间规聚苯乙烯及间规聚丙烯结晶研究
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摘要
八十年代以来，对茂金属佑化剂的深入研究使高间规度聚烯烃的合成成为可
能，随之诞生了一系列性能优异、应用前景广阔的聚烯烃新品种，间规聚苯乙烯
（s－PS）和间规聚丙烯（s－PP）就是其中令人瞩目的两种。二者均具有复杂的多晶型
现象和独特的优良性能。s干S分子中，分于链两旁均匀间隔地分布着侧基苯环，
这种有序结构赋予s干S优良的耐热性、耐化学性、结晶性和尺寸稳定性；s干P
则具有较高的透明度、耐冲击强度、韧性及弹性。
S干S可划分为四种品型：Q、e、Y和6品型。其中，Q和p晶型具有平面
锯齿形链构象，等同周期 0．sin。，（二者又可以不同有序程度的变体存在）；
s和6晶型则具有S（2八）2螺旋构象分子链，等同周期0．77urn。s干S结晶的晶
型可受结晶方式（熔融或溶液结晶）、压力、退火等多种因素的影响。
S干P结晶也有四种品型：品型 1、11、Ill、IV。其中晶型 1、11均具有 T。G。
链构象，晶型1是于一般结晶条件卜所得样品中最稳定的品型，品型11常出现在
退火的＊－叮纤维样品中／ 梨m具有平面锯齿形链构象，常出现于冷拉样品
中；晶型IV则具有T，G。T币。构象，将晶型IllS干P样品暴露于有机溶剂蒸汽中可
得。
S－PS及S－PP均是具有多品型的半品性高聚物，其晶型、品体结构及结晶形
态等对加工应用有十分重要的影响，近年来二者结品研究已取得一定进展，但仍
存在如下一些薄弱环节。首先，熔体结品在加厂过程中非常常见，但熔体结晶条
件对品体结构的影响尚无系统研究；其次，不同品兜之间在升温过程中是否存在
晶型转变及如何转变尚无系统研究；此外，对二者非等温结晶动力学过程的处理
文献报道较少，且多是以cia。a和Jezioeny方法进行，所得结果不能说明结晶
前、后期成核机理的差异；此外，以人球晶存在的S千S 极易具存性脆的缺点，
故其聚集态结构对性能有十分重要的影响，但此方面系统研究尚未见文献报道。
基于以上儿点，本论文做了如下卜作，以拙对选择合适加工卜艺、提高材料性能
提供一定的理论指导。
首先系统研究结晶条什对等温熔体结晶 S干S的影响。发现不同温度（Tc）
下结晶所得s千S均为口、6两品型的混合物，高温下结晶有利于p晶型的生
成，分子量和间规度的提高有利于形成。品型。晶面间距山。；．、山；；，随＊升高而
－VI－
增加，do。卜 d。。。、d＊受间规度及分于量影响较人，d门受间规度及分于量影响
影响较小。分于链规整度的提高使S－PS沿各方向结品速率提高。
其次，对S干S 不同条件结晶样品的熔融行为进行了系统研究。发现骤冷样
品冷结晶只形成口品型，冷结晶样品的熔融过程伴随有再结晶现象。冷结晶时间
（t。）与升温速率m）关系为t。二1215．6R“‘”’（S），冷结品温度随R增加而升高，
凸 H。则变化不大。非等温熔体结晶 S－PS 则为口、p两晶型的混合物，缓速降温
有利于生成p品型，且使所得S－PS结品度增加。
此外，在文献基础上设计了较简便方法制得两种溶剂诱导结晶 S－PS：Y、6
晶型c并以变温 X射线衍射和 DSC相结合动态研究了二晶型在升温过程中的晶型
转变。发现在10K／min升温过程中，Y晶型s千S丁190－Z10t发生Y－。转变，
5晶型 S斗S在 150C左心发生 CHCI，；分于的“脱笼”，180－200T和 200－Z15’C
分别发生6－Y和Y－口转变。
另外，还以BOp。X。bCkUfi方法系统研究了 S干S和 S干P的非等温结品动力
学，发现二者非等温结晶过程中 t；。。和 t。、均随降温速率（a）增加呈指数卜降，
s－PS、s－PP 的 t；。和 t．，。关系式分别为 b。＝1007a““”t。、t。－＝1102a‘””‘’
t。。。S－PS、S千P非等温结品过种中均存在二次结晶现象，结晶前、后期成核机
理有明显差异。结晶前期二者成核机理受a影响较人，结晶后期s干S 为异相成
核、二维生K：S干P 为二维条带和圆形生K且后划结晶速率人了前期。S干S 和
s－PP的非等温结品活化能分别为382．OKJ／。of和 137．3KJ，mol，s－PS的冷结品
活化能为158．ZKJ／mol。
以偏光显微镜（PLM）和扫描电镜（SEM）研究了S－PS 等温熔体结晶的球品结
构，发现S－PS出昂熔体结品样品随结品温度不同可形成七类球品。220230oC可得
止光性羽毛状球品，其品片较人、堆砌松散，品片沿品核向四周．发散排列：230℃
以上形成的羽毛状球品则为混光性，其品片细小、堆砌紧密；240℃形成人量八瓣
球品和个别四瓣球品，八瓣球晶与前二者相比品片更为细小且无规排列、相互交
联：此外，230C左心还可能有螺旋品和末品形成。S斗S进行SE＼1观察的刻蚀条
什为：铬酸刻蚀液T 80aC氧化刻蚀 27min。
最后，系统研究了不同条件
As two kinds of potential engineering plastics, syndiotactic
polystyrene (s-PS) and syndiotactic polypropylene (s-PP) have enjoyed
intense industrial and academic interest, due to their good performance
and complex polymorphic behavior.
In the past, the work in structure of s-PS demonstrated that four
different crystalline forms is possible by different processing behavior:
a, P, i~ and 6. The crystalline Q and P forms are characterized by
