拜耳水性分散体资料

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 • Amine chain extenders 氨基链增长剂 • Hydrophilic groups 亲水基团 • Neutralizers 中和剂
O R NCO + R' NH2 R'NH C NH
O
R
Isocyanate + amine
Isocyanate + water
3)
4)
R NCO + H2O
R'NH C OH
O O
R NH2 + CO2
O
R NCO + R" COOH
RNH C O C OR"
RNH C R" + CO2 Isocyanate + acid
Dispersion of Polyurethane-Urea in Water/Solvent
Acetone Removal
Aqueous Dispersion of Polyurethane-Urea
Acetone Process 丙酮工艺
• Use acetone as a solvent for polymerization
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
– 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
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
聚氨酯分散体化学中重要的反应
O
1)
2)
R
NCO + R'OH
R'O C NH
R
Isocyanate + alcohol
O
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
• 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
O OCN R NHCO
O
O
O
O OCNH R NCO
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
Stable Dispersed Products
稳定的分散体

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

Stabilization can be done through 稳定是通过
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
• 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
– 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
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
• 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
• 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.
– 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
基片上颗粒沉积 Deposition of Particles on Substrate
Diisocyanates Commonly Used in PUDs PUD中常用的异氰酸脂
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
CH3
2n HO
OH + n HOCH2C CH2OH + 4n OCN R NCO CO2 H
O OCN R NHCO
O
O
CH3
O
O
O
OCNH R NCO
OCNH R NHCO CH2C CH2OCNH R NHCO CO2 H NR3 O CH3
– -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 Dispersion
• 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
Typical Film Properties 常见的薄膜性能
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®）
Stabilization 稳定化
Ionic + + + - - + + - -+ +-+ +- + +- + -+ -+ + + - -+ - -+ + + 离子型
位阻型
Steric
ຫໍສະໝຸດ Baiduynthetic Variables
• Soft segment polyols
– Polyethers - flexibility – Polyesters - weatherability, hardness – Polycarbonates - hydrolytic stability
X
+
Y
-
X
Y
X
+
+
Y
-
X
+
Y
-
X
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
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 Y Y Y X
+
Y
-
More X
Y
+
X
+
Y
-
X
+
Y
-
X
+
Y
-
X Y
-
+
Y
-
» 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
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
Acetone Method 丙酮法
n HO O OCN R NHCO OH + 2 n OCN R NCO O OCNH R NCO Acetone H 2NR'N HR'SO3 Na O O O O
O
O
OCHN R NHC NHR' NCHN R NHCO R'SO Na 3 Water
OCNH R NHCO