Global Trends for kp? Expanding the Frontier of Ester Side Chain

acrylates are additionally included; however, stearyl acrylate (SA) and behenyl acrylate (BeA)—the analogous acrylates to ...... Nicholas Ballar...
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Global Trends for kp? Expanding the Frontier of Ester Side Chain Topography in Acrylates and Methacrylates Alexander P. Haehnel, Maria Schneider-Baumann, Kai U. Hiltebrandt, Andrea M. Misske, Christopher Barner-Kowollik* Exemplary SEC chromatograms are shown for each monomer at 4 temperatures as well as tables with the exact samples conditions. Furthermore, the temperature dependent density curves for each monomer and the differential scanning calorimetry (DSC) curves are provided and the results are summarized in Table 1 in the main article. Additionally, as a typical example, the success of the fractionation – required for the MHKS parameter determination – is demonstrated for pBeMA as polymer system; the data points incorporated into the individual MHKS plots of each monomer are stated in Table S9. Furthermore, exemplary triple detector SEC traces are shown for each polymer system.

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Figure S1. Exemplary molecular weight distributions (red dotted lines) and their first derivative (solid black lines) of SMA in bulk (upper four diagrams) and in 1 molar solution in butyl acetate (lower four diagrams). The sample specific conditions are displayed in the diagrams and also collated in Table S1 for bulk and in Table S2 for 1 molar solution in butyl acetate. The typical PLP structure is observed for all samples.

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Figure S2. Exemplary molecular weight distributions (red dotted lines) and their first derivative (solid black lines) of BeMA in bulk (upper four diagrams) and in 1 molar solution in butyl acetate (lower four diagrams). The sample specific conditions are displayed in the diagrams and also collated in Table S3 for bulk and in Table S4 for 1 molar solution in butyl acetate. The typical PLP structure is observed for all samples.

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Figure S3.

Exemplary molecular weight distributions (red dotted lines) and their first

derivative (solid black lines) of C17A in bulk (upper four diagrams) and of C17MA (lower four diagrams). The sample specific conditions are displayed in the diagrams and also collated in Table S5 for C17A and in Table S6 for C17MA. The typical PLP structure is observed for all samples.

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Figure S4.

Exemplary molecular weight distributions (red dotted lines) and their first

derivative (solid black lines) of PHA in bulk (upper four diagrams) and of PHMA (lower four diagrams). The sample specific conditions are displayed in the diagrams and also collated in Table S7 for PHA and in Table S8 for PHMA. The typical PLP structure is observed for all samples.

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sample AH479 AH558 AH562 AH565 AH569 AH706 AH708 AH711 AH438 AH571 AH443 AH439 AH485 AH489 AH531 AH535

f Hz 35 25 30 50 75 40 50 100 75 125 150 75 100 200 100 200

n – 100 150 150 300 300 150 150 300 300 300 300 150 150 150 150 150

Table S1.

θ T-1 °C 10-3 K-1 30.8 3.290 31.7 3.280 40.0 3.193 40.2 3.191 50.3 3.092 50.4 3.091 60.3 2.999 60.7 2.995 70.2 2.912 70.8 2.907 80.2 2.830 80.5 2.828 90.8 2.748 91.4 2.743 102.0 2.666 102.0 2.666

ln(kp1) kp1/kp2 M1 – – g·mol-1 6.4627 1.101 15700 6.4778 1.152 22300 6.6809 1.153 22600 6.7670 1.105 14800 7.0944 1.103 13600 7.0272 1.139 23800 7.2795 1.138 24300 7.4072 1.104 13800 7.4388 1.171 18800 7.5921 1.107 13200 7.7991 1.120 13400 7.6465 1.153 23000 7.9142 1.155 22300 8.0562 1.116 12900 8.0790 1.132 26100 8.1922 1.111 14600

M2 cM -1 g·mol mol·L-1 28600 2.602 38800 2.600 39300 2.582 26800 2.581 24600 2.559 41800 2.559 42700 2.538 25000 2.537 32100 2.513 23800 2.515 23900 2.492 39800 2.491 38700 2.472 23100 2.471 46100 2.448 26300 2.448

kp1 mol·L-1 s-1 641 651 797 869 1205 1127 1450 1648 1701 1982 2439 2093 2736 3153 3226 3613

kp2 mol·L-1 s-1 582 565 691 786 1093 990 1274 1493 1452 1790 2178 1815 2368 2826 2849 3252

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer SMA in bulk.

