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1、聚胺酯(PU)彈性體之設計及應用,施 文 昌,Outline,IntroductionClassification of PU elastomersSynthesis and Characterization of PU elastomersApplication of of PU elastomersQuestions and discussions,One of the most versatile polymers ever invented. It can be made as a soft or rigid foam or a soft or hard elastomeric str
2、ong plastic. By changing the chemistry a infinite range of materials can be made.,A broad family of rubber-like condensation polymers generally composed of:,A high molecular weight hydroxyl terminated polyol A low molecular weight diol or diamine chain extender or curative A polyisocyanate Catalysts
3、,additives,etc.,PU樹脂由於具有不相容的軟段（Soft Segment）及硬段（Hard Segment），產生相分離，導致硬段在PU結構中呈現類似海島的結晶相，使PU在室溫下有物理交聯（即假性交聯）的現象，因此PU分子量雖僅有數萬，但由於相分離所產生的物理交聯，使得其機械性質十分優異。,What are PU elastomers?,Unique of PU elastomers,Hardness of PU elastomers from shore 000 to shore D-80,Flexible/Rigid Foam,Slabstock Laminated Mold
4、ed RIM Spray,Elastomers,TPU Cast RIM Spray Fiber Millable,ACS,Adhesive Coating Hot Melt Sealant,Urethane/Urea Chemical,Thermoplastic polyurethanes-Available as granules or pellets suitable for conventional thermoplastic processing such as extrusion,calendaring or injection moulding.,Cast elastomers-
5、Made by low-pressure mixing and casting the liquid components into a mould to form a solid article with typical applications being high performance industrial wheels,seals,rollsetc.,RIM elastomers-Produced by high-pressure mixing and injection into a closed mould with typical applications as automot
6、ive bumper fascias,body panels plus body components for a variety of other vehicles.,The definition of PU elastomers,Spray elastomers-Made by high-pressure mixing and spraying on to a substrate where the key applications are industrial protective coatings for bridges,pipes or linings for transport c
7、ontainers.,Elastomeric fibers-These are made by solution spinning directly from the polymerisation mixture,Millable polyurethane gums-Available as slabs or crumb that are processed by the traditional methods used in the rubber industry,Isocyanates,Isomers of monomeric MDI,PU樹脂二異氰酸酯原料之特性比較,二異氰酸酯之相對反應
8、速率之比較,Oligomerols,The special monomer of polyols,Ester vs.ether for PU elastomers,1=最好 5=最差,Comparison of the polyol for PU elastomers,反應型防火劑/阻燃劑,2.:Solvay Company-,High performance halogenated polyether polyol: Hydroxyl number=200300,3.ADEKA POLYETHERS,4.,Fyrol 6=Diethyl-N,N-bis(2-hydroxyethyl)amin
9、omethyl phosphonateHydroxyl number=400500,IXOL-M125/B251,Tin and Lead Carboxylic Acid Salts,Gelation,Blowing,Blowing,Isocyanate -Water Reaction,Isocyanate-Polyol Reaction,Gelation,Mercury Salts,TD-33A DMCHAZR-50TD-20 DMEAPMDETAZR-70ZF-51 ZF-53ZF-57ZF-65ZF-52ZF-62DMP DM-70 E-40MM-70PM ZF-20ZF- 54 NMM
10、, NEM M-75DMDEE,Catalysts for the NCO/OH/H2O reaction,Metal Cat. act as Lewis acid and activate the isocyanate.,Amine Cat. act as Lewis bases and activate the hydroxyl groups.,Lewis base Catalysis-Amine Cat.,processing characteristics may be significantly effected and equipment operations optimized
11、by altering the way the raw materials are formulated.,*,Basic composition of an 80-85 shore A elastomer,These are:,FULL prepolymer systems,QUASI prepolymer systems,ONE-SHOT systems,Preparation of FULL prepolymer casting system,Properties: Forced block co-polymer,improved resilience,higher modulus,be
12、tter flex fatigue,Processing: High prepolymer viscosity forced 80-1000C.processing-note wide ratio,not suitable for small,repetitive shots.,Preparation of QUASI prepolymer casting system,47.1,52.9,NCO=18.6% Vis=3001000cps,Polyol Vis=200400cps,Properties: Semi block co-polymer,good properties,more ph
13、ase mixing,more versatile formulating.,Processing: Matched viscosities and mix ratio permit 600C processing, suitable for short shots,easily process on high/low pressure equipment.,Preparation of ONE-SHOT system,28.3,71.7,NCO=33.6% Vis=10100cps,Polyol Vis=200400cps,Properties: Random block co-polyme
14、r,good properties,increased phase mixing,more versatile formulating.,Processing: Viscosities and ratio differ but still suitable for short shots and easily process on high/low pressure equipment at 600C.Higher exothermic,suitable for RIM.,NCO%之計算務必使用,如5.6%而不是0.056.,PU預聚合物合成當量與用量之計算:,範例:欲設計以pure MDI(
15、當量=125.13)為硬鏈段,polyol-2000(當量=1000)為軟鏈段,含13.8%之PU預聚合物時, pure MDI 及polyol-2000之用量各為何?,取polyol-2000=100 g,而pure MDI之用量=X,X=91.05g,PU樹脂主劑及硬化劑之設計,範例:欲設計含3.6%之PU預聚合物的重量為100 g,index設計成95%,而OH.(硬化劑)之當量為157,則OH.(硬化劑)的使用量應為何?,(sol.): NCO=3.6%; OH.之當量為157;NCO.index=0.95,then,OH.(硬化劑)之用量計算:,Calculation of soft
16、/hard segment for PU structure,2.應力/應變模量100/200/300-ASTM D412Die“C”:這些數值表示在一定條件下，將樣品拉伸100，200和300所需的力。Die“C”用於切割測試樣品的形狀。(測試試樣要直線切割成2mm厚和6mm寬)。,1.硬度(Shore000/A/C和D)-ASTM D2240:硬度測試是將聚合物在承載的壓頭下所顯示的壓痕硬度。可從0100，沒有計量單位，在shoreA90以上，和shoreD20以下讀數重疊。,3.撕裂-ASTM D3574: 把割口的測試樣品的兩邊在拉伸測試機上夾緊，採用標準的分離速度。測試在規定的分離速度下撕裂樣品所需要的能量。,4.回彈:回彈百分數是將柱塞落到指定樣品上測其彈回的高度。此值愈大，則被測試樣品吸收的能量愈少。樣品直徑28mm,厚1213mm(還可用DIN法)，ASTM法是完全垂直的，而DIN法是從水平向垂直擺動，DIN法測試的數值一般比ASTM法測得的高。,
