聚合物材料=高分子材料 论 A Polymer is a substance composed of molecules characterized by the multiple repetition of one or more species of atoms or groups of atoms (constitutional repeating 第三章 units) linked to each other in amounts ufficient to provide a set of properties that do not vary markedly with the addition of 聚合物材料 one or a few of the constitutional repeating 高分子材料的来源 General Characteristics >Insulation 口 Static accumulation 天然高分子 纤维素、木质素、天然橡胶、蛋白 >Easy molding DIfficult recycling 口 Low mech properties /Extremely light weight LOw service T 合成高分子 聚合反应 聚合反应:将小分子(单体)连接成 >Chemical resistance AGing 高分子的反应 Colorability 口 Flammable Origin of the Characteristics 聚合物产生年代表 今 Covalent bonds g Contain mainly carbon in their backbone Long chain molecules 然重胺果苯并球
1 材料 导论 第三章 聚合物材料 A Polymer is a substance composed of molecules characterized by the multiple repetition of one or more species of atoms or groups of atoms (constitutional repeating units) linked to each other in amounts sufficient to provide a set of properties that do not vary markedly with the addition of one or a few of the constitutional repeating units. 聚合物材料＝高分子材料 高分子材料的来源 二、合成高分子——聚合反应 聚合反应：将小分子（单体）连接成 高分子的反应。 一、天然高分子 纤维素、木质素、天然橡胶、蛋白 质、蚕丝 ¾Insulation ¾Easy molding Low mech properties ¾Extremely light weight ¾Transparency ¾Colorability General Characteristics Difficult recycling Static accumulation Low service T ¾Chemical resistance Aging Flammable Contain mainly carbon in their backbone Covalent bonds Long chain molecules Origin of the Characteristics 聚合物产生年代表
聚合物材料的分类 32塑料 合就料 塑料 隐慢斜 性斜 热塑性塑料热固性塑料 通用塑料 工程塑料先进工程塑料 321通用塑料 General categories of plastics 通用塑料 Plastic group Typical member ommodity Intermediate Polyethylene terephthalate 2 聚乙烯聚丙烯豪氯乙烯聚苯乙烯 Engineering Polyamide(PA) High performance Polyetheretherketone -CHrCH--CH-CH- -CH-CH- -CH-CH- CH3 3.2.2 工程塑料 Styrene-Acry lonitriles -CHrCH- -CHy CH- SAN 氯塑料豪甲醛有机玻璃 L共聚物 CFrCFr-CH-O- C -CHrCH- -CH CH- -CH-C- CH,CH-CH-CH,. ABS 聚酰胺(尼龙) COOCH, 聚碳酸 -CHr CH- -CHr CH- +-CH--C- MBS cm)-、(cH CH○)0-0 COoCH
2 聚合物材料的分类 涂料 粘合剂 弹性体 热塑性塑料 热固性塑料 塑料 合成纤维 天然聚合物 生物系统 聚合物材料 3.2 塑料 通用塑料 工程塑料 先进工程塑料 热塑性塑料 热固性塑料 塑料 Plastic group Typical member Relative price Commodity Polystyrene (PS) 1 Intermediate Polyethylene terephthalate 2 Engineering Polyamide (PA) 6 High performance Polyetheretherketone 83 General categories of plastics 通用塑料 聚乙烯 聚丙烯 聚氯乙烯 聚苯乙烯 −CH2− CH2− −CH2− CH− CH3 −CH2− CH− Cl −CH2− CH− 3.2.1 通用塑料 氟塑料 聚酰胺（尼龙） 聚碳酸酯 苯乙烯－丙 烯腈共聚物 −CF2− CF2− −CH2− 3.2.2 聚甲醛 有机玻璃 CH3 ＝ O CH3 −O O CH －C－ O－ −CH2− C− COOCH3 CH3 −N-(CH2)n-N −C-(CH2)n-C− ＝ H O − H − ＝ O SAN， ABS， MBS， OSA，ASA 工程塑料 Styrene-Acrylonitriles −CH2− CH− CN −CH2− CH− + SAN −CH2− CH− CN −CH2− CH− + + CH2= CH-CH=CH2 ABS −CH2− CH− CN −CH2− CH− + −CH2− C− COOCH3 CH3 + MBS
Styrene-Acrylonitriles Family Characteristics -CHr-CH--CH-CH--CH-CH Superior processibility and appearance ASA Low creep -CH2-CH-_CH-ch- High strength and rigidity 乙丙橡胶 Good dimensional stability ABS OSA ASA 3.2.3 Advanced thermoplastics Density, g/em L.2/10 MPa MPa57-7532-393936-39 Polyet modulus, GP: 18-2.21.1 2.0-4.5 olvether-imlde d izod 550 8-8590-113102 polyester POLYPHENYLEN Poly phenylene oxide(PPo) A good heat resistance, with decomposition temperatures of the order of 400C The polymer is brittle, insoluble and infusible
