拜耳水性分散体资料.ppt

1、Overview of Bayer Waterborne Technology - PUD/2K H2O,水性聚氨酯体系Waterborne PU Systems,聚氨酯分散体PUD（Bayhydrol） 多应用于单组分体系 特殊情况下也应用于类双组分体系 可与丙稀酸乳液拼用 水性聚氨酯多羟基化合物（Bayhydrol） -OH Functional 羟基 应用于双组分体系 水溶性聚异氰酸酯（Bayhydur） 含-NCO端基 改性后可在水中分散 应用于双组分体系,水性双组份聚氨酯涂料Bayhydur/Bayhydrol,聚氨酯分散体PUD,聚氨酯分散体PUD - Polyurethane D

2、ispersion 完全反应的聚氨酯聚合物分散在水相中； 不含活性的-OH基和-NCO基； 成膜机理不是由于-OH基和-NCO基的反应固化，而是由于水和助溶剂的挥发，聚合物微粒聚结成膜。,Coalescence 聚合物微粒聚结成膜,Dispersion Concentration Coalescence Maturation,聚氨酯分散体化学中重要的反应,反应速率：胺 醇/水 酸 Reaction rates: amine alcohol / water acid,Components of a PUD 成份,Isocyanates 异氰酸脂 Polyols and glycols 多醇 Am

3、ine chain extenders 氨基链增长剂 Hydrophilic groups 亲水基团 Neutralizers 中和剂,Diisocyanates Commonly Used in PUDsPUD中常用的异氰酸脂,HDI - Hexamethylene Diisocyanate,IPDI - Isophorone Diisocyanate,Desmodur W - 4,4-Dicyclohexylmethane Diisocyanate,O,C,N,N,C,O,O,C,N,N,C,O,N,C,O,O,C,N,Prepolymer Mixing Methods 预聚物混合法,2n

4、,H,O,O,H,+,n,H,O,C,H,2,C,C,H,2,O,H,C,H,3,C,O,2,H,+,4n,O,C,N,R,N,C,O,O,C,N,R,N,H,C,O,O,R,N,H,C,O,N,H,C,O,C,H,2,C,C,H,2,O,C,N,H,R,O,C,N,H,O,O,C,H,3,C,O,2,H,O,O,O,C,N,H,R,N,C,O,O,O,C,N,R,N,H,C,O,O,O,C,N,H,R,N,C,O,O,R,N,H,C,O,N,H,C,O,C,H,2,C,C,H,2,O,C,N,H,R,O,C,N,H,O,O,C,H,3,C,O,2,O,O,H,N,R,3,N,R,3,Hydr

5、ophilic Isocyanate Terminated Prepolymer,O,C,N,H,R,N,H,C,O,C,H,2,C,C,H,2,O,C,N,H,R,N,H,C,N,H,R,N,H,C,N,H,R,N,H,C,O,C,H,3,C,O,2,O,O,O,O,O,O,H,N,R,3,Aqueous Dispersion of Polyurethane-Urea,预聚物混合法,Advantages 优点 Easiest process to perform 容易操作的程序 Broad range of chemistries accessible 可容广范围的化学反应 Disadvan

6、tages 缺点 High viscosity of prepolymer requires co-solvent 高粘的预聚物需用溶剂 Use of aromatic di-isocyanates 不可用芳香族的异氰酸脂 Limit on neutralizing amines 中和用的氨基试剂有限 Reproducibility 重复性差,Acetone Method 丙酮法,Acetone Process 丙酮工艺,Use acetone as a solvent for polymerization 利用丙酮为聚合反应溶剂来 Buildup prepolymer 生成预聚物 Chain

7、 extend 增链 Add in neutralizing agent 加入中和剂 Disperse in water 分散于水中 Distill off acetone 将丙酮蒸出 Allows for development of products with controlled architecture 允许开发预定分子结构的产品 Products can be made with no solvent 产品内无溶剂,Stable Dispersed Products,Particles Should Remain Discrete 粒子保持独立 No Flocculation 不粘连

8、 No Settling or Floating of Particles 没有沉积或浮游的粒子 Stabilization can be done through 稳定是通过 Ionic Repulsion 离子相斥 Steric Repulsion 空间位阻 Viscosity Independant of Internal Phase 粘度与内相无关 High Molecular Weight Possible 可达高分子量 Control of Particles Size and Distribution 可控制颗粒度及其分布,Discrete Particles in Aqueou

9、s Media,稳定的分散体,Internal Emulsifier 内乳化: Effect of Increasing Neutralization 增加中和剂的影响,More X,At increased level of neutralization the particle swells with water,This increases the effective volume of the particle 中和剂越多, 颗粒为水膨胀, 有效体积增加,Stabilization 稳定化,Ionic,Steric,离子型,位阻型,Synthetic Variables,Soft se

