第一章绪论二、聚合物的分类

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1 Polymer Chemistry I Qi Wang Department of Polymer Science and Engineering, Zhejiang University

2 Content Polymer and its structure Mechanism of polymerization reactions Process of polymerization The reactions of polymer 2

3 Schedule Chapter 1 Introduction 6 hr Chapter 2 Radical Polymerization 10 Chapter 3 Radical Copolymerization 6 Chapter 4 Polymerization Process 4 Reports & Discussion 6 Score assignments(20%)+reports and discussion(30%) +final exam(50%) 3

4 Reference Books 冯新德, 高分子合成化学化学工业出版社,1980 林尚安等, 高分子化学科学出版社,2000 Malcolm P. Stevens Polymer Chemistry, an Introduction, 3rd ed., Oxford University Press, 1999 George Odian, Principles of Polymerization, 2nd ed., John Wiley &Sons, Inc., New York,

5 Chapter I Introduction 5

6 1. Fundamental Concepts 6

7 Chemicals in kitchen Salt Sugar Starch NaCl Inorganic Organic molecule Macromolecule

8 1.1 What is a polymer? 8

9 1.1 What is a polymer? Polymer in solution measured by AFM J.Am.Chem.Soc.127:

10 1.1 What is a polymer? A polymer is a large molecule comprised of repeating structural units joined by covalently bonds. (Hermann.Staudinger,1924) Polymer in solution measured by AFM J.Am.Chem.Soc.127: poly comes from the Greek word for "many mer comes from the Greek word for "parts. 10

11 degree of polymerization 聚合度 Note that all three representations are equivalent. One usually chooses the representation that emphasizes the monomer ( 单体 ) from which the polymer was made. There are end groups on the chain that are different from the repeat units, but these usually represent a negligible portion of the molecule, so they are seldom drawn. 11

12 Polymer( 聚合物 ) vs Macromolecule( 大分子 ) Macromolecule Polymer molecule with high molecule weight molecule comprised of repeating unit Sample polymer macromolecule Polyethylene DNA Protein 12

13 1.2 Flowchart of Polymeric Materials Inorganic Natural Clays Bricks Cement Pottery Sands Glass Synthetic Fibers Organic Natural Polysaccharides Proteins Polyisoprene Synthetic Plastics Fibers Rubbers Adhesive Coatings 13

14 Polymer is everywhere 14

15 In Nature Cellulose, Starch, DNA, Protein 甲壳素壳聚糖 15

16 Synthetic Materials Annual Production of Polymer Materials (million ton) Year Plastics (11*) Synthetic fiber (6.4) Synthetic rubber (0.9) Total * China 16

17 General Plastics( 通用塑料 ) 有机玻璃密胺餐具烤瓷假牙 ABS 旅行箱保鲜膜 ( 线性低密度聚乙烯 ) 水立方 ( 聚氟乙烯薄膜 ) 透明薄膜椅 ( 聚氨酯薄膜 )

18 Engineering plastics( 工程塑料 ) 聚四氟乙烯轴承 18

19 Synthetic fibers( 合成纤维 ) 涤纶长丝帘子布 ( 尼龙 ) 防弹衣 ( 芳纶, 超高分子量聚乙烯纤维 ) 安全手套 ( 芳纶 )

20 Synthetic rubber, elastomer ( 合成橡胶和弹性体 ) 乳胶手套 ( 天然橡胶 ) 轮胎 ( 天然橡胶, 丁苯橡胶, 顺丁橡胶 ) 洞洞鞋 (EVA) 记忆枕 ( 发泡聚氨酯 )

21 Functional polymers( 功能高分子 ) 过滤器 N95 口罩尿不湿不粘锅鲨鱼皮泳衣隐形眼镜植入假体时间控制释放材料薄膜太阳能电池

22 Fine polymers( 精细高分子 ) 22

23 Plastics vs Steel 23

24 Energy Consumption 24

25 1. 选择一种饮料 2. 喝一杯咖啡 A B C D E F 什么样的选择对自然界的负荷最小? A: 玻璃瓶 B: 塑料瓶 C: 铝质易拉罐 D: 陶瓷杯 E: 纸杯 F: 塑料杯

