Citation: Hai Wang, Chun-Ji Wu, Dong-Mei Cui, Yong-Feng Men. Equilibrium Crystallization Temperature of Syndiotactic Polystyrene γ Form[J]. Chinese Journal of Polymer Science, ;2018, 36(6): 749-755. doi: 10.1007/s10118-018-2059-1 shu

Equilibrium Crystallization Temperature of Syndiotactic Polystyrene γ Form

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Corresponding author: Yong-Feng Men, men@ciac.ac.cn
Received Date: 22 August 2017
Accepted Date: 7 October 2017
Available Online: 29 January 2018

The crystallization behavior of syndiotactic polystyrene (sPS) γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl's crystallization theory. On the basis of the differential scanning calorimetric results, it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness, which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization. Further temperature dependent small-angle X-ray scattering (SAXS) measurement revealed the evolution of the γ form lamellae upon heating until phase transition, involving three different regimes:lamellae stable region (25-90℃), melt-recrystallization region (90-185℃) and pre-phase transition region (185-195℃). As a result, recrystallization line, equilibrium recrystallization line and melting line were developed for the sPS γ form crystallization process. Since the melt of γ form involved a γ-to-α/β form phase transition, the melting line was also denoted as the phase transition line in this special case. Therefore, the equilibrium crystallization temperature and melting (phase transition) temperatures were determined at around 390 and 220℃ on the basis of the thermodynamic phase diagram of the sPS γ form.
- Syndiotactic polystyrene γ form,
- Crystallization behavior,
- Equilibrium crystallization temperature,
- Equilibrium melting temperature
1. [1]
  Auriemma F., Petraccone V., Poggetto F. D., de Rosa C., Guerra G., Manfredi C., Corradini P.. Mesomorphic form of syndiotactic polystyrene as composed of small imperfect crystals of the hexagonal (α) crystalline form[J]. Macromolecules, 1993,26(15):3772-3777. doi: 10.1021/ma00067a008
2. [2]
  Petraccone V., Auriemma F., Poggetto F. D., de Rosa C., Guerra G., Corradini P.. On the structure of the mesomorphic form of syndiotactic polystyrene[J]. Makromol. Chem., 1993,194(5):1335-1345. doi: 10.1002/macp.1993.021940508
3. [3]
  Ishihara N., Seiniya T., Kuramoto M., Uoi M.. Crystalline syndiotactic polystyrene[J]. Macromolecules, 1986,19(9):2464-2465. doi: 10.1021/ma00163a027
4. [4]
  Guerra G., de Rosa C., Petraccone V., Corradini P.. Polymorphism in melt crystallized syndiotactic polystyrene samples[J]. Macromolecules, 1990,23(5):1539-1544. doi: 10.1021/ma00207a050
5. [5]
  de Rosa C., Guerra G., Petraccone V., Corradini P.. Crystal structure of the α-form of syndiotactic polystyrene[J]. Polym. J., 1991,23(12):1435-1442. doi: 10.1295/polymj.23.1435
6. [6]
  Chatani Y., Shimane Y., Inoue Y., Inagaki T., Ishioka T.. Structural study of syndiotactic polystyrene 1[J]. polymorphism. Polymer, 1992,33(3):488-492.
7. [7]
  Corradini P., de Rosa C., Guerra G., Napolitano R., Petraccone V., Pirozzi B.. Confirmational and packing energy of the crystalline α modification of syndiotactic polystyrene[J]. Eur. Polym. J., 1994,30(10):1173-1177. doi: 10.1016/0014-3057(94)90255-0
8. [8]
  de Rosa C.. Crystal structure of the trigonal modification (α form) of syndiotactic polystyrene[J]. Macromolecules, 1996,29(26):8460-8465. doi: 10.1021/ma960905q
9. [9]
  Cartier L., Okihara T., Lotz B.. The α" superstructure of syndiotactic polystyrene:a frustrated structure[J]. Macromolecules, 1998,31(10):3303-3310.