10、gment polyols Polyethers - flexibility Polyesters - weatherability, hardness Polycarbonates - hydrolytic stability Hard segment polyols Glycols Diols Amine chain extenders Dispersing agents Internal External,Choice of Diisocyanate异氰酸脂的选择,aliphatics yield light and weather stability 脂肪族耐光, 具耐候性 Aroma

11、tic too reactive 芳香族的反应性过高 Hexamethylene diisocyanate (HDI) Elasticity 弹性 low temperature flexibility 低温下柔软性 Isophorone diisocyanate (IPDI) Hardness 硬度 High Tg 高Tg Hydrogenated MDI (H12MDI) mechanical properties-toughness 韧性 water / solvent resistance 耐水, 耐溶剂,Polyether Polyols 聚醚型共反应物,Advantages 优点

12、excellent stability against hydrolysis 优秀的抗水解性 good mechanical properties 良好的机椷性能 low Tg 低Tg low cost 价廉 Disadvantages 缺点 poor oxidative stability 抗氧化性差 high monool content 单体含量高,Polyester Polyols聚酯型共反应物,Advantages 优点 good weather stability 耐候性好 excellent mechanical properties (hardness, elasticity)

13、 机椷性能 (硬度, 弹性等)好 excellent compatibility with other raw materials (additives, pigments, other binders) 与其他原材料互容性好 Disadvantages 缺点 strong influence of polyester monomers on hydrolytic stability 聚酯单体影响水解稳定性,Polycarbonate Polyols聚碳酸脂共反应物,Advantages 优点 excellent stability against hydrolysis 优秀的抗水解性 exc

14、ellent stability against light and heat优秀的耐热,耐光 excellent weathering resistance优秀的耐候性 good mechanical properties 良好的机椷性能 Disadvantages 缺点 higher cost 价高,Advantages of Urethanes/Ureas聚脲/聚氨脂的优点,Hydrogen bonding (氢键) Acts as a crosslink Will release under strain Allows for thermoplastic flow to relieve

15、 stress andallow self healing of defects.,Typical Film Properties常见的薄膜性能,Solvent Resistance 耐溶剂性,Linear solvent swell after 24 hour immersion,Hydrolytic Stability % Retention of tensile properties,*films exposed at 70 C and 95% R.H.,聚氨酯分散体的技术特性Technical Aspects of PUDs,低溶剂含量 环保 高分子量下相对低的粘度 单组分应用，室温或

16、低温烘焙 具有典型的聚氨酯性能 可交联,聚氨酯分散体涂料的优异特征Outstanding Features of PUDs,分散稳定性 Dispersion Stability 抗磨损性 Abrasion Resistance 附着性 Substrate Adhesion 抗溶剂/水性 Solvent/Water Resistance 弹性 Elasticity 水解稳定性 Hydrolytic Stability 光稳定性 Light Stability,聚氨酯分散体可再交联Crosslinkable PUDs,双组分 异氰酸酯 Aziridines 单组分 封闭型异氰酸酯 三聚氰胺 Mel

17、amines,交联的影响 Effects of Crosslinking,提高性质 硬度 Hardness 抗溶剂/水性 Solvent/Water Resistance 抗磨损性 Abrasion resistance 模量 Modulus 可能降低的性质 弹性 Flexibility,拜耳的水性聚氨酯分散体产品AQUEOUS POLYURETHANE DISPERSIONS From Bayer,商品名Tradenames Bayhydrol 用于工业涂料 Baybond 用于玻璃光纤 Dispercoll U 用于胶粘 剂 Impranil 用于纺织品,Applications of B

18、ayhydrol Products Bayhydrol产品的应用,Wood Coatings 木器涂料 Automotive Coatings 汽车涂料 Electronic Products 电子产品涂料 Glass Coatings 玻璃涂料 Flooring 地板涂料 Others 其他,Bayhydrol Toolbox for Wood- and Parquet Coatings,Hardness,BHMR,Abrasion Resistance,NMP based,Bayhydrol VP LS 2342 5% NMP, Fatty acid mod., Solids*: 35%,

19、NMP free,Bayhydrol XP 2500 8% NMP, Fatty acid mod. Solids*: 35%,Bayhydrol VP LS 2450 8% NMP, Hard-elastic Solids*: 35%,Bayhydrol XP 2557 Solv. free / IRL 4670, Solid*: 35%, pH*: 8.0,Bayhydrol XP 2593 Solv. free / IRL 4690, Solid*: 35%, pH*: 8.0,Bayhydrol XP 2558 Solv. free / IRL 4680, Solid*: 38%, p

