1、Noveon 功能性原料Carbopol, Pemulen和 Avalure 聚合物特性和應用,諾譽化工有限公司 Consumer Specialties Group Personal Care Division,概述,I.Carbopol and Pemulen Polymers 的介紹 II.Carbopol ETD Polymers III.Carbopol Ultrez 10 Polymer IV.Pemulen Polymeric 乳化劑,V.Avalure 成膜劑 VI.表面活性劑體系中的應用 VII.個人護理產品中應用 VIII.H2O2 凝膠中的流變調節(jié),Noveon 功能性原

2、料 Carbopol 和 Pemulen高分子流變調節(jié)劑,諾譽化工有限公司 Consumer Specialties Group Personal Care Division,Carbopol and Pemulen 高聚物介紹,概要 A.什么是 Carbopol and Pemulen 高分子聚合物? B. Carbopol and Pemulen高分子聚合物的六種主要功能 C.Carbopol高分子聚合物的特性 D.Carbopol 凝膠的流變性 E.Carbopol and Pemulen 敏感性 F.Carbopol and Pemulen高分子聚合物的使用 G.疑難解答,Carbop

3、ol高分子聚合物是.,流變修飾劑 聚丙烯酸 樹脂 高分子量 交聯(lián)作用 CTFA/INCI 名: Carbomer (均聚物) Acrylates/C10-30 Alkyl Acrylate Crosspolymer (共聚物),C,C,C,O,OH,n,H,H,H,Carbopol 在個人護理產品中的應用,頭發(fā)護理 香波 定型著哩 摩絲 染發(fā)產品 燙發(fā)產品,皮膚護理 保濕著哩 膏霜和乳液 含酒精的著哩膠 防曬產品 沐浴露 脫毛膏,Carbopol在藥用產品中的應用,藥片和膠囊 口腔護理產品（牙膏） 生物粘附應用 局部給藥著哩膠 局部給藥霜和乳液 含漱乳液及外敷乳液 獸用藥,Carbopol 用

4、于家居護理 and I短流 均聚物5984奶油狀感覺;對鹽敏感 940980 Ultrez 10非常高黏度;短流;均聚物ETD 2001*奶油狀感覺; 對鹽敏感 941981 ETD 2050低黏度;長流 均聚物 拉絲結構;對鹽敏感 13421382 ETD 2020高黏度; 長流共聚物Pemulen TR-1拉絲結構Pemulen TR-2對鹽敏感不高,易分散的 Carbopol 樹脂,凝膠特性,樹脂類型,*ETD 2001 對鹽更不敏感,Carbopol 25 C,RheologicalSymbol, PropertyUnits934940941Ultrez 10ETD 2020 ETD

5、2001 RigidityGO, Pa74043026980326540 ThixotropicT.I., 3054353101283 IndexPa/s.cm3 Yield Stressyld, Pa9510014110150124 Viscosity, mPa.s (cP)74,50075,80010,70084,30063,20077,300,Carbopol,Carbopol,Carbopol,Carbopol,Carbopol 微膠體的硬度,PolymerRigidityMucilage Texture Carbopol 13426Long rheology/Soft Carbopo

6、l 94125Long rheology/Soft Carbopol 940430Short rheology/Soft Carbopol 934790Short rheology/Soft,Carbopol 和Pemulen 的敏感性,Carbopol 和 Pemulen 聚合物的敏感性,Mechanical shear Ions and salts Cationics UV light Temperature Microbes,Effect of Mechanical Shear,Prolonged homogenization is not recommended Irreversibl

7、e loss of viscosity and yield value may occur Neutralized Carbopol polymer Prolonged shearing results in viscosity loss Pumping of gel best done with diaphragm and positivedisplacement pumps Unneutralized Carbopol polymer Less susceptible to shear degradation (except for 941 “type”) Marine-blade agi

8、tation recommended Lower cross-linked Carbopol polymers are the most sensitive,Effect of Turbine Shear on Viscosity of 0.5% Carbopol Polymer Mucilage,Tekmar rotor-stator homogenizer 8,500 rpm,Shear Time (minutes),50,000,40,000,30,000,20,000,10,000,0,0,5,10,20,980, 940,981, 941,1382, 1342,Carbopol Po

9、lymer,pH = 7.0 Brookfield RVT 20 rpm,Viscosity, cP (mPas),Effect of Electrolytes on Viscosity,Effect: Permanent loss of viscosity Reduction of clarity Multi valent ions cause more serious impact Solution: Minimize electrolytes whenever possible Increase concentration of Carbopol polymer,Electrolyte

