高分子材料加工成型第二章添加剂.ppt

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1、高分子材料加工成型第二高分子材料加工成型第二章添加剂章添加剂现在学习的是第1页，共36页第一节第一节 稳定剂稳定剂 StabilizerStabilizer 老化老化aging：高分子材料在使用和成型加工过程中受高分子材料在使用和成型加工过程中受内在因素，如分子结构、成型加工时选用内在因素，如分子结构、成型加工时选用的添加剂及其用量、成型加工方法等；的添加剂及其用量、成型加工方法等；外界因素如物理（光、热、应力、电场、外界因素如物理（光、热、应力、电场、射线）、化学（氧、臭氧、重金属离子、射线）、化学（氧、臭氧、重金属离子、化学介质）和生物因素（微生物、昆虫等）化学介质）和生物因素（微生物、昆

2、虫等）的作用下，发生表面状态、物理机械性能的作用下，发生表面状态、物理机械性能和结构的变化，甚至失去使用价值。和结构的变化，甚至失去使用价值。现在学习的是第2页，共36页老化的表现形式老化的表现形式老化的表现形式老化的表现形式modalitymodality外观外观appearance物理性能物理性能physical performance机械性能机械性能mechanical performance电性能电性能electrical performance结构结构structure老化的原因老化的原因老化的原因老化的原因reasonreason光光光光lightlight、热、热、热、热heat

3、heat、氧、氧、氧、氧oxygenoxygen是主要因素是主要因素是主要因素是主要因素自动氧化自动氧化自动氧化自动氧化+热分解热分解热分解热分解聚合物降解聚合物降解聚合物降解聚合物降解automatic oxidation+heat decompositionautomatic oxidation+heat decompositionpolymer degradationpolymer degradation 现在学习的是第3页，共36页防止或抑制老化的方法防止或抑制老化的方法引入带有功能性基团的单体共聚改性引入带有功能性基团的单体共聚改性可采用加稳定剂可采用加稳定剂 （此为主要方法）（此为

4、主要方法）对活泼端基作消活处理对活泼端基作消活处理现在学习的是第4页，共36页StabilizerStabilizerPoly(vinyl chloride)is relatively unstable to Poly(vinyl chloride)is relatively unstable to heatheat and and lightlight.Thermal initiation involves loss of a chlorine.Thermal initiation involves loss of a chlorine atom adjacent(atom adjacent

5、(邻近的邻近的邻近的邻近的)to some structural abnormality)to some structural abnormality(变态变态变态变态,畸形畸形畸形畸形,异常性异常性异常性异常性)which reduces the stability of)which reduces the stability of the C-Cl bond,such as terminal unsaturationthe C-Cl bond,such as terminal unsaturation（不（不（不（不饱和现象）饱和现象）饱和现象）饱和现象）.The chlorine rad

6、ical so formed abstracts a.The chlorine radical so formed abstracts a hydrogen to form HCl;the resulting chain radical then hydrogen to form HCl;the resulting chain radical then reacts to form chain unsaturation with regeneration of a reacts to form chain unsaturation with regeneration of a chlorine

7、 radicalchlorine radical.现在学习的是第5页，共36页The reaction can also be initiated by ultraviolet light which is absorbed at unsaturated structures with liberation of an adjacent chlorine atom.In the presence of oxygen,both chain reactions are accelerated,and ketonic(酮酮)structures are formed in the chain.现在学

8、习的是第6页，共36页一、热稳定剂一、热稳定剂主要用于主要用于PVC塑料中塑料中1、PVC稳定性的影响因素稳定性的影响因素influencing factor温度温度temperature氧氧oxygen光光light型号型号type脱出的脱出的HCl现在学习的是第7页，共36页2、热稳定剂的作用、热稳定剂的作用补救和预防补救和预防中和中和HCl取代不稳定氯原子取代不稳定氯原子钝化杂质钝化杂质防止自动氧化防止自动氧化与不饱和部位反应与不饱和部位反应破坏碳正离子盐破坏碳正离子盐现在学习的是第8页，共36页Stabilizers are almost invariably added to imp

9、rove the heat and light stability of the polymer.Metallic salts of lead(铅盐铅盐),barium(钡钡),tin（锡）（锡）,or cadmium（镉）（镉）are used.Oxides（氧化物）（氧化物）,hydroxides（氢氧化物）（氢氧化物）,or fatty-acid salts（脂肪酸盐）（脂肪酸盐）are most effective.Epoxy plasticizers aid materially in stabilizing the resin.Free radical acceptance app

10、ears to be a prominent mechanism of stabilization.HCl acceptors have been used.现在学习的是第9页，共36页3 3、热稳定剂的种类及选择、热稳定剂的种类及选择、热稳定剂的种类及选择、热稳定剂的种类及选择the kind of heat stabilizers and how to choicethe kind of heat stabilizers and how to choice常用热稳定剂常用热稳定剂常用热稳定剂常用热稳定剂in common usein common use，表，表，表，表2-1(P702-1

