Shanghai Daoqin Plastics Co., Ltd.

 1. PET brief introduction  
terephthalic acid ester (PET) is types property can excellent thermoplastic property plastics , its melt temperature degree and 玻璃化转变 temperature degree relatively high, tool has good heat resistant property, resistant creep property, fatigue resistance, resistant scratch and abrasion loss property, electrical insulation property and chemical resistant product property, by used for combined formed fiber, film , engineering plastics , and day use product and other field/area. PET price low 廉, 20世纪60 year 代便开始 as is engineering plastics application development, currently already used for automotive, electrical machine, electronics, use electrical appliances and machine 械 and other industry.  
PET因 separation in rigid property ring in and flexible carbon 烷链段 short, its crystallization (均 versus formed 核) speed rate slow, in melt fast speed cooling (如 injection molding) process in crystallization degree low, formed products force strong/high degree, rigid property (dimensional stability) and heat resistant property 差. in injection molding processing in, usually 不 不 long time maintain mold temperature degree 于100℃ above, in versus for relatively slow cooling speed rate lower to 予足够 time let PET melt separation crystallization, therefore processing can consumption high, cycle long, production cost high, made PET in automotive, electrical and construction and other field/area engineering application.
therefore, need separation 发挥PET high property can, low cost advantages, must for its crystallization modified, make its can low temperature fast speed molding, crystallization degree versus for relatively high, most can improvement methods is add crystallization nucleating agent or crystallization promote agent.  
2. PET formed and crystallization  
PET separation tool has relatively high structure property, tool relatively strong/high crystallization can force, is due to its separation rigid property large, 玻璃化 temperature degree high, retardant its separation 子链 运动, therefore PET is types semi crystallization property material 质, in melting point and 玻璃化转变 temperature degree between scope/range inner PET都 can formed crystallization, melt if speed cooling, formed transparent 无定形 structure. 无定形PET density is 1.33g/cm3, full crystallization PET density is 1.445g/cm3, and other polymer 一样PET can separation crystallization, very difficult to full crystallization degree.  
different high poly material crystallization speed degree has is is separation expand dispersion 砌入晶格 需 active can different. usually, structure simple, for property high, crystallization speed degree large. polyethylene (PE) structure simple, for property good, crystallization speed degree fast, make in liquid gas lower cold method to full 无定形态. 而PET large separation upper has -C-O-基 make for property decline, upper also has ring, make separation rigid property increase large, for 链段运动起 to retardant function, effect/influence separation expand dispersion speed degree, crystallization speed degree ratio slow more. make and is polyester PBT versus ratio, crystallization speed degree slow more, this main/primary is is PBT separation upper ratio PET more 两 亚甲基, make PBT flexible ratio PET good, crystallization speed degree ratio PET fast.  
high poly material formed 核包括初 grade formed and grade formed 核. its in grade formed also separation is versus formed and versus formed types. versus formed melt separation 子链段自身 hot generate has 序排列 链束 or 折叠链 as is 晶核, in crystallization process in is 不断生 formed, therefore development formed large small 不一, temperature degree usually comparison low;异 versus formed is outer 杂质, polymer 晶体, is add dispersion small pellets or container is in 心, polymer as has 序排列而形 formed 晶核, versus formed temperature degree effect/influence relatively small, can in relatively high temperature degree lower 发生. therefore, outer add nucleating agent (promote versus formed 核) can significantly promote PET crystallization.  
most rear, polymer crystallization and low separation crystallization has very more different. polymer crystallization remove 受本身 structure effect/influence outer, also need very more outer factors effect/influence, ratio temperature degree, molecular weight and molecular weight distribution, additives and other factors effect/influence.  
for/regarding PET而言, molecular weight large PET熔 melt temperature degree high, crystallization property can 也越差;而 for/regarding grade PET, increase extrusion temperature degree and add 入 nucleating agent 则 has its 晶核 生 long, can significantly improvement most product force property can; remove outer, in selection specific PET grade 时, low alcohol (DEG) content PET tool has more good crystallization property can; due to industrial combined formed 时, generally need use catalytic agent , main/primary has Mn, Zn, Pb, Cd, Mg, Ca, Ce, Co, Li, Na, and Sb and other, tool has relatively low melting point catalytic agent 则 is active property most high nucleating agent, can as is selection standards.  