10. [10]
  Lotz B.. An intrinsic crystallographic disorder in the frustrated α" phase of syndiotactic polystyrene[J]. Polymer, 2015,56(15):245-251.
11. [11]
  Vittoria V., Filho A. R., de Candia F.. Structural organization of syndiotactic polystyrene films crystallized in the β form[J]. J. Macromol. Sci. Part B, 1992,31(2):133-148. doi: 10.1080/00222349208215508
12. [12]
  De Rosa C., Rapacciuolo M., Guerra G., Petraccone V., Corradini P.. On the crystal structure of the orthorhombic form of syndiotactic polystyrene[J]. Polymer, 1992,33(7):1423-1428. doi: 10.1016/0032-3861(92)90117-F
13. [13]
  Chatani Y., Shimane Y., Ijitsu T., Yukinari T.. Structural study on syndiotactic polystyrene 3[J]. crystal structure of planar form I. Polymer, 1993,34(8):1625-1629.
14. [14]
  Napolitano R., Pirozzi B., Chimica D., Ii F.. The role of molecular mechanics in the prediction of the chain conformation of polymers in the crystalline state:syndiotactic polymers[J]. Macromol. Theory. Simul., 1999,8(1):15-25. doi: 10.1002/(ISSN)1521-3919
15. [15]
  Tosaka M., Tsuji M., Kohjiya S., Cartier L., Lotz B.. Crystallization of syndiotactic polystyrene in β-form[J]. 4. crystal structure of melt-grown modification. Macromolecules, 1999,32(15):4905-4911.
16. [16]
  de Candia F., Romano G., Russo R., Vittoria V.. Solvent crystallized syndiotactic polystyrene[J]. thermal and dynamic-mechanical behavior. Colloid Polym. Sci., 1993,271(5):454-459.
17. [17]
  Handa Y. P., Zhang Z., Wong B.. Effect of compressed CO₂ on phase transitions and polymorphism in syndiotactic polystyrene[J]. Macromolecules, 1997,30(26):8499-8504. doi: 10.1021/ma9712209
18. [18]
  Naddeo C., Guadagno L., Aciemo D., Vittoria V., Chimica I., Salemo U., Ponte V., Melillo D., Salemo F.. Studies of the γ to α transition in syndiotactic polystyrene[J]. Macromol. Symp., 1999,138(1):209-214. doi: 10.1002/masy.v138.1
19. [19]
  Rizzo P., Albunia A. R., Guerra G.. Polymorphism of syndiotactic polystyrene:γ phase crystallization induced by bulky non-guest solvents[J]. Polymer, 2005,46(23):9549-9554. doi: 10.1016/j.polymer.2005.07.063
20. [20]
  Immirzi A., de Candia F., Iannelli P., Zambelli A.. Solvent-induced polymorphism in syndiotactic polystyrene[J]. Makromol. Chem., Rapid Commun., 1988,9:761-764. doi: 10.1002/marc.1988.030091108
21. [21]
  Kobayashi M.. Polymorphic structures and molecular vibrations of syndiotactic polystyrene[J]. Macromolecules, 1989,22(11):4377-4382. doi: 10.1021/ma00201a037
22. [22]
  Chatani Y., Shimane Y., Inagaki T., Ijitsu T., Yukinari T. S. H.. Structural study on syndiotactic polystyrene:2[J]. crystal structure of molecular compound with toluene. Polymer, 1993,34(8):1620-1624.