3 −CH2− CH− CN −CH2− CH− + + −CH2− CH− COOR ASA Styrene-Acrylonitriles −CH2− CH− CN −CH2− CH− + + 乙丙橡胶 OSA Family Characteristics Superior processibility and appearance Good dimensional stability Low creep High strength and rigidity Property SAN (30%) ABS OSA ASA Density, g/cm3 1.07- 1.08 1.02 1.05- 1.06 Tensile strength, MPa 57-75 32-39 39 36-39 Tensile modulus, GPa 3.4-3.6 1.8-2.2 1.1 2.3 Elongation at yield, % 2.0-4.5 30 - Notched Izod impact strength, J/m 13-24 270- 400 750 500- 550 Rockwell hardness 78-85 90-113 102 96 3.2.3 Advanced thermoplastics Processing Yield Modulus Strain Notched Polymer Temperature Strength MPa at break Izod J/m °C MPa Polyetheretherketone ~400 100 3.10 >40 85 Polyarylene ketone ― 81.6 2.48 13 ― Polyphenylene sulfide ~343 82.1 4.34 5 160 Polyarylene sulfide ~329 100 3.24 7.3 42 PAI(Torlon) ~400 63.4 4.60 1.4 144 Polyether-imide ~343 105 2.96 60 53 Polyimide ~343 120 3.12 4.8 ― Polyimde sulfone ~343 62.7 4.96 1.3 ― Polysulfone ~300 70.3 2.48 >50 64 Polyaryl sulfone ~330 71.7 2.14 60 64 Polyarylether sulfone ~300 84.1 2.62 >40 85 Polyester ~400 138 16.5 4.9 128 A good heat resistance, with decomposition temperatures of the order of 400°C The polymer is brittle, insoluble and infusible. POLYPHENYLENE Polyphenylene oxide (PPO) n O－ CH3 CH3 － － －
Family Characteristics Poly phenylene Sulfides(PPs) High moisture resistance Heat-deflection temperatures range from 80 to 155 Notched Izod impact: 106 to 530 J/m Ci-O-a+ Nas- to-sf Excellent dimensional stability, heat resistance ow creep values with long-term continuous load Applications Polymer Properties Electrical and Electronic: integrated-circuit and capacitor encapsulations, switches, electronic watch bases, and Good thermal stability and unusual insolubility resistance to chemical environments Mechanical and Chemical: Pump housings, impeller diffusers, pump vanes, end plates, oil field hardware, heat nherent flame resistance shields, boiler sensor Good resistance to thermal degradation at up to 370°c Appliance: microwave oven components, computer disk drives Insoluble in organic solvents below 200C Automotive: Emission-control system, sensoring devices A high oxygen index of 44 fuel, ignition and braking systems, light sockets, cooling system, air-conditioning Family Characteristics Polysulfones(PsU) Transparent, rigid, ductile A clear, rigid, tough thermoplast capable of continuous use at Tg=185° c heat-deflection temperature of174°C temperatures up to 160C Excellent thermal stability and chemical inertness. Superior resistance to thermal degradatio sistance and ductility that are {@@@◎叶 retained to temperatures below 0C Resistance to burning, does not require the addition of flame retardants