3.  nucleating agent for PET crystallization modified  
nucleating agent improvement PET crystallization property can main/primary is through to versus formed function, system in if in nucleating agent, melt cooling 时 生 formed small more, versus generate internal stress small but also dispersion, from improvement products application property can.  
therefore, through add nucleating agent can to below/following 目:  
improve/increase  PET  crystallization (formed 核) temperature degree, long crystallization temperature degree scope/range; 
抑 made 导致 PET 脆裂 large 球晶形 formed; 
诱导 generate small 而规整 crystallization structure.  
nucleating agent types type very more, main/primary separation is has machine nucleating agent, machine nucleating agent, polymer/macromolecule nucleating agent and composite/compounding nucleating agent and other.  
（1）无 machine nucleating agent  
无 machine type nucleating agent basic upper is polymer commonly used machine filler, machine type nucleating agent in crystallization process in versus 当于第二 versus small pellets in 于PET in melt in, in high temperature this pellets 处于不熔状态, in drop temperature process in, PET separation 子链就以 this pellets is in 心, to pellets upper as has 序排列而形 formed product 核. therefore, this small separation machine material as is versus nucleating agent 时, reduce PET形 formed product 核时 需 active can, for rear crystallization long process, 即PET separation 子链段 by 吸附于晶核 surface 而进入晶格 process effect/influence large.  
但 is due to machine filler and PET基体 interface combined can force comparison 差, if in melt conditions lower 直接 无 machine material and PET mixed combined 并不容 easy in PET基体 inner dispersion uniform, but also easy 发生团 poly, therefore, machine filler generally need surface modified 处理.  
Common PET无 machine filler type nucleating agent is viscous 土, oxidation material and hydrogen oxidation material, machine salt, in addition also has Si3N4, carbon nano tube/pipe /石墨, zinc powder and 叶腊石 and other.  
viscous type nucleating agent  
蒙脱土 is types structure machine material, this type of material raw materials 丰富, price 便宜, but also add in polymer in also can has improve/increase material retardant property can, and PET composite/compounding rear can made good 封装材 material, remove 蒙托土, its it viscous material 如 high 岭土, 累托土 and other, can made dispersion good nano composite/compounding material, but also can has improve/increase PET crystallization, hot 学, retardant property can.  
usually using/adopting melt methods will 蒙脱石(MMT) add to PET in. 例如, will chlorine 代十六烷-三苯基膦(CHDTPP) as is MMT modifier , formed OMMT, again melt can made PET / OMMT nano composite/compounding material, table/sheet 明, made PET/OMMT composite/compounding material crystallization speed rate is pure PET 4-5倍, in injection molding can large degree reduce mold temperature degree, 蒙脱土 quality separation is 1%时, composite/compounding material mold temperature degree can drop 至约80℃, pure PET必 must in 130%; not only 如此, PET/OMMT in add nucleating agent and toughening agent 情况 lower, and glass fiber (GF) composite/compounding can to excellent force property can and heat resistant property engineering plastics .  
water slip 石(HT)也 can used for PET crystallization modified, research table/sheet 明, 当HT quality separation is 0.5%-1.0%时, HT as is PET crystallization nucleating agent relatively 佳; using/adopting di screw melt blending method made PET /凹凸 rod 土(AT) composite/compounding material crystallization property can obvious to improvement.  
oxidation material type nucleating agent  
SiO2 nucleating agent is use most more machine filler nucleating agent 之一. as is PET versus nucleating agent, its add amount is 2% left right formed 核效果 most good, add amount is 约0 .2%时, PET comprehensive force property can most 佳. add and other quality separation 数时, SiO2 relatively MMT for PET versus formed function need more good, and large more machine nucleating agent similar, SiO2添 add amount more in PET基体 in poly, 不利于PET crystallization. therefore, is make SiO2达 to more good formed 核效果, must improve/increase its and PET基体 versus property and dispersion property. dispersion good SiO2因 formed more made PET球晶 生 long, therefore in improve/increase PET crystallization speed rate meanwhile increase its transparent degree.  