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sample AH581 AH578 AH713 AH582 AH715 AH537 AH327 AH543 AH545 AH547 AH333 AH335 AH550 AH551 AH555 AH724 AH727 AH728 AH731 AH732

f Hz 7 3 10 5 15 8 10 15 10 20 10 30 15 30 30 40 30 50 35 70

n – 1200 800 1200 800 1200 800 800 800 800 800 800 800 1200 800 800 800 1200 800 1200 800

Table S2.

θ T-1 °C 10-3 K-1 0.8 3.650 0.9 3.649 10.1 3.530 11.1 3.518 18.7 3.426 19.7 3.415 29.9 3.300 30.5 3.293 39.9 3.194 40.2 3.191 50.0 3.095 50.0 3.095 60.4 2.998 60.4 2.998 70.7 2.908 70.9 2.907 80.9 2.824 81.2 2.822 91.8 2.740 91.6 2.742

ln(kp1) – 5.3802 5.1523 5.8302 5.4448 6.1737 5.8093 6.1504 6.2135 6.3176 6.5301 6.5896 6.8911 6.8605 7.0374 7.1776 7.4088 7.4566 7.6204 7.6550 7.8800

kp1/kp2 M1 – g·mol-1 1.174 10000 1.136 18600 1.164 11700 1.113 14800 1.191 10900 1.103 13600 1.111 15500 1.122 10700 1.126 17700 1.143 10900 1.145 23600 1.195 10600 1.149 19800 1.134 11800 1.109 13500 1.108 13300 1.089 18400 1.097 13000 1.108 19000 1.144 11900

M2 g·mol-1 17100 32800 20100 26600 18300 24600 28000 19100 31400 19100 41200 17800 34600 20900 24300 24000 33800 23700 34300 20800

cM mol·L-1 0.979 0.978 1.041 0.968 1.032 0.987 1.003 0.976 0.966 0.966 0.982 0.982 0.945 0.945 0.935 0.976 0.966 0.965 0.954 0.954

kp1 mol·L-1 s-1 217 173 340 232 480 333 469 499 554 685 727 983 954 1138 1310 1650 1731 2039 2111 2644

kp2 mol·L-1 s-1 185 152 292 208 403 302 422 445 492 600 635 823 830 1004 1181 1489 1590 1859 1906 2311

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer SMA in 1molar solution in butyl acetate.

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sample AH1030 AH1031 AH1033 AH1035 AH1037 AH1041 AH1043 AH1044 AH1047 AH1048 AH1051 AH1052 AH1054 AH1056 AH1059 AH1061 AH1062

f n θ T-1 Hz – °C 10-3 K-1 25 300 35.0 3.245 50 150 35.0 3.245 30 150 44.8 3.145 50 150 44.9 3.144 60 15000 44.9 3.144 40 300 55.2 3.046 80 300 55.2 3.046 50 150 65.9 2.949 100 300 66.3 2.946 75 150 75.4 2.869 150 300 75.4 2.869 75 150 85.7 2.787 150 150 86.0 2.784 100 150 96.2 2.707 200 300 96.2 2.707 100 300 107.0 2.631 200 150 107.0 2.631

Table S3.