10、Sensitivity of Carbopol and Pemulen Polymers,Sources of electrolytes: Formulation Inorganic salts, ionic surfactants, botanicals, some preservatives Water Sodium ions from soft water Calcium and magnesium ions from hard water Chloride from treated tap water Note: Deionized water is recommended,Relat

11、ive Electrolyte Sensitivity ofCarbopol Polymers,Each Carbopol polymer can tolerate certain levels of electrolytes Carbopol ETD 2020 1342 ETD 2001 ETD 2050 941 940 934 Ultrez 10 In all cases, electrolytes reduce thickening efficiency,Effect of Salt on Carbopol Polymer Gels,Before Salt Addition:,Swoll

12、en Microgel,Suspended Particle,Effect of Salt on Carbopol Polymer Gels,After Salt Addition:,Collapsed Microgel,Particle,Effect of Mono- and Divalent Saltson Carbopol Polymer,0.01,0.02,0.05,0.10,0.20,0.50,1.00,100,250,500,1,000,2,500,5,000,10,000,Polymer (wt %),941 (1.00 wt %) effect of NaCl effect o

13、f CaCl2,941 (0.25 wt %) effect of NaCl effect of CaCl2,pH = 7.0 Brookfield RVT 20 rpm,Viscosity, cP (mPas),% NaCl Effect on Carbopol Polymer Gel Viscosities,1.0% Polymer pH 7.0 - 7.3,NaCl Concentration (wt %),80,000,70,000,60,000,50,000,40,000,30,000,20,000,10,000,0,0,0.2,0.4,0.6,1.0,980, 940,5984,

14、934,981, 941,1382, 1342,Carbopol Polymer,Brookfield RVT 20 rpm,0.8,Viscosity, cP (mPas),Viscosity Response of Carbopol Gels to Salt,45,000,40,000,35,000,30,000,25,000,20,000,15,000,10,000,5,000,0.0,0.2,0.4,0.6,0.8,1.0,NaCl Concentration (wt %),1382,ETD 2020,1342,1.0% Polymer pH 7.0,Brookfield RVT 20

15、 rpm,Viscosity, cP (mPas),Viscosity Response of Carbopol Gels to Salt,NaCl Concentration (wt %),1.0% Polymer pH 7.0,Brookfield RVT 20 rpm,Carbopol Polymer,Viscosity, cP (mPas),Viscosity vs. Polymer Concentrationin NaCl Solution,( in 1% NaCl salt solution at pH 7.6 ),Carbopol 934,Carbopol 940,Carbopo

16、l 941,Carbopol ETD 2020,Carbopol Ultrez 10,Thickening a 5% NaCl Solution,100,000,10,000,1,000,100,1.0,2.0,3.0,4.0,5.0,Polymer Concentration (wt %),Carbopol 1342,Carbopol 941,Carbopol 940,Brookfield RVT 20 rpm,Viscosity, cP (mPas),陽離子的影響,陽離子的影響 透明度下降 黏度損失 Complexation of anionic polymer causes precip

17、itation 因由 Carbopol 樹脂是陰離子聚合物 解決方法 使用非常低濃度的陽離子 加入陽離子之前中和 采用低電荷密度高分子量的陽離子 比如: 聚季胺鹽-39, 陽離子瓜爾膠 采用耐離子的Carbopol ETD 2020,紫外光的影響,紫外光的影響: 黏度損失 透明度下降 解決方法: 加入紫外吸收劑 (如二苯甲酮-4) 加入EDTA二鈉 注意:紫外吸收劑 和EDTA二鈉有增效作用 紫外吸收劑用量: 0.05%,溫度的影響,Dry Carbopol polymer:- Stable to 104 C (Tg of Carbopol polymer) - Decomposition c

18、omplete in 30 minutes at 260 C Carbopol polymer in formulations:- Useful under freeze-thaw conditions- Minimal viscosity change with temperature- Stable at high temperatures,Broad Temperature Stability,100,000,10,000,1,000,0,10,20,30,40,50,60,Temperature (C),Carbopol 940,Carbopol 941,Carbopol 934,Po

19、lymer Concentration = 0.5% wt Brookfield RVT 20 rpm,Viscosity, cP (mPas),微生物影響,Carbopol and Pemulen polymers will not promote or support bacteria or fungus growth Preservatives should be used in stock dispersions or with any aqueous formula Compatible with typical levels of preservatives (not compat

