1、表面活性剂化学及应用表面活性剂化学及应用东华大学化学化工与生物工程学院东华大学化学化工与生物工程学院张张 煊煊第1页，共41页。第二章第二章 表面活性剂的分类表面活性剂的分类有“工业味精”之称。最早的表面活性剂肥皂第2页，共41页。上堂课的回顾 表面活性剂结构特征不对称双亲结构 亲水基亲水性 亲油基疏水性 熵驱动G H TS0u 表面活性表（界）面吸附和胶束化 吸附降低表面张力、润湿、乳化、分散、洗涤等；胶束化增溶 第3页，共41页。第4页，共41页。u 勘误page 5:表2-1 聚氧乙烯基亲水基u 电子作业格式:邮件主题表面活性剂习题；附件采用word文档(版本)，附件名 “专业-No-姓
2、名(第次)”第二章思考题第二章思考题1、表面活性剂按疏水基分类有哪几种？它们分别有什么特征？2、表面活性剂按亲水基分类有哪几种？它们分别有什么特征？3、除了传统意义上的表面活性剂之外，还有哪些表面活性剂？它们分别有什么特征？第5页，共41页。1、表面活性剂的分类、表面活性剂的分类一、以表面活性剂的疏水基分类一、以表面活性剂的疏水基分类 三大类三大类：1、碳氢链（R一般C8-C20）（1）碳氢链的分类a.烷基(Alkyl)常见的例如：十二烷基（月桂基）dodecyl（lauric）十四烷基（肉豆蔻基）tetradecyl（myristic）十六烷基（棕榈基）cetyl（palmitic）十八烷基
3、（硬脂基）octadecyl（stearic）CH3-(CH2)n-COOMe第6页，共41页。b.链稀基（Alkenyl)有双键，易诱导极化。亲水性高于同碳原子数的烷基。例如:硬脂酸与 油酸（9-十八烯酸 oleic acid），CH3(CH2)7CH=CH(CH2)7COOMe 亚油酸（9,12-十八二烯酸linoleic acid）CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOMe 亲水性逐个增加。又例如，6个碳的苯环的疏水性只相当于3.5个亚甲基。CH3(CH2)11-C6H4-SO3Na R=C15.5第7页，共41页。c.含极性基烃同上，亲水性高于同碳原子数的烷基。
4、例如，蓖麻油酸(ricinoleic acid)12-羟基-9-十八烯酸的亲水性高于油酸。CH3(CH2)5CHCH2CH=CH(CH2)7COOMeOH第8页，共41页。（2）碳氢疏水链对表面活性剂的影响（a）碳氢疏水基的链长(Hydrophobic Group)碳氢疏水基愈长，则在水中的溶解度愈小，在有机溶剂中的溶解度愈大；引起紧密聚集；增加吸附与胶束化倾向；提高熔点；增加对反离子的敏感性第9页，共41页。（b）支链与不饱和度的影响 （Branching and Un-saturation）增加支链与不饱和度溶解度增大；降低熔点降低；引起疏松聚集与抑制液晶形成;不饱和组分易氧化和变色;有支
5、链组分生物降解性下降。第10页，共41页。（c）芳环（脂环）的影响（Aromatic Nucleus）增加在极性界面的吸附；降低生物降解性；引起界面膜疏松（脂环更甚）。（d）聚氧丙烯链(Polyoxypropylene Chain H(OC3H6)x-)增加在极性界面的吸附；增加在有机溶剂的溶解度。第11页，共41页。2、含硅烷（silane）常见的是硅氧烷（siloxane）。一般含硅烷的疏水性强于碳氢链，降低表面张力的能力更强。3、含氟碳链碳氢链的氢部分或全部被氟取代。例如，CF3(CH2)6CH2-和CF3(CF2)6CF2-。全氟碳链的疏水性最强，不仅疏水，而且疏油。第12页，共41页
6、。4、常见的疏水基（Hydrophobic Grougs）(1)直链烃(C8-C20)(2)支链烃(C8-C20)(3)长链(C8-C15)烷基苯基(R-C6H4-)(4)烷基萘基(RC3)(R-C10H8-)(5)松香衍生物（脂肪环）(6)高分子量的聚环氧丙烯基 (7)木质素衍生物 (8)聚硅氧烷 (9)部分或全氟代烃第13页，共41页。其它 OthersurfactantsContinue表面活性剂离子型表面活性剂非离子表面活性剂阴离子型表面活性剂 Anionics两性离子型表面活性剂 Zwitterionics阳离子型表面活性剂 Cationics复合型表面活性剂Double-Hydro
7、philic Group Surfactants多元醇表面活性剂 Polyalcohol Nonionics聚氧乙烯醚表面活性剂 Polyoxyethylenated Nonionics二、以表面活性剂的亲水基分类二、以表面活性剂的亲水基分类第14页，共41页。（1）阴离子型表面活性剂ANIONICS表面活性片段是阴离子RCOO-Na+(soap).RC6H4SO3-Na+(alkylbenzene sulfonate).v 脂肪酸盐Carboxylic Acid Saltsv 磺酸盐Sulfonic Acid Saltsv 硫酸酯盐Sulfuric Acid Ester Saltsv 磷酸酯
8、盐Phosphoric and Poly-phosphoric Acid Esters第15页，共41页。羧酸盐(Carboxylic Acid Salts)CH3(CH2)nCOO-Me+u肥皂Soapsl牛脂（animal fat）l椰子油(Sodium and Potassium Salts of Coconut Oil)l妥尔油酸(by-product of paper manufacture is a mixture of fatty acids and rosin acids 松香酸)u其它lN-月桂酰肌氨酸钠RCON(CH3)CH2COO-Na+l乙酰化多酞l全氟羧酸第16页，共