ln(kp1) – 6.6085 6.7210 6.8505 6.9496 7.0425 7.1241 7.2333 7.3711 7.5043 7.6510 7.7634 7.7943 7.9212 8.0248 8.1467 8.1805 8.2740

kp1/kp2 – 1.131 1.111 1.107 1.111 1.047 1.117 1.095 1.104 1.099 1.141 1.097 1.104 1.103 1.132 1.100 1.065 1.098

M1 g·mol-1 25300 14200 26700 17000 16200 26100 14600 26500 15100 23200 13000 26500 15000 24800 14000 28600 15700

M2 cM -1 g·mol mol·L-1 44800 2.336 25500 2.336 48200 2.316 31800 2.316 30900 2.316 46700 2.299 26600 2.299 48000 2.277 27500 2.277 40600 2.258 23600 2.258 48000 2.237 27200 2.237 43800 2.216 25400 2.216 53600 2.188 28600 2.188

kp1 mol·L-1 s-1 741 830 944 1043 1144 1242 1385 1589 1816 2103 2353 2427 2755 3056 3452 3571 3921

kp2 mol·L-1 s-1 655 747 853 939 1093 1111 1264 1440 1653 1843 2146 2198 2497 2699 3138 3351 3571

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer BeMA in bulk.

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sample AH1064 AH1066 AH1068 AH1071 AH1072 AH1074 AH1076 AH1078 AH1080 AH1082 AH1084 AH1090 AH1093 AH1094 AH1096 AH1098 AH1100 AH1102

f Hz 8 15 10 15 10 20 10 30 15 30 20 40 30 50 35 70 45 90

Table S4.

n – 800 800 800 1200 800 800 800 800 800 800 800 800 1200 800 800 800 800 800

θ T-1 °C 10-3 K-1 19.5 3.417 19.4 3.418 30.0 3.299 30.3 3.295 40.0 3.193 40.0 3.193 50.0 3.095 50.0 3.095 60.0 3.002 60.0 3.002 70.0 2.914 70.0 2.914 80.2 2.830 80.3 2.829 90.0 2.754 90.0 2.754 100.0 2.680 100.0 2.680

ln(kp1) – 5.9243 6.1702 6.2623 6.3523 6.5041 6.6571 6.7023 6.9917 7.0022 7.1183 7.2485 7.3597 7.4707 7.5711 7.6507 7.8380 7.8182 8.0313

kp1/kp2 M1 M2 cM -1 -1 – g·mol g·mol mol·L-1 1.109 17300 31200 1.012 1.146 11800 20600 1.012 1.129 19200 34000 1.001 1.111 14000 25200 1.001 1.131 24200 42800 0.991 1.115 14100 25300 0.991 1.090 29200 53600 0.980 1.130 13000 23000 0.980 1.118 26000 46500 0.970 1.106 14600 26400 0.970 1.120 23800 42500 0.926 1.077 13300 24700 0.926 1.110 19600 35300 0.915 1.088 13000 23900 0.915 1.115 19900 35700 0.906 1.086 12000 22100 0.906 1.074 18100 33700 0.896 1.103 11200 20300 0.896

kp1 mol·L-1 s-1 374 478 524 574 668 778 814 1088 1099 1234 1406 1571 1756 1941 2102 2535 2485 3076

kp2 mol·L-1 s-1 337 417 464 516 591 698 747 962 983 1116 1255 1459 1581 1784 1886 2335 2314 2788

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer BeMA in 1molar solution in butyl acetate.

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sample AH491 AH681 AH686 AH494 AH690 AH689 AH498 AH691 AH694 AH693 AH501 AH502 AH697 AH698 AH699 AH505 AH597 AH702 AH507 AH509 AH599 AH601 AH511 AH512 AH602 AH603 AH515 AH517

f Hz 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500

n – 150 100 200 100 200 100 100 100 200 100 100 150 100 200 100 150 100 200 50 150 50 150 50 100 50 100 50 100

Table S5.

