EP3661497A1 - Recyclable polymers based on ring-fused gamma-butyrolactones - Google Patents
Recyclable polymers based on ring-fused gamma-butyrolactonesInfo
- Publication number
- EP3661497A1 EP3661497A1 EP18928207.2A EP18928207A EP3661497A1 EP 3661497 A1 EP3661497 A1 EP 3661497A1 EP 18928207 A EP18928207 A EP 18928207A EP 3661497 A1 EP3661497 A1 EP 3661497A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomer
- polymer
- formula
- alkyl
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 140
- 239000000178 monomer Substances 0.000 claims abstract description 134
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 41
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 30
- 150000002596 lactones Chemical class 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 229920000728 polyester Polymers 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 24
- 229920005565 cyclic polymer Polymers 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 125000003158 alcohol group Chemical group 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 239000012038 nucleophile Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 229920005604 random copolymer Polymers 0.000 claims description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- ZDYNTRMQDURVDM-UHFFFAOYSA-N bis(trimethylsilyl)azanide;lanthanum(3+) Chemical group [La+3].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C ZDYNTRMQDURVDM-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 abstract description 41
- -1 poly(4-hydroxybutyrate) Polymers 0.000 abstract description 24
- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- 230000015572 biosynthetic process Effects 0.000 abstract description 19
- 229920001577 copolymer Polymers 0.000 abstract description 18
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- 238000002156 mixing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000001149 thermolysis Methods 0.000 abstract description 5
- 229920000071 poly(4-hydroxybutyrate) Polymers 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
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- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 238000005481 NMR spectroscopy Methods 0.000 description 34
- 239000000243 solution Substances 0.000 description 33
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 125000004122 cyclic group Chemical group 0.000 description 25
- 239000011541 reaction mixture Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 16
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- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 238000000113 differential scanning calorimetry Methods 0.000 description 10
- 238000003818 flash chromatography Methods 0.000 description 10
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- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
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- 238000011068 loading method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 238000003873 derivative thermogravimetry Methods 0.000 description 6
- 101150065749 Churc1 gene Proteins 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- 238000002474 experimental method Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000002602 lanthanoids Chemical class 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 125000006239 protecting group Chemical group 0.000 description 5
- 125000000547 substituted alkyl group Chemical group 0.000 description 5
- 125000003107 substituted aryl group Chemical group 0.000 description 5
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- 238000001757 thermogravimetry curve Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 229920006158 high molecular weight polymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 229910052747 lanthanoid Inorganic materials 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000007525 superbases Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/26—Polythioesters
Definitions
- reaction conditions can be used to select the direction of the monomer-polymer equilibrium or the closed-loop chemical cycle, with low temperatures and bulk or high monomer concentrations favoring polymerization and high temperatures or dilution triggering depolymerization.
- Several classes of recently designed recyclable polymers operate under this thermodynamic principle, such as poly[2-(2- hydroxyethoxybenzoate)], poly(P-methyl-5-valerolactone), and a polycarbonate (PC) derived from copolymerization of CO2 with a meso-e poxide.
- a notable example for depolymerization selectivity is biodegradable poly(L-lactide) [P(L- LA)], which produces a mixture of many products upon thermolysis or a mixture of LA stereoisomers and cyclic oligomers upon chemolysis with a tin (Sn) catalyst, thus requiring substantial separation and purification before the recovered L-LA can be reused.
- Polymers with a low ceiling temperature ( T c ) are readily depolymerizable under mild conditions, but they typically do not have robust enough physical and mechanical properties to be useful for most common applications.
- PGBL poly(y-butyrolactone)
- ROP ring-opening polymerization
- thermodynamically highly stable five-membered g-butyrolactone can be selectively and quantitatively depolymerized back to GBL upon heating of the bulk material at 260° or 300°C, depending on PGBL topology.
- GBL thermodynamically highly stable five-membered g-butyrolactone
- PGBL thermodynamically highly stable five-membered g-butyrolactone
- Tm melting transition temperature
- Another example of a completely recyclable polymer was produced through the chemoselective ROP of bioderived a-methylene-y-butyrolactone; however, not only was a low temperature (-60°C) required for the polymer synthesis, but the resulting polymer was also a noncrystalline amorphous material.
