Carbomer树脂通论PPT课件

1、Noveon 功能性原料 Carbopol 和 Pemulen高分子流变调节剂,Carbopol and Pemulen 高聚物介绍,概要 A.什么是 Carbopol and Pemulen 高分子聚合物? B. Carbopol and Pemulen高分子聚合物的六种主要功能 C.Carbopol高分子聚合物的特性 D.Carbopol 凝胶的流变性 E.Carbopol and Pemulen 敏感性 F.Carbopol and Pemulen高分子聚合物的使用 G.疑难解答,Carbopol高分子聚合物是.,流变修饰剂 聚丙烯酸 树脂 高分子量 交联作用 CTFA/INCI 名:

2、Carbomer (均聚物) Acrylates/C10-30 Alkyl Acrylate Crosspolymer (共聚物),C,C,C,O,OH,n,H,H,H,Carbopol 在个人护理产品中的应用,头发护理 香波 定型着哩 摩丝 染发产品 烫发产品,皮肤护理 保湿着哩 膏霜和乳液 含酒精的着哩胶 防晒产品 沐浴露 脱毛膏,Carbopol在药用产品中的应用,药片和胶囊 口腔护理产品（牙膏） 生物粘附应用 局部给药着哩胶 局部给药霜和乳液 含漱乳液及外敷乳液 兽用药,Carbopol 用于家居护理 and I短流 均聚物5984奶油状感觉;对盐敏感 940980 Ultrez 10

3、非常高黏度;短流;均聚物ETD 2001*奶油状感觉; 对盐敏感 941981 ETD 2050低黏度;长流 均聚物 拉丝结构;对盐敏感 13421382 ETD 2020高黏度; 长流共聚物Pemulen TR-1拉丝结构Pemulen TR-2对盐敏感不高,易分散的 Carbopol 树脂,凝胶特性,树脂类型,*ETD 2001 对盐更不敏感,Carbopol 25 C,RheologicalSymbol, PropertyUnits934940941Ultrez 10ETD 2020 ETD 2001 RigidityGO, Pa74043026980326540 Thixotropic

4、T.I., 3054353101283 IndexPa/s.cm3 Yield Stressyld, Pa9510014110150124 Viscosity, mPa.s (cP)74,50075,80010,70084,30063,20077,300,Carbopol,Carbopol,Carbopol,Carbopol,Carbopol 微胶体的硬度,PolymerRigidityMucilage Texture Carbopol 13426Long rheology/Soft Carbopol 94125Long rheology/Soft Carbopol 940430Short r

5、heology/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 Irreversible loss of viscosity and yield value may occur Ne

6、utralized 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 agitation recommended Lower cross-linked Carbopol p

7、olymers 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 Polymer,pH = 7.0 Brookfield RVT 20 rpm,Viscosity,

8、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 Sensitivity of Carbopol and Pemulen Polymers,Sou

9、rces 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,Relative Electrolyte Sensitivity ofCarbopol Polymers,

10、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:,Swollen Microgel,Suspended Particle,Effect of Salt on

11、 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 of CaCl2,941 (0.25 wt %) effect of NaCl effect of

12、 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, 934,981, 941,1382, 1342,Carbopol Polymer,Brookfi

13、eld 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 rpm,Viscosity, cP (mPas),Viscosity Response of

14、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,Carbopol 941,Carbopol ETD 2020,Carbopol Ultrez 10,Thick

15、ening 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),阳离子的影响,阳离子的影响 透明度下降 黏度损失 Complexation of anionic polymer causes precipitation 因由 Carbopol 树脂是阴离子聚合物 解决方法 使用非常低浓度的阳离子 加

16、入阳离子之前中和 采用低电荷密度高分子量的阳离子 比如: 聚季胺盐-39, 阳离子瓜尔胶 采用耐离子的Carbopol ETD 2020,紫外光的影响,紫外光的影响: 黏度损失 透明度下降 解决方法: 加入紫外吸收剂 (如二苯甲酮-4) 加入EDTA二钠 注意:紫外吸收剂 和EDTA二钠有增效作用 紫外吸收剂用量: 0.05%,温度的影响,Dry Carbopol polymer:- Stable to 104 C (Tg of Carbopol polymer) - Decomposition complete in 30 minutes at 260 C Carbopol polymer

17、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,Polymer Concentration = 0.5% wt Brookfield RVT 20

18、rpm,Viscosity, cP (mPas),微生物影响,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 compatible with biocidal quaterniums),Putting Carbopol

19、 and Pemulen Polymers to Work,How to disperse Carbopol polymers How to neutralize Carbopol systems How to handle Carbopol polymers,分散准备,Dispersion Viscosities of Various Carbopol Polymers,Unneutralized,5,000,4,000,3,000,2,000,1,000,0,Ultrez 10,ETD 2020,981,980,941,940,Polymer = 1.0 ( wt % ),Brookfie

