拜耳水性分散体资料

• 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) 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
Stable Dispersed Products
稳定的分散体
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Particles Should Remain Discrete 粒子保持独立
» No Flocculation 不粘连 » No Settling or Floating of Particles 没有沉积或浮游的粒子
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Stabilization can be done through 稳定是通过
Isocyanate + water
R NH2 + CO2
O
RNH C O C OR"
RNH C R" + CO2 Isocyanate + acid
反应速率：胺 > 醇/水 > 酸 Reaction rates: amine > alcohol / water > acid
Components of a PUD 成份
OCN
NCO
IPDI Isophorone Diisocyanate
OCN
NCO
Desmodur W 4,4’-Dicyclohexylmethane Diisocyanate
OCN
NCO
HDI Hexamethylene Diisocyanate
Prepolymer Mixing Methods 预聚物混合法
Stabilization 稳定化
Ionic + + + + - + + - - + + +- + +- + -+ -+ + + - -+ + + + 离子型
位阻型 Steric
Synthetic Variables
• Soft segment polyols
– Polyethers - flexibility – Polyesters - weatherability, hardness – Polycarbonates - hydrolytic stability
– -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 水性双组份聚氨酯涂料 ®/Bayhydrol ® Bayhydur Bayhydur® /Bayhydrol®
» Ionic Repulsion 离子相斥 » Steric Repulsion 空间位阻
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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
OCNH R NHCO CH2C CH2OCNH R NHCO CO2 HNR3 1. Water 2. H2N R' NH2 O O
Hydrophilic Isocyanate Terminated Prepolymer
O
O CH3 O OCNH R NH C O CH2C CH2OCNH R NHCNH R' NHCNH R NHCO CO2HNR3 Aqueous Dispersion of Polyurethane-Urea
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 extend 增链 – Add in neutralizing agent 加入中和剂
X Y
Y X+YX+Y-
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
O
预聚物混合法
Βιβλιοθήκη Baidu• 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
• Disadvantages 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
•
•
Polyether Polyols
聚醚型共反应物
• Advantages 优点
– 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
基片上颗粒沉积 Deposition of Particles on Substrate
联结成连续的膜 Coalescence into Continuous Film
Coalescence 聚合物微粒聚结成膜
Dispersion Concentration Coalescence Maturation
CH3 2n HO OH + n HOCH2C CH2OH + 4n OCN R NCO CO2 H O CH3 O O O OCNH R NCO
O OCN R NHCO
O
OCNH R NHCO CH2C CH2OCNH R NHCO CO2 H NR3 O CH3
O OCN R NHCO
O
O
O
O OCNH R NCO
Polycarbonate Polyols 聚碳酸脂共反应物 • Advantages 优点 – excellent stability against hydrolysis 优秀的抗水解性 – excellent 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
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®）
• 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 Aromatic 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
• 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
Advantages of Urethanes/Ureas 聚脲/聚氨脂的优点
O N H O N H O N H O N H O N H O N H O N H O N H O N H N H O N H
• Hydrogen bonding (氢键)
– Acts as a crosslink – Will release under strain – Allows for thermoplastic flow to relieve stress and allow self healing of defects.
Acetone Method 丙酮法
n HO O OCN R N H CO OH + 2 n OCN R N CO O H R N CO OCN CNH Acetone H 2NR'N HR'SO3 N a O O O O N R N H CO CHN N R N H C NHR' N CH OCH CHN R'SO N a 3 Water Dispersion of Polyurethane-Urea in Water/Solvent Acetone Removal Aqueous Dispersion of Polyurethane-Urea O O H R N H CO OCN CNH
• Isocyanates 异氰酸脂 • Polyols and glycols 多醇 • Amine chain extenders 氨基链增长剂 • Hydrophilic groups 亲水基团 • Neutralizers 中和剂
Diisocyanates Commonly Used in PUDs PUD中常用的异氰酸脂
Discrete Particles in Aqueous Media
Internal Emulsifier 内乳化: Effect of Increasing Neutralization 增加中和剂的影响
X Y
+ + -
X+YY Y Y X+YX
+
More X
Y
-
X+Y-
X+YX+YX+YX+Y-
聚氨酯分散体PUD
urethane Dispersion • 聚氨酯分散体PUD - Poly olyu
– 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。
水介质中的离散颗粒 Discrete Particles in Aqueous Media
聚氨酯分散体化学中重要的反应
O
1) 2) 3) 4)
R
NCO + R'OH
R'O C NH
R
Isocyanate + alcohol
O R NCO + R' NH2 R'NH C NH
O R NCO + H2O R'NH C OH
O R NCO+ R" COOH O
R
Isocyanate + amine