Shanghai Daoqin Plastics Co., Ltd.

injection molding processing very more parts use to polyurethane ester,现 in 我们会 use shallow introduction 形状记忆 polyurethane ester elastomer polyurethane ester elastomer is types polymer/macromolecule combined formed material, tool has excellent machine physical properties, relatively good tensile strength, modulus, wear resistance and resistant property, widely used in 国民经济 各 field/area. polyurethane ester elastomer separation 子链段 generally is soft and hard formed, soft usually polyester, polyether and polyolefin more alcohol formed; hard usually expand agent and acid ester and other raw materials formed. due to polyurethane ester elastomer in soft hard 段 不 versus property, tool has micro versus separation structure, through 改变材 material raw materials and chemical formed, expand agent types type, soft versus for separation quality and other, to 改变材 material property 质 目. 形状记忆 polyurethane ester elastomer is tool has types different 玻璃化转变 temperature degree polymer/macromolecule material polymerization formed copolymer, is can outer ring 境 变化(如 temperature degree, force, electrical magnetic and solvent agent and other)而 for its material mechanical properties (如形状, and and other)进行 adjustment, to its setting 状态, therefore 形状记忆材 material is can material or machine material. combined formed 形状记忆 polyurethane ester elastomer design requirements main/primary has 3点: (1) soft versus and hard versus micro versus separation need separation, separation degree high, 形状记忆 property can good; (2) hard content 适当, to material crosslinked function; (3) soft 段 玻璃化转变 temperature degree and melting point relatively high, in room temperature can 够冻结 tensile 形变. 1 实验部 separation 1.1 实验 raw materials and specifications polyester more alcohol PES-3, Mn=2000, polyester more alcohol PES-4, Mn=3000; polyester more alcohol PES-5, Mn=5000, cationic chemical industry has company; 2,4-甲苯二异氰 acid ester (TDI), industrial grade, Japan polyurethane ester industrial company; 1,4- butanediol (BDO), industrial grade, Mitsubishi chemical 株式会社, antioxidant 1010, industrial grade, Taiwan di company; outer absorption agent, industrial grade, Domestic. 1.2 polyester more alcohol combined formed process will more acid and more alcohol 准确计 amount, add 入不锈钢 reaction in add hot rise temperature 并通N2保护, reaction temperature degree rise 至140℃时, reaction system 开始出 water, control water speed degree and 回流塔塔顶 temperature degree, at atmospheric pressure temperature degree in 100-102℃ between relatively good, rear will inner temperature degree slow rise 至160-180℃并保 temperature 2-3 h, main/primary is adjustment polyester more alcohol versus for separation quality distribution. rear again will inner temperature degree slow rise 至220-230℃, 当理论出 water amount basic formed, temperature 2h, 取样测 acid value, value and water separation and other indicators combined rear, 开始抽 true 空, improve/increase reaction plant/unit true degree, to most large true degree 约需4 h. high true 空期间, 每间隔一段 time 取样测 acid value, value and water separation, inner temperature degree maintain 不变, to indicators combined rear 才开始 drop temperature material, most product is white wax solid or viscous liquid 体. 1.3 thermoplastic polyurethane (TPU) process through 连续本体 method combined formed polyurethane ester 胶粒, rear through film, injection molding, calendering made formed various products. process: in has electrical 动搅拌 plant/unit, add hot plant/unit, temperature degree and true 空入口 三口烧 bottle in add 入准确计 amount more alcohol add hot rise temperature 至100-120℃, in true degree small 于0.67 kPa lower, water 1-2 h, 取样测 water separation quality separation small 于0.1%时 drop temperature, temperature degree in 60-90℃ between 时, add already drying amount expand agent, antioxidant and outer absorption agent and other additives, make its and more alcohol full uniform mixed combined, rear add 入异氰 acid ester, fast speed 搅拌并抽 true 空脱泡3-10 min. bubbles basic 抽完时停止搅拌, understanding remove true 空, already preheating coating has demolding agent mold in, 于110-120℃ 烘箱 in solid 化4h left right, demolding, in room temperature 放置1周, rear 测各项 property can indicators. 1.4 analysis testing water separation 按GB 12008.6-89测定; acid value 按HG/T2708-95测定; value 按HG/T 2709-95测定. 