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
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