23. [23]
  De Rosa C., Guerra G., Petraccone V.. Crystal structure of the emptied clathrate form (δ_e form) of syndiotactic polystyrene[J]. Macromolecules, 1997,30(14):4147-4152. doi: 10.1021/ma970061q
24. [24]
  Reverchon E., Guerra G., Venditto V.. Regeneration of nanoporous crystalline syndiotactic polystyrene by supercritical CO₂[J]. J. Appl. Polym. Sci., 1999,74(8):2077-2082. doi: 10.1002/(ISSN)1097-4628
25. [25]
  Rani D. A., Yamamoto Y., Saito A., Sivakumar M., Tsujita Y., Yoshimizu H., Kinoshita T.. Structure and properties of the mesophase of syndiotacticpolystyrene. Ⅱ. Effect of stepwise extraction on the preparation of the mesophase[J]. J. Polym. Sci., Part B:Polym. Phys., 2003,41(3):269-273. doi: 10.1002/(ISSN)1099-0488
26. [26]
  Ma W., Yu J., He J.. Empty δ crystal as an intermediate form for the δ to γ transition of syndiotactic polystyrene in supercritical carbon dioxide[J]. Macromolecules, 2005,38(11):4755-4760. doi: 10.1021/ma050488u
27. [27]
  Vittoria V., de Candia F., Iannelli P., Immirzi A.. Solvent-induced crystallization of glassy syndiotactic polystyrene[J]. Makromol. Chem., Rapid Commun., 1988,9:765-769. doi: 10.1002/marc.1988.030091109
28. [28]
  Gowd E. B., Tashiro K., Ramesh C.. Structural phase transitions of syndiotactic polystyrene[J]. Prog. Polym. Sci., 2009,34(3):280-315. doi: 10.1016/j.progpolymsci.2008.11.002
29. [29]
  Ma W., Yu J., He J.. Direct formation of γ form crystal of syndiotactic polystyrene from amorphous state in supercritical CO₂[J]. Macromolecules, 2004,37(18):6912-6917. doi: 10.1021/ma0491715
30. [30]
  Ma W., Yu J., He J.. Stability of crystal forms of syndiotactic polystyrene correlated with their formation in different media having different solubility parameters[J]. Polymer, 2005,46(24):11104-11111. doi: 10.1016/j.polymer.2005.09.002
31. [31]
  de Rudder J., Berghmans H., Arnauts J.. Phase behaviour and structure formation in the system syndiotactic polystyrene cyclohexanol[J]. Polymer, 1999,40(21):5919-5928. doi: 10.1016/S0032-3861(98)00819-2
32. [32]
  Reiter G., Strobl G.. "Progress in understanding of polymer crystallization"[J]. Springer-Verlag, Berlin-Heidelberg, 2007p 481.
33. [33]
  Strobl G.. Colloquium:laws controlling crystallization and melting in bulk polymers[J]. Rev. Mod. Phys., 2009,81(3):1287-1300. doi: 10.1103/RevModPhys.81.1287
34. [34]
  Al-Hussein M., Strobl G.. The mechanisms of recrystallization after melting in syndiotactic polypropylene and isotactic polystyrene[J]. Eur. Phys. J. E, 2001,6(4):305-314. doi: 10.1007/s10189-001-8045-5
35. [35]
  Al-Hussein M., Strobl G.. The melting line, the crystallization line, and the equilibrium melting temperature of isotactic polystyrene[J]. Macromolecules, 2002,35(5):1672-1676. doi: 10.1021/ma011345k
36. [36]
  Al-Hussein M., Strobl G. J.. On the mechanisms of recrystallization after melting in semicrystalline polymers:the effect of the initial melt state[J]. J. Macromol. Sci. Part B Phys., 2003,B42(3-4):677-685.