chains in the trans planar conformation with an identity period of
c=0.Slnm, can be obtained from the melt or the glassy state of s-PS
under different thermal condition, whereas the crystalline Y and 6
forms have chains in the S(2/1)2 helical conformation with an identity
period of c=0.78nm, are formed under condition where solvents are
in vol ~Ted.
s-PP presents polymorphism in the solid state, too. It can be divided
as four kind of crystalline forms that were named as form I . II , III and
IV, respectively. Both form I and II were characterized by chains in
helical (TTGG)~ conformation, crystalline form III have chains in trans-
planar conformation, and form IV presents chains in a (T6G2T2G2)~
conformation which intermediate between the helical (TTGG)~ and the
trans-planar conformation.
The research on the crystal of s-PS and s-PP have made progress
these years but still need step further in some fields. In this paper, the
crystal structure, crystal form transition, melting, morphology and
-lx-
kinetics was studied by WAXD, DSC, successive WAXD, PLM, SEM
and TG, respectively.
Based on WAXD diffraction patterns of isothermal melt
crystallization, the conclusion that s-PS crystallized from melt contain
a and P s-PS. The increasing of T~ and degree of syndiotacticity is
benefit to the formation of P and a s-PS, respectively. Crystal plane
distance (d) and crystallite dimension is influenced by T~ greatly. The
decreasing of cooling rate (a) benefit to the formation of P s-PS.
The relation of cool crystallization time (ta) of quenched s-PS and
heating rate (R) is calculated as t~12l5.6R0843. The crystal formed
within cool crystallization could be only a s-PS, and the melt of it is
company with re-crystallization.
Two kind of solvent-induced s-PS: v and 6 s-PS was prepared by a
new simple way. Corresponding to successive WAXD patterns during
heating at 10K/mm of Y and 6 s-PS, y s-PS transform to a s-PS
within 190-2100C before melt. 6 s-PS transform to y s-PS at 180-200
憕C and transform continue to a form at 200-2150C. 6 - y and y - a
transition is endothermal and exothermal process, respectively.
To the nonisothermal crystallization of s-PS, the nucleation
mechanism of earlier and later stage is different. The mechanism of
earlier stage is influenced by cooling rate greatly, by that Qf later stage
is heterogeneous nucleation and three-dimension growing. Energy of
nonisothermal and cool crystallization is 382KJ/mol and 158.2KJ/mol,
respectively.