through 二阶熔 melt blending method can made 备PET/ nano oxidation titanium composite/compounding material, research table/sheet 明, nano TiO2 pellets in PET基体 resin in tool has nucleating agent function, can obvious improve/increase resin crystallization temperature degree and crystallization speed rate. nano Ti02 for PET crystallization function make its for generate obvious reinforcement function, in 3% content scope/range inner material and tensile strength increase 约25%; a small amount of nano TiO2 can make PET tough property has 一定程 degree increase, 1% content scope/range inner material notched impact strength increase 约10%;而 in relatively high content lower, nano Ti02 for PET tough property loss relatively is obvious. composite/compounding material in Ti02 content is 1%时 tool has relatively good comprehensive force property can.  
nano MgO for PET也 has very good formed function, research table/sheet 明, use nano MgO as is nucleating agent 时, in 60℃ or 80℃ mold temperature lower injection molding. Sample impact strong/high degree, flexural strength, most large bending force, bending elastic property modulus ratio use nano SiO2 as nucleating agent good. in mono add nano MgO lower, mold temperature separation is 60℃ and 80℃时, Sample tensile strength, impact strong/high degree, bending elastic property modulus 差异不 large. in 60℃ mold temperature lower, injection molding process in products viscous 贴, warpage, can demolding. this add nano nucleating agent rear. has can can make injection molding mold temperature degree 进一步 reduce.  
无 machine salt type nucleating agent  
carbon acid 钙, acid 钡, slip powder, separation 子筛(MMS) and heavy and other is commonly used machine salt type nucleating agent. its in, slip powder relatively carbon acid 钙, viscous 土, SiO2 and TiO2 for PET formed 核效果 need good, add amount is 5%时 crystallization property can most excellent.  
add quality separation is 1% nano BaSO4就 can make PET crystallization temperature increase 6.8℃, 说明BaS04起 to relatively good versus formed 核效果. BaSO4 for PET formed 核效果随BasO4添 add amount increase has most amount, its quality separation is 2%时, PET/ nano Bas04 composite/compounding material force property can most excellent. comparison pure PET Sample, its tensile strength and flexural strength separation improve/increase 16% and 18.6%, tensile elastic property modulus and bending elastic property modulus separation improve/increase 32% and 14%, notched impact strength has decline.  
（2） has machine small separation nucleating agent  
has machine type nucleating agent main/primary is 一元梭 acid Na, Li, Ba, Mg, Ca salt, 安息香 acid Na, K, Ca salt, aromatic 羟基磺 acid salt, has machine combined material Mg, Zn salt, its in relatively good is acid salt and acid salt. 例如, 含钠离子 polymer by is is PET industrial upper most has nucleating agent, its in 商业化 PET nucleating agent lower table/sheet 示.  

has machine type nucleating agent formed mechanism main/primary and its chemical structure has 关, this nucleating agent in to versus formed meanwhile, also to chemical formed function, from not only improve/increase formed can force also improve/increase 晶核 生 long speed degree, is it in provide versus meanwhile reduce PET separation expand dispersion 进入晶格 expand dispersion can.  
(取代)苯甲 acid and hard acid and its it versus nucleating agent different, in high temperature lower it can solvent 于PET melt, PET and upper acid salt in high temperature lower extrusion 时会发生 chemical reaction, formed PET-COONa material 质, in belt/tape has 离子端基 PET melt between formed 离子簇, 离子簇 will formed is nucleating agent in melt in to formed function, separation 子链规整排列 fast speed crystallization;另一方面, due to reaction process in separation fracture, local versus for separation quality reduce, from local crystallization add fast promote system crystallization, this 两方面共同 function make crystallization speed rate large improve/increase. 但苯甲 acid and PET hydrophilic 核取代 reaction, formed resin degradation. types can methods is add expand agent 以补充PET molecular weight, commonly used expand agent main/primary ring oxidation material, acid ester, acid 酐, 噁唑啉 type and other.  
research table/sheet 明, add acid nucleating agent can make PET crystallization 诱导期 shrink short, crystallization active can decrease small, crystallization speed degree add large;但随添 add amount increase make crystallization degree reduce, 不利于 blending material property can stability, therefore, acid used for PET时, must attention/notes use amount, meanwhile also and its it modifier 配 combined use.  
remove outer, long saturated and 脂肪链(C26-C32) acid is very good PET nucleating agent, research table/sheet 明, acid nucleating agent 烷基链越 long, 则PET crystallization speed rate fast, but also tool has more long carbon 烷链段 煤褐 acid formed can force relatively (取代)苯甲 acid more good.