- ring-opening polymerization of cyclic esters or lactones is currently the most effective route for the chemical synthesis of technologically important, biodegradable and/or biocompatible aliphatic polyesters.
- This method is applicable only to common 4-, 6-, and 7-membered lactones with relatively high strain energy.
- the five- membered y-butyrolactone (GBL) is a desirable monomer for the chemical synthesis of the corresponding biopolymer poly(y-butyrolactone), PGBL, a structural equivalent of the microbial poly(4-hydroxybutyrate) (P4HB), which has been shown to exhibit several desirable properties for biomedical applications.
- GBL is a biomass-derived renewable monomer produced in a large industrial scale and PGBL can be completely recyclable back to its building block monomer in quantitative yield by simply heating the bulk material at 220 °C (for the linear PGBL) or 300 °C (for the cyclic PGBL) or in the presence of a catalyst at room temperature (Hong, M.; Chen, E. Y.-X. Nat. Chem.
- GBL due to its low strain energy (i.e., high thermodynamic stability) of the five-membered lactone ring, GBL can only be ring-open polymerized under extreme conditions, such as ultrahigh pressure (e.g., 20,000 atm), into low molecular weight oligomers.
- ultrahigh pressure e.g., 20,000 atm
- the ROP of GBL can take place under ambient pressure, but it requires very low temperature and high monomer concentration conditions (below -40 °C), producing PGBL with limited molecular weight ( n up to 30 kg/mol).
- polymers are required to possess sufficiently high molecular weight to render them sufficient physical integrity and mechanical strength to be practically useful.
- polyesters with relatively high molecular weight ( n > 100 kg/mol) and chemical recyclability (depolymerization back to monomer in high to quantitative selectivity).
- This disclosure provides a class of new ring-fused poly(4-hydroxybutyrate)s that exhibit robust thermal stability and mechanical strength, quantitative recyclability to the building block monomers via thermolysis and/or chemical catalysis, and convenient production from the chemical ring-opening polymerization under ambient temperature and pressure.
- Q and R are the terminal ends of the polymer, or Q and R taken together form a cyclic polymer of Formula I, Formula II, or Formula III;
- G is O, S, or NR Z ;
- R x , R y and R z are each independently H or -(Ci-Cs)alkyl
- m is about 20 to about 10 10 ;
- n 1-20; wherein the R y substituents have a /rani-configuration relative to each other, each -(Ci-Cs)alkyl moiety is independently branched or unbranched, and each ring-embedded carbon independently has an optional -(Ci-Cs)alkyl substituent or phenyl substituent.
- This disclosure also provides a method for polymerization comprising contacting a monomer with a catalyst and an optional protic initiator to form a polymer via ring opening polymerization reaction of the monomer, wherein the monomer is a monomer of Formula IV or Formula V :
- G 3 is O, S, or NR Z ;
- R x , R y and R z are each independently H or -(Ci-C 8 ) alkyl
- n 0-20;
- each -(Ci-Cs)alkyl moiety is independently branched or unbranched, and each ring-embedded carbon independently has an optional -(Ci-Cs)alkyl substituent or phenyl substituent.
- This disclosure also provides novel polymers (or copolymers), such as polymers of Formulas I- III, monomers and other intermediates for the synthesis of polymers (or copolymers), such as Formulas I- III, as well as methods of preparing polymers (or copolymers), such as Formulas I-III.
- novel polymers (or copolymers) such as polymers of Formulas I- III, monomers and other intermediates for the synthesis of polymers (or copolymers), such as Formulas I- III, as well as methods of preparing polymers (or copolymers), such as Formulas I-III.
- the invention also provides polymers (or copolymers), such as Formulas I-III, that are useful as intermediates for the synthesis of other useful polymers (or copolymers).
- FIG. 1 Thermal transitions and spectroscopic properties.
- A DSC first-heating- scan curves (l0°C/min).
- B DSC second-heating-scan curves [5°C/min for (a) and (b) or l°C/min for (c), after first cooling at l0°C/min]
- C Overlays of FTIR spectra in the carbonyl stretching region str, stretching frequency.
- D Powder XRD profiles.
- Figure 4 Mechanical and rheological properties.
