High-Tg PLA copolymers via base-catalyzed transesterification of PLA with 2,5,7-trioxabicyclo[2.2.2]octan-6-one
Zhou, Tong; Guo, Yu-Ting; Yang, Chun; Meng, Xian-Bin; Du, Fu-Sheng; Li, Zi-Chen; Polymer Chemistry 15 (2024) 156–165; doi:10.1039/D3PY01250F

data_1570473
_publ_section_title
;
 High-Tg PLA copolymers via base-catalyzed transesterification of PLA with
 2,5,7-trioxabicyclo[2.2.2]octan-6-one
;
_journal_issue                   3
_journal_name_full               'Polymer Chemistry'
_journal_page_first              156
_journal_page_last               165
_journal_paper_doi               10.1039/D3PY01250F
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C12 H14 O5'
_chemical_formula_sum            'C12 H14 O5'
_chemical_formula_weight         238.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-10-31 deposited with the CCDC.	2023-11-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.8010(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.18050(10)
_cell_length_b                   9.24640(10)
_cell_length_c                   11.14820(10)
_cell_measurement_reflns_used    12736
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      75.0360
_cell_measurement_theta_min      4.0890
_cell_volume                     1108.945(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -97.00 -36.00   0.50    0.05    --  -47.32 -40.00-159.00  122
  2  \w    -40.00  22.00   0.50    0.05    --  -47.32  40.00  -6.00  124
  3  \w     36.00 120.00   0.50    0.05    --   47.32  40.00  -6.00  168
  4  \w    -19.00  34.00   0.50    0.05    --   47.32 -40.00-159.00  106
  5  \w   -151.00-126.00   0.50    0.15    --  -99.00 -40.00-159.00   50
  6  \w     90.00 158.00   0.50    0.15    --  103.25  40.00  -6.00  136
  7  \w    -23.00  20.00   0.50    0.05    --  -47.32  19.00 150.00   86
  8  \w    -71.00 -25.00   0.50    0.05    --  -47.32 -77.00  60.00   92
  9  \w     59.00  86.00   0.50    0.05    --   47.32  38.00  60.00   54
 10  \w     27.00  77.00   0.50    0.05    --   47.32  77.00  60.00  100
 11  \w   -121.00 -85.00   0.50    0.15    --  -99.00 -94.00 -60.00   72
 12  \w   -167.00-136.00   0.50    0.15    --  -99.00 -30.00 150.00   62
 13  \w   -104.00 -79.00   0.50    0.15    --  -99.00 -71.00 109.87   50
 14  \w    -62.00 -28.00   0.50    0.15    --  -99.00  61.00 120.00   68
 15  \w   -118.00 -86.00   0.50    0.15    --  -99.00 -46.00 138.90   64
 16  \w   -168.00-139.00   0.50    0.15    --  -99.00 -67.00 122.82   58
 17  \w   -128.00 -82.00   0.50    0.15    --  -99.00 -67.00 122.82   92
 18  \w    -60.00 -30.00   0.50    0.15    --  -99.00  61.00 150.00   60
 19  \w   -158.00 -82.00   0.50    0.15    --  -99.00 -65.00  55.12  152
 20  \w   -119.00 -94.00   0.50    0.15    --  -99.00 -30.00 150.00   50
 21  \w   -105.00 -79.00   0.50    0.15    --  -99.00 -69.00  92.22   52
 22  \w   -110.00 -80.00   0.50    0.15    --  -99.00 -68.00  81.05   60
 23  \w   -159.00-127.00   0.50    0.15    --  -99.00 -94.00 -60.00   64
 24  \w   -162.00-121.00   0.50    0.15    --  -99.00 -48.00  94.94   82
 25  \w   -142.00 -83.00   0.50    0.15    --  -99.00 -61.00  60.00  118
 26  \w   -107.00 -81.00   0.50    0.15    --  -99.00 -73.00 101.88   52
 27  \w   -157.00-131.00   0.50    0.15    --  -99.00 -30.00 -90.00   52
 28  \w    -65.00 -27.00   0.50    0.15    --  -99.00  61.00  30.00   76
 29  \w   -160.00-122.00   0.50    0.15    --  -99.00 -77.00 150.00   76
 30  \w   -103.00 -77.00   0.50    0.15    --  -99.00 -77.00 150.00   52
 31  \w    -66.00 -33.00   0.50    0.15    --  -99.00  61.00   0.00   66
 32  \w   -132.00 -86.00   0.50    0.15    --  -99.00 -45.00 120.00   92
 33  \w   -102.00 -76.00   0.50    0.15    --  -99.00 -77.00  85.35   52
 34  \w   -164.00 -85.00   0.50    0.15    --  -99.00 -48.00  86.00  158
 35  \w   -166.00 -76.00   0.50    0.15    --  -99.00 -76.00 -55.27  180
 36  \w   -105.00 -80.00   0.50    0.15    --  -99.00 -68.00 130.38   50
 37  \w    -63.00 -36.00   0.50    0.15    --  -99.00  61.00-150.00   54
 38  \w    -61.00 -29.00   0.50    0.15    --  -99.00  61.00-180.00   64
 39  \w    -67.00 -27.00   0.50    0.15    --  -99.00  61.00-120.00   80
 40  \w   -116.00 -86.00   0.50    0.15    --  -99.00 -48.00  94.94   60
 41  \w   -107.00 -81.00   0.50    0.15    --  -99.00 -66.00 114.45   52
 42  \w     48.00 104.00   0.50    0.15    --  103.25 -94.00  60.00  112
 43  \w     44.00  74.00   0.50    0.15    --  103.25 -61.00 150.00   60
 44  \w     31.00  75.00   0.50    0.15    --  103.25 -61.00-150.00   88
 45  \w    140.00 166.00   0.50    0.15    --  103.25 125.00-120.00   52
 46  \w     80.00 124.00   0.50    0.15    --  103.25 125.00-120.00   88
 47  \w     31.00  65.00   0.50    0.15    --  103.25 -61.00 -90.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0307742000
_diffrn_orient_matrix_UB_12      0.0110427000
_diffrn_orient_matrix_UB_13      -0.1430630000
_diffrn_orient_matrix_UB_21      0.1194605000
_diffrn_orient_matrix_UB_22      -0.0844175000
_diffrn_orient_matrix_UB_23      0.0024424000
_diffrn_orient_matrix_UB_31      -0.0727056000
_diffrn_orient_matrix_UB_32      -0.1432214000
_diffrn_orient_matrix_UB_33      -0.0125016000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0160
_diffrn_reflns_av_unetI/netI     0.0089
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            14573
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.201
_diffrn_reflns_theta_min         4.109
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.941
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_description       plate
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2202
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0336
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0431P)^2^+0.3639P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0867
_refine_ls_wR_factor_ref         0.0869
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2154
_reflns_number_total             2202
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3py01250f2.cif
_cod_data_source_block           tx5187
_cod_depositor_comments
'Adding full bibliography for 1570470--1570474.cif.'
_cod_database_code               1570473
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHO
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C10(H10A,H10B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5A), C6(H6)
2.d Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_shelx_res_checksum              568
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.510
_oxdiff_exptl_absorpt_empirical_full_min 0.823