26 1.3. Definitions CH 2 CH Cl n O O NH(CH 2 ) 6 NHC(CH 2 ) 4 C n structural unit 结构单元 repeating unit 重复单元 The degree of polymerization (DP) in a polymer molecule is the number, n, of repeating units in the polymer chain. Mw DP m repeating unit 26

27 Polymers are large molecules. Fortunately, they are not random collections of atoms; if this were the case, they would be impossible to study. Polymers are built up from smaller molecules (monomers), and therefore possess a characteristic chain structure consisting of multiple repeat units that are related chemically The repeat units can all be identical, in which case the compound is a homopolymer( 均聚物 ). 27

28 If the repeat units are different, the result is a copolymer( 共聚物 ). Consider a copolymer made from just two ingredients: the two can be sequenced along the backbone in various modes. 交替嵌段无规接枝 28

29 The chain itself can have many different topologies 线型环状 macrocycle 支化交联 dendrimer 树枝状 29

30 1.4 Produce of polymer Nature precise control on molecular structure Starch, Natural rubber, Polysaccharides( 多糖 ) Synthetic Various families and large quantities, but less precise 30

31 1.5 Polymer Disciplines Polymer chemistry Polymer science Polymer physics Polymer material Polymer process Polymerization engineering 31

32 Content Polymer Chemistry Polymer and its structure Polymerization mechanism and kinetics Polymer reaction Frontier Novel synthetic method and polymer family Design and control on the chain structure of polymer Recycle of polymer 32

33 2. Categories and Nomenclature of Polymer 33

34 2.1 Classification Rules There is no uniform system of classification of polymers. The terminology has evolved along with polymer science, and there are numerous exceptions to categories. The way people classify polymers depends their experience. Widely used historical terms or trade names lacking information content. 34

35 A: According to application Plastics Fibers General Industry Polymer Rubbers Coatings Adhensives Fine Functional 35

36 B. According to Processability 结晶无定形 Molecules in a thermoplastic ( 热塑性 )are held together by relatively weak intermolecular forces, so that the material softens when exposed to heat and then returns to its original condition when cooled A thermosetting( 热固性 ) plastic, or thermoset, solidifies or "sets" irreversibly when heated. Elastomers( 弹性体 ) are rubbery polymers that can be stretched easily to several times their unstretched length and which rapidly return to their original dimensions when the applied stress is released. 36

37 C: According to chemical composition Carbon-chain polymer backbone composed of carbon atom C C C C C Hetero chain polymer composed of both carbon and other atoms, e.g. O, N, S, P etc. C C O C C O Element polymer no carbon in backbone CH 3 CH 3 CH 3 Si O Si O Si O CH 3 CH 3 CH 3 37

38 Carbon chain Polymer( 碳链高分子 ) Vinyl polymers a. Polyolefin ( 聚烯烃 ) : polymer derived from alkene Polyethylene( 聚乙烯 ), polypropylene ( 聚丙烯 ), etc b. Polystyrene: PS ( 聚苯乙烯, 1839 by Eduard Simon) and its families (ABS, SBS,SBR); c. Polyvinylchloride:PVC ( 聚氯乙烯,1872 by Eugen Baumann) and its copolymers, d. Acrylic polymers: PMMA ( 聚甲基丙烯酸甲酯 ), PA ( 聚丙烯酸 ),; f. Polydiene: synthetic rubber, PBd( 聚丁二烯 ), PIp ( 聚异戊二烯 ), 38

39 Heterochain polymer( 杂链高分子 ) 聚酯聚醚聚酰亚胺 Polyamide/Nylon( 聚酰胺 ), Polyurethane( 聚氨酯 ) Polyurea( 聚脲 ) Polysulfone( 聚砜 ), Phenolic ( 酚醛 ), Ureas( 脲醛 ) 39

