结构与性能11_635908200

nullnullStructure and Properties of Polymers— for graduate students —null高聚物结构与性能 课程号:70340023，332室 nullnullWe are deeply saddened to announce that Steve Jobs passed away today。 Steve’s brilliance, passion and energy were the source of countless innovations that enrich and improve all of our lives. The world is immeasurably better because of Steve。 His greatest love was for his wife, Laurene, and his family. Our hearts go out to them and to all who were touched by his extraordinary gifts。nullWhat are you going to talk about in your course ?nullPreface nullStructure and Properties in Polymers (48 h)   Topic 1, Structure of Macromolecules (18 h) 1.1, Constitution of macromolecules 1.1.1, Capacity of elements to form chains 1.1.2, Substituents 1.1.3, Cross-linkage 1.2, Configuration of macromolecules 1.2.1, Configurational isomerism 1.2.2, Fischer projection 1.2.3, R/S nomenclature for configurational isomers 1.2.4, Tacticity 1.2.5, Characterization of tacticity in real polymers 1.3, Conformation of macromolecules 1.3.1, Rotational isomers 1.3.2, Types of rotational isomers 1.3.3, Several typical potential curves 1.3.4, Flexibility 1.3.5, Constitutional influence null 1.3.6, Mean square end-to-end distance 1.3.7, Shape and dimension of freely jointed chains 1.3.8, Conformation in polymer crystals 1.3.9, Types of macroconformation Topic 2, Structure of Polymer Crystals (9 h) 2.1, Chain folding 2.1.1, Presentation of folded chain models 2.1.2, How widespread is chain folding ? 2.1.3, What affects chain folding ? 2.1.4, Does chain folding mean adjacent reentry ? 2.1.5, What is the nature of the fold surface ? 2.1.6, How stable is the chain fold ? 2.1.7, What are the reasons for chain folding ?null2.2, Microscopic defects 2.2.1, Amorphous defects 2.2.2, Surface defects 2.2.3, Dislocation 2.2.4, Point defects   2.3, New field 2.3.1, Crystallization of single polymer chain 2.3.2, Confined crystallization of polymers Topic 3, Polymer Blends and Block Copolymers (9h) 3.1, Thermodynamics of Mixing 3.2, Mechanism of Phase Separation 3.3, Nanophase Structure of Block Copolymer Topic 4, Mechanical Property of Polymers (12 h) 4.1, Modulus estimation for polymer materials   null4.1.1, Simple estimation for the chain-direction modulus 4.1.2, Complete set of elastic constants 4.1.3, Modulus estimation for two-phase polymers 4.2, Yield in polymer materials 4.2.1, Tresca yield criterion 4.2.2, Von Mises yield criterion 4.2.3, Pressure-dependent yield behaviour 4.2.4, Temperature and rate dependence of yield 4.2.5, Craze criteria 4.3, Fracture of polymer materials 4.3.1, Definition and goal 4.3.2, Ductile-brittle transitions 4.3.3, Brittle fracture 4.3.4, Linear elastic fracture mechanics 4.4, Toughening mechanisms of plastics 4.4.1, Toughening of plastics 4.4.2, Particle deformation 4.4.3, Shear yielding 4.4.4, Crazing null   4.4.5, Simultaneous shear yielding and crazing 4.4.6, Crack pinning 4.5, Reinforced polymers 4.5.1, Introduction 4.5.2, Reinforced plastic 4.5.3, The mechanics of fibre reinforcementnullThe title of debate for this year is:nullTopic 1 Structure of Macromolecules Topic 2 Structure of Polymer Crystals Topic 3 Polymer Blends and Block Copolymers Topic 4 Mechanical Properties of Polymers OthersContentsnull1. Macromolecular Science and Engineering: New Aspects Y. Tanaba (Ed.) Springer (1999)Bibliography 2. The physics of Polymers Gert R. Strobl Springer (1996)3. The Science of Polymer Molecules Richard H. Boyd, Paul J. Phillips Cambrige University Press (1993)4. Polymer Data Handbook J. E. Mark Oxford University Press (1999)5. Polymer Data Handbook J. E. Mark Oxford University Press (1999)null1.1 Constitution(构造) of Macromolecules 1.2 Configuration(构型) of Macromolecules 1.3 Conformation(构象) of MacromoleculesTopic 1 Structure of Macromoleculesnull Constitution Chemical Structure Single Configuration Molecular Structure Structure Conformation (bridge) Orientation Aggregated Physical Structure State Crystallinity Structure nullnull1.1 Constitution of Macromolecules