20、ible with biocidal quaterniums),Putting Carbopol and Pemulen Polymers to Work,How to disperse Carbopol polymers How to neutralize Carbopol systems How to handle Carbopol polymers,分散準備,Dispersion Viscosities of Various Carbopol Polymers,Unneutralized,5,000,4,000,3,000,2,000,1,000,0,Ultrez 10,ETD 2020

21、,981,980,941,940,Polymer = 1.0 ( wt % ),Brookfield RVT 20 rpm,Viscosity, cP (mPas),Concentration Dependence ofDispersion Viscosity,pH = 2.5 - 3.5 Brookfield RVT 20 rpm,Polymer Concentration (wt %),934,940,941,Ultrez 10,ETD 2020,Viscosity, cP (mPas),三種 Carbopol 樹脂 (未中和)分散后外觀比較,Carbopol 940 1% Weight

22、3,425 cP Brookfield RVT 20 rpm, #3 spindle Homogenous,Carbopol ETD 2020 1% Weight 85 cP Brookfield RVT 20 rpm, #1 spindle Layered Phases,Carbopol Ultrez 10 1% Weight 15 cP Brookfield RVT 20 rpm, #1 spindle Settled,Overview.ppt, slide 104,BFGoodrich,Carbopol分散初始階段所需的濕潤時間*,Carbopol 934 940 941 Ultrez1

23、0 ETD2020,濕潤時間, 分鐘 50 50 50 5 15,* 2.5 克Carbopol粉末撒在500毫升去離子水的表面.,如何分散傳統(tǒng)的Carbopol 樹脂,將Carbopol以細微顆粒緩慢加入(可用篩子, 噴射器 或其他機械分散裝置) 如果可能，首先將Carbopol加入配方 盡可能在過程最后中和 (增稠) 如有可能，先將Carbopol 分散在非極性油相中。,分散方法,直接法 (將聚合物分散在水中) 間接法 (將聚合物分散在油相) 再加入水中,Carbopol 樹脂的分散 準備 直接加入,-將樹脂通過20 - 30 目的不銹鋼篩子緩慢地撒在水旋渦面上 - 盡可能早將Carbop

24、ol 加入配方中 - 加少量無機酸減少黏度并防止有氣泡混入 - 盡可能在過程最后中和 - 推薦配制 2.0% 聚合物濃度的分散液,Carbopol Polymer Dispersion - Eductor,Polymer pulled into water by vacuum Up to 4% polymer concentration possible Add 50 pound box of polymer to water in 20 - 30 minutes Use cold deionized water Requires minimum 3/4 inch diameter for w

25、ater and 35 psig Water flow must commence before addition ofpolymer to funnel,Eductor Diagram,Funnel,Air Vent Holes,Eductor Outlet,Make-Up Water Inlet,Carbopol Polymer Dispersion - Helpful Hints,Use deionized water- Hard water ( Ca+2, Mg+2) will cause Carbopol to precipitate- DM/ion exchanged water

26、is a good second choice Use room temperature water (30 C) with anydirect addition method Warm / hot water will increase dispersion time (traditional polymers) Note: Warm water will decrease dispersion time for Carbopol ETD and Ultrez polymers ( 60 C) Steam from very hot water will clump the polymer

27、powder Disperse polymer in water containing no salts or alkali,Indirect Addition: Dispersion Preparation,Applicable for oil phase introduction (O/W emulsions) Polymer added to homogeneous oil phase Temperature of oil should be 70 C or polymer may clump or plasticize Oil/polymer mixture is added to a

28、gitating water phase Polymer migrates from oil to water phase Mix 20 - 30 minutes after mixing of phases; then neutralize and continue mixing,中和 Carbopol 和 Pemulen 分散液,Carbopol 聚合物分散液和黏液的定義,Carbopol 聚合物 分散液: 部分溶脹的聚合物, Carbopol 聚合物在酸性狀態(tài)下平衡穩(wěn)定(Carbopol 聚合物 + 水) Carbopol 聚合物 黏液: 完全溶脹的聚合物Carbopol 聚合物在其聚陰

29、離子狀態(tài)下平衡穩(wěn)定(Carbopol聚合物 + 水+ 堿),堿中和Carbopol 樹脂形成黏液,無機堿( NaOH, KOH, NH4OH, etc. ) 水溶性銨鹽 ( TEA1, AMP2 or TRIS Amino3 ) 醇溶性胺鹽 (AMP2, Neutrol TE4, DIPA5, Ethomeen C-256 ),1 TEA: Triethanolamine (99%) 2 AMP: (Aminomethyl Propanol) 3 TRIS Amino: ANGUS (Tromethamine) 4 Neutrol TE: BASF (Tetrahydroxy propyl e