9、41页。磺酸盐（Sulfonic Acid Salts）CH3(CH2)nC6H4SO3Meu 直链烷基苯磺酸盐Linear Alkyl Benzene Sulfonates(LAS)u烷基苯磺酸盐(Higher Alkyl benzene sulfonates)u异丙基苯磺酸盐(Cumene-sulfonates)u 木质素磺酸盐(Ligninsulfonates)u石油磺酸盐(Petroleum Sulfonates)u N-乙酰基牛磺酸盐(N-Acyl-n-Alkyltaurates),RCON(R)CH2CH 2SO3-M+第17页，共41页。uSAS仲烷基磺酸盐(Secondary
10、n-lkanesulfonates)R1(R2)CH-SO3Meu AOS-烯烃磺酸盐(-Olefin Sulfonates)u 磺基丁二酸酯（Sulfosuccinate Esters）ROOCC H2CH(SO3-M+)COORu烷基萘磺酸盐(Alkylnaphthalenesulfonates)u 萘磺酸盐的甲醛缩合物u 脂肪酸亚乙基磺酸盐（Isethionates）RCOOCH2CH2SO3-M+第18页，共41页。硫酸酯盐Sulfuric Acid Ester Salts u 烷基硫酸盐(Sulfated Linear Primary Alcohols)(AS)CH3(CH2)nOS
11、O3Me u 硫酸化油脂Sulfated Triglyceride OilsProduced by sulfation of hydroxy group and/or double boud in fatty acid portion of the triglyceride(Iodine values碘值：40-140).Mainly castor oil 蓖麻油used(12-hydroxyoleic acid),but also fish oils,tallow牛脂,sperm oils鲸油.第19页，共41页。磷酸或多磷酸酯盐Phosphoric and Poly-phosphoric
12、Acid Esters第20页，共41页。（2）阳离子型表面活性剂CATIONICS表面活性片段是阳离子v 长链胺及其盐Long-Chain Amines and Their Salts；v 二胺、多胺及其盐Diamines and Polyamines and Their Salts；v 季铵盐Quaternary Ammonium Salts;v 氧化胺Amine Oxides 第21页，共41页。u 长链胺及其盐l Primary amines CH3(CH2)11-17NH2,l Secondary R1(R2)NH,l Tertiary amines R1(R2)NR3.u 二胺、多
13、胺及其盐 for example:CH3(CH2)nN(CH3)1-2HHCl第22页，共41页。u季铵盐l 四烷基氯化铵（R2N+(CH3)2Cl-）l 咪唑啉（Imidazolinium salts）u 氧化胺(Amine Oxides)第23页，共41页。Table 1-1 Some Uses of Cationics Resulting from Their Adsorption onto Solid Substrates第24页，共41页。（3）两性离子型表面活性剂ZWITTERIONICS(AMPHIONICS)表面活性片段是两性离子 for example,RN+H2CH2COO
14、-(long-chain amino acid),RN+(CH3)2CH2CH2SO3-(sulfobetaine).v 弱碱型：例如氨基酸型CH3(CH2)nNH2CH2CH2COOv 强碱型：例如甜菜碱型CH3(CH2)nN(CH3)2CH2COO第25页，共41页。pH-Sensitive Zwitterionics:weak acid&weak base weak acid&strong base strong acid&weak base pH-Insensitive Zwitterionics strong acid&strong base第26页，共41页。weak acid&w
15、eak base1、-N-Alkylaminopropionic Acid,RN+(H2)CH2CH2COO-IEP at pH 4.Very soluble in aqueous solutions of strong acids and alka1ies,even in the presence of electrolytes like NaCl.Solubility is low in most organic solvents,including ethanol and isopropyl alcohol.Adsorb from aqueous so1ution onto skin,t
16、extiles,fibers,and metals.第27页，共41页。2、烷基亚氨基二丙酸盐（N-Alkyl-iminodipropionic Acids）,IEP,pH l.7-3.5.More soluble in water than corresponding mono-propionic acid derivatives.Show very low order of skin and eye irritation.May be removed from substrates onto which they have adsorbed at pHs below their iso-e