40 Element chain polymer( 元素高分子 ) Polysilicone CH 3 CH 3 CH 3 Si O Si O Si O CH 3 CH 3 CH 3 40

41 2.2 Nomenclature Polymer nomenclature is complicated for a variety of reasons: Most polymer names are based on the names of monomer (source-based system) IUPAC system is not widely used Some polymer structures are so complicated: branching or crosslinking; Polymer science has some fairly sharp defined boundaries: rubber chemist vs plastic chemist; Describe polymer based on its characteristics 41

42 A. According to the name of monomer : vinyl polymers Homopolymer: poly(monomer) polystyrene, PS; poly(methyl methacrylate), PMMA Copolymer: poly(monomer-co-monomer) poly(ethylene-co-propylene), 乙烯 - 丙烯共聚物 poly(ethylene-r-propylene), 乙烯 - 丙烯无规共聚物 poly(ethylene-b-propylene), 乙烯 - 丙烯嵌段共聚物 poly(ethylene-g-propylene), 乙烯 - 丙烯接枝共聚物 poly(ethylene-a-styrene), 乙烯 - 苯乙烯交替共聚物 42

43 B. According to the functional group : condensation polymer Polyester; polyether, polyamide ( OCH 2 CH 2 OCO CO ) n Poly(ethylene terephthalate) 聚对苯二甲酸乙二醇酯 ( NH(CH 2 ) 6 NHCO(CH 2 ) 4 CO ) n poly(hexamethyleneadipamide) ( 聚己二酰己二胺 ) 43

44 C. According to the monomer employed phenol-formaldehyde resin 酚醛树脂 ( 苯酚 + 甲醛 ) epoxy resin 环氧树脂 ( 双酚 A+ 环氧氯丙烷 ) D. IUPAC system poly(oxyethylene) polymethylene poly(ethylene oxide) polyethylene (CH 2 CH 2 O) n 44

45 E. Slang and Trade Names These slang names often contain vestiges of the chemical description of the polymer, but shortened or corrupted. The trade names have short, snappy-sounding names that could be easily remembered and spelled by their customers. Nylon 6 polycaprolactam( 聚己内酰胺 ) EPR ethylene-propylene rubber F. Abbreviations LDPE PVC PET low densitypolyethylene polyvinylchloride poly(ethylene terephthalate) 45

46 3. Polymerization Reaction 46

47 3.1 Addition( 加成 ) vs. Condensation( 缩合 ) Carothers originally classified polymers based on a comparison of the atoms in the monomer to the atoms in the repeat unit. Addition polymerization ( 加成聚合 ) Polymer has the same atoms as their monomers n n Condensation polymerization ( 缩合聚合 ) polymer has fewer atoms in the repeat unit (i.e., some small molecule was emitted during polymerization). n HOOC COOH + nhoch 2 CH 2 OH OOC COOCH 2 CH 2 + n H 2 O n 47

48 Condensation or Addition? O O C O R C O R n O HO R COOH R C O + H 2 O n 48

49 3.2 Chain( 连锁 ) vs Step( 逐步 ) Polymerization reactions are characterized according to its mechanism Chain polymerization ( 连锁聚合 ) The molecular weight increases by the successive and fast linking of monomer molecules to the end of a growing chain. Step Polymerization ( 逐步聚合 ) Polymer chain are built up in a stepwise fashion by the random union of monomer molecules to form dimers, trimers and higher species throughout the monomer matrix 49

50 Comparison between Chain and Step Polymerization monomer polymer Chain Step 50

51 Differences between Chain and Step Polymerization Chain Step Growth occurs only by addition of monomer to active chain end. Monomer is present throughout, but its concentration decreases. Polymer begins to form immediately. Chain growth is usually very rapid (second to microseconds). MW and yield depend on mechanism details. Only monomer and polymer are present during reaction. Usually (but not always) polymer repeat unit has the same atoms as had the monomer Any two molecular species can react. Monomer disappears early. Polymer MW rises slowly. Growth of chains is usually slow (minutes to days). Long reaction times increase MW, but yield of polymer hardly changes. All molecular species are present throughout. Usually (but not always) polymer repeat unit has fewer atoms than had the monomer. 51