11、(P70）：）：）：）：铅盐铅盐铅盐铅盐salts of leadsalts of lead硬脂酸盐硬脂酸盐硬脂酸盐硬脂酸盐stearatestearate有机锡有机锡有机锡有机锡organic tinorganic tin复合稳定剂复合稳定剂复合稳定剂复合稳定剂compound stabilizerscompound stabilizers稀土稀土稀土稀土rare earth stabilizersrare earth stabilizers环氧化合物等环氧化合物等环氧化合物等环氧化合物等Epoxy stabilizersEpoxy stabilizers选择热稳定剂的依据（选择热稳定剂的依

12、据（选择热稳定剂的依据（选择热稳定剂的依据（P71P71）：）：）：）：the basis to choice heat stabilizersthe basis to choice heat stabilizers现在学习的是第10页，共36页二、抗氧剂（防老剂）二、抗氧剂（防老剂）antioxidant1、自动氧化老化、自动氧化老化概念：高分子材料在制备、成型加工和使用概念：高分子材料在制备、成型加工和使用过程中会发生氧化反应。这种反应通常发生过程中会发生氧化反应。这种反应通常发生在室温至在室温至150之间，按典型的链式自由基理之间，按典型的链式自由基理进行，具有自动催化特征进行，具有自动

13、催化特征 机理：机理：P73臭氧老化：取代基、空间位阻、立体化学等臭氧老化：取代基、空间位阻、立体化学等 结构因素结构因素 现在学习的是第11页，共36页2、抗氧剂的作用及分类、抗氧剂的作用及分类作用：抑制作用：抑制inhibiting或延缓或延缓staving高分子高分子材料自动氧化速度材料自动氧化速度auto-oxidizing-rate类型：类型：链终止型链终止型预防型预防型 过氧化物分解剂过氧化物分解剂过氧化物分解剂过氧化物分解剂 金属离子钝化剂金属离子钝化剂金属离子钝化剂金属离子钝化剂用量用量塑料中塑料中 0.1-1%橡胶中橡胶中1-5份份现在学习的是第12页，共36页抗臭氧剂和抗氧

14、剂的区别抗臭氧剂和抗氧剂的区别抗臭氧剂的分类抗臭氧剂的分类物理防护物理防护化学防护化学防护3、常见的抗氧剂、常见的抗氧剂P75表表2-4，较多的是酚类和对苯二胺类，较多的是酚类和对苯二胺类现在学习的是第13页，共36页4、抗氧剂的选用、抗氧剂的选用加入方式加入方式材料合成后立即加入材料合成后立即加入在材料成型加工中加入在材料成型加工中加入选用原则选用原则色污现象色污现象稳定性稳定性溶解性和乳化性溶解性和乳化性相容性和迁移性相容性和迁移性挥发性和毒性挥发性和毒性现在学习的是第14页，共36页三、光稳定剂三、光稳定剂高分子材料的光降解作用及分类高分子材料的光降解作用及分类聚烯烃的光氧化作用聚烯烃的

15、光氧化作用光稳定剂的作用和分类光稳定剂的作用和分类按其作用机理分为：按其作用机理分为：光屏蔽剂光屏蔽剂紫外线吸收剂紫外线吸收剂猝灭剂猝灭剂自由基捕捉剂自由基捕捉剂常见品种：常见品种：P80表表2-7四、生物抑制剂（自学）四、生物抑制剂（自学）现在学习的是第15页，共36页 第二节第二节第二节第二节 增塑剂增塑剂增塑剂增塑剂 plasticizersplasticizers一、作用与分类一、作用与分类一、作用与分类一、作用与分类增塑剂能使高分子材料制品塑性增加，改进其柔韧性、增塑剂能使高分子材料制品塑性增加，改进其柔韧性、增塑剂能使高分子材料制品塑性增加，改进其柔韧性、增塑剂能使高分子材料制品塑

16、性增加，改进其柔韧性、延伸性和加工性延伸性和加工性延伸性和加工性延伸性和加工性Plasticizers are added to plastics to improve its Plasticizers are added to plastics to improve its workability,flexibility,distensibility,processability,workability,flexibility,distensibility,processability,and to reduce the brittleness(and to reduce the britt

17、leness(脆性脆性脆性脆性)of the product.)of the product.This is achieved by lowering the glass transition This is achieved by lowering the glass transition temperature below room temperature,thus temperature below room temperature,thus achieving a change in properties from those of a achieving a change in pr