20、H*: 8.0,* = approx.,Diisocyanates,Hydrophilic group (ionic / non-ionic),Diols: monomeric, e.g. hexanediol polymeric, e.g. polyester,Polyester acrylate / Epoxy acrylate / Polyether acrylate / etc. ,UV Curable Polyurethane Dispersions 光固化水性聚氨酯分散体,- UV curing polyurethane dispersions,Bayhydrol UV,紫外光固化

21、水性聚氨脂分散体,high- grade polyurethane chemistry with all possible variations no mixtures with PAC, PU-PAC dispersions reactive thinners molecular weights emulsions : 10,000 g/mol dispersions: 200,000 g/mol,UV- curing polyurethane dispersion,Bayhydrol UV,Characteristic properties of.,UV- systemswithin wa

22、terborne coatings technology UV- waterborne systems are: chemical crosslinking 1C - systems they have no pot-life, yield high level of chemical andphysical resistance have a good recyclability use no dangerous crosslinkers,Bayhydrol UV,Waterborne systemswithin UV technologyUV- waterborne systems are

23、: easy to matt superior in adhesion simple and easy applied by spraying,Tool Box for Soft Feel Coatings柔 感 涂 料,Softfeel Coating,Component Ia:,HO,OH,OH,COO-,COO-,R3N+H,org. Cosolvent,Polyol-Dispersion in water (Bayhydrol),Neutralization Amine (i.e. DMEA),i.e. NMP,Component Ib:,PUR-Dispersion in water

24、, non-functional (Bayhydrol),O,H N,H N,C,Additives/Pigments:,Pigments,Componente II:,Polyisocyanate (Desmodur, Bayhydur),Waxes Defoamer Wetting Agent Matting Agent Fillers,i.e Aquacer 535 i.e. Defomer DNE i.e. Tego-Wet KL 245 i.e. OK 412, Talkum IT extra i.e. Pergopak M3 i.e. Bayferrox 318 M,org. Co

25、solvent,OCN,NCO,NCO,i.e. MPA, NMP,R3N+H,Formulations,Guide Formulation 柔 感 涂 料 配 方,柔 感 涂 料 配 方,Bayhydrol,Bayhydrol,Bayhydur/ Desmodur,+,Nichtfunktionelle flexible PUR-Dispersion,OH-funktionelle flexible PES-PUR-Dispersion,Polyisocyanat,+,Soft Feel Coatings柔 感 涂 料,Hyundai: Getz, Tucson Ford: Focus, M

26、ondeo Opel: Astra, Vectra VW: Golf, Passat, Multivan Audi: A4, A6, TT DaimlerChrysler: A, C, E, S, M Class& Maybach BMW: 1, 3 & 5 series Porsche: Cayenne LG & Miele Vacuum Cleaner IBM Laptop & Computer Mouse Housings for Mobile Phones,Hair Dryer, Power Drills & Pan Handle,Instrument panel, airbag li

27、d, center console, door handle, door trim, seat cover, buttons, housings etc. for.,玻璃纤维 浸润剂,玻璃纤维 浸润剂,Products-Specifications,Products / Properties,Polyurethane Dispersions,Backup,Components for 2K Waterborne PUR,Hydrophobic Polyisocyanates Advantages Higher % NCO Less water sensitivity Disadvantages

28、 Poor emulsion stability Poor compatibility polyol resin dependant Higher shear dependence Requires solvent for dispersibility,Components for 2K Waterborne PUR,Hydrophilically Modified Polyisocyanates Advantages Better Compatibility Easy of Mixing Disadvantages Lower % NCO Can have higher water sens

29、itivity,Waterborne Systems Emulsifying Polyisocyanates,External Emulsifier, ionic or non-ionic surfactants may migrate out of the coating leading to: blistering, decreased water resistance and gloss reduction,Not linked to the polyisocyanate,Polyisocyanates,Hydrophobic,Hydrophilic,1,1,+,Polyether,Al

30、ternative surfactants: SO3-,Aminosulfonic acid modified Polyisocyanates, Storage stability: no side reactions with NCO Benefits to polyether modified polyisocyanates: - lower amount of hydrophilic moieties- improved weatherability - increased hardness- improved chemical resistance Benefits to hydrophobic polyisocyanates: - improved dispersibility,Patented: WO 01/88006,Hydrophilic Polyisocyanates for Waterborne 2K PUR,Bayhydur XP 2487,Polyols for Waterborne 2K-PUR-Coatings,* : shall be withdrawn mid 2004,Polyols for Waterborne 2K-PUR-Coatings,Reactions of Importance in PUD Chemistry,Reaction r