37. [37]
  Lu Y., Wang Y., Jiang Z., Men Y.. Molecular weight dependency of surface free energy of native and stabilized crystallites in isotactic polypropylene[J]. ACS Macro Lett., 2014,3(11):1101-1105. doi: 10.1021/mz500599r
38. [38]
  Iijima M., Strobl G.. Isothermal crystallization and melting of isotactic polypropylene analyzed by time and temperature-dependent small-angle X-ray scattering experiemnts[J]. Macromolecules, 2000,33(14):5204-5214. doi: 10.1021/ma000019m
39. [39]
  Lu Y., Wang Y., Fu L., Jiang Z., Men Y.. Crystallization, recrystallization, and melting lines in syndiotactic polypropylene crystallized from quiescent melt and semicrystalline state due to stress-induced localized melting and recrystallization[J]. J. Phys. Chem. B, 2014,118(45):13019-13023. doi: 10.1021/jp5093702
40. [40]
  Hiss R., Hobeika S., Lynn C., Strobl G.. Network stretching, slip processes, and fragmentation of crystallites during uniaxial drawing of polyethylene and related copolymers. A comparative study[J]. Macromolecules, 1999,32(13):4390-4403. doi: 10.1021/ma981776b
41. [41]
  Fu Q., Heck B., Strobl G., Thomann Y.. A temperature- and molar mass-dependent change in the crystallization mechanism of poly(1-butene):transition from chain-folded to chain-extended crystallization?[J]. Macromolecules, 2001,34(8):2502-2511. doi: 10.1021/ma0015875
42. [42]
  Wang Y., Jiang Z., Fu L., Lu Y., Men Y.. Stretching temperature dependency of lamellar thickness in stress-induced localized melting and recrystallized polybutene-1[J]. Macromolecules, 2013,46(19):7874-7879. doi: 10.1021/ma401326g
43. [43]
  Wang Y., Lu Y., Jiang Z., Men Y.. Molecular weight dependency of crystallization line, recrystallization line, and melting line of polybutene-1[J]. Macromolecules, 2014,47(18):6401-6407. doi: 10.1021/ma501272a
44. [44]
  Heck B., Hugel T., Iijima M., Sadiku E., Strobly G.. Steps in the transition of an entangled polymer melt to the partially crystalline state[J]. New J. Phys., 1999,117.1.
45. [45]
  Cho T. Y., Strobel G.. Temperature dependent variations in the lamellar structure of poly(L-lactide)[J]. Polymer, 2006,47(4):1036-1043. doi: 10.1016/j.polymer.2005.12.027
46. [46]
  Liu, D.; Wang, R.; Wang, M.; Wu, C.; Wang, Z. Chem. Commun. 2015, 51, 4685-4688. doi: 10.1039/C5CC00470E
47. [47]
  Liu D., Yao C., Wang R., Wang M., Wang Z., Wu C., Lin F.. Angew[J]. Chem. Int. Ed., 2015,54(17):5205-5209. doi: 10.1002/anie.v54.17
48. [48]
  Glatter, O.; Kratky, O. "Small-angle X-ray scattering", Academic Press, London, 1982, p. 119.
49. [49]
  Strobl G. R., Schneider M.. Model of partial crystallization and melting derived from small-angle X-ray scattering and electron microscopic studies on low-density polyethylene[J]. J. Polym. Sci., Part B:Polym. Phys., 1980,18(6):1343-1359. doi: 10.1002/pol.1980.180180614
50. [50]
  Stribeck, N. "X-ray scattering of soft matter", Springer-Verlag, Berlin Heidelberg, 2007, p. 110.
51. [51]
  Gowd E. B., Shibayama N., Tashiro K.. Structural changes during thermally induced phase transitions observed for uniaxially oriented δ form of syndiotactic polystyrene[J]. Macromolecues, 2007,40(17):6291-6295. doi: 10.1021/ma0703913
52. [52]
  Gowd E. B., Tashiro K.. Effect of solvent molecules on phase transition phenomena of syndiotactic polystyrene[J]. Macromolecues, 2007,40(15):5366-5371. doi: 10.1021/ma070558s
53. [53]
  Strobl G.. From the melt via mesomorphic and granular crystalline layers to lamellar crystallites:a major route followed in polymer crystallization? Eur[J]. Phys. J. E, 2000,3(2):165-183.