18、operties from those of a hard brittle,glasslike solid to those of a soft,hard brittle,glasslike solid to those of a soft,flexible,tough material.flexible,tough material.现在学习的是第16页，共36页按作用方式有外增塑和内增塑按作用方式有外增塑和内增塑外增塑外增塑external plasticization 低分子量低分子量化合物或聚合物化合物或聚合物 External plasticization is achieved t

19、hrough incorporation of a plasticizing agent into a polymer through mixing and/or heating.内增塑内增塑internal plasticization 共聚树脂共聚树脂Internal plasticization can be produced through copolymerization giving a more flexible polymer backbone or by grafting another polymer onto a given polymer backbone，alteri

20、ng the molecular structure of the polymer 现在学习的是第17页，共36页按塑化效果按塑化效果塑化效率塑化效率 plasticizer efficiency 主增塑剂主增塑剂primary plasticizer辅助增塑剂辅助增塑剂secondary plasticizer增量剂增量剂incremental agent现在学习的是第18页，共36页二、增塑剂的性质：二、增塑剂的性质：1、与树脂的相容性、与树脂的相容性compatibility 相容性的衡量相容性的衡量measurement溶解度参数溶解度参数solubility data相互作用参数相互

21、作用参数interaction data特性黏度特性黏度viscosity 现在学习的是第19页，共36页2、加工性、加工性凝胶化速度的影响凝胶化速度的影响热稳定性的影响热稳定性的影响粘性和润滑性的影响粘性和润滑性的影响现在学习的是第20页，共36页3、对材料性能的影响、对材料性能的影响玻璃化温度降低玻璃化温度降低耐寒性提高耐寒性提高力学性能力学性能电性能电性能老化性能老化性能毒性等毒性等 现在学习的是第21页，共36页三、品种（三、品种（P84表表2-9）The selection of a particular plasticizer depends to a large extent u

22、pon empirical results rather than theoretical predictions.types of plasticizers in common use:常用的主要有：常用的主要有：DOP di-2-ethylhexyl phthalateTCP tricresyl phosphateDBS Dibutyl sebacate现在学习的是第22页，共36页四、选用原则四、选用原则1 1、相容性和稳定性的协调、相容性和稳定性的协调、相容性和稳定性的协调、相容性和稳定性的协调 compatibility and compatibility and permanenc

23、epermanenceThe plasticizer must be miscible with the polymer.The plasticizer must be miscible with the polymer.一般要求溶解度参数相近，为了稳定性要求分子量大些。一般要求溶解度参数相近，为了稳定性要求分子量大些。一般要求溶解度参数相近，为了稳定性要求分子量大些。一般要求溶解度参数相近，为了稳定性要求分子量大些。在实际使用中，以能混进去、不析出来为准则在实际使用中，以能混进去、不析出来为准则在实际使用中，以能混进去、不析出来为准则在实际使用中，以能混进去、不析出来为准则2 2、使用性能、

24、使用性能、使用性能、使用性能useuse3 3、加工性能、加工性能、加工性能、加工性能processprocess4 4、成本、成本、成本、成本priceprice5 5、并用、并用、并用、并用mon.6 6、用量、用量、用量、用量dosagedosage现在学习的是第23页，共36页Plasticizers should be relatively nonvolatile,nonmobile,inert,inexpensive,nontoxic,and compatible with the system to be plasticized.现在学习的是第24页，共36页 第三节第三节 润滑

25、剂润滑剂lubricantLubricants are added to improve the flow characteristics of a material during its processing.They operate by reducing the melt viscosity or by decreasing adhesion between the metallic surfaces of the processing equipment and the material being processed.现在学习的是第25页，共36页一、一、作用与分类作用与分类作用：主

26、要是降低熔体之间和熔体与加作用：主要是降低熔体之间和熔体与加工机械之间的摩擦及粘附，改善流动性，工机械之间的摩擦及粘附，改善流动性，提高加工性能。提高加工性能。分类：分类：内润滑剂内润滑剂Internal lubricants 外润滑剂外润滑剂external lubricants 现在学习的是第26页，共36页Internal lubricants reduce molecular friction,consequently decreasing the materials melt viscosity and allowing it to flow more easily.External

27、 lubricants act by increasing the flow of the material by decreasing the friction of the melted material as it comes into contact with surrounding surfaces.In reality,lubricants such as waxes,amides,esters,acids,and metallic stearates act as both external and internal lubricants.现在学习的是第27页，共36页润滑剂与增