The m7orphology of melting-crystallization s-PS which has different
content of a and P forms was observed by PLM and SEM. There are
eight kinds of spherulite formed as crystalline temperature (Ta) changed
from 220 0C to Tm. Four-sectional spherulite and eight-sectional
spherulites can be obtained when crystallized in higher temperature
(T~>2400C). The spherulite is feathered and lamellae structure is bulking
As T~ low
能，随之诞生了一系列性能优异、应用前景广阔的聚烯烃新品种，间规聚苯乙烯
（s－PS）和间规聚丙烯（s－PP）就是其中令人瞩目的两种。二者均具有复杂的多晶型
现象和独特的优良性能。s干S分子中，分于链两旁均匀间隔地分布着侧基苯环，
这种有序结构赋予s干S优良的耐热性、耐化学性、结晶性和尺寸稳定性；s干P
则具有较高的透明度、耐冲击强度、韧性及弹性。
S干S可划分为四种品型：Q、e、Y和6品型。其中，Q和p晶型具有平面
锯齿形链构象，等同周期 0．sin。，（二者又可以不同有序程度的变体存在）；
s和6晶型则具有S（2八）2螺旋构象分子链，等同周期0．77urn。s干S结晶的晶
型可受结晶方式（熔融或溶液结晶）、压力、退火等多种因素的影响。
S干P结晶也有四种品型：品型 1、11、Ill、IV。其中晶型 1、11均具有 T。G。
链构象，晶型1是于一般结晶条件卜所得样品中最稳定的品型，品型11常出现在
退火的＊－叮纤维样品中／ 梨m具有平面锯齿形链构象，常出现于冷拉样品
中；晶型IV则具有T，G。T币。构象，将晶型IllS干P样品暴露于有机溶剂蒸汽中可
得。
S－PS及S－PP均是具有多品型的半品性高聚物，其晶型、品体结构及结晶形
态等对加工应用有十分重要的影响，近年来二者结品研究已取得一定进展，但仍
存在如下一些薄弱环节。首先，熔体结品在加厂过程中非常常见，但熔体结晶条
件对品体结构的影响尚无系统研究；其次，不同品兜之间在升温过程中是否存在
晶型转变及如何转变尚无系统研究；此外，对二者非等温结晶动力学过程的处理
文献报道较少，且多是以cia。a和Jezioeny方法进行，所得结果不能说明结晶
前、后期成核机理的差异；此外，以人球晶存在的S千S 极易具存性脆的缺点，
故其聚集态结构对性能有十分重要的影响，但此方面系统研究尚未见文献报道。
基于以上儿点，本论文做了如下卜作，以拙对选择合适加工卜艺、提高材料性能
提供一定的理论指导。
首先系统研究结晶条什对等温熔体结晶 S干S的影响。发现不同温度（Tc）
下结晶所得s千S均为口、6两品型的混合物，高温下结晶有利于p晶型的生
成，分子量和间规度的提高有利于形成。品型。晶面间距山。；．、山；；，随＊升高而
－VI－
增加，do。卜 d。。。、d＊受间规度及分于量影响较人，d门受间规度及分于量影响
影响较小。分于链规整度的提高使S－PS沿各方向结品速率提高。
其次，对S干S 不同条件结晶样品的熔融行为进行了系统研究。发现骤冷样
品冷结晶只形成口品型，冷结晶样品的熔融过程伴随有再结晶现象。冷结晶时间
（t。）与升温速率m）关系为t。二1215．6R“‘”’（S），冷结品温度随R增加而升高，
凸 H。则变化不大。非等温熔体结晶 S－PS 则为口、p两晶型的混合物，缓速降温
有利于生成p品型，且使所得S－PS结品度增加。
此外，在文献基础上设计了较简便方法制得两种溶剂诱导结晶 S－PS：Y、6
晶型c并以变温 X射线衍射和 DSC相结合动态研究了二晶型在升温过程中的晶型
转变。发现在10K／min升温过程中，Y晶型s千S丁190－Z10t发生Y－。转变，
5晶型 S斗S在 150C左心发生 CHCI，；分于的“脱笼”，180－200T和 200－Z15’C
分别发生6－Y和Y－口转变。
另外，还以BOp。X。bCkUfi方法系统研究了 S干S和 S干P的非等温结品动力
学，发现二者非等温结晶过程中 t；。。和 t。、均随降温速率（a）增加呈指数卜降，
s－PS、s－PP 的 t；。和 t．，。关系式分别为 b。＝1007a““”t。、t。－＝1102a‘””‘’
t。。。S－PS、S千P非等温结品过种中均存在二次结晶现象，结晶前、后期成核机
理有明显差异。结晶前期二者成核机理受a影响较人，结晶后期s干S 为异相成
核、二维生K：S干P 为二维条带和圆形生K且后划结晶速率人了前期。S干S 和
s－PP的非等温结品活化能分别为382．OKJ／。of和 137．3KJ，mol，s－PS的冷结品
活化能为158．ZKJ／mol。
以偏光显微镜（PLM）和扫描电镜（SEM）研究了S－PS 等温熔体结晶的球品结
构，发现S－PS出昂熔体结品样品随结品温度不同可形成七类球品。220230oC可得
止光性羽毛状球品，其品片较人、堆砌松散，品片沿品核向四周．发散排列：230℃
以上形成的羽毛状球品则为混光性，其品片细小、堆砌紧密；240℃形成人量八瓣
球品和个别四瓣球品，八瓣球晶与前二者相比品片更为细小且无规排列、相互交
联：此外，230C左心还可能有螺旋品和末品形成。S斗S进行SE＼1观察的刻蚀条
什为：铬酸刻蚀液T 80aC氧化刻蚀 27min。
最后，系统研究了不同条件
As two kinds of potential engineering plastics, syndiotactic
polystyrene (s-PS) and syndiotactic polypropylene (s-PP) have enjoyed
intense industrial and academic interest, due to their good performance
and complex polymorphic behavior.
