostatic Stabilization靜電排斥作用GhGmaxElectrostatic靜電學(xué)Electrosteric靜電空間GhGh 132dM h G h d2dp Monomer單體-Polymer高分子Steric Stabilization空間位阻作用空間位阻是由于非離子表里面活性劑和/或高分子表面活性劑提供的Steric barriers are produced by adsorption of nonionic surfactants and/or polymeric surfactant由于鏈的不利交叉排斥和熵值作用對(duì)重大交疊的影響Repu

8、lsion is due to unfavourable mixing of the chains and entropic effects on significant overlap14Functions of surfactants表面活性劑的功能Wet 潤(rùn)濕Disperse 分散15Functions of surfactants表面活性劑的功能Wet 潤(rùn)濕作用Dynamic molecules to wet surface during milling stage在砂磨期間動(dòng)態(tài)分子潤(rùn)濕新鮮的表面Smaller molecules 分子量較小Negative regarding sta

9、bility 對(duì)穩(wěn)定性有負(fù)面影響Disperse 分散作用Larger molecules to stabilise suspended particles大分子對(duì)粒子提供穩(wěn)定的懸浮支撐作用Act slow 作用進(jìn)程緩慢16Size does matter 分子大小關(guān)系Dispersed Phase 分散內(nèi)相CONVENTIONAL DISPERSANT 常規(guī)分散劑POLYMERIC DISPERSANT 高分子分散劑Dispersed Phase 分散內(nèi)相172dM h G h d2dp Monomer單體-Polymer高分子Steric Stabilization空間位阻作用空間位阻是由

10、于非離子表里面活性劑和/或高分子表面活性劑提供的Steric barriers are produced by adsorption of nonionic surfactants and/or polymeric surfactant由于鏈的不利混合排斥和熵值作用對(duì)重大交疊的影響Repulsion is due to unfavourable mixing of the chains and entropic effects on significant overlap18Rheology pro agent vs. polymeric dispersant 潤(rùn)濕劑與高分子分散劑流變性特征對(duì)

11、比Wetting agent 潤(rùn)濕劑 Polymeric dispersant高分子分散劑 No shear effect polymeric dispersant flow curve: suspension is properly stabilized高分子分散劑在剪切作用下的流變曲線無(wú)影響：懸浮液相對(duì)穩(wěn)定 Wetting agent flow curve increases hugely at low shear: insufficient stabilisation潤(rùn)濕劑在低剪切作用下的流變曲線明顯增大：不夠穩(wěn)定 If wetting agent is required, use at

12、 low possible concentration!如果潤(rùn)濕劑是必須添加的，盡可能在最低添加量下使用19To make an SC 水懸浮劑制備Preparation of oil droplets in waterPreventing coalescencePreventing sedimentation 沉淀的預(yù)防20Stokes law 斯托克斯定律 Vs = velocity of settling /creaming粒子沉降速度，cm/s; = viscosity 水懸浮劑粘度，Pa.S;g = gravity 重力加速度， cm/s;r = radius of sphere 分

13、散介質(zhì)粒子直徑，cm; = density difference sphere & continuous phase 分散粒子的密度與水的密度差Vs=-92gr221Stokes law 斯托克斯定律 Vs=-92gr2No sedimentation if density of suspended matter and water phase are equal如果懸浮介質(zhì)和水相之間沒有密度差，沉淀問題就不可能發(fā)生固相/液相密度差=022Stokes law 斯托克斯定律 Vs=-92gr2The smaller the particle size, the lesser sedimenta

14、tion粒徑越小沉淀越慢Note this a square function值得注意的是稱將速度與粒徑的平方正相關(guān)10 times the particle size is 100 times faster sedimentation10倍的粒徑大小差異將導(dǎo)致100倍的沉降速度差別粒徑大小23Stokes law 斯托克斯定律 Vs=-92gr2Increased viscosity will reduce sedimentation提高粘度有利于減少沉降However viscosity cannot be increased infinitely然而粘度不可能被無(wú)限制的增加Need of

15、 shear thinning rheology modifier需要使界面內(nèi)剪切力變小的流體改性物Xanthan or Kelzan Gum provides this effect黃原膠可以提供這種作用體系粘度24Rheology pro gum黃原膠的流變學(xué)特征粘度轉(zhuǎn)速25SC 水懸浮劑General formula:一般配方組成 成份 用量Suspended phase分散相40%Dispersant分散劑4%Wetting agent潤(rùn)濕劑 0.5%Glycerine 防凍劑5.2%Anti foam 消泡劑0.1%Preservative防腐劑 0.1%Kelzan gum增稠劑

16、0.1%Water水50%Issue: long term stability and emulsion stability upon dilution 問題：經(jīng)時(shí)穩(wěn)定性和乳液的稀釋穩(wěn)定性26Croda SC recommendation英國(guó)禾大公司在水懸浮劑方面的核心產(chǎn)品Dispersants:分散劑Atlox 4913 羧酸鹽枝接物Atlox Metasperse 100L 羧酸鹽修飾物Atlox Metasperse 500L 羧酸鹽修飾物Co dispersant/wetting agent:助分散劑/潤(rùn)濕劑Atlas G-5000 高分子嵌段共聚物Atlas G-5002L 高分子前

17、段共聚物Atlox 4894 高分子前段共聚物Traditional wetting agent: 傳統(tǒng)潤(rùn)濕劑Synperonic A7 聚氧乙烯醇醚27Further guidelines 使用說明Dispersant level 10% of dispersed phase 分散劑的用量通常是分散內(nèi)相的10%30 % dispersed phase 30%的分散內(nèi)向3% total surfactants 需要3%的總的分散劑Ratio dispersant/co-dispersant: 2:1分散劑和助分散劑的比例為2：12% Atlox 4913 分散劑1% Atlox 4894 助分

18、散劑With traditional wetting agent: 配以傳統(tǒng)的潤(rùn)濕劑2% Atlox 4913 分散劑1% Atlas G-5002L 助分散劑Minimum amount Synperonic A7 最小量的潤(rùn)濕劑28With traditional wetting agent傳統(tǒng)的潤(rùn)濕劑用量的確定Optimum approach:最理想的途徑三元復(fù)配組合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 65 66 67Dispersant 分散劑Co-dispersant 助分散劑Wetting agent 潤(rùn)濕劑Performance criteria:評(píng)估標(biāo)準(zhǔn)Milling efficiency 砂磨的效率Storage stability 儲(chǔ)存穩(wěn)定性29Crystal growth; part II結(jié)晶增長(zhǎng)PolymericDispersant高分子分散劑Polymeric plus monomeric Dispersant高分子/單體分散劑30Crystal