20、ld 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),三种 Carbopol 树脂 (未中和)分散后外观比较,Carbopol 940 1% Weight 3,425 cP Brookfield RVT 20 rpm, #3 spindle Homog

21、enous,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分散初始阶段所需的湿润时间*,Carbopol 934 940 941 Ultrez10 ETD2020,湿润时间, 分钟 50 50 50 5 15,* 2.5 克Carbopol

22、粉末撒在500毫升去离子水的表面.,如何分散传统的Carbopol 树脂,将Carbopol以细微颗粒缓慢加入(可用筛子, 喷射器 或其他机械分散装置) 如果可能，首先将Carbopol加入配方 尽可能在过程最后中和 (增稠) 如有可能，先将Carbopol 分散在非极性油相中。,分散方法,直接法 (将聚合物分散在水中) 间接法 (将聚合物分散在油相) 再加入水中,Carbopol 树脂的分散 准备 直接加入,-将树脂通过20 - 30 目的不锈钢筛子缓慢地撒在水旋涡面上 - 尽可能早将Carbopol 加入配方中 - 加少量无机酸减少黏度并防止有气泡混入 - 尽可能在过程最后中和 - 推荐配

23、制 2.0% 聚合物浓度的分散液,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 water and 35 psig Water flow must commence before

24、 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 is a good second choice Use room temperature wat

25、er (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 powder Disperse polymer in water containing no s

26、alts 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 agitating water phase Polymer migrates from oil t

27、o 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义,Carbopol 聚合物 分散液: 部分溶胀的聚合物, Carbopol 聚合物在酸性状态下平衡稳定(Carbopol 聚合物 + 水) Carbopol 聚合物 黏液: 完全溶胀的聚合物Carbopol 聚合物在其聚阴离子状态下平衡稳定(Carbopol聚合物 + 水+ 碱),碱中和Carbopol 树脂形成黏液

28、,无机碱( NaOH, KOH, NH4OH, etc. ) 水溶性铵盐 ( TEA1, AMP2 or TRIS Amino3 ) 醇溶性胺盐 (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 ethylenediamine) 5 DIPA: Diisopropanolamine 6 Eth

29、omeen C-25: AKZO (Peg-15 Cocamine),pH值与粘度的关系,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值与粘度的关系,0.5% Dispersion of Carbopol Polymer in Water,1,000,10,000,100,000,Ultrez 10,pH,ETD 2020,ETD 2050,

30、Brookfield RVT 20 rpm,粘度, cP (mPas),如何中和 Carbopol 树脂,无机碱(e.g. NaOH) - 低成本- 可得到稍高的粘度 有机碱(e.g. TEA) - 容易避免中和过度- 中和有机溶剂,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),部分中和时的粘度响应,pH,pH,*Brookfield RVT 20 rpm Neutralized with

31、 NaOH (18%),Carbopol Ultrez 10,Carbopol ETD 2020,粘度 cP (mPas),粘度, cP (mPas),中和至 pH 7.0 时所需中和剂比率,NaOH (18%)氢氧化钠水溶液2.3/1.0 Ammonia (28%)氢氧化铵水溶液0.7/1.0 KOH (18%)氢氧化钾水溶液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 TETetrahydroxypropylBASF2.3/1.0 Ethylenediamine TEA (99%)三乙醇胺1.

32、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 from the manufacturer. Do not use the pre-dispersed

33、 solution from the manufacturer as it contains many impurities.,中和剂中和剂 INCI /重量比商品名CTFA 名生产厂碱/Carbopol,Thickening Hydroalcoholic Gels,如中和剂选择不当Carbopol 会从溶液中沉淀出来,Recommended Neutralizers for Hydroalcoholic Systems Up to % Alcohol Neutralizer 20%Sodium Hydroxide30%Potassium Hydroxide 60%Triethanolamin

34、e 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 moisture pickup Avoid contact with water Avoid dus

35、ting,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 decrease dispersion time with an indirect dispers

36、ion method When using Carbopol ETD and Ultrez polymers, heat will increase dispersion rate (up to 60 C),Problem Solving,鱼眼的产生,Semi-translucent gelled particles Result from incomplete wetting of agglomerated polymer particles during dispersion May eventually dissolve requiring several days,Graininess

37、,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 levels of electrolytes and ingredients that compl

38、ex 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 di

39、spersion 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 rise to surface.,pH Variation,Erratic or inconsistent measured pH value Caused by incomp

40、lete swelling of Carbopol polymer pH will stabilize within one day Carbopol ETD and Ultrez polymers uncoil more slowly, pH decreases and stabilizes within 8 hours,Low Viscosity in Finished Formula - Immediate,Causes: Polymer concentration is too low Polymer was oversheared due to homogenization Salt

41、 or ion content in formula is too high Formula is under neutralized Wrong polymer is being used Solutions: Increase polymer concentration Do not homogenize, or reduce settings or number of cycles Reduce amount of salts or ions in formula, or increase level of Carbopol polymer Add additional neutralizer as needed Use Carbopol ETD 2020,Loss of Viscosity Over Time,V