Fully Biobased Aliphatic Anionic Oligoesters: Synthesis and Properties

<div>The MALDI-TOF MS spectrum of PBISu<sub>70</sub>Ss<sub>30</sub>. <svg height="14.1649pt" id="M54" style="vertical-align:-5.529pt" version="1.1" viewbox="-0.0498162 -8.6359 43.9612 14.1649" width="43.9612pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M541 160L512 170C485 116 462 88 439 67C411 41 376 35 318 35C272 35 238 37 224 48C207 61 205 85 212 121L290 533C305 611 308 615 391 622L397 650H139L133 622C217 615 221 612 206 533L126 118C111 41 103 34 23 26L17 0H474C489 31 528 124 541 160Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,8.294,3.132)"><path d="M309 -142C211 -61 151 99 151 271S210 601 309 683L288 710C141 611 75 451 75 272V271C75 90 141 -72 288 -169L309 -142Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,11.552,3.132)"><path d="M504 89L488 119C453 85 428 69 416 69C408 69 405 75 412 102L462 304C492 438 460 451 436 451S388 441 356 423C311 397 229 336 170 256H168L189 340C208 418 200 451 177 451C144 451 82 413 24 352L40 322C65 345 98 369 108 369C114 369 119 363 112 335L28 -3L36 -12C54 -3 83 4 112 10C125 73 138 122 153 174C205 258 328 382 376 382C395 382 399 369 384 305L330 93C312 25 323 -12 351 -12C378 -12 439 21 504 89Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,16.211,3.132)"><path d="M98 134C72 134 46 117 46 90C46 73 55 65 60 64C95 55 124 32 124 -4C124 -42 95 -68 44 -89L57 -123C122 -104 194 -60 194 22C194 94 136 134 98 134Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,18.368,3.132)"><path d="M781 91L765 118C733 86 702 70 693 70C686 70 685 77 692 106L738 297C772 439 736 451 712 451S675 445 647 431C605 410 526 356 452 257H450L459 294C491 426 459 451 429 451C403 451 386 445 361 431C312 404 239 343 170 253H168L188 333C208 411 205 451 175 451C148 451 85 417 24 346L39 318C57 338 100 374 112 374C120 374 122 372 115 339C91 226 62 112 28 -6L37 -12C59 -4 87 3 114 6C125 68 142 127 154 168C184 227 316 383 372 383C397 383 396 366 381 289C362 192 338 92 312 -6L317 -12C339 -5 367 3 396 6L434 170C468 234 598 383 650 383C668 383 676 369 664 319L609 90C593 23 600 -12 629 -12C654 -12 722 23 781 91Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,25.694,3.132)"><path d="M98 134C72 134 46 117 46 90C46 73 55 65 60 64C95 55 124 32 124 -4C124 -42 95 -68 44 -89L57 -123C122 -104 194 -60 194 22C194 94 136 134 98 134Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,27.85,3.132)"><path d="M563 395C563 428 543 451 519 451C500 451 480 438 472 423C468 415 465 403 470 394C477 381 482 368 482 347C482 272 386 136 342 74H340C334 163 323 257 312 337C302 410 290 451 257 451C214 451 160 385 127 338L145 310C169 341 203 373 209 373C219 373 225 369 232 325C249 215 269 62 271 -15C220 -80 135 -165 18 -231L26 -257L142 -230C254 -105 279 -74 342 13C394 85 484 211 526 286C553 334 563 365 563 395Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,33.193,3.132)"><path d="M98 134C72 134 46 117 46 90C46 73 55 65 60 64C95 55 124 32 124 -4C124 -42 95 -68 44 -89L57 -123C122 -104 194 -60 194 22C194 94 136 134 98 134Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,35.35,3.132)"><path d="M481 445L456 468C426 437 403 427 388 427C372 427 356 428 302 438C256 447 221 451 187 451C159 451 130 428 105 384C93 363 80 340 65 305L96 290C122 342 149 381 193 381C216 381 267 377 294 374S346 372 365 376L75 105C37 70 24 35 24 16C24 2 30 -5 35 -8C42 -8 46 -6 48 -2C58 14 75 35 90 