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1、-1 CAPA Polycaprolactones in Speciality Urethane ApplicationsCAPA 聚己内酯在特殊聚氨酯中的应用Dr R C WassonSolvay CaprolactonesBaronet RoadWarringtonCheshire, WA4 6HBUnited Kingdom2The Monomer Process 单体合成过程3Typical Adipate Preparation 己二酸型聚酯制备过程4Ring Opening Polymerisation of Caprolactone 己内酯开环聚合过程5CAPA Polyol K
2、ey Parameters CAPA聚合物的关键参数 Functionality 特性 Molecular Weight 分子量 Polydispersity 聚合物分散性 PU reactivity PU 反应性 Acid Value 酸值 Initiator 链引发剂 Co Polymer 共聚物6Functionality 特性 The exact functionality of the CAPA polyol is simple to control and is determined by the functionality of the initiator 在引发剂（起始剂）的作
3、用下，CAPA聚合物可以能够精确和方便的得以控制 Difunctional initiator gives difunctional polyol 双官能团引发剂生成双官能团聚合物 Trifunctional initiator gives trifunctional polyol and so on三元的生成三元聚合物 等等7Typical CAPA Diol Structure 标准的聚酯二元醇结构式8CAPA Triol Structure标准的聚酯三元醇结构式9Typical CAPA Tetrol标准的聚酯四元醇结构式（季戊四醇）粘度分子量熔点10. CAPA Triols & Te
4、trols聚酯三、四元醇的性能表格11. Molecular Weight 分子量 The molecular weight of the polyol is controlled by the ratio of initiator to monomer 一般通过控制单体中引发剂的比率来控制多元醇的分子量大小 The reaction is a ring opening polymerisation, not a condensation reaction 反应属于开环反应而不是缩合反应 Current molecular weight range is from 300 - 80,000 a
5、nd we can make any molecular weight in between 现在我们能制作出的分子量从30080000，以及介于其中的各种分子量12. Polydispersity聚合物分散性 The polydispersity, or molecular weight distribution of CAPA polyols is narrow compared to conventional polyesters聚合物分散性或者是CAPA分子量的分布，与通常的聚酯多元醇相比分布窄 This leads to lower viscosity polyols and hen
6、ce higher solids contents in coatings这样可以获得低粘度多元醇，在涂料制备时可以获得高固含量 This can also have a large effect in the generation of physical properties分子量分布窄对下游产品物理性质有极大的改善13Viscosities of Various Polyols at 60 60不同的多元醇黏度对比表14Viscosities of Various Polyols at 80 80不同多元醇的黏度对比表15Viscosities of Various Polyols at
7、8016Polyurethane Reactivity聚亚安酯反应 All reaction components stay in the product所有的反应成分留在产品中 This includes catalysts这里包括各种催化剂 As the reaction conditions are mild catalyst levels are normally very low因为反应条件非常温和，剩余催化剂含量非常低 These residual catalysts can be used to control the reactivity of the polyol in th
8、e reaction with isocyanates剩余的催化剂可以控制与异氰酸酯的反应17Ring Opening Polymerisation of Caprolactone己内酯开环聚合18Examples of Commercial Products19Acid Value酸值 The residual acid value in CAPA polyols is always very low - in most cases less than 0.1 mg KOH/gCAPA的酸值一般都是非常低的，甚至低于0.1 mg KOH/g Special grades are made w
9、ith acid values of less than 0.05 mg KOH/g - effectively zero特殊型号的酸值可以达到低于0.05 mg KOH/g甚至为零 Acid value has a big influence on hydrolysis resistance酸值会对耐水解性有很大影响20Change in Stress at Break压缩变定值 变形（%）21Change in Stress at Break压缩变定值 变形（%）22Change in Stress at Break压缩变定值 变形（%）23Copolymers 共聚物 Both bloc
10、k and random copolymers are possible结晶与无定型结构的共聚物都是存在的 Block copolymers are most common结晶的共聚物更为普遍PTMEG - CAPA 7201 A Polycarbonate polyol Polyethers Polyesters Poly bd .24CAPA Polyol Properties CAPA多元醇的特性Compared to other Polyesters 与其他聚酯的比较 Hydrolysis resistance 耐水解性 Tear strength 撕裂强度 Cold flex 低温柔
11、软性 Flex fatigue 弯曲疲劳性 Low density Pus 低密度 Low viscosity polyol 低黏度多元醇 Consistent reactivity 反应可控，易加工 Narrow molecular weight distribution 分子量分布窄 Low acid value 低酸值 Primary hydroxyl groups 伯羟基基团25CAPA Polyol Properties CAPA多元醇的特性Compared to Polyethers 与聚醚的比较 Chemical resistance 耐化学性 UV stability 紫外光稳
12、定性 Solvent/oil resistance 耐溶剂(油)性 Cut and tear strength 剪切和撕裂强度好 Abrasion resistance 抗磨损性 All primary hydroxyl groups 全部是伯羟基 Narrow molecular weight distribution 分子量分布窄 Controlled functionality 可控的官能团26New Developments新的发展 Solvay are constantly looking for new opportunities to expand the product ran
13、geSolvay公司仍在不断开拓和寻找此类产品的新应用领域 As CAPA chemistry is so versatile products can be tailored to make specific functionality, molecular weight and reactivity combinations此类产品依其特殊的性能，分子量和其优越的性能已经成为通用的产品27Polyurethane Dispersions (PUDS)聚亚安酯的色散曲面 Issues 论点 VOC reduction VOC缩减量 Solventless systems 固化系统 Water
14、 borne systems 水负荷系统 Components 成分 Isocyanate - Hard Segment 异氰酸盐 硬段 Chain extender - DMPA - Hard Segment 链混合剂DMPA硬段 Polyol - CAPA - Soft Segment CAPA软段28New Initiators新的引发剂2,2 dimethylol propionic acid (DMPA)二羟甲基丙酸29Preparation of CAPA HC含羧基官能团的聚合物30CAPA HC Grades含羧基官能团的聚合物 DMPA converted from high
15、 melting solid to low melting wax二羟甲基丙酸将高熔点的固体转变为低熔点的蜡状物 Low viscosity so easy to handle低黏度易处理 Part of soft segment软段部分31New Developments新的发展 Solvay are always looking for new products苏威公司一直在不断的开发新的产品 We are willing to discuss ideas with customers to develop tailor made products.我们也非常乐意按照我们的客户的要求来定制
16、我们的产品32Conclusions结束语 CAPA Polyols聚酯多元醇 Speciality soft segment for urethanes 特殊的软段可以利用到聚氨酯橡胶中 Available as diols, triols and tetrols 也可同样应用于二醇，三醇和四醇中 Performance polyols for high performance applications 功能性聚氨酯可以应用于提高应用性能33Acknowledgements感谢！ Solvay Interox Inc.Solvay Interox公司 Tri-Iso Inc.Tri-Iso公司对文章内出现的错误，希望阅读者能给予我纠正，也请谅解。谢谢！翻译：王政校对：史庆华第 21 页-