54. [54]
  Strobl G.. Crystallization and melting of bulk polymers:new observations, conclusions and a thermodynamic scheme[J]. Prog. Polym. Sci., 2006,31(4):398-442. doi: 10.1016/j.progpolymsci.2006.01.001
55. [55]
  Chen R., Lu Y., Jiang Z., Men Y.. Initial lamellar thickness dependency of recrystallization behavior of poly(4-methyl-1-pentene)[J]. J. Polym. Sci., Part B:Polym. Phys., 2018,56(3):219-224. doi: 10.1002/polb.24536
56. [56]
  Su C. H., Jeng U., Chen S. H., Cheng C. Y., Lee J. J., Lai Y. H., Su W. C., Tsai J. C., Su A. C.. Thermodynamic characterization of polymorphs in bulk-crystallized syndiotactic polystyrene via small/wide-angle X-ray scattering and differential scanning calorimetry[J]. Macromolecules, 2009,42(12):4200-4207. doi: 10.1021/ma900384b
1. [1]
  Jun Lu , Jinrui Yan , Yaohao Guo , Junjie Qiu , Shuangliang Zhao , Bo Bao . Controlling solid form and crystal habit of triphenylmethanol by antisolvent crystallization in a microfluidic device. Chinese Chemical Letters, 2024, 35(4): 108876-. doi: 10.1016/j.cclet.2023.108876
2. [2]
  Rongliang Deng , Yihang Chen , Xiaotong Fan , Guolong Chen , Shuli Wang , Changzhi Yu , Xiao Yang , Tingzhu Wu , Zhong Chen , Yue Lin . Break of thermal equilibrium between optical and acoustic phonon branches of CsPbI₃ under continuous-wave light excitation and cryogenic temperature. Chinese Chemical Letters, 2024, 35(7): 109346-. doi: 10.1016/j.cclet.2023.109346
3. [3]
  Yarui Li , Huangjie Lu , Yingzhe Du , Jie Qiu , Peng Lin , Jian Lin . Highly efficient separation of high-valent actinide ions from lanthanides via fractional crystallization. Chinese Journal of Structural Chemistry, 2025, 44(4): 100562-100562. doi: 10.1016/j.cjsc.2025.100562
4. [4]
  Dian-Xue Ma , Yu-Wu Zhong . Achieving highly-efficient room-temperature phosphorescence with a nylon matrix. Chinese Journal of Structural Chemistry, 2024, 43(9): 100391-100391. doi: 10.1016/j.cjsc.2024.100391
5. [5]
  Ping Liu , Fei Yu . Covalent organic framework ionomers for medium-temperature fuel cells. Chinese Journal of Structural Chemistry, 2025, 44(4): 100465-100465. doi: 10.1016/j.cjsc.2024.100465
6. [6]
  Na Wang , Wang Luo , Huaiyi Shen , Huakai Li , Zejiang Xu , Zhiyuan Yue , Chao Shi , Hengyun Ye , Leping Miao . Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system. Chinese Chemical Letters, 2024, 35(5): 108696-. doi: 10.1016/j.cclet.2023.108696
7. [7]
  Kun Zhang , Ni Dan , Dan-Dan Ren , Ruo-Yu Zhang , Xiaoyan Lu , Ya-Pan Wu , Li-Lei Zhang , Hong-Ru Fu , Dong-Sheng Li . A small D-A molecule with highly heat-resisting room temperature phosphorescence for white emission and anti-counterfeiting. Chinese Journal of Structural Chemistry, 2024, 43(3): 100244-100244. doi: 10.1016/j.cjsc.2024.100244
8. [8]
  Linjing Li , Wenlai Xu , Jianyong Ning , Yaping Zhong , Chuyue Zhang , Jiane Zuo , Zhicheng Pan . Revealing the intrinsic mechanisms for accelerating nitrogen removal efficiency in the Anammox reactor by adding Fe(II) at low temperature. Chinese Chemical Letters, 2024, 35(8): 109243-. doi: 10.1016/j.cclet.2023.109243
9. [9]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
10. [10]
