CAPA聚己內(nèi)酯在特殊聚氨酯中的應(yīng)用

1、1. CAPA - Polycaprolactones in Speciality Urethane ApplicationsCAPA ?聚己酯在特殊聚氨酯中的應(yīng)用Dr R C WassonSolvay CaprolactonesBaronet RoadWarringtonCheshire, WA4 6HBUnited Kingdom.solvaycaprolactones.2. The Monomer Process 單體合成過程IkQ, + CHKOOH F= CHiCOOOEl + HJ)Peracetic acid3. Typical Adipate PreparationCycloh

2、exanoneCaprolactone己二酸型聚酯制備過程4. Ring Opening Polymerisation of Caprolactone己酯開環(huán)聚合過程特性 分子量 聚合物分散性 PU反響性 酸值 鏈引發(fā)劑 共聚物特性5. CAPA? Polyol Key Parameters CAPA 聚合物的關(guān)鍵參數(shù)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在引發(fā)劑起始劑的作用下,CAPA聚合物可以能夠精確和方便的得以限制? Difunctional initiator gives difunctional polyol雙官能團(tuán)引發(fā)劑生成雙官能團(tuán)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標(biāo)準(zhǔn)的聚酯二

4、元醇結(jié)構(gòu)式MPG IdilM3 c Polyol8. CAPA? Triol Structure標(biāo)準(zhǔn)的聚酯三元醇結(jié)構(gòu)式9. Typical CAPA Tetrol標(biāo)準(zhǔn)的聚酯四元醇結(jié)構(gòu)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一般通過限制單體中引發(fā)劑的比率來限制多元醇的分子量大小? The reaction is a ring opening polymerisation, not a condensation reaction反響屬于開環(huán)反響而不是縮合反響? Current molecul

6、ar weight range is from 300 - 80,000 and we can make any molecular weight in between現(xiàn)在我們能制作出的分子量從300 80000,以及介于其中的各種分子量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,與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這樣可以獲得低粘度多元醇,在涂料制備時可以獲得高固含量? This can also have a large effect in the generation of physical properties分子量分布窄對下游產(chǎn)品物理性質(zhì)有極大的改善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聚亞安酯反響? All reaction components stay i

9、n the product所有的反響成分留在產(chǎn)品中? This includes catalysts這里包括各種催化劑? As the reaction conditions are mild catalyst levels are normally very low由于反響條件非常溫和,剩余催化劑含量非常低? These residual catalysts can be used to control the reactivity of the polyol in the reaction with isocyanates剩余的催化劑可以限制與異氟酸酯的反響17. Ring Opening

10、 Polymerisation of Caprolactone己酯開環(huán)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特殊型號的酸值可以到達(dá)低于0.05 mg KOH/g甚至為零? Acid value has a big influence on hydrolysis resistance酸值會對耐水解性有很大影響20. Change in Stress at Break壓縮變定值 變形-P

12、TVEG ?00QNPG Hi國用 CAPA1,4L3l>0 haed CARADEG hbaed CAP八l； jt/fce Ao pnta 3DW21. Change in Stress at Break壓縮變定值變形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 黃宮)&cs£o 米22. Change in Stress at B

13、reak壓縮變定值變形AILSU Sherc A,urjKrscJ ingt 蝦IPTMEG卻如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結(jié)晶與無定型結(jié)構(gòu)的共聚物都是存在的? Block copolymers are most common結(jié)晶的共聚物更為普遍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 與其他聚酯的比擬? Hydrolysis resistance? Tear strength? Cold flex? Flex fatigue? Low density Pus? Low viscosity polyol? Consistent reactivity耐水解性撕裂強(qiáng)度低溫柔軟性彎曲疲勞性低密度低黏度多元醇反響可控,易加工? Narrow molecular weight d

15、istribution分子量分布窄? Low acid value低酸值? Primary hydroxyl groups伯羥基基團(tuán)25. CAPA Polyol Properties CAPA 多元醇的特性與聚醛的比擬耐化學(xué)性Compared to Polyethers ? Chemical resistanceUV stabilitySolvent/oil resistance Cut and tear strength Abrasion resistance All primary hydroxyl groups紫外光穩(wěn)定性 耐溶劑油性 剪切和撕裂強(qiáng)度好 抗磨損性 全部是伯羥基Narro

16、w molecular weight distribution分子量分布窄Controlled functionality可控的官能團(tuán)26. New Developments新的開展? Solvay are constantly looking for new opportunities to expand the product rangeSolvay公司仍在不斷開拓和尋找此類產(chǎn)品的新應(yīng)用領(lǐng)域? As CAPA? chemistry is so versatile products can be tailored to make specific functionality, molecul

17、ar weight and reactivity combinations此類產(chǎn)品依其特殊的性能,分子量和其優(yōu)越的性能已經(jīng)成為通用的產(chǎn)品27. Polyurethane Dispersions (PUD' S)聚亞安酯的色散曲面? Issues 論點(diǎn)-VOC reduction VOC 縮減量-Solventless systems固化系統(tǒng)- - Water borne systems水負(fù)荷系統(tǒng)一? Components 成分- -Isocyanate - Hard Segment 異氟酸鹽硬段- -Chain extender - DMPA - Hard Segment鏈混合劑一 D

18、MPA 一硬段Polyol - CAPA? - Soft Segment CAPA一軟段28. New Initiators新的引發(fā)劑2,2 dimethylol propionic acid (DMPA)二羥甲基丙酸29. Preparation of CAPA HC含竣基官能團(tuán)的聚合物Dimelh)loJ Propionic Acid (DMPA kUM PA Iniljalcd luKcapiixacUiiie30. CAPA? HC Grades含竣基官能團(tuán)的聚合物? DMPA converted from high melting solid to low melting wax二羥甲基丙酸將高熔點(diǎn)的固體