In the past, the work in structure of s-PS demonstrated that four
different crystalline forms is possible by different processing behavior:
a, P, i~ and 6. The crystalline Q and P forms are characterized by
chains in the trans planar conformation with an identity period of
c=0.Slnm, can be obtained from the melt or the glassy state of s-PS
under different thermal condition, whereas the crystalline Y and 6
forms have chains in the S(2/1)2 helical conformation with an identity
period of c=0.78nm, are formed under condition where solvents are
in vol ~Ted.
s-PP presents polymorphism in the solid state, too. It can be divided
as four kind of crystalline forms that were named as form I . II , III and
IV, respectively. Both form I and II were characterized by chains in
helical (TTGG)~ conformation, crystalline form III have chains in trans-
planar conformation, and form IV presents chains in a (T6G2T2G2)~
conformation which intermediate between the helical (TTGG)~ and the
trans-planar conformation.
The research on the crystal of s-PS and s-PP have made progress
these years but still need step further in some fields. In this paper, the
crystal structure, crystal form transition, melting, morphology and
-lx-
kinetics was studied by WAXD, DSC, successive WAXD, PLM, SEM
and TG, respectively.
Based on WAXD diffraction patterns of isothermal melt
crystallization, the conclusion that s-PS crystallized from melt contain
a and P s-PS. The increasing of T~ and degree of syndiotacticity is
benefit to the formation of P and a s-PS, respectively. Crystal plane
distance (d) and crystallite dimension is influenced by T~ greatly. The
decreasing of cooling rate (a) benefit to the formation of P s-PS.
The relation of cool crystallization time (ta) of quenched s-PS and
heating rate (R) is calculated as t~12l5.6R0843. The crystal formed
within cool crystallization could be only a s-PS, and the melt of it is
company with re-crystallization.
Two kind of solvent-induced s-PS: v and 6 s-PS was prepared by a
new simple way. Corresponding to successive WAXD patterns during
heating at 10K/mm of Y and 6 s-PS, y s-PS transform to a s-PS
within 190-2100C before melt. 6 s-PS transform to y s-PS at 180-200
憕C and transform continue to a form at 200-2150C. 6 - y and y - a
transition is endothermal and exothermal process, respectively.
To the nonisothermal crystallization of s-PS, the nucleation
mechanism of earlier and later stage is different. The mechanism of
earlier stage is influenced by cooling rate greatly, by that Qf later stage
is heterogeneous nucleation and three-dimension growing. Energy of
nonisothermal and cool crystallization is 382KJ/mol and 158.2KJ/mol,
respectively.