  Shaojie Ding , Henan Wang , Xiaojing Dai , Yuru Lv , Xinxin Niu , Ruilian Yin , Fangfang Wu , Wenhui Shi , Wenxian Liu , Xiehong Cao . Mn-modulated Co–N–C oxygen electrocatalysts for robust and temperature-adaptative zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100302-100302. doi: 10.1016/j.cjsc.2024.100302
11. [11]
  Huan Hu , Ying Zhang , Shi-Shuang Huang , Zhi-Gang Li , Yungui Liu , Rui Feng , Wei Li . Temperature- and pressure-responsive photoluminescence in a 1D hybrid lead halide. Chinese Journal of Structural Chemistry, 2024, 43(10): 100395-100395. doi: 10.1016/j.cjsc.2024.100395
12. [12]
  Jiayin Zhou , Depeng Liu , Longqiang Li , Min Qi , Guangqiang Yin , Tao Chen . Responsive organic room-temperature phosphorescence materials for spatial-time-resolved anti-counterfeiting. Chinese Chemical Letters, 2024, 35(11): 109929-. doi: 10.1016/j.cclet.2024.109929
13. [13]
  Jiaqi Lin , Pupu Yang , Yimin Jiang , Shiqian Du , Dongcai Zhang , Gen Huang , Jinbo Wang , Jun Wang , Qie Liu , Miaoyu Li , Yujie Wu , Peng Long , Yangyang Zhou , Li Tao , Shuangyin Wang . Surface decoration prompting the decontamination of active sites in high-temperature proton exchange membrane fuel cells. Chinese Chemical Letters, 2024, 35(11): 109435-. doi: 10.1016/j.cclet.2023.109435
14. [14]
  Yan Wang , Si-Meng Zhai , Peng Luo , Xi-Yan Dong , Jia-Yin Wang , Zhen Han , Shuang-Quan Zang . Vapor- and temperature-triggered reversible optical switching for multi-response Cu₈ cluster supercrystals. Chinese Chemical Letters, 2024, 35(11): 109493-. doi: 10.1016/j.cclet.2024.109493
15. [15]
  Yu Hong , Yuqian Jiang , Chenhuan Yuan , Decai Wang , Yimeng Sun , Jian Jiang . Unraveling temperature-dependent supramolecular polymorphism of naphthalimide-substituted benzene-1,3,5-tricarboxamide derivatives. Chinese Chemical Letters, 2024, 35(12): 109909-. doi: 10.1016/j.cclet.2024.109909
16. [16]
  Zhiqing Ge , Zuxiong Pan , Shuo Yan , Baoying Zhang , Xiangyu Shen , Mozhen Wang , Xuewu Ge . Novel high-temperature thermochromic polydiacetylene material and its application as thermal indicator. Chinese Chemical Letters, 2024, 35(11): 109850-. doi: 10.1016/j.cclet.2024.109850
17. [17]
  Shuai Zhu , Mingjie Chen , Haichao Shen , Hanming Ding , Wenbo Li , Junliang Zhang . Palladium/Xu-Phos-catalyzed enantioselective arylalkoxylation reaction of γ-hydroxyalkenes at room temperature. Chinese Chemical Letters, 2024, 35(11): 109879-. doi: 10.1016/j.cclet.2024.109879
18. [18]
  Meng Wang , Yan Zhang , Yunbo Yu , Wenpo Shan , Hong He . High-temperature calcination dramatically promotes the activity of Cs/Co/Ce-Sn catalyst for soot oxidation. Chinese Chemical Letters, 2025, 36(1): 109928-. doi: 10.1016/j.cclet.2024.109928
19. [19]
  Ying-Yu Zhang , Jia-Qi Luo , Yan Han , Wan-Ying Zhang , Yi Zhang , Hai-Feng Lu , Da-Wei Fu . Bistable switch molecule DPACdCl₄ showing four physical channels and high phase transition temperature. Chinese Chemical Letters, 2025, 36(1): 109530-. doi: 10.1016/j.cclet.2024.109530
20. [20]
  Xiao-Tong Sun , Hao-Fei Ni , Yi Zhang , Da-Wei Fu . Hybrid perovskite shows temperature-dependent photoluminescence and dielectric response triggered by halogen substitution. Chinese Journal of Structural Chemistry, 2024, 43(6): 100212-100212. doi: 10.1016/j.cjsc.2023.100212

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(698)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142