28、塑剂的区别：润滑剂与增塑剂的区别：润滑剂仅在加工时有作用；而增塑剂同润滑剂仅在加工时有作用；而增塑剂同时在加工和使用中起作用时在加工和使用中起作用二、主要品种：表二、主要品种：表2-12（P88）现在学习的是第28页，共36页三、选用原则三、选用原则1、有些稳定剂兼具润滑剂的作用、有些稳定剂兼具润滑剂的作用2、一般用量、一般用量1%左右，过多会左右，过多会“喷霜喷霜”3、注意内外润滑作用的平衡、注意内外润滑作用的平衡4、当填充剂用量大时应适当增加润滑剂用量、当填充剂用量大时应适当增加润滑剂用量四、广义意义的润滑剂四、广义意义的润滑剂光泽剂光泽剂脱模剂脱模剂开口剂开口剂现在学习的是第29页，共3

29、6页第四节第四节 交联剂及相关助剂交联剂及相关助剂curing(crosslinking)agent一、交联作用及交联剂一、交联作用及交联剂交联反应的类型交联反应的类型热固性树脂的固化热固性树脂的固化curing热塑性树脂的交联热塑性树脂的交联crosslinking橡胶的硫化橡胶的硫化vulcanization交联对材料的作用交联对材料的作用物理机械性能物理机械性能耐化学药品性能耐化学药品性能常用的交联剂常用的交联剂 P90表表2-13现在学习的是第30页，共36页二、交联用其它添加剂二、交联用其它添加剂1、硫化促进剂、硫化促进剂酸性促进剂酸性促进剂碱性促进剂碱性促进剂中性促进剂中性促进剂2

30、、硫化活性剂、硫化活性剂无机活性剂无机活性剂有机活性剂有机活性剂现在学习的是第31页，共36页3、防焦剂、防焦剂亚硝基化合物类亚硝基化合物类有机酸类有机酸类硫氮类硫氮类4、配合剂、配合剂乙烯基类乙烯基类甲基丙烯酸类甲基丙烯酸类丙烯酰胺类丙烯酰胺类环氧化合物类环氧化合物类现在学习的是第32页，共36页5、选用原则、选用原则被交联的高分子化合物类型被交联的高分子化合物类型加工工艺加工工艺对最终制品的要求对最终制品的要求其它添加剂对交联体系的影响其它添加剂对交联体系的影响现在学习的是第33页，共36页Initiators such as benzoyl peroxide are used not I

31、nitiators such as benzoyl peroxide are used not only for the initiation of chain reaction polymerization only for the initiation of chain reaction polymerization but also for the curing of polyesters and ethylene-but also for the curing of polyesters and ethylene-propylene copolymers and for the gra

32、fting of styrene propylene copolymers and for the grafting of styrene on elastomeric polymer chains.Peroxides such as on elastomeric polymer chains.Peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3(2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3(特丁基特丁基过氧化物过氧化物)are used for crosslinking HDPE.Si

33、nce these)are used for crosslinking HDPE.Since these compounds contain weak covalent bonds,precautions compounds contain weak covalent bonds,precautions must be taken in their storage and use to prevent must be taken in their storage and use to prevent explosions.Free radicals for crosslinking may a

34、lso be explosions.Free radicals for crosslinking may also be produced by electrons,rays,or UV irradiation.The latter produced by electrons,rays,or UV irradiation.The latter is more effective in the presence of additives such as the is more effective in the presence of additives such as the methyl et

35、her of benzoinmethyl ether of benzoin（安息香胶）（安息香胶）.现在学习的是第34页，共36页Unsaturated polymers such as alkyd resins may be cured or“dried”in the presence of oxygen,a salt of a heavy metal,and an organic acid called a drier.The commonly used metals are cobalt,lead,and manganese(Mn),and the most common organic

36、 acids are linoleic(亚麻酸)and tall oil fatty acids.现在学习的是第35页，共36页第五节第五节 填充剂填充剂Fillers and Reinforcements一、分类与作用一、分类与作用一、分类与作用一、分类与作用填充剂填充剂填充剂填充剂增加制品的体积和降低成本增加制品的体积和降低成本增加制品的体积和降低成本增加制品的体积和降低成本a filler is a relatively inert material added to a plastic to modify its a filler is a relatively inert mater

37、ial added to a plastic to modify its strength,permanence,working properties,or other qualities or to lower strength,permanence,working properties,or other qualities or to lower costs.costs.wood flour,calcium carbonate wood flour,calcium carbonate 补强剂补强剂补强剂补强剂提高制品的力学性能提高制品的力学性能提高制品的力学性能提高制品的力学性能a rei

38、nforced plastic is one with some strength properties greatly a reinforced plastic is one with some strength properties greatly superior to those of the base resin resulting from the presence of superior to those of the base resin resulting from the presence of high-strength fillers embedded in the c

39、omposition.According to high-strength fillers embedded in the composition.According to ASTM,plastic laminates are the most common and the strongest ASTM,plastic laminates are the most common and the strongest type of reinforced plastic.type of reinforced plastic.carbon black,amorphous silica.carbon black,amorphous silica.现在学习的是第36页，共36页