52 conversion (%) Variation of Conversion and MW Step chain chain M n step time time 52

53 There are far too many exceptions. Step polymerization by addition of alcohols to diisocyanates to form polyurethanes: Chain polymerization (ring opening of heterocycle) with loss of CO 2 to form polypeptide. 53

54 Other terminologies Ring-opening polymerization ( 开环聚合 ) Ring-opening Metathesis polymerization( 开环异位聚合 ) Group transfer Polymerization( 基团转移聚合 ) 54

55 3.3 Homogeneous vs heterogeneous bulk ( 本体 ) solution ( 溶液 ) emulsion ( 乳液 ) dispersion ( 分散 ) precipitation ( 沉淀 ) suspension ( 悬浮 ) surface ( 表面 ) solid state ( 固相 ) 55

56 4. Molecular Weight and Molecular Weight Distribution 56

57 4.1 Molecular Weight Distribution( 分子量分布 ) Because all polymers are mixtures of many large molecules (polydispersity), one must resort to averages to describe molecular weight. 57

58 4.2 Average Molecular Weight( 平均分子量 ) Among many possible ways of reporting averages, four are commonly used: Number Average M n N M i N i i M Average N N i i M M q i q 1 i M η PDI M M w n M Z Average z N M 3 i i 2 NiM i Weight Average M w N M i N M i 2 i i Viscosity Average M N i N M i +1 i M i 1/ M z >M w >M η >M n 58

59 The weight average is probably the most useful, because it fairly accounts for the contributions of different sized chains to the overall behavior of the polymer, and correlates best with most of the physical properties of interest, e.g. melt viscosity. The ratio of M w to M n is known as the polydispersity index (PDI, 多分散性指数 ), and provides a rough indication of the breadth of the distribution. The PDI approaches 1.0 (the lower limit) for special polymers with very narrow MW distributions, but, for typical commercial polymers, is typically greater than 2 (occasionally much greater). 59

60 4.3 Dependence of Polymer Properties on MW Small molecules have small values the properties level off as the chains become long enough to be true polymers there is a sharp rise in properties as the chains grow to intermediate size 60

61 Many polymer properties of interest (T g, modulus, tensile strength, etc.) follow a peculiar pattern with increasing MW. The goal of polymer synthesis is not to make the largest possible molecules, but rather, to make molecules large enough to get onto the plateau region. A few properties are dictated by the repeat units alone, and therefore these are not changed much by MW. Examples: color, dielectric constant, and refractive index. 61

62 5. Polymer Structure 62

63 5.1 Chain Structure Structure unit CH 2 CH 3 CH 2 CH C CH 2 CH 3 CH 3 63

64 5.1 Chain Structure Structure unit CH 2 CH 3 CH 2 CH C CH 2 CH 3 CH 3 Monomer sequence head-tail CH 2 CH CH 2 CH CH 2 CH CH 2 CH CH CH 2 CH 2 CH Cl head-head Cl Cl Cl Cl Cl -AABBBABABBABB- -AAAAABBBBBBBB- 64

65 5.1 Chain Structure Structure unit CH 3 CH 2 CH CH 2 C CH 3 CH 2 CH 3 Monomer sequence head-tail -AABBBABABBABB- CH 2 CH CH 2 CH CH 2 CH Cl Cl Cl Stereoregularity ( 立构规整性 ) -AAAAABBBBBBBB- CH 2 CH CH CH 2 CH 2 CH Cl Cl Cl head-head R R R R R isotactic cis R R R R R syndiotactic trans 65

66 5.1 Chain Structure Structure unit CH 3 CH 2 CH CH 2 C CH 3 CH 2 CH 3 Monomer sequence head-tail -AABBBABABBABB- CH 2 CH CH 2 CH CH 2 CH Cl Cl Cl Stereoregularity ( 立构规整性 ) -AAAAABBBBBBBB- CH 2 CH CH CH 2 CH 2 CH Cl Cl Cl head-head R R R R R isotactic cis R R R R R syndiotactic trans Topology ( 拓朴结构 ) 66

