聚胺酯弹性体之设计及应用

按一下以編輯母片標題樣式,按一下以編輯母片,第二層,第三層,第四層,第五層,*,高分子彈性體研討會,勤益技術學院,/,Tim shih/Aug. 18,2005,聚胺酯,(PU),彈性體之設計及應用,施 文 昌,1,Outline,Introduction,Classification of PU elastomers,Synthesis and Characterization of PU elastomers,Application of of PU elastomers,Questions and discussions,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,2,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,What is a Polyurethane?,One of the most versatile polymers ever invented.,It can be made as a soft or rigid foam or a soft or hard elastomeric strong plastic.,By changing the chemistry a infinite range of materials can be made.,3,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Isocyanate,Polyol,Urethane groups,What is a Polyurethane?,4,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,What are PU elastomers?,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,additives,etc.,5,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,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?,6,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Unique of PU elastomers,Hardness of PU elastomers from,shore 000,to,shore D-80,PU elastomers,7,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Flexible/Rigid Foam,Slabstock,Laminated,Molded,RIM,Spray,Elastomers,TPU,Cast,RIM,Spray,Fiber,Millable,ACS,Adhesive,Coating,Hot Melt,Sealant,Urethane/Urea Chemical,8,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,The definition of PU elastomers,Thermoplastic polyurethanes,-Available as granules or pellets suitable for conventional thermoplastic processing such as extrusion,calendaring or injection moulding.,Cast elastomers,-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 automotive bumper fascias,body panels plus body components for a variety of other vehicles.,9,The definition of PU elastomers,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,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 containers.,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,10,Isocyanates,11,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,The special monomer of isocyanates,12,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Isomers of monomeric MDI,13,分類,NCO,種類,優點,缺點,(環),脂,肪,族,IPDI,耐磨耗性佳、屈曲性佳,耐候性、耐熱性不佳,HDI,耐熱性佳、機械性質優,價格高、,人體毒性高,H,12,MDI,耐熱性佳、機械性質優,價格高、,人體毒性高,、反應較慢,TMXDI,人體毒性較低、柔軟性佳,耐熱性不佳、反應更慢,芳,香,族,MDI,價格低、機械性優異、反應快,黃變型,TDI,價格低、柔軟性佳、反應快,黃變型、,人體毒性高,PU,樹脂二異氰酸酯原料之特性比較,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,14,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,二異氰酸酯之相對反應速率,之比較,15,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Oligomerols,16,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,The special monomer of polyols,17,Property polyester polyether,Compression set ,Low temp. flexibility ,Oil/solvent resistance ,Hydrolytic resistance ,Heat aging ,Wear resistance ,UV./O,3,stability ,:,favorable,:,unfavorable,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Ester vs.ether for PU elastomers,18,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,1=,最好,5=,最差,性能,PTMEG,POLYESTER,PPG,拉伸強度,1,1,4,耐撕裂,1,2,4,動態力學性能,2,4,4,回彈,1,5,3,耐衝擊磨損,2,4,5,耐滑動摩擦,3,1,4,熱穩定性,(60),3,2,5,水解穩定性,1,4,1,耐油,/,溶劑,4,1,5,UV,穩定性,4,1,4,耐黴菌性,1,4,1,價格,3,2,1,Comparison of the polyol for PU elastomers,19,Cross-linkers/chain extenders-OH,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,20,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Cross-linkers/chain extendersNH,2,21,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,反應型防火劑,/,阻燃劑,22,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,2.,:Solvay Company-,High performance halogenated polyether polyol:,Hydroxyl number=200300,3,.ADEKA POLYETHERS,4.,Fyrol 6=Diethyl-N,N-bis(2-hydroxyethyl)aminomethyl phosphonate,Hydroxyl number=400500,IXOL-M125/B251,23,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Tin and Lead Carboxylic Acid Salts,Gelation,Blowing,Blowing,Isocyanate -Water,Reaction,Isocyanate-Polyol,Reaction,Gelation,Mercury,Salts,TD-33A,DMCHA,ZR-50,TD-20,DMEA,PMDETA,ZR-70,ZF-51,ZF-53,ZF-57,ZF-65,ZF-52,ZF-62,DMP,DM-70,E-40,MM-70,PM,ZF-20,ZF- 54,NMM,NEM,M-75,DMDEE,Catalysts for the NCO/OH/H,2,O reaction,24,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Lewis acid Catalysis-Tin Cat.,Metal Cat. act as Lewis acid and activate the isocyanate.,25,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Amine Cat. act as Lewis bases and activate the hydroxyl groups.,Lewis base Catalysis-Amine Cat.,26,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,The design of PU elastomer,processing characteristics may be significantly effected and equipment operations optimized by altering the way the raw materials are formulated.,*,Basic composition of an 80-85 shore A elastomer,Component,Eq. W.,Mole,Parts,W(%),Polyol-2000,1000,1.0,1000,64.5,1,4 BD,45,2.5,112.5,7.2,Pure