- A Overlay of storage modulus E and loss modulus E" for .sc-P(M l ) measured by DMA (tension film mode, 0.05% strain, 1 Hz, 3°C min -1 ).
- B Stress-strain curves for rac-P(Ml) and .s -P(M l ) measured by tensile testing (5.0 mm/min, room temperature, with the break point indicated by x).
- C Rheology master curve (dynamic storage modulus G' and loss modulus G" versus angular frequency co) for rac-P(Ml), reported as a time-temperature superposition curve at reference temperature 2l5°C.
- D Dynamic shear viscosity of rac-P(Ml) as a function of the shear rate measured at 2l5°C.
- T6GBL]/[La[N(SiMe3)2]3]/[Ph2CHCH20H] 1000/1/3; middle, the colorless liquid product obtained after thermal degradation at 300 °C for 1 h; top, 3,4-T6GBL monomer for comparison.
- FIG 22 Overlay of storage modulus E and loss modulus ' for rac-P(Ml) measured by DMA (tension film mode, 0.05% strain, 1 Hz, 3 °C min -1 ).
- Figure 23 Overlay of a representative curve of tan d of amorphous rac-P(Ml) and crystalline soP(M 1 ) determined by DMA.
- Some polymers such as polyethylene terephthalate in soft drink bottles, can be depolymerized back to the starting monomers. This makes it possible to repolymerize true virgin material for repeated use.
- Described herein is a polymer based on a five-membered ring cyclic monomer derived from g-butyrolactone that could be produced at ambient temperature and mild conditions.
- the high-molecular-weight polymers exhibited high crystallinity and thermal stability. However, at effectively hot conditions, or at lower temperatures in the presence of a zinc chloride catalyst, the polymers could be returned to its starting monomers and thus recycled into new material.
- This disclosure provides ring-fused GBL monomer structures, the resulting RF-P4HB polymer structures, and catalysts/initiators used to produce such polymer structures.
- references in the specification to "one embodiment”, “an embodiment”, etc., indicate that the embodiment described may include a particular aspect, feature, structure, moiety, or characteristic, but not every embodiment necessarily includes that aspect, feature, structure, moiety, or characteristic. Moreover, such phrases may, but do not necessarily, refer to the same embodiment referred to in other portions of the specification. Further, when a particular aspect, feature, structure, moiety, or characteristic is described in connection with an embodiment, it is within the knowledge of one skilled in the art to affect or connect such aspect, feature, structure, moiety, or characteristic with other embodiments, whether or not explicitly described.
- the phrase can mean one, two, three, four, five, six, ten, 100, or any upper limit approximately 10, 100, or 1000 times higher than a recited lower limit.
- ranges recited herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof, as well as the individual values making up the range, particularly integer values. It is therefore understood that each unit between two particular units are also disclosed. For example, if 10 to 15 is disclosed, then 11, 12, 13, and 14 are also disclosed, individually, and as part of a range.
- a recited range e.g., weight percentages or carbon groups
- any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, or tenths.
- each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc.
- all language such as “up to”, “at least”, “greater than”, “less than”, “more than”, “or more”, and the like include the number recited and such terms refer to ranges that can be subsequently broken down into sub-ranges as discussed above.
- all ratios recited herein also include all sub-ratios falling within the broader ratio. Accordingly, specific values recited for radicals,
- contacting refers to the act of touching, making contact, or of bringing to immediate or close proximity, including at the cellular or molecular level, for example, to bring about a chemical reaction, or a physical change, e.g., in a solution, in a reaction mixture.
- an “effective amount” refers to an amount effective to bring about a recited effect, such as an amount necessary to form products in a reaction mixture. Determination of an effective amount is typically within the capacity of persons skilled in the art, especially in light of the detailed disclosure provided herein.
- the term “effective amount” is intended to include an amount of a compound or reagent described herein, or an amount of a combination of compounds or reagents described herein, e.g., that is effective to form products in a reaction mixture.
- an “effective amount” generally means an amount that provides the desired effect.
- substantially is a broad term and is used in its ordinary sense, including, without limitation, being largely but not necessarily wholly that which is specified.
- the term could refer to a numerical value that may not be 100% the full numerical value.