67 5.1 Chain Structure Structure unit CH 3 CH 2 CH CH 2 C CH 3 CH 2 CH 3 Monomer sequence head-tail -AABBBABABBABB- CH 2 CH CH 2 CH CH 2 CH Cl Cl Cl Stereoregularity ( 立构规整性 ) -AAAAABBBBBBBB- CH 2 CH CH CH 2 CH 2 CH Cl Cl Cl head-head R R R R R isotactic cis R R R R R syndiotactic trans Topology ( 拓朴结构 ) 67

68 5.2 Conformation( 构象 ) random coil rigid rod helical hexagonal 68

69 5.3 Aggregation Morphology( 聚集态结构 ) Most small molecule behavior can be understood in terms of three states: gas, liquid, and solid. Polymers are large molecules with strong intermolecular force and tangled chains, and do not have a vapor phase. The length of polymer molecules also makes it difficult for the large crystals found in the solid phases of most small molecules to form. Instead solid polymers can be modeled in terms of two phases - crystalline and amorphous. Thus the behavior of polymers can better be understood in term of the three phases: melt( 熔融 ), crystalline( 结晶 ), and amorphous ( 无定形 ) 69

Crystalline Polymer molecules are very large so it might seem

It now is known that regular polymers may form lamellar

When a molten crystallizable polymer cools, the crystals grow

70 Crystalline Polymer molecules are very large so it might seem that they could not pack together regularly and form a crystal. It now is known that regular polymers may form lamellar (platelike 片晶 ) crystals with a thickness of 10 to 20 nm. When a molten crystallizable polymer cools, the crystals grow from individual nuclei and radiate out like the spokes of a bicycle wheel. The crystalline portions actually radiate out in in three dimensions, forming spheres that are called spherulites ( 球晶 ). 70

71 Amorphous ( 无定型 ) Polymer chains with branches or irregular pendant groups cannot pack together regularly enough to form crystals. These polymers are said to be amorphous. Amorphous polymers are softer, and are penetrated more by solvents than are their crystalline counterparts. 71

72 Semi-crystalline Semi-crystalline polymers have both crystalline and amorphous regions. Semi-crystallinity is a desirable property for most plastics because they combine the strength of crystalline polymers with the flexibility of amorphous. Semi-crystalline polymers can be tough with an ability to bend without breaking If we model a polymer as having distinct crystalline and amorphous regions, then the percentage of the polymer that is crystalline is called the percent crystallinity. The percent crystallinity has an important influence on the properties of the polymer. 72

73 Aggregation Morphology( 聚集态形态 ) Liqid crystalline Orientation 73

74 Aggregation Morphology Blend 共混物 PS-b-PIp (PS-b-PnBA) n X 74

75 6. Important Properties 75

76 Mechanical properties: Tensile strength, Impact resistant, etc Processing properties: melt viscosity Thermal stability: T g, T m, T c Flame resistance Chemical resistance Degradability Others 76

77 Tensile Strength( 拉伸强度 ) stress needed to break a sample 77

78 % Elongation to Break( 断裂伸长率 ) strain on a sample when it breaks Fibers have a low elongation-to-break and elastomers have a high elongation-to-break 78

79 Young s Modulus( 杨氏模量 ) Young's modulus is the ratio of stress to strain. It also is called the modulus of elasticity or the tensile modulus Rigid materials, such as metals, have a high Young's modulus. In general, fibers have high Young's modulus values, elastomers have low values, and plastics lie somewhere in between 79

80 Toughness( 韧性 ) The toughness is a measure of the energy a sample can absorb before it breaks There is a difference between toughness and strength, as is illustrated in the three plots. 80