The m7orphology of melting-crystallization s-PS which has different
content of a and P forms was observed by PLM and SEM. There are
eight kinds of spherulite formed as crystalline temperature (Ta) changed
from 220 0C to Tm. Four-sectional spherulite and eight-sectional
spherulites can be obtained when crystallized in higher temperature
(T~>2400C). The spherulite is feathered and lamellae structure is bulking
As T~ low
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40 F. De Candia, G. Romano, R.Russo et al., Colloid Polym. Sci., 1990, 269, 720
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65 H. Maezawa H., M. Kuramoto, U. S. Pat., 5 023 322,1991
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67 许学翔，周鼎，谢光华，高分子学报，1997，6，746
68 祝方明，王群芳，林尚安，涂建军，周文乐，陈德铨，石油化工，1999，28，224
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72 滕凤恩，王煜明，姜小龙 主编，X射线结构分析与材料性能表征，科学出版社，第五章
73 吴人洁 主编，现代分析技术—在高聚物中的应用，上海科学技术出版社
74 莫志深等，现代高分子物理学与方法，科学技术出版社，待出版
75 R. H. Lin, E. M. Woo, Polymer, 2000,41,121
76 A. J. Pasztor. Jr, B. G. Landes, P. J. Karjala, Thermochimica Acta., 1991,177,187
77 杨始堃，黎少华，陈玉君，刘佑习，潘鉴元，高分子材料科学与工程，1988，6，1
78 G. Guerra, C. Manfredi, P. Musto, S. Tavone, Macromolecules, 1998,31,1329
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92 李海鹏，沈家瑞，祝方明，应用化学，1999，16(2)，27
93 R. D. Wesson, Polym. Eng. and Sci., 1994,34,1157
94 S. Cimmino, E. Di Pace, E. Martuscelli et al., Polymer, 1991,32(6),1080
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96 Kissinger H. E., J. Res. Natl. Stds., 1956,57,217
97 E. M. Woo, Fu Sun Wu, J. Polym. Sci. Part B-Polym. Phys., 1998, 36, 2725
98 朱诚身，李修道，李华光，杨桂萍，高分子学报，1992，4，457
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102 季寿元，王德滋，晶体光学，人民教育出版社，1961，163
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110 于英宁，张宏放，莫志深，高分子学报，待发表
111 朱诚身，加成核剂等规聚丙烯非等温结晶研究(硕士论文)，中山大学，1985，7
112 L. B. Morgan, J. Appl. Chem., 1954,4,160
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43 ACS Polym. Prepr., 1993, 34, 1
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60 J. Loos, J. Petermann, A. Waldofner, Colloid & Polym. Sci., 1997,275,1088
61 N. Ishihara., M. T. Kuramoto, M. Uio., Macromolecules, 1988,21,3356
62 T. Quyoum, Q. Wang, J. M. Judoret et al., J. Am. Chem. Soc., 1994,116,6435
63 P. Foster, W. C. Chien, D. M. Rausch, Organometallics, 1996,15,2404
64 T. E. Ready, J. C. W. Chine, D. M. Rausch, J. Organomet. Chem., 1996,519,21
65 H. Maezawa H., M. Kuramoto, U. S. Pat., 5 023 322,1991
66 祝方明，林尚安，周文乐，涂建军，陈德铨，石油化工，1999，28，224
67 许学翔，周鼎，谢光华，高分子学报，1997，6，746
68 祝方明，王群芳，林尚安，涂建军，周文乐，陈德铨，石油化工，1999，28，224
69 R. Po, N. Cardi, L. Abis, Polymer, 1998,39(4),959
