CAPA聚己内酯在特殊聚氨酯中的应用

1、1. CAPA - Polycaprolactones in Speciality Urethane ApplicationsCAPA ?聚己酯在特殊聚氨酯中的应用Dr R C WassonSolvay CaprolactonesBaronet RoadWarringtonCheshire, WA4 6HBUnited Kingdom.solvaycaprolactones.2. The Monomer Process 单体合成过程IkQ, + CHKOOH F= CHiCOOOEl + HJ)Peracetic acid3. Typical Adipate PreparationCycloh

2、exanoneCaprolactone己二酸型聚酯制备过程4. Ring Opening Polymerisation of Caprolactone己酯开环聚合过程特性 分子量 聚合物分散性 PU反响性 酸值 链引发剂 共聚物特性5. CAPA? Polyol Key Parameters CAPA 聚合物的关键参数Functionality Molecular Weight Polydispersity PU reactivity Acid Value Initiator Co - Polymer6. Functionality? The exact functionality of th

3、e CAPA? polyol is simple to control and is determined by the functionality of the initiator在引发剂起始剂的作用下,CAPA聚合物可以能够精确和方便的得以限制? 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7. Typical CAPA Diol Structure标准的聚酯二

4、元醇结构式MPG IdilM3 c Polyol8. CAPA? Triol Structure标准的聚酯三元醇结构式9. Typical CAPA Tetrol标准的聚酯四元醇结构式季戊四醇GradeMWOH(mg KOH/g)Acid(mg KOH/g)Viscosityt1)Melting PointFC)CAPA30313.56(1< 1.01710-1CAPA拈 3041400560< 1,01620-1 (PC540310< LO1S70-11CCAPA"： 30919001S3< 1.01640-10CCAPA l:4K)llOOfi218<

5、; 1,025S10,0 c(1) Shear rate = 500 sec temperature = 6011. Molecular Weight分子量? The molecular weight of the polyol is controlled by the ratio of initiator to monomer一般通过限制单体中引发剂的比率来限制多元醇的分子量大小? The reaction is a ring opening polymerisation, not a condensation reaction反响属于开环反响而不是缩合反响? Current molecul

6、ar weight range is from 300 - 80,000 and we can make any molecular weight in between现在我们能制作出的分子量从300 80000,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? Thi

7、s leads to lower viscosity polyols and hence 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13. Viscosities of Various Polyols at 60 C60 c不同的多元醇黏度比照表o4020力 Bxlu 白»00»4o00001002003

8、00400500600Shear Rato 1Js2000 Mw HDO Adpata 2000 Mw BDO AdipateKivu FG AflieM Cana 夕14. Viscosities of Various Polyols at 80 C80 c不同多元醇的黏度比照表5 40:-一二一diViscosities of Various Polyols at 80 CBOO60040020000100200300400500600Shear Rate Vs16. Polyurethane Reactivity聚亚安酯反响? All reaction components stay i

9、n the product所有的反响成分留在产品中? This includes catalysts这里包括各种催化剂? As the reaction conditions are mild catalyst levels are normally very low由于反响条件非常温和,剩余催化剂含量非常低? These residual catalysts can be used to control the reactivity of the polyol in the reaction with isocyanates剩余的催化剂可以限制与异氟酸酯的反响17. Ring Opening

10、 Polymerisation of Caprolactone己酯开环聚合18. Examples of Commercial ProductsPRODUCT MOLECULAR ACIDNAME WEIGHT VALUECAPA® 22002000CAPA® 2220A2000< 0 05CAPA® 22012000CAPA® 2201A2000REACTIVITYfastfastslowslow19. Acid Value酸值? The residual acid value in CAPA? polyols is always very lo

11、w - 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 with acid values of less than 0.05 mg KOH/g - effectively zero特殊型号的酸值可以到达低于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20. Change in Stress at Break压缩变定值 变形-P

12、TVEG ?00QNPG Hi国用 CAPA1,4L3l>0 haed CARADEG hbaed CAP八l； jt/fce Ao pnta 3DW21. Change in Stress at Break压缩变定值变形All酌 Stuwt A,itiMiicrsjCij m ulium XOC.FTULG2D0Q-二4 BDO Prpm.fr Grt醴L t j Fem jn 3radeHsGPr<Jlbjn 3fWUEutflpne &$paie? 2D0C£001 0 黄宫)&cs£o 米22. Change in Stress at B

13、reak压缩变定值变形AILSU Sherc A,urjKrscJ ingt 虾IPTMEG却如Piwniun Jra目eiDEG Premiurn Gna4ehPG F'nemi m Graoe再匕 pEi阮 2Z0'3具 on. 0 aswueu.家23. Copolymers 共聚物? Both block 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 APolycarbonate polyo

14、l- -Polyethers- -Polyesters- -Poly bd 24. CAPA Polyol Properties CAPA 多元醇的特性Compared to other Polyesters 与其他聚酯的比拟? Hydrolysis resistance? Tear strength? Cold flex? Flex fatigue? Low density Pus? Low viscosity polyol? Consistent reactivity耐水解性撕裂强度低温柔软性弯曲疲劳性低密度低黏度多元醇反响可控,易加工? Narrow molecular weight d

15、istribution分子量分布窄? Low acid value低酸值? Primary hydroxyl groups伯羟基基团25. CAPA Polyol Properties CAPA 多元醇的特性与聚醛的比拟耐化学性Compared to Polyethers ? Chemical resistanceUV stabilitySolvent/oil resistance Cut and tear strength Abrasion resistance All primary hydroxyl groups紫外光稳定性 耐溶剂油性 剪切和撕裂强度好 抗磨损性 全部是伯羟基Narro

16、w molecular weight distribution分子量分布窄Controlled functionality可控的官能团26. New Developments新的开展? Solvay are constantly looking for new opportunities to expand the product rangeSolvay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, molecul

17、ar 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27. Polyurethane Dispersions (PUD' S)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 borne systems水负荷系统一? Components 成分- -Isocyanate - Hard Segment 异氟酸盐硬段- -Chain extender - DMPA - Hard Segment链混合剂一 D

18、MPA 一硬段Polyol - CAPA? - Soft Segment CAPA一软段28. New Initiators新的引发剂2,2 dimethylol propionic acid (DMPA)二羟甲基丙酸29. Preparation of CAPA HC含竣基官能团的聚合物Dimelh)loJ Propionic Acid (DMPA kUM PA Iniljalcd luKcapiixacUiiie30. CAPA? HC Grades含竣基官能团的聚合物? DMPA converted from high melting solid to low melting wax二羟甲基丙酸将高熔点的固体