81 81

82 The Glass Transition( 玻璃化转变 ) At a low temperature the amorphous regions of a polymer are in the glassy state. In this state the molecules are frozen on place. They may be able to vibrate slightly, but do not have any segmental motion in which portions of the molecule wiggle around. In the glassy state, the motion of the red molecule in the schematic diagram at the right would NOT occur. When the amorphous regions of a polymer are in the glassy state, it generally will be hard, rigid, and brittle. 82

83 Melting Point( 熔点 ) Polymers do not have a single well-defined melting point. When a polymer "melts" it slowly becomes "leathery," then "tacky," and then liquid over a fairly broad temperature range. The crystalline portion of the polymer is a nonequilibrium distribution of a large number of crystallites of different sizes and in different environments. They all do not melt at exactly the same temperature. 83

84 Comparison between glass transiton and melting Glass Transition Property of the amorphous region Below T g : Disordered amorphous solid with immobile molecules Above T g : Disordered amorphous solid in which portions of molecules can wiggle around A second order transition (see below) Melting Property of the crystalline region Below T m : Ordered crystalline solid Above T m : Disordered melt A first-order transition (see below) 84

85 Deformation State transition glass elastic viscoelastic Tg Tf Temperature 85

86 Summery: Characteristics of Polymer High molecular weight derived from small molecules (MW: ) No clear standard in MW Small molecule - oligomer - polymer Complicated chain structure: monomer sequence, topology, regiosequence, tacticity Special properties different from small molecule Soft material in addition to gas, liquid and solid 86

87 Famous Polymer Chemists Nobel Prize Winners H. Staudinger (1953) polymer chain formula. K. Ziegler & G. Natta (1963) Coordination polymerization and stereoregular polymers. 87

molecular weight distribution, solution theory. B.

88 Famous Polymer Chemists Nobel Prize Winners P. Flory (1974) Polymer thermodynamics, kinetics, molecular weight distribution, solution theory. B. Merrifield (1984) Solid phase polypeptide synthesis. 88

89 Famous Polymer Chemists Nobel Prize Winners Donald J. Cram; Jean-Marie Lehn; Charles J. Pedersen (1987) for their development and use of molecules with structurespecific interactions of high selectivity 89

90 Famous Polymer Chemists Nobel Prize Winners P. DeGennes (1991) Polymer solid state theory and liquid crystals. Alan Heeger, Alan MacDiarmid, and Shirakawa (2000) Electrically conducting and semiconducting polymers 90

91 8. History and future 91

92 Modern History 1800 Vulcanization of rubber discovered. Styrene polymerized. Product not understood Isoprene first polymerized; attempt to make rubber. Chain structure hypothesis gains acceptance. Nylon and polyester synthesized Many polymer properties explained. Successful commercialization of numerous polymers. Biopolymer advances lead to DNA technology. Polymers for hightech application developed Foundations of chemistry Various unsaturated monomer polymerized. Studies of natural macromolecules. Industrial production of phenolic resin Synthetic rubber produced for war effort 1950 Thermally stable polymers, other special materials

93 1. 历史和现状 19 世纪 : 天然高分子的改性 1832 年 -- 天然橡胶硫化改性 ( 交联 ), 使橡胶不发粘有高弹性, 成为重要的材料 ; 1868 年 -- 制成硝化纤维塑料 ( 赛璐珞 ); 1892 年 -- 制成粘胶纤维 ( 天然纤维再生制成的人造纤维 ); 20 世纪初 -- 开始生产醋酸纤维素 ( 玻璃纸 ); 年 : 出现最早的合成高分子材料 1872 年 --A. Bayer 发现 : 苯酚加乙醛反应生成树脂状产物 ; 1907 年 --L. Baekeland 发明酚醛树脂的合成与加工方法, 开始大规模应用酚醛塑料 ; 1909 年 -- 出现最早的使异戊二烯聚合的专利 ( 最早的合成橡胶 ); 93