形状记忆 property can testing using/adopting 形状记忆 alloy testing methods, will sample 置于90℃ hot water in add outer force make sample bending formed is 90 degree 角, maintain 1 min, rear will sample speed cooling 至0℃, maintain 1 min, again outer force, sample deformation 状态, testing 时, will deformation sample rise temperature in, rise temperature speed degree is 2℃/min, amount 并记录 sample degree is △θ, can sample 形变回复 rate is: 形变回复 rate (%)=△θ/90×100%, meanwhile can 形变回复 rate and sample temperature degree between 曲线图. 2 结果 and 讨论 2.1 polyurethane ester elastomer crystallization property separation micro versus separation 离直接 effect/influence polyurethane ester elastomer 结 晶 property, for material property can has relatively large effect/influence. 形状记忆 polyurethane ester elastomer soft and hard formed, soft versus and hard versus has 序排列 or random 状态. 形状记忆 function main/primary through soft crystallization -熔 melt achieve, therefore soft crystallization property can for polyurethane ester elastomer maintain, 形变恢复 speed degree and property can and other has non obvious effect/influence.

polyester more alcohol versus for separation quality for products property can effect/influence.   versus for separation quality for property can effect/influence PBA Mn hard quality separation 数/% Tg/℃ crystallization degree /% 2000 17.98 -39.78 2000 26.00 -25.39 2000 32.57 -19.34 3000 12.75 -44.87 30.7 3000 18.98 -35.00 28.7 3000 24.36 -25.38 24.8 5000 8.06 -62.98 35.1 5000 12.32 -48.31 29.5 5000 16.19 -39.28 24.8 polyurethane ester elastomer in, soft versus for separation quality relatively low usually crystallization, has in 一特定 临界 versus for separation quality scope/range inner, soft crystallization degree increase, soft versus for separation quality increase large, its crystallization degree increase high. versus for separation quality increase high, its crystallization degree 趋于平缓. table/sheet 1 can 看出PBA versus for separation quality is 2000时, its made polyurethane ester elastomer, has crystallization phenomenon, 当PBA versus for separation quality is 3000 above 时, polyurethane ester elastomer in obvious in soft crystallization phenomenon; meanwhile its crystallization degree hard content increase reduce. therefore, in 以PBA is soft combined formed polyurethane ester elastomer in, soft versus for separation quality large or and other 于3000时, tool has 形状记忆 function. hard versus crystallization for 形状记忆 polyurethane ester elastomer shrinkage speed degree and shrinkage force has relatively large effect/influence, hard crystallization degree large, polyurethane ester elastomer shrinkage speed degree and shrinkage force large, hard content increase 时, crystallization degree increase, versus 应 形变状恢复 temperature degree improve/increase. 2.2 more alcohol versus for separation quality for 形变回复 rate effect/influence in 形状记忆 polyurethane ester in, 形变回复 rate more alcohol versus for separation quality effect/influence, soft versus for separation quality large, versus separation degree high, soft versus inner solvent understanding hard content low, make polyurethane ester easy 发生塑 property 形变. 如图1(略) 示.

more alcohol versus for separation quality for 形状记忆 polyurethane ester elastomer rate has relatively large effect/influence, more alcohol versus for separation quality small 于2000时, polyurethane ester elastomer rate can to 30%, versus for separation quality large 于3000时, especially to 5000时, 形状记忆 function to 99% left right. therefore in combined formed 形状记忆 polyurethane ester elastomer 时, polyester more alcohol versus for separation quality small 于3000 relatively is 适宜. this is is for/regarding structure polyester more alcohol, versus for separation quality increase, crystallization property can increase, combined formed polyurethane ester elastomer crystallization property increase large, micro versus separation degree large, 形状记忆 function strong/high. due to polyether more alcohol 玻璃化转变 temperature degree relatively low, combined formed polyurethane ester elastomer in relatively low temperature degree lower tool has good 形状记忆 function, polyether more alcohol combined formed polyurethane ester elastomer material versus solvent property relatively good, commonly used combined formed medical grade 形状记忆 polyurethane ester. 2.3 expand agent effect/influence expand agent is made polyurethane ester elastomer commonly used types function property additives, features is versus for separation quality small, short, reaction property active 泼. combined formed 形状记忆 polyurethane ester elastomer commonly used to expand agent is structure 规整 线 property binary alcohol type, ethylene glycol, 1,4- butanediol and alcohol and other. is this binary alcohol and 二异氰 acid ester reaction formed polyurethane ester elastomer in normal temperature lower 几乎完 full crystallization, and in melt processing separation understanding.