- the full numerical value may be less by aboutl%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, or about 20%.
- substituted or“substituent” is intended to indicate that one or more (for example., 1-20 in various embodiments, 1-10 in other embodiments, 1, 2, 3, 4, or 5; in some embodiments 1, 2, or 3; and in other embodiments 1 or 2) hydrogens on the group indicated in the expression using“substituted” (or“substituent”) is replaced with a selection of group(s), or with a suitable group known to those of skill in the art, provided that the indicated atom’s normal valency is not exceeded, and that the substitution results in a stable compound.
- the carbon(s) (or carbon atom(s)) indicated in a Formula disclosed herein can have a suitable substituent or group known to those of skill in the art.
- Suitable substitutions or substituents include, for example, alkyl, alkenyl, alkynyl, alkoxy, halo, haloalkyl, hydroxy, hydroxyalkyl, aryl, heteroaryl, heterocycle, cycloalkyl, alkanoyl, alkoxycarbonyl, amino, alkylamino, dialkylamino, trifluoromethylthio,
- difluoromethyl difluoromethyl, acylamino, nitro, trifluoromethyl, trifluoromethoxy, carboxy, carboxyalkyl, keto, thioxo, alkylthio, alkylsulfmyl, alkylsulfonyl, and cyano.
- substituents that can be bonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR', OC(0)N(R')2, CN, CF 3 , OCF 3 , R, O, S, C(0), S(0), methylenedioxy, ethylenedioxy, N(R) 2 , SR, SOR', SO2R', S0 2 N(R)2, S0 3 R, C(0)R, C(0)C(0)R',
- R can be hydrogen or a carbon-based moiety, and wherein the carbon-based moiety can itself be further substituted.
- R can be hydrogen or a carbon-based moiety, and wherein the carbon-based moiety can itself be further substituted.
- a substituent is monovalent, such as, for example, For Cl, it is bonded to the atom it is substituting by a single bond.
- a divalent substituent such as O, S, C(O), S(O), or S(0) 2 can be connected by two single bonds to two different carbon atoms.
- O a divalent substituent
- the O can be bonded to each of two adjacent carbon atoms to provide an epoxide group, or the O can form a bridging ether group between adjacent or non-adjacent carbon atoms, for example bridging the 1, 4-carbons of a cyclohexyl group to form a [2.2. l]-oxabicyclo system.
- any substituent can be bonded to a carbon or other atom by a linker, such as (CFb)n or (CR'2)n wherein n is 1, 2, 3, or more, and each R' is independently selected.
- halo or halide refers to fluoro, chloro, bromo, or iodo.
- halogen refers to fluorine, chlorine, bromine, and iodine.
- alkyl refers to a branched or unbranched hydrocarbon having, for example, from 1-20 carbon atoms, and often 1-12, 1-10, 1-8, 1-6, or 1-4 carbon atoms.
- the term“alkyl” also encompasses a“cycloalkyl”, defined below.
- the alkyl can be unsubstituted or substituted, for example, with a substituent described above.
- the alkyl can also be optionally partially or fully unsaturated.
- cycloalkyl refers to cyclic alkyl groups of, for example, from 3 to 10 carbon atoms having a single cyclic ring or multiple condensed rings.
- the cycloalkyl can be unsubstituted or substituted.
- the cycloalkyl group can be monovalent or divalent, and can be optionally substituted as described for alkyl groups.
- the cycloalkyl group can optionally include one or more cites of unsaturation, for example, the cycloalkyl group can include one or more carbon-carbon double bonds.
- ee enantiomerically enriched
- ee enantiomerically enriched
- Reactions that provide one enantiomer present to a greater extent than another would therefore be“enantioselective” (or demonstrate“enantioselectivity”).
- the term “enantiomerically enriched” refers to mixtures that have one enantiomer present to a greater extent than another. Reactions that provide one enantiomer present to a greater extent than another would therefore be“enantioselective” (or demonstrate“enantioselectivity”).
- the term “enantiomerically enriched” refers to mixtures that have one enantiomer present to a greater extent than another. Reactions that provide one enantiomer present to a greater extent than another would therefore be“enantioselective” (or demonstrate“enantioselectivity”).