94 年 : 提出高分子的概念及理论初创期 1920 年 --H. Staudinger 发表关于聚合反应的论文, 提出高分子的长链结构概念 ( 此前对高分子的认识与小分子的缔合物相混淆 ) 1930 年 --Staudinger 提出高分子稀溶液粘度公式 :[ ] M, 奠定了表征高分子结构的重要基础高分子化学的基础理论初步建立 ; 年 : 合成高分子工业的初创期, 高分子理论走向成熟 1935 年 --W. H. Carothers 合成出尼龙 -66,1938 年实现工业化 ( 缩聚的开端 ) 1940 年 -- 涤纶合成成功, 于 1945 年实现工业化 ; 年期间,PVC,PS,PMMA( 有机玻璃 ) 聚四氟乙烯 (Teflon), 高压聚乙烯 (LDPE) 等自由基聚合产品相继实现工业化 ; 1935 年 --H.Mark 提出加聚动力学方程 ; 1939 年 --P. J. Flory 提出缩聚中官能团等活性分子量与反应程度关系等理论 ; 年 -- 建立了一系列测定聚合物分子量的方法 ( 最著名的为 Mark- Houwink 方程 : [ ] = K M ); 1942 年 -- 发展高分子溶液的统计热力学理论 (Flory, Huggins 等 ); 年 -- 对自由基加聚机理的研究已趋于成熟 ; 94

95 年 : 配位聚合与离子聚合的发现与发展 1953 年 --K. Ziegler 发现 TiCl4/ 有机铝催化乙烯聚合 ( 低压聚乙烯 ), 开创配位聚合领域, 将金属有机化学引入到高分子合成中 ; 1954 年 --G. Natta 发现全同立构聚丙烯及其合成方法, 开辟立构规整聚合的领域 ; 1955 年 --Szwarc 发现活性阴离子聚合, 为嵌段聚合物 (SBS 等 ) 奠定基础 ; 1956 年 -- 合成出与天然橡胶十分接近的高顺式聚异戊二烯 ; 29 世纪年代 : 大品种通用高分子发展成熟, 工程塑料发展期年逐步发展烯烃聚合的高效催化剂工艺和一系列新品种, 产量迅速增加 ; 年 -- 聚甲醛聚碳酸酯等工程塑料实现工业化 ; 新型工程塑料及高强度耐高温塑料和纤维迅速发展 ; 精细高分子功能高分子进入发展期和初创期 95

96 年 : 功能高分子进入发展期, 可控聚合反应进一步发展, 通用高分子高性能化发展一大批功能高分子品种 -- 离子交换树脂, 螯合树脂, 高分子试剂, 高分子催化剂, 导电高分子, 光敏树脂, 膜分离材料, 高分子光电导材料, 电致发光材料, 高分子非线性光学材料, 高分子磁性材料, 生物相容性材料, 高分子药物载体, 等 ; 茂金属催化剂及烯烃的可控聚合 -- 实现聚烯烃的分子量分布与组成分布的可控, 大幅度提高材料性能 ; 实现丙烯和苯乙烯的间规聚合 -- 立体定向聚合的重要进展 ; 实现阳离子开环及自由基等机理下的活性聚合 -- 开辟了合成大批结构高度可控的新型高分子材料的途径 ; 发展了合成树枝状高分子和超支化聚合物的新方法 ; 合成通用高分子的生产工艺更加先进, 装置大型化, 能耗和污染排放显著减少, 产品性能不断提高 ; 96

97 2. 发展趋势发现新类型的聚合反应的机会在逐渐减少, 但对已有聚合方法的改进和发展仍十分活跃目标 :(1) 提高反应效率, 降低生产成本, 减少对环境的有害影响 ; (2) 更精确地控制聚合物的链结构, 提高材料性能, 并为设计与合成结构更复杂精细的高分子创造条件进一步发展功能高分子材料, 解决实用化的瓶颈问题, 开拓更多新的功能关键 :(1) 利用高分子合成的成果来设计和制备具有各种复杂和精细结构的高分子, 实现功能的强化和优化 ; (2) 借鉴材料物理生物信息等学科的理论和技术, 进行多学科交叉, 建立功能高分子的基础理论与生命科学相互交叉和渗透, 发展仿生高分子, 解决环境问题和可持续发展问题 97

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