due to ethylene glycol has 2 C原子, combined formed polyurethane ester elastomer crystallization property relatively 差, 而1,4- butanediol and alcohol combined formed polyurethane ester elastomer hard structure 规整, crystallization degree high, micro versus separation degree relatively large, from its hardness, tensile strength, strong/high degree and strong/high degree and other force property can relatively large, crystallization is ethylene glycol < butanediol <己二 alcohol. is improve/increase polyurethane ester elastomer chemical crosslinked degree, improvement 形状记忆 function and machine force property can, can using/adopting 一 三羟基 more alcohol 如三羟甲基丙烷 as expand agent. 2.4 hard content for 形变回复 rate effect/influence hard 段 组 formed and content 决定形状记忆 polyurethane ester elastomer heat deflection temperature (HDT) and shrinkage speed degree fast slow, as is 形状记忆材 material polyurethane ester elastomer, its soft crystallization melting point and 玻璃化转变 temperature degree and hard melting point 差别应足够 large, can ensure polyurethane ester elastomer in its high elastic property 态实施 tensile, expand and other processing, still tool has relatively high strong/high degree and tough property. has ring hard structure, its hardness, strong/high degree and modulus comparison large, melting point relatively high, and soft melting point versus relatively 远, has polyurethane ester elastomer processing. aliphatic 二异氰 acid ester formed hard structure, melting point comparison low, 不适于形状记忆 polyurethane ester elastomer processing process requirements, generally relatively less use. hard content for 形变回复 rate effect/influence 见图2(略). 由图2(略) can 看出, hard content relatively low 时, polyurethane ester elastomer rate comparison low, hard content to or large 于20%时, has relatively high 形变回复 rate. this is is, has hard content relatively large 时, hard has can can poly formed hard micro 区, to material crosslinked function. 3 形状记忆 polyurethane ester elastomer application 形状记忆 polyurethane ester material is in recent years development new type polymer/macromolecule combined formed material, widely used in electronics power/electricity, aviation aerospace, medical, packaging, machine engineering and active day commonly used product and other 方面, has vast application outlook/prospects. 形状记忆 polyurethane ester elastomer 形变回复 rate relatively large, temperature degree can through structure 变化自由 adjustment, can through injection molding, extrusion or calendering and other processing methods processing. use made as various device, widely used in 牙科, and other, can used for construction filler 密封材 material and other, in automotive 保险杆, 运动保护 device and other industry has relatively large application. currently 形状记忆 polyurethane ester elastomer in automotive, aviation and other field/area has use. polyurethane ester elastomer can use solvent agent solvent understanding processing, made 备形状记忆 polyurethane ester viscous agent, use made as 形状记忆 coating material and other. according to polyurethane ester elastomer anti water wet function made as clothing/apparel, according to polyurethane ester elastomer 玻璃化转变 temperature degree and 形状记忆 function made outer inner and other, for/regarding easy deformation belt/tape, clothing/apparel and other has application. 4 结束语 形状记忆 polyurethane ester elastomer versus for separation quality large or and other 于3000 线 type polyester more alcohol is soft 段, expand agent and acid ester is hard 段, tool has structure, flexible crystallization -熔 melt versus 转变而 tool 备形状记忆, has hard content large certain value 时, can to material crosslinked function, tool has shrinkage force and relatively fast 形变回复 rate. already combined formed in -30℃～70℃ scope/range inner selection 形变恢复 temperature degree polyurethane ester elastomer material, widely used in 国民经济 各 field/area.