- the term “enantiomerically enriched” refers to mixtures that have one enantiomer present to
- enantiomerically enriched refers to a mixture having at least about 2% ee to about 99% ee.
- the term“enantiomerically enriched” includes enantiomerically pure mixtures which are mixtures that are substantially free of the species of the opposite optical activity or one enantiomer is present in very low quantities, for example, 0.01%, 0.001% or 0.0001%.
- repeat unit refers to the moiety of a polymer that is repetitive.
- the repeat unit may comprise one or more repeat units, labeled as, for example, repeat unit A, repeat unit B, repeat unit C, etc.
- Repeat units A-C may be covalently bound together to form a combined repeat unit.
- Monomers or a combination of one or more different monomers can be combined to form a (combined) repeat unit of a polymer or copolymer.
- molecular weight for the copolymers disclosed herein refers to the average number molecular weight (Mn).
- Mw weight average molecular weight
- the copolymers disclosed herein can comprise random or block copolymers.
- the copolymers described herein as random copolymers are indicated by the "r” over the bond between the units of the copolymer.
- the copolymers described herein as block copolymers are indicated by the "b” over the bond between the units of the copolymer.
- the ends of the copolymer is a low molecular weight moiety (e.g. under 500 Da), such as, H, OH, OOH, CH 2 OH, CN, NH 2 , or a hydrocarbon such as an alkyl (for example, a butyl or 2-cyanoprop-2-yl moiety at the initiator and terminal end), alkene or alkyne, or a moiety as a result of an elimination reaction at the first and/or last repeat unit in the copolymer.
- the end of the polymer can also be Ph 2 CHCH 2 0-.
- This disclosure provides a polymer comprising Formula I, Formula II, or Formula III:
- Q and R are the terminal ends of the polymer, or Q and R taken together form a cyclic polymer of Formula I, Formula II, or Formula III;
- G is O, S, or NR Z ;
- R x , R y and R z are each independently H or -(Ci-Cs)alkyl
- m is about 20 to about 10 10 ;
- n 1-20;
- each -(Ci-Cs)alkyl moiety is independently branched or unbranched, and each ring-embedded carbon (other than the carbons substituted with R y ) independently has an optional -(Ci- Csjalkyl substituent or phenyl substituent.
- each or the carbon atoms in the ring portion of Formulas I-III is independently substituted with an alkyl group or an aryl group, wherein the alkyl group is branched or unbranched, the alkyl group is optionally substituted, and the aryl group (e.g., a phenyl) is optionally substituted.
- G is O.
- R x is H, or R y is H.
- m is about 2 to about 20 or to about 10 20 .
- n is 0 to about 50.
- Q is -(Ci-Cs)alkyl, N(R A ) 2 , OR A , or SR A , and R is H, wherein each R A is independently H, -(Ci- C 8 )alkyl, Ph 2 CHCH 2 -, or -Si[(Ci-C 8 )alkyl] 3 .
- one or more ring-embedded carbons further comprise a (Ci-Cs)alkyl substituent or aryl substituent, and/or optionally the carbon atom of
- the R x substituents of Formula III have a c .s-con figuration or a trans- configuration relative to each other.
- the -(Ci-Cs)alkyl substituent is further substituted.
- the polymer has a number average molecular weight ( M n ) of about 0.1 kg mol 1 to about 5 x 10 6 kg mol 1 , and/or the polymer has a polydispersity index of about 1 to about 3.
- M n can be about 10 5 kg mol 1 , about 10 4 kg mol 1 , about 10 3 kg mol 1 , about 10 2 kg mol 1 , about 10 kg mol 1 , or about 1 kg mol 1 .
- the stereochemistry of the repeating unit (m) is ( R , R ) or ( S , S ). The stereochemistry can also be ( R , S ), ( S , R), ( R , R), ( S , S ), or a combination thereof.
- the polymer is thermally depolymerizable or chemically depolymerizable to a monomer. In yet other embodiments, thermal or chemical
- depolymerization of the polymer provides about 95% or greater conversion of the polymer to the monomer (wherein the monomer is the monomer that can form the polymer by the ring opening polymerization reaction described herein). In other embodiments, the polymer provides about 50% to about 95% conversion of the polymer to the monomer.
- This disclosure also provides a