30、thylenediamine) 5 DIPA: Diisopropanolamine 6 Ethomeen C-25: AKZO (Peg-15 Cocamine),pH值與粘度的關系,2,4,6,8,10,12,pH,100,000,10,000,1,000,100,Carbopol 941,Carbopol 934,Carbopol 940,0.5% (wt) Polymer Brookfield RVT 20 rpm,粘度, cP (mPas),rev. 3/29/99,pH值與粘度的關系,0.5% Dispersion of Carbopol Polymer in Water,1,00

31、0,10,000,100,000,Ultrez 10,pH,ETD 2020,ETD 2050,Brookfield RVT 20 rpm,粘度, cP (mPas),如何中和 Carbopol 樹脂,無機堿(e.g. NaOH) - 低成本- 可得到稍高的粘度 有機堿(e.g. TEA) - 容易避免中和過度- 中和有機溶劑,50% Triethanol-amine,10% Sodium Hydroxide,100,000,50,000,20,000,10,000,2,4,6,8,10,12,14,pH,Brookfield RVT 20 rpm,粘度, cP (mPas),部分中和時的粘度

32、響應,pH,pH,*Brookfield RVT 20 rpm Neutralized with NaOH (18%),Carbopol Ultrez 10,Carbopol ETD 2020,粘度 cP (mPas),粘度, cP (mPas),中和至 pH 7.0 時所需中和劑比率,NaOH (18%)氫氧化鈉水溶液2.3/1.0 Ammonia (28%)氫氧化銨水溶液0.7/1.0 KOH (18%)氫氧化鉀水溶液2.7/1.0 L-Arginine精氨酸Ajinomoto4.5/1.0 AMP-95 氨基甲基丙醇Angus0.9/1.0 Neutrol TETetrahydroxyp

33、ropylBASF2.3/1.0 Ethylenediamine TEA (99%)三乙醇胺1.5/1.0 Tris Amino (40%)*TromethamineAngus3.2/1.0 Ethomeen C-25PEG-15 CocamineAkzo6.2/1.0 DiisopropanolamineDiisopropanolamine Dow1.2/1.0 TriisopropanolamineTriisopropanolamineDow1.5/1.0,*Note: The 40% solution should be made from Tris Amino crystals fro

34、m the manufacturer. Do not use the pre-dispersed solution from the manufacturer as it contains many impurities.,中和劑中和劑 INCI /重量比商品名CTFA 名生產廠堿/Carbopol,Thickening Hydroalcoholic Gels,如中和劑選擇不當Carbopol 會從溶液中沉淀出來,Recommended Neutralizers for Hydroalcoholic Systems Up to % Alcohol Neutralizer 20%Sodium H

35、ydroxide30%Potassium Hydroxide 60%Triethanolamine 60%Tris Amino 80%AMP-95 90%Neutrol TE 90%Diisopropanolamine 90%Triisopropanolamine 90%Ethomeen C-25,Handling Carbopol Polymers,How to Handle and StoreCarbopol Polymers,Polymers are very hygroscopic Containers should be kept tightly closed to avoid mo

36、isture pickup Avoid contact with water Avoid dusting,Polymer Moisture Content,Polymer is supplied 2% Equilibrium moisture content is 8% at 50% R.H.,Dispersion Water Temperature,In general, use cold (30 C) water with any direct dispersion method for traditional Carbopol polymers Warm/hot water will d

37、ecrease dispersion time with an indirect dispersion method When using Carbopol ETD and Ultrez polymers, heat will increase dispersion rate (up to 60 C),Problem Solving,魚眼的產生,Semi-translucent gelled particles Result from incomplete wetting of agglomerated polymer particles during dispersion May event

38、ually dissolve requiring several days,Graininess,Grainy surface texture, most apparent when gel is spread as thin film Causes Insufficient mixing time for dispersion Carbopol polymer and ingredient complexation Solution electrolytes Carbopol ETD polymers tend to swell more slowly Remedies Minimize l

39、evels of electrolytes and ingredients that complex with polymer, or add after neutralization Use good dispersing techniques With Carbopol ETD polymers - partially neutralize,Entrapped Air Bubbles,Freeing entrapped air from dispersions: Acidify dispersion with a very small amount of HCI or H3PO4 (0.5% of Carbopol polymer weight) 1 - 2 hours for dispersion to sit without mixing to break foam Cl or HPO4 residual salt concentration is low; not affecting mucilage viscosity When using Carbopol ETD or Ultrez polymers, low dispersion viscosity will allow air to ris