4 High moisture resistance. Heat-deflection temperatures range from 80 to 155 °C Notched Izod impact: 106 to 530 J/m Excellent insulators Excellent dimensional stability, heat resistance, Low creep values with long-term continuous load. Family Characteristics Polyphenylene Sulfides (PPS) Cl − −Cl + Na S 2S − − − n Good thermal stability and unusual insolubility, resistance to chemical environments, Inherent flame resistance. Good resistance to thermal degradation at up to 370 °C. Insoluble in organic solvents below 200 °C A high oxygen index of 44 Polymer Properties Mechanical and Chemical: Pump housings, impeller diffusers, pump vanes, end plates, oil field hardware, heat shields, boiler sensor Applications Appliance: microwave oven components, computer disk drives Automotive: Emission-control system, sensoring devices, fuel, ignition and braking systems, light sockets, cooling system, air-conditioning Electrical and Electronic: integrated-circuit and capacitor encapsulations, switches, electronic watch bases, and relay components A clear, rigid, tough thermoplastic capable of continuous use at temperatures up to 160 °C Polysulfones (PSU) SO2 n － CH3 CH3 −O CH O－ Resistance to burning, does not require the addition of flame retardants. Family Characteristics Transparent, rigid, ductile Tg = 185 °C heat-deflection temperature of 174 °C Excellent thermal stability and chemical inertness. Superior resistance to thermal degradation Impact resistance and ductility that are retained to temperatures below 0°C
PSU mechanical properties Value Test Applications Tensile stength at yield, MPa Microwave cookware Tensilemodulus GPa Electrical and electronic Tensile elongation at break, Membrane support Poissons ratio at 0.5% strain Polyaryl Sulfones(PAS) Family Characteristics Mechanical properties Flexural modulus of 2.75 GPa o@@0m Outstanding impa high tensile strength Thermal Properties gh Tg heat-deflection temperature: 205C Characteristics Polyether Sulfones(PES) Thermal Stability. can be used for many thousands of hours up to 200C without significant loss of strength. Dimensional Stability: Changes in dimensions at up to 200° are negligible Electrical Variations are small between -75 to 200.c Flammability. Inherently flame retardant and emits very low levels of toxic gases and smoke when burned The chemical resistance is excellent in the case of most solvents, gasoline, oils, acids, and alkalis
5 Property Value Test method Tensile suength at yield, MPa 70.3 D 638 Tensilemodulus, GPa 2.48 D 638 Tensile elongation at break, % 75 D 638 Tensile impact, kJ/m2 420 D 1822 Poisson's ratio at 0.5% strain 0.37 ... Notched Izod at 6 2 mm 64 D PSU mechanical properties Microwave cookware Electrical and electronic Membrane support Applications Polyaryl Sulfones (PAS) SO2 − n －O－ －O－ Mechanical properties Flexural modulus of 2.75 GPa Outstanding impact strength high tensile strength. Thermal Properties high Tg: 210 °C heat-deflection temperature: 205 °C Family Characteristics Polyether Sulfones (PES) n S O O O General Characteristics Thermal Stability. can be used for many thousands of hours up to 200 °C without significant loss of strength. Dimensional Stability. Changes in dimensions at up to 200 °C are negligible. Creep Resistance. can carry substantial loads for long periods at up to 180 °C The chemical resistance is excellent in the case of most solvents, gasoline, oils, acids, and alkalis. Electrical. Variations are small between -75 to 200 ° C Flammability. Inherently flame retardant and emits very low levels of toxic gases and smoke when burned