70 C. De Rosa, G. Guerra, V. Petraccone, P. Corradini, Polym. J., 1991,23(12),1435
71 M. Kobayashi, T. Nakaoki, N. Ishihara, Macromolecules, 1989,22,4377
72 滕凤恩，王煜明，姜小龙 主编，X射线结构分析与材料性能表征，科学出版社，第五章
73 吴人洁 主编，现代分析技术—在高聚物中的应用，上海科学技术出版社
74 莫志深等，现代高分子物理学与方法，科学技术出版社，待出版
75 R. H. Lin, E. M. Woo, Polymer, 2000,41,121
76 A. J. Pasztor. Jr, B. G. Landes, P. J. Karjala, Thermochimica Acta., 1991,177,187
77 杨始堃，黎少华，陈玉君，刘佑习，潘鉴元，高分子材料科学与工程，1988，6，1
78 G. Guerra, C. Manfredi, P. Musto, S. Tavone, Macromolecules, 1998,31,1329
79 C. De Rosa, G. Guerra, V. Petraccone, B. Pirozzi, Macromolecules, 1997,30,4147
80 A. Immirzi, F. de Candia, P. Iannelli, A. Zambelli, Makromol. Chem., Rapid Commun., 1988,9,761
81 V. Vittoria, F. de Candia, P. Iarmelli, A. Immirzi, Makromol. Chem., Rapid Commun., 1988,9,765
82 S. Moyses, S. J. Spells, Polymer, 1999,40,3269
83 C. Manfredi, M. A. Del Nobile, G. Mensitieri, G. Guerra, M. Rapacciuolo, J. Polym. Sci. Part B-Polym. Phys., 1997,35,133
84 C. Manfredi, C. De Rosa, G. Guerra, M. Rapacciuolo, F. Auriemma, P. Corradini, Macromol. Chem. Phys., 1995,196,2795
85 C. De Rosa, P. Rizzo, O. R. De Ballesteros, V. Petraccone, G. Guerra, Polymer, 1999,40,2103
86 K. Tsutsui, T. Katsumata, Y. Yamamoto, H. Fukatsu, H. Yoshimizu, T. Kinoshita, Y. Tsujita, Polymer, 1999,40,3815
87 T. Ozawa, Polymer, 1971,12,150
88 A. Jeziorny, Polymer, 1978,19,1142
89 薛小芙，杨宝泉，莫志深，高分子学术报告会预印集，1992，长春
90 B. A. Bopoxobckuǚ, Bucornol. Coeg. Kpa. Cool., 1975,Ⅶ(1),35
91 A. Ziabicki, Appl. Polym. Symp., 1967,6,1
92 李海鹏，沈家瑞，祝方明，应用化学，1999，16(2)，27
93 R. D. Wesson, Polym. Eng. and Sci., 1994,34,1157
94 S. Cimmino, E. Di Pace, E. Martuscelli et al., Polymer, 1991,32(6),1080
95 许光学，林尚安，高分子材料科学与工程，1999，15(2)，65
96 Kissinger H. E., J. Res. Natl. Stds., 1956,57,217
97 E. M. Woo, Fu Sun Wu, J. Polym. Sci. Part B-Polym. Phys., 1998, 36, 2725
98 朱诚身，李修道，李华光，杨桂萍，高分子学报，1992，4，457
99 J. A. Lovinger, B. Lotz, D. D. Davis, Polymer, 1990,31,2253
100 J. A. Lovinger, B. Lotz, D. D. Davis, Macromolecules, 1991,24,552
101 于同隐，平郑骅，徐又一，高分子通讯，1983，3，231
102 季寿元，王德滋，晶体光学，人民教育出版社，1961，163
103 O. Greis, Y. Xu, T. Asano, J. Petermann, Polymer, 1989,30,590
104 汪昆华，周传秋，周啸，聚合物近代仪器分析，清华大学出版社，1991，203
105 高家武 主编，高分子材料近代测试技术，北京航空航天大学出版社，北京，1994，274
106 于英宁，张宏放，莫志深，陈伟，孙春燕，应用化学，1998，15(6)，77
107 L. Guadagno, C. Fontanella, V. Vittoria, P. Longo, J. Polym. Sci. Part B-Polym. Phys., 1999,37,173
108 于英宁，张宏放，莫志深，陈伟，孙春燕，高分子学报，1999，3，302
109 L. Mandelkem, Crystallization of Polymers, New York: Mcagraw-Hill, 1964,213
110 于英宁，张宏放，莫志深，高分子学报，待发表
111 朱诚身，加成核剂等规聚丙烯非等温结晶研究(硕士论文)，中山大学，1985，7
112 L. B. Morgan, J. Appl. Chem., 1954,4,160