17、lectric points by raising the pH.Uses.Fabric softeners.第28页，共41页。3、Imidazoline carboxlates,R from RCOOH of commercially available fatty acids.When R is H they are ampholytic（两性）.Compatib1e with anionics,cationics,and nonionics,soluble in water in the presence of high concentrations of electrolytes,a
18、cids,and alkalies.第29页，共41页。v When R contains a second carboxylic acid group,products show a very low order of skin and eye irritation.v Uses.Cosmetic and toilet preparations,fabric softener(which can be removed from substrate by increase in pH to the alkaline side).第30页，共41页。weak acid&strong base1、
19、羧基甜菜碱N-Anylbetaines,RN+(CH3)2CH2COO）These materials are zwitterionic at pHs at and above their iso-electric points(neutral and alkaline pHs)and cationic below their iso-electric points(acid pHs).They show no anionic properties.Compatible with al1 classes of surfactants at all pHs except that at low
20、pHs they yield precipitates with anionics.Acid and neutral aqueous so1utions are compatible with alkaline earth(碱土)and other metallic ions(A13+,Cr3+,Cu2+,Ni2+,Zn2+).第31页，共41页。strong acid&weak baseRN+(H2)CH2CH2SO3-第32页，共41页。pH-Insensitive Zwitterionicsstrong acid&strong base These rnaterials are zwit
21、terionics at all pHs(at no pH do they actmere1y like anionics or cationics).Sulfobetaines（磺基甜菜碱）,Sultaines,RN+(CH3)2(CH2)2SO3 Adsorb onto charged surfaces at all pHs without forming hydrophobic films.Good lime soap(钙皂)dispersants.Uses.Similar to other zwitterionics.Lime soap dispersants in soap-dete
22、rgent formulations.第33页，共41页。Phosphated Zwitterionics lecithin(卵磷脂)Double Chains第34页，共41页。(5)非离子型表面活性剂(NONlONlCS)表面活性片段是非离子 for example：多元醇：如甘油、山梨醇(RCOOCH2-CHOHCH2OH monoglyceride of long-chain fatty acid)聚氧乙烯醚(RC6H4(OC2H4OH)xOH polyoxyethylenated alkylphenol)第35页，共41页。u烷基酚聚氧乙烯醚(APE)OP-n series:C8-1
23、2H17-25-C6H4-O-EOn OP-10:n=10u 脂肪醇聚氧乙烯醚(AE)JFc:C7-9H15-19-O-EO5-6;平平加O(20):C12-18H25-37-O-EO20 u脂肪胺聚氧乙烯醚u 硫醇聚氧乙烯醚 RSO CH2CH2OyHu 长链脂肪酸聚氧乙烯醚酯第36页，共41页。聚氧乙烯化的硅氧烷Polyoxyethylenated Silicones 第37页，共41页。u 脂肪酸甘油酯u 脂肪酸山梨醇酯 斯潘系列u 烷基多糖类(Alkylpolyglycosides)第38页，共41页。6.复合型表面活性剂复合型表面活性剂Surfactants of Double-hydrophilic Group Nonionic&Nonionic Surfactants Anionic&Nonionic Surfactants Cationic&Nonionic Surfactants第39页，共41页。u 聚氧乙烯醚脂肪酸山梨醇酯 吐温系列第40页，共41页。n 脂肪醇聚氧乙烯醚硫酸酯盐(AES),R(OC2H4)xSO4-M+(x=3,usually)n 聚氧乙烯醚化的烷基磷酸酯u长链胺聚氧乙烯醚 RN(CH2CH2O)xH2第41页，共41页。