pplications Polyketones(PEEK, PEK, PEKK, Electrical and Electronic High-temperature PAEK, PEEKK) performance with dimensional stability \CL in Automotive. Resistance to oils and gasoline at elevated temperatures, low flammability CH,Cl,20°C Aerospace. good rain erosion resistance and Medical. ability to withstand repeated sterilization, ko0-0k+c◎0 Properties of peek PEK(1986) ropern Neat 30%o glass 30 carbon Tensile strength, MPa @c@0@0 PEEK(1977) 0- PEKK.384 Elongation to break, Izod impact strength, kI/mm PAEK.416 12 cc◎0@0-PEKK Heat-deflection >300 Properties of PAEK Family Characteristics E-1000E-1130EP3 (1)high degree of oxidative stability (2)extremely low flammability Tensile elongation,% (3)Extremely low smoke emission 530 (4)A high softening point
6 Applications Electrical and Electronic. High-temperature performance with dimensional stability Automotive. Resistance to oils and gasoline at elevated temperatures, low flammability Aerospace. good rain erosion resistance and microwave transparency Medical. ability to withstand repeated sterilization, its resistance to chemicals and its transparency. Fluid Handling. excellent long-term hydrolysis resistance Polyketones (PEEK, PEK, PEKK, PAEK, PEEKK) −O－ −COCl AlCl3 in CH2Cl2 20°C − −CO－ −O − KO − −CO－ −F − −CO－ −O − KO− −CO－ −O −OK + F − −CO－ −O −F － CO −O－ － CO −O－ −O－ － CO −CO－ −O－ － CO −CO－ −O－ −O－ － O −CO－ −O－ PEEKK 160, - PAEK -, 416 PEKK -, 384 PEEK(1977) 144, 335 PEK(1986) 154, 361 Property Neat 30% glass 30% carbon Tensile strength, MPa At 23 °C 100 160 215 At 100 °C 66 130 185 At 150 °C 35 75 l00 Elongation to break, % >40 ... ... Izod impact strength, kJ/mm Notched 0.09 0.12 0.06 Unnotched No break ... 0.64 Heat-deflection temperature °C 152 >300 >300 Properties of PEEK Property E-1000 E-1130 EP3140 Tensile strength, MPa At 23 °C 93.1 163 155 At 250 °C 8.62 32.4 28.1 Tensile elongation, % 50 2.2 1.5 Heat-deflection temperame, °C 306 340 340 Izod impact, J/m Notched 85 96 64 Unnotched No break 720 530 Tensile impact, kJ/m2 115 135 525 Properties of PAEK Family Characteristics (1) high degree of oxidative stability (2) extremely low flammability (3) Extremely low smoke emission (4) A high softening point
Other notable features Applications (1)Excellent toughness and wear resistance Aircraft/aerospace applications such as engine (2) Excellent fatigue resistance components, cabin interior material, air ducts, and (3)Excellent hydrolytic stability nonstructural exterior parts. Other applications (hot water at 125"C, under which polyimides are liable to fail.) include wire and cable in the electrical/electronics (4)Good radiation resistance market, pump components in the chemical (5) Very good low-friction properties of bearing grat rocessing market. Thermoplastic Polyimides(TPl) 了o -NH-X-NH COOH hysical and mechanical properties of TPl Polyamide-imides(PAl) Avimid K-lll Ultem 1000 Torlon4203 Tensile strength, MPa 102 Tensile modulus GPa 3.8 notched Izod. J/m strain-to-failure