Here only talk about: ◆ Capacity of elements to form chains (元素成链能力) * Types of cross linkage * Some substituents Constitution means a certain linking sequence and linking type for each atom existed in a molecule with a certain chemical composition. nullnull* to develop new kinds of polymers such as functional polymer, inorganic polymer, liquid crystal polymer * to probe into plasma polymerization reactionWhy we emphasize the capacity of elements to form chains ?nullnullnull isolatable chain(可分离链) elements compounds layered structure cross-linked network *isolatable ── can be separated into single molecules in a fluid form: gas, solution, melt isochain (均链) identical atoms in a main chain at least three successive atoms heterochain (杂链) different atoms in a main chainnullCapacity of elements to form isochains strongly depends on its position in the periodic table* number at the right side of element symbol is the highest chain-link number * number at the underside the relative electronegativity of element * only 11 elements can form isochain, 3 elements (C,Si,S) can form long isochain * only C element can form long and stable isochainnull ozone modification oxygen isochains low temperatureO＝O＝O －O－O－O－O－O－O－ SP2 (hybridization) SP3 hydrogen azide nitrogen isochains1000℃ L－N2 H H H H H H －N－N－N－N－N－N－ammonium azideΔ－125℃O ∞？∞？氢的叠氮化合物N ∞？nullC ∞MW of polyolefin ── 104 ～ 107Si 45number of Si ≤ 45 ── isolatable chain such as silane H ( SiH2 )n HS 30000 This is for inorganic polymer －S－S－S－S－S－S but not for organic polymer polysulfide rubber: (－R－Sn－)m n ≈ 4Cross-coupling ReactionCross-coupling ReactionNobel Prize in Chemistry 2010nullan empirical selection rules elements to form long, stable, isolatable isochains at normal condition X ── the relative electronegativity of element E1── single bond energy E2── double bond energy 2 E1 > E2 ── elements prefer to form chains with single bondsnullRelevant data of six elementsnullHow about the element B ?nullIsochain or heterochain ?B2H6 gas B4H10 gas B5H9 liquid B5H11 ? B6H10 unstable B10H14 unstable n ~ 5bi-electron three-center bridge bond （双电子桥式三中心键）bond order=2＝2－02＝1Nb ：number of electrons on bonding orbit Nanti：number of electrons on antibonding orbit Nb－NantiIIIAnullHow about the element Be ? Isochain? / heterochain ?IIAbi-electron three-center bridge bond （双电子桥式三中心键）spiro-compoundnullnullelements to form stable and isolatable heterochainsnull bond ∑ Δ C－O 6 1 C－N 5.5 0.5 Si－O 5.3 1.7 C－Be 4 1 B－H 4.1 0.1 Examples H H H H －C－O－C－O－C－O－C－O－ Polyoxymethylene H H H H H H H H H H urea- －N－C－N－C－N－C－N－C－ formaldehyde O H O H resin CH3 CH3 CH3 －Si－O－Si－O－Si－O－ Polysiloxane CH3 CH3 CH3 Bond E1 2 E1 E2 E3 (kJ/mol bond) C～N 240 480 ＞ 350 750 C～O 340 680 ～ 680 Si～O 420nullWhether there is any possibility to form heterochains or not between following pairs of elements:－B－N－B－N－ －Sn－O－Sn－O － －P－N－P－N－ －Ge－O－Ge－O－ －Si－S－Si－S－ －Pd－Cl－Pd－Cl－?nullnullnullnull─CH2─CH─CH2─CH─CH2─CH─ NH2 NH2 NH2nullnullnullcontrastpolyionpolyradicalmacroionmacroradicalnull锂藻土( Laponi te):表面带负电Kazutoshi Haraguchi, Macromolecules 2002, 35, 10162 -10171MeifangZhu ,Macromol.RapidCommun. 2006, 27,1023–1028nullKazutoshi Haraguchi, Macromolecules 2002, 35, 10162 10171 NC2.5表示粘土含量为： 16.14%; 类似的NC3: 18.77%； NC4: 23.55%; NC5.5: 29.76% NC7: 35.03%样条含水量约89%，长200mm，直径5.5mm；nullnullCross-linkbranched molecule ── soluble cross-linked ──── insoluble In principlebutIf macromolecule very small a few cross-link points per chain solublenullnullnormal irregular cross-linked networkMacroreticular (大网眼) cross-linked networknulltype 0 / cage polymer nullSpiro-polymerCondensed ring polymerBridged ring polymer( Ladder polymer )( Heat-resistant polymer )null2 dimension / layer or planar polymers Graphite and its derivatives / certain cell walls of bacteria nullnullnullY.-T. Liu, X.-M. Xie, X.-Y. Ye, J. Materials Chemistry 2011, in press铜离子配位的碳纳米管/石墨烯杂化网络填料填充的 聚合物纳米复合材料的制备示意图.nullY.-T. Liu, Q.-P. Feng, X.-M. Xie, et al., Carbon 2011, 49(10): 3371null3 dimension / network polymer diamond