θ T-1 °C 10-3 K-1 -8.4 3.777 -5.6 3.738 -0.1 3.662 1.1 3.646 5.0 3.595 5.2 3.593 9.5 3.538 9.9 3.533 14.4 3.478 14.5 3.476 19.8 3.414 20.0 3.411 25.6 3.347 26.3 3.339 30.1 3.298 30.1 3.298 35.1 3.244 35.2 3.243 40.1 3.192 40.1 3.192 44.6 3.147 45.3 3.140 50.0 3.095 50.2 3.093 54.5 3.052 55.1 3.046 60.0 3.002 60.3 2.999

ln(kp1) – 9.1946 9.3647 9.4540 9.3004 9.6022 9.5567 9.8324 9.6376 9.8263 9.7740 10.0334 10.0497 9.9646 9.8564 9.9992 10.2662 10.1015 10.1740 10.4016 10.3032 10.2525 10.2932 10.4836 10.4463 10.3916 10.4128 10.6998 10.7376

kp1/kp2 – 1.078 1.083 1.068 1.026 1.083 1.102 1.105 1.129 1.170 1.158 1.132 1.096 1.114 0.931 1.054 1.041 1.081 1.060 1.054 0.938 1.110 1.110 1.017 1.095 1.125 1.126 1.091 1.171

M1 g·mol-1 17700 20500 22300 19500 25800 24600 33000 26600 32000 30300 40000 40600 36400 32600 37500 50000 41100 44500 56800 51500 47400 49400 61100 58900 54000 55200 75200 78100

M2 cM -1 g·mol mol·L-1 32800 2.891 37800 2.827 41700 2.814 38000 2.869 47600 2.803 44700 2.802 59700 2.849 47100 2.791 54700 2.781 52400 2.781 70600 2.825 74100 2.825 65300 2.756 70100 2.754 71200 2.745 96100 2.801 76000 2.714 84000 2.734 107700 2.778 109700 2.778 85400 2.693 88900 2.691 120200 2.755 107500 2.754 96100 2.670 98000 2.669 137900 2.731 133400 2.731

kp1 mol·L-1 s-1 9844 11669 12759 10942 14797 14139 18627 15330 18515 17570 22776 23150 21260 19080 22008 28744 24380 26214 32912 29827 28354 29531 35726 34416 32585 33282 44347 46054

kp2 mol·L-1 s-1 9133 10779 11942 10667 13667 12832 16862 13582 15829 15177 20115 21122 19077 20494 20888 27622 22550 24741 31212 31808 25546 26609 35127 31432 28976 29566 40634 39344

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer C17A.

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sample AH201 AH199 AH206 AH205 AH211 AH216 AH218 AH403 AH407 AH187 AH347 AH195 AH408 AH351 AH411 AH414 AH417 AH418 AH420 AH422

f Hz 15 5 15 5 5 15 10 20 40 15 20 50 40 20 30 50 40 70 40 70

n – 300 300 600 300 200 100 700 400 400 200 200 200 250 200 500 250 500 300 300 300

Table S6.

θ °C -6.6 -6.4 0.8 0.9 9.9 10.1 20.0 20.1 30.0 30.3 40.0 40.1 49.9 50.0 60.1 60.1 70.3 70.3 80.5 80.5

T-1 10-3 K-1 3.752 3.749 3.650 3.649 3.533 3.530 3.411 3.410 3.299 3.295 3.193 3.192 3.095 3.095 3.001 3.001 2.912 2.912 2.828 2.828

ln(kp1) – 5.4519 5.1861 5.6331 5.3744 5.6596 5.8589 5.9962 5.9307 6.3582 6.3254 6.5585 6.7743 6.8339 6.7232 6.9041 7.0480 7.2483 7.3570 7.4116 7.5605

kp1/kp2 M1 M2 cM -1 -1 – g·mol g·mol mol·L-1 1.028 13900 27000 2.756 1.020 32000 62700 2.755 1.040 16600 31900 2.739 1.040 38400 73700 2.739 1.165 50700 86900 2.719 1.087 20600 37900 2.718 1.106 35200 63600 2.696 1.117 16500 29500 2.693 1.126 12500 22200 2.671 1.129 32300 57200 2.674 1.160 30400 52400 2.654 1.119 15100 26900 2.652 1.137 19800 34800 2.627 1.125 35500 63100 2.632 1.045 28100 53700 2.605 1.132 19500 34400 2.605 1.087 29500 54200 2.582 1.114 18800 33700 2.582 1.109 34400 62000 2.560 1.157 22800 39400 2.560

kp1 mol·L-1 s-1 233 179 280 216 287 350 402 376 577 559 705 875 929 831 996 1151 1406 1567 1655 1921

kp2 mol·L-1 s-1 227 175 269 207 246 322 363 337 513 495 608 782 817 739 953 1016 1293 1407 1493 1660

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer C17MA.

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sample AH111 AH112 AH114 AH115 AH616 AH617 AH618 AH619 AH622 AH623 AH625 AH626 AH628 AH629 AH631 AH632 AH633 AH734 AH735 AH737 AH739

f Hz 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500

n – 150 100 150 100 100 150 50 100 100 150 100 150 100 150 100 150 50 150 50 150 100

Table S7.

θ T-1 °C 10-3 K-1 -7.3 3.762 -7.3 3.762 0.8 3.650 0.1 3.660 10.3 3.528 10.3 3.528 19.1 3.422 19.6 3.416 30.2 3.297 30.3 3.295 35.3 3.242 35.3 3.242 40.2 3.191 40.2 3.191 45.3 3.140 45.3 3.140 50.1 3.094 50.2 3.093 55.1 3.046 55.3 3.045 60.4 2.998

ln(kp1) – 8.7628 8.7083 8.9330 8.9145 9.2835 9.2705 9.4489 9.5076 9.6487 9.6666 9.7583 9.7663 9.8388 9.8610 9.9446 9.9208 10.0030 10.1394 10.1835 10.1926 10.2725

kp1/kp2 M1 – g·mol-1 1.091 11400 1.076 10800 1.014 13400 1.033 13200 1.079 18600 1.076 18400 1.110 21900 1.107 23200 1.101 26500 1.100 27000 1.079 29500 1.072 29700 1.076 31900 1.079 32600 1.102 35300 1.093 34500 1.095 37400 1.122 42800 1.115 44600 1.163 45000 1.193 48600

M2 g·mol-1 20900 20100 26500 25600 34500 34200 39400 41900 48200 49100 54700 55500 59300 60500 64100 63200 68200 76300 80000 77400 81500

cM mol·L-1 4.199 4.199 4.179 4.181 4.076 4.076 4.055 4.054 4.029 4.029 4.017 4.017 4.006 4.006 3.994 3.994 3.982 3.980 3.969 3.968 3.956

kp1 mol·L-1 s-1 6392 6053 7578 7439 10759 10620 12694 13462 15502 15782 17297 17437 18748 19168 20840 20348 22094 25322 26464 26704 28927

kp2 mol·L-1 s-1 5861 5626 7472 7200 9970 9867 11436 12163 14074 14352 16024 16267 17425 17772 18904 18625 20177 22571 23734 22966 24255

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer PHA.

12

sample AH305 AH307 AH311 AH313 AH635 AH637 AH639 AH641 AH643 AH645 AH647 AH650 AH651 AH653 AH776 AH777 AH779 AH780 AH782 AH783

f Hz 10 30 30 50 10 20 12 25 15 30 30 60 30 60 30 60 40 80 50 100

n – 800 800 800 800 800 800 800 800 800 800 800 1200 800 800 1200 800 800 800 1200 800

Table S8.

θ T-1 °C 10-3 K-1 -8.5 3.779 -8.8 3.783 30.0 3.299 30.1 3.298 0.0 3.661 -0.1 3.662 9.9 3.533 9.4 3.539 19.8 3.414 19.4 3.418 39.6 3.197 40.3 3.190 50.2 3.093 50.3 3.092 60.2 3.000 60.1 3.001 69.9 2.915 70.5 2.910 80.7 2.826 80.3 2.829

ln(kp1) – 4.8900 5.1204 6.1508 6.4335 5.2054 5.3481 5.5083 5.6389 5.8167 5.9217 6.3748 6.5615 6.6880 6.8557 6.9009 7.0748 7.2014 7.3292 7.3985 7.5298

kp1/kp2 M1 – g·mol-1 1.085 11900 1.070 5000 1.081 13500 1.096 10800 1.072 16200 1.133 9400 1.091 18100 1.112 9900 1.097 19600 1.079 10900 1.082 16800 1.098 10100 1.123 22700 1.069 13400 1.026 27900 1.071 16600 1.096 28000 1.067 15900 1.061 27000 1.066 15400

M2 g·mol-1 22000 9400 25000 19700 30300 16500 33200 17800 35700 20100 31000 18400 40500 25100 54400 31000 51100 29800 50900 28900

cM mol·L-1 3.963 3.964 3.828 3.827 3.933 3.933 3.898 3.900 3.863 3.865 3.794 3.791 3.757 3.756 3.726 3.726 3.692 3.690 3.654 3.655

kp1 mol·L-1 s-1 133 167 469 622 182 210 247 281 336 373 587 707 803 949 993 1182 1341 1524 1634 1863

kp2 mol·L-1 s-1 123 156 434 568 170 185 226 253 306 346 542 644 715 888 968 1103 1224 1428 1540 1748

Detailed PLP sample conditions, absolute molecular weights of the first two

inflection points and the resulting propagation rate coefficients of the monomer PHMA.

13

14

Figure S5.

Temperature dependent densities for the studied monomers SMA, BeMA, C17A,

C17MA, PHA and PHMA as well as the 1 molar solutions in butyl acetate of SMA and BeMA. Methyl

hydroquinone

(MeHQ)

was

added

in

replacement

of

2,2-dimethoxy-2-

phenylacetophenone (DMPA) to prevent the solutions from polymerization inside the density measurement device. The temperature dependent densities are summarized in Table 1.

Figure S6.

Differential scanning calorimetry of pBeMA. No glass transition temperature is

detectable in the temperature range between -150°C and 125°C. The observed melting point is provided in Table 1.

15

Figure S7.

Differential scanning calorimetry of pSMA. No glass transition temperature is

detectable in the temperature range between -150°C and 125°C. The observed melting point is provided in Table 1.

16

Figure S8.

Differential scanning calorimetry of pC17A (upper part) and pC17MA (lower

part). The glass transition temperatures are summarized in Table 1.

17

Figure S9.

Differential scanning calorimetry of pPHA (upper part) and pPHMA (lower part).

The glass transition temperatures are summarized in Table 1. The glass transition effect of PHMA is relatively less pronounced, however the handling experiences (brittle/hard below 20°C, chewy/sticky above 20°C) underpin the measured effect.

18

Figure S10.

Typical fractions of a PLP polymer sample for the MHKS parameter

determination procedure via triple detector SEC. The black, bold and solid line corresponds to the complete pBeMA (PDI = 13.35) polymer sample, produced under various PLP conditions (i.e. various PLP samples were combined and the polymer isolated), which was used for the fractionation. The various colored dashed lines correspond to the individual fractions obtained via a SEC fractionation as described in the Experimental Section. The PDI values of the obtained fractions range between 1.05 and 1.25.

19

SMA

BeMA

M1 g·mol-1

[η]

ml·g

420760 415271 298414 265614 173082 176468 127826 129280 84883 90591 56633 53393 38965 37796 21207 22259

43.51 44.81 33.65 36.00 29.40 28.05 20.04 19.98 16.19 16.75 12.81 12.85 11.18 9.95 6.98 7.05

-1

Table S9.