7 Other notable features (1) Excellent toughness and wear resistance (2) Excellent fatigue resistance (3) Excellent hydrolytic stability (hot water at 125°C, under which polyimides are liable to fail.) (4) Good radiation resistance (5) Very good low-friction properties of bearing grad Aircraft/aerospace applications such as engine components, cabin interior material, air ducts, and nonstructural exterior parts. Other applications include wire and cable in the electrical/electronics market, pump components in the chemical processing market. Applications Thermoplastic Polyimides (TPI) −C + NH2—X—NH2 −C O ＝ O ＝ O C− C− O O ＝ ＝ O −COOH −C－NH－X－ ＝ O ＝ O ∼X－NH－C− HOOC− O ＝ ＝ O −COOH −C－N∼ ＝ O ＝ O NH－C− HOOC− O ＝ ＝ O H −C −C ＝ O ＝ O C− C− O ＝ ＝ O ∼X－N N－X－N −C −C ＝ O ＝ O C− C− O ＝ ＝ O N ∼ Avimid K-III Ultem l000 Torlon4203 Density, g/cm3 1.31 1.27 1.38 Tensile strength, MPa 102 104 186 Tensile modulus, GPa 3.8 3.0 4.4 notched Izod, J/m -- 53.4 133.5 strain-to-failure, % 14 60 20 Tg ° C 250 210 267 Physical and mechanical properties of TPIs Polyamide-imides (PAI) −C ＝ O C− C− N O ＝ ＝ O H N Ar
Family Characteristics of PAl Polyether-imide Exceptional dimensional stability:(high Tg, no 1982 crystallinity) Retention ot properties after thermal aging Exceptional mechanical strength Low coefficient of thermal expansio Outgassing characteristics Family Characteristics Liquid Amorphous structure: excellent dimensional Ine Tg=217cAt180°c remain in excess of 41 MPa polymers H3-(CH,h-O\,O-(CH,)-CH3 CH4C120⑨NN0Cm CH3-(CH,h ○)0(CH)2xCH CH3-(CH,h-O CN⊙0(m2<H WOre W
8 Exceptional dimensional stability: (high Tg, no crystallinity) Wide range of temperature capability: (from –170 to 260 °C) Retention of properties after thermal aging Family Characteristics of PAI Radiation stability Ultraviolet stability Inherent flame resistance Exceptional mechanical strength Low coefficient of thermal expansion Outgassing characteristics Outstanding wear characteristics Polyether-imide O C CH3 CH3 O O O N O O N 1982 Amorphous structure: excellent dimensional stability, low shrinkage, and highly isotropic mechanical properties Tg = 217°C At 180 °C, tensile modulus remain in excess of 41 MPa Family Characteristics Liquid crystalline polymers O O-(CH2) CH3 N=N 2 –CH3 -(CH2)2 - O O-(CH2)2 CN –CH3 Tail Tail Core Core Tail O-(CH2) CH3 2 –CH3 -(CH2)2 - O CH3 -(CH2)2 - O CH3 -(CH2)2 - O O-(CH2)2 –CH3 O-(CH2)2 –CH3 Core Tail
Nematic hectic A 8 Smectic C Discotic nematic 25 42 22222 Discotic Hexagonal Ordered Discotic hexagonal disordered D
9 Nematic N Smectic A SA α Smectic C SC Discotic Nematic DN Discotic Hexagonal Ordered Dho Discotic Hexagonal Disordered Dhd
Cholesteric bis-(p-heptyloxy phenyl) terephthalate CH3(CH2)O O(CH2)CH3 152.3 1760 194.8T/°C Crystal -smetic Ch-smectic AF.Nematic.isotropic Chiral Nematic 1.7 AH/kJmol-1 Bragg equation Chiral smectic 2d sin b=nA d=P temperature sensible Macromolecule Main chain Plcs from calamities cores Poly merized liquid Liquid crystal crystals(PLCs) polymers(LCPs) Main-cha Side-chain Thermotropic
10 Crystal smectic C smectic A Nematic isotropic 152.3 176.0 180.8 194.8 T/°C 56.2 0.3 0.9 1.7 ∆H/kJmol-1 CH3(CH2)6O OC O C O O O(CH2)6CH3 bis-(p-heptyloxyphenyl) terephthalate P Chiral Nematic N* Cholesteric c n Chiral Smectic Sc* nz ny n P z ny n θ 2d sin θ = n λ Bragg equation d d d d =P temperature sensible Polymerized liquid crystals (PLCs) Liquid crystal polymers (LCPs) Main-chain Side-chain lyotropic Thermotropic Macromolecular liquid crystal Main chain PLCs from calamitic cores Spacer