MDI,125,3.5,437.5,28.3,27,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,The design of PU elastomer,We will now look at products made from three different technologies and formulations which all use these same basic chemicals and formula weights,*,These are:,FULL,prepolymer systems,QUASI,prepolymer systems,ONE-SHOT,systems,28,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Preparation of FULL prepolymer casting system,Component,W(%),Polyol-2000,64.5,1,4 BD,7.2,Pure MDI,28.3,RX,92.8,7.2,NCO=7.1%,Vis=20005000cps,Curative,Vis=50100cps,Properties:,Forced block co-polymer,improved resilience,higher modulus,better flex fatigue,Processing:,High prepolymer viscosity forced 80-100,0,C.processing-note wide ratio,not suitable for small,repetitive shots.,29,Preparation of QUASI prepolymer casting system,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Component,W(%),Polyol-2000,64.5,1,4 BD,7.2,Pure MDI,28.3,47.1,52.9,NCO=18.6%,Vis=3001000cps,Polyol,Vis=200400cps,RX,18.8,45.7,Properties:,Semi block co-polymer,good properties,more phase mixing,more versatile formulating.,Processing:,Matched viscosities and mix ratio permit 60,0,C processing, suitable for short shots,easily process on high/low pressure equipment.,30,Preparation of ONE-SHOT system,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Component,W(%),Polyol-2000,64.5,1,4 BD,7.2,Pure MDI,28.3,28.3,71.7,NCO=33.6%,Vis=10100cps,Polyol,Vis=200400cps,Properties:,Random block co-polymer,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 60,0,C.Higher exothermic,suitable for RIM.,31,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,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(,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,32,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,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,:,33,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Calculation of soft/hard segment for PU structure,34,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,PU,彈性體工業上常用的測試方法,2.,應力,/,應變模量,100/200/300,-ASTM D412,Die“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,0,100,，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,12,13mm(,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。,35,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,PU,彈性體工業上常用的測試方法,6.,壓縮變形,-ASTM D393:,通過持久的壓縮載荷使聚合物産生的永形變形的程度。,7.NBS,磨耗,-ASTM 1630:,有兩種類型的磨擦：滑動和衝擊。滑動是將相近表面通過橡膠表面，衝擊是通過砂粒撞擊表面測得橡膠的磨損。實際應用的磨耗是滑動和衝擊兼而有之。厚,6mm,，,4040mm,2,的樣品放到砂輪上磨擦。,8.DIN,磨耗,DIN53516:,直徑,12mm,厚,10mm,的樣品在砂輪上施力磨損。,9.DeMattia Flexer-ASTM D430,撓曲試驗,:,撓曲試驗就是産生彎曲破壞。測量開始破壞時的彎曲時間或次數。試驗在,DeMattia,疲勞機上進行。樣品尺寸,6“1”1/4“,，在試樣中心具有,0.094”,的圓度凹模，機器運行,300,周,/,分。,5.,壓縮變形,ASTM D393:,通過持久的壓縮載荷使聚合物産生的永久變形程度。,36,PU,彈性體工業上常用的測試方法,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,13.,滯後現象,:,滯後現象是指給定應力作用下産生的應變能和彈性能之間的差別。動力學測試一周，就有一部分能量以熱的形式損失掉。,11.Vicat softening(,維卡軟化點,)-ASTM D1525:,維卡軟化溫度是表徵聚合物熱軟化性的很好的方法。,12.,動態力學模量,:,在動態剪切載荷作用下材料的複合模量。等同於靜態剪切模量和損耗模量的總和。動力學模量考慮到材料變形，能量以熱的形式損失掉。,10.Ross Flexer-ASTM D1052:,另一種確定彈性體耐疲勞性的方法是測定重復彎曲的增長，測試樣品的撓曲面在直徑爲,3/8,的棒上通過,90,角自由彎曲。測試樣品的一端由試驗者抓住，另一端放在兩個輥子間，每周都以允許樣品自由彎曲運動，機械轉速爲,100,周,/,分。,37,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,DMA,DMA analysis for various product types,38,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,DMA analysis for various product types,39,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,PU,與金屬相比，有如下優點,:1,量輕,2,噪音,3,損耗及加工費用低,4,耐腐蝕。,PU,與塑膠相比具有以下優點,:1,不發脆,2,具有彈性記憶,3,耐磨。,PU,與橡膠相比具有以下優點,:1,耐磨,2,耐切割，耐撕裂,3,高承載性,4,透明，半透明,5,耐臭氧,6,可灌封，可澆注,7,硬度範圍廣。,PU,彈性體之特性,40,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Polyurethanes verses Other Elastomers:Physical Properties,Typical elastomer characteristics,Primary variables,VQM,FKM,ACM,NBR,SBR,NR,AU,EU,CR,Resilience,G,G,G,G,G,E,E,E,E,Load bearing,U,G,G,G,G,G,E,E,G,Bonding to metal,G,U,G,E,E,E,E,E,E,Compression set,E,E,G,G,G,G,G,G,G,Impact resistance,U,U,U,G,E,E,E,E,E,Abrasion resistance,U,G,G,E,E,E,E,E,E,Radiation resistance,G,G,U,G,G,G,G,E,G,Oxidation resistance,E,E,E,G,G,G,E,E,G,Ozone resistance,E,E,E,U,U,U,E,E,E,Water resistance,G,G,G,E,E,E,G,E,E,41,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,VQM-Silicone,FKM-Fluoroelastomers,ACM-Polyacrylate,NBR-Nitrile Butadiene,NR-Natural Rubber,AU-Polyester Urethane,EU-Polyether Urethane,CR-Neoprene,Polyurethanes verses Other Elastomers:Physical Properties,E=Excellent,G=Good,U=Unsatisfactory,42,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Polyurethanes verses Other Elastomers:Use Temperature,USEFUL TEMPERATURE RANGE,OF COMMERCIAL ELASTOMERS,-200,-100,0,100,200,300,400,500,0,20,40,60,80,100,FFKM,FKM,Polyacrylate,Polyurethane,Polysulfide,NEOPRENE,Silicones,EPDM,BR,CR,SBR,NR,NBR,Temp.(,0,F),43,高分子彈性體研討會,勤益技術學院,/,材料與化學工程研究所,Tim shih/Aug. 18,2005,Questions and Discussions?!,44,Thank You,45,