C17A

M1 g·mol-1

[η]

ml·g

3196530 3285380 2146160 2038310 1232840 1248200 481277 502077 311452 320904 206987 216550 126705 125656 82377 80551 49876 54358 34538 32617 20008 24501 14702 14946

177.94 177.74 127.27 136.55 86.28 95.88 51.22 45.15 34.20 34.42 25.80 25.03 21.64 20.47 15.85 17.17 13.36 13.60 10.55 11.07 8.94 9.32 7.47 6.36

-1

PHA

C17MA

M1 g·mol-1

[η]

ml·g

3141210 3162980 2384870 2272960 1601770 1615360 1153750 1118750 824059 784855 602561 639773 451774 438230 360878 345812 264632 241880 166412 187979 123214

230.05 1860680 123.56 229.54 1046820 83.68 175.09 1124960 80.15 178.89 740137 70.82 142.68 748385 68.94 145.11 522746 50.54 116.04 495502 54.04 115.39 344849 39.28 92.38 330983 38.29 91.30 257439 27.38 64.81 254872 27.87 65.85 172381 22.34 49.59 156313 23.65 52.10 112315 18.31 42.32 116869 18.51 41.04 74856 13.13 32.11 85458 13.02 30.13 50251 10.48 25.77 51679 10.54 26.75 22.52

-1

M1 g·mol-1

[η] -1

ml·g

PHMA

M1 g·mol-1

[η]

ml·g

2241190 2332610 1415320 1472620 912463 930324 587693 601895 400524 416109 275266 265763 189829 190774 127922 130556 104454 102663 62919 62757 43143 44191

288.36 277.97 218.1 211.05 156.35 152.79 113.36 113.13 82.6 78.21 62.2 60.45 41.89 40.29 34.2 35.39 26.75 27.99 21.95 19.54 16.68 16.64

-1

M1 g·mol-1

ml·g-1

917986 601755 584072 417877 419889 282858 304783 192146 189405 129326 132866 88424 95817 47179 68006 47746 42907 32563 31499

110.89 86.19 84.23 62.08 60.88 45.41 42.46 33.49 33.71 25.45 25.06 20.25 20.45 14.44 18.59 14.09 13.46 11.91 10.4

Weight average molecular weight, MW, and related intrinsic viscosity, [θ], data

employed for the determination of the MHKS parameters. The MW and [θ] were determined via the MALLS detector as well as the viscosimeter of the triple SEC set-up.

20

[η]

Figure S11. Exemplary triple detector SEC traces: refractive index (RI, black solid line), viscosimeter (Visco, red dashed line) and MALLS detector signal (MALLS at 90°, blue dotted line of pSMA (upper part) and pBeMA (lower part). The entire set of samples incorporated into the MHKS determination is collated in Table S9. All samples feature a sufficiently low signal to noise ratio in each detector signal.

21

Figure S12. Exemplary triple detector SEC traces: refractive index (RI, black solid line), viscosimeter (Visco, red dashed line) and MALLS detector signal (MALLS at 90°, blue dotted line of pC17MA (upper part) and pPHMA (lower part). The entire set of samples incorporated into the MHKS determination is collated in Table S9. All samples feature a sufficiently low signal to noise ratio in each detector signal.

22

Figure S13. Exemplary triple detector SEC traces: refractive index (RI, black solid line), viscosimeter (Visco, red dashed line) and MALLS detector signal (MALLS at 90°, blue dotted line of pC17A (upper part) and pPHA (lower part). The entire set of samples incorporated into the MHKS determination is collated in Table S9. All samples feature a sufficiently low signal to noise ratio in each detector signal.

Scheme S1 Three possible structures of the highly branched heptadecanyl alcohol employed in the synthesis of the heptadecanyl methacrylate and acrylate.

23