41C102 46 116 46 147 32C200 8 267 -21 298 -21C347 -21 390 12 448 126L420 151C369 77 338 56 311 56C287 56 249 68 212 81C180 92 149 100 127 98C212 172 353 308 413 372L481 445Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,39.946,3.132)"><path d="M283 271C283 451 220 610 70 710L48 683C146 603 207 443 207 271S149 -59 48 -142L70 -169C220 -67 283 90 283 271Z"></path></g></svg> corresponds to linear species oligomer containing 1,4-butanediol end groups with <svg height="6.1673pt" id="M55" style="vertical-align:-0.2063904pt" version="1.1" viewbox="-0.0498162 -5.96091 6.6501 6.1673" width="6.6501pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M495 86L479 114C446 82 419 66 409 66C401 66 401 72 406 97C420 166 436 231 453 297C489 435 454 448 428 448C406 448 384 439 354 422C305 394 222 327 161 247H159L183 345C200 415 194 448 173 448C143 448 82 410 23 351L38 325C64 349 95 371 105 371C111 371 116 365 109 336L25 -4L31 -12C50 -4 77 3 107 9C119 69 132 122 145 168C197 254 321 381 370 381C387 381 393 374 378 305L329 95C309 17 320 -12 345 -12C372 -12 430 19 495 86Z"></path></g></svg> and <svg height="9.39034pt" id="M56" style="vertical-align:-3.42943pt" version="1.1" viewbox="-0.0498162 -5.96091 7.65486 9.39034" width="7.65486pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M556 393C556 426 537 448 514 448C496 448 478 435 471 420C468 414 462 401 466 394C473 382 480 368 480 346C480 268 392 143 338 67H336C329 163 319 253 309 330S286 448 254 448C215 448 160 383 127 337L143 311C167 344 200 373 208 373S222 365 229 320C246 214 264 66 268 -20C219 -83 131 -171 17 -239L25 -261L137 -235C248 -110 273 -79 335 8C384 77 481 215 520 287C544 332 556 363 556 393Z"></path></g></svg> succinate and sulfonated repeating units associated to 1,4-butanediol, <svg height="6.1673pt" id="M57" style="vertical-align:-0.2063904pt" version="1.1" viewbox="-0.0498162 -5.96091 10.3951 6.1673" width="10.3951pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M766 88L752 113C719 83 690 64 681 64C674 64 672 74 679 103L724 292C758 436 724 448 701 448C680 448 666 442 639 429C594 407 514 350 441 252H439L447 289C476 423 450 448 419 448C398 448 379 441 355 427C307 400 234 344 162 249H160L180 324C203 409 197 448 170 448C144 448 82 413 23 349L35 321C57 343 96 374 108 374C115 374 117 371 111 341C87 227 57 112 24 -6L32 -12C53 -4 81 4 108 6C119 68 134 128 149 171C177 229 309 383 364 383C387 383 388 355 373 282C354 190 330 92 303 -6L309 -12C332 -4 356 3 386 6C396 63 411 122 424 171C458 236 590 383 642 383C658 383 664 369 652 315L603 91C587 20 593 -12 619 -12C642 -12 708 23 766 88Z"></path></g></svg> and <svg height="6.44133pt" id="M58" style="vertical-align:-0.29774pt" version="1.1" viewbox="-0.0498162 -6.14359 6.59789 6.44133" width="6.59789pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M475 445L452 468C423 436 401 426 385 426S352 427 305 436C268 443 216 448 185 448C156 448 128 425 102 382C89 360 77 338 64 304L89 291C117 340 143 380 190 380C214 380 268 376 295 373C320 370 344 371 362 374L70 101C32 65 23 36 23 18C23 5 27 -3 31 -8C36 -8 39 -6 42 -1C52 15 67 31 80 40S110 49 143 33C195 8 257 -20 290 -20C339 -20 382 11 439 129L416 148C366 74 334 55 305 55C278 55 236 68 203 81C169 94 141 100 122 96C205 170 348 308 411 376L475 445Z"></path></g></svg> succinate and sulfonated repeating units associated to isosorbide. <svg height="17.6175pt" id="M59" style="vertical-align:-6.1814pt" version="1.1" viewbox="-0.0498162 -11.4361 43.9612 17.6175" width="43.9612pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M541 160L512 170C485 116 462 88 439 67C411 41 376 35 318 35C272 35 238 37 224 48C207 61 205 85 212 121L290 533C305 611 308 615 391 622L397 650H139L133 622C217 615 221 612 206 533L126 118C111 41 103 34 23 26L17 0H474C489 31 528 124 541 160Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,7.185,-5.741)"><path d="M310 541L304 571C290 586 211 619 185 610L80 76L131 52L310 541Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,8.294,3.784)"><path d="M309 -142C211 -61 151 99 151 271S210 601 309 683L288 710C141 611 75 451 75 272V271C75 90 141 -72 288 -169L309 -142Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,11.552,3.784)"><path d="M504 89L488 119C453 85 428 69 416 69C408 69 405 75 412 102L462 304C492 438 460 451 436 451S388 441 356 423C311 397 229 336 170 256H168L189 340C208 418 200 451 177 451C144 451 82 413 24 352L40 322C65 345 98 369 108 369C114 369 119 363 112 335L28 -3L36 -12C54 -3 83 4 112 10C125 73 138 122 153 174C205 258 328 382 376 382C395 382 399 369 384 305L330 93C312 25 323 -12 351 -12C378 -12 439 21 504 89Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,16.211,3.784)"><path d="M98 134C72 134 46 117 46 90C46 73 55 65 60 64C95 55 124 32 124 -4C124 -42 95 -68 44 -89L57 -123C122 -104 194 -60 194 22C194 94 136 134 98 134Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,18.368,3.784)"><path d="M781 91L765 118C733 86 702 70 693 70C686 70 685 77 692 106L738 297C772 439 736 451 712 451S675 445 647 431C605 410 526 356 452 257H450L459 294C491 426 459 451 429 451C403 451 386 445 361 431C312 404 239 343 170 253H168L188 333C208 411 205 451 175 451C148 451 85 417 24 346L39 318C57 338 100 374 112 374C120 374 122 372 115 339C91 226 62 112 28 -6L37 -12C59 -4 87 3 114 6C125 68 142 127 154 168C184 227 316 383 372 383C397 383 396 366 381 289C362 192 338 92 312 -6L317 -12C339 -5 367 3 396 6L434 170C468 234 598 383 650 383C668 383 676 369 664 319L609 90C593 23 600 -12 629 -12C654 -12 722 23 781 91Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,25.694,3.784)"><path d="M98 134C72 134 46 117 46 90C46 73 55 65 60 64C95 55 124 32 124 -4C124 -42 95 -68 44 -89L57 -123C122 -104 194 -60 194 22C194 94 136 134 98 134Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,27.85,3.784)"><path d="M563 395C563 428 543 451 519 451C500 451 480 438 472 423C468 415 465 403 470 394C477 381 482 368 482 347C482 272 386 136 342 74H340C334 163 323 257 312 337C302 410 290 451 257 451C214 451 160 385 127 338L145 310C169 341 203 373 209 373C219 373 225 369 232 325C249 215 269 62 271 -15C220 -80 135 -165 18 -231L26 -257L142 -230C254 -105 279 -74 342 13C394 85 484 211 526 286C553 334 563 365 563 395Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,33.193,3.784)"><path d="M98 134C72 134 46 117 46 90C46 73 55 65 60 64C95 55 124 32 124 -4C124 -42 95 -68 44 -89L57 -123C122 -104 194 -60 194 22C194 94 136 134 98 134Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,35.35,3.784)"><path d="M481 445L456 468C426 437 403 427 388 427C372 427 356 428 302 438C256 447 221 451 187 451C159 451 130 428 105 384C93 363 80 340 65 305L96 290C122 342 149 381 193 381C216 381 267 377 294 374S346 372 365 376L75 105C37 70 24 35 24 16C24 2 30 -5 35 -8C42 -8 46 -6 48 -2C58 14 75 35 90 41C102 46 116 46 147 32C200 8 267 -21 298 -21C347 -21 390 12 448 126L420 151C369 77 338 56 311 56C287 56 249 68 212 81C180 92 149 100 127 98C212 172 353 308 413 372L481 445Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,39.946,3.784)"><path d="M283 271C283 451 220 610 70 710L48 683C146 603 207 443 207 271S149 -59 48 -142L70 -169C220 -67 283 90 283 271Z"></path></g></svg> corresponds to linear species oligomer containing isosorbide end groups with <svg height="6.1673pt" id="M60" style="vertical-align:-0.2063904pt" version="1.1" viewbox="-0.0498162 -5.96091 6.6501 6.1673" width="6.6501pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M495 86L479 114C446 82 419 66 409 66C401 66 401 72 406 97C420 166 436 231 453 297C489 435 454 448 428 448C406 448 384 439 354 422C305 394 222 327 161 247H159L183 345C200 415 194 448 173 448C143 448 82 410 23 351L38 325C64 349 95 371 105 371C111 371 116 365 109 336L25 -4L31 -12C50 -4 77 3 107 9C119 69 132 122 145 168C197 254 321 381 370 381C387 381 393 374 378 305L329 95C309 17 320 -12 345 -12C372 -12 430 19 495 86Z"></path></g></svg> and <svg height="9.39034pt" id="M61" style="vertical-align:-3.42943pt" version="1.1" viewbox="-0.0498162 -5.96091 7.65486 9.39034" width="7.65486pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M556 393C556 426 537 448 514 448C496 448 478 435 471 420C468 414 462 401 466 394C473 382 480 368 480 346C480 268 392 143 338 67H336C329 163 319 253 309 330S286 448 254 448C215 448 160 383 127 337L143 311C167 344 200 373 208 373S222 365 229 320C246 214 264 66 268 -20C219 -83 131 -171 17 -239L25 -261L137 -235C248 -110 273 -79 335 8C384 77 481 215 520 287C544 332 556 363 556 393Z"></path></g></svg> succinate and sulfonated repeating units associated to the 1,4-butanediol, <svg height="6.1673pt" id="M62" style="vertical-align:-0.2063904pt" version="1.1" viewbox="-0.0498162 -5.96091 10.3951 6.1673" width="10.3951pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M766 88L752 113C719 83 690 64 681 64C674 64 672 74 679 103L724 292C758 436 724 448 701 448C680 448 666 442 639 429C594 407 514 350 441 252H439L447 289C476 423 450 448 419 448C398 448 379 441 355 427C307 400 234 344 162 249H160L180 324C203 409 197 448 170 448C144 448 82 413 23 349L35 321C57 343 96 374 108 374C115 374 117 371 111 341C87 227 57 112 24 -6L32 -12C53 -4 81 4 108 6C119 68 134 128 149 171C177 229 309 383 364 383C387 383 388 355 373 282C354 190 330 92 303 -6L309 -12C332 -4 356 3 386 6C396 63 411 122 424 171C458 236 590 383 642 383C658 383 664 369 652 315L603 91C587 20 593 -12 619 -12C642 -12 708 23 766 88Z"></path></g></svg> and <svg height="6.44133pt" id="M63" style="vertical-align:-0.29774pt" version="1.1" viewbox="-0.0498162 -6.14359 6.59789 6.44133" width="6.59789pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M475 445L452 468C423 436 401 426 385 426S352 427 305 436C268 443 216 448 185 448C156 448 128 425 102 382C89 360 77 338 64 304L89 291C117 340 143 380 190 380C214 380 268 376 295 373C320 370 344 371 362 374L70 101C32 65 23 36 23 18C23 5 27 -3 31 -8C36 -8 39 -6 42 -1C52 15 67 31 80 40S110 49 143 33C195 8 257 -20 290 -20C339 -20 382 11 439 129L416 148C366 74 334 55 305 55C278 55 236 68 203 81C169 94 141 100 122 96C205 170 348 308 411 376L475 445Z"></path></g></svg> succinate and sulfonated repeating units associated to isosorbide.</div>

International Journal of Polymer Science

fig12

Figure 12

Figure 12: Fully Biobased Aliphatic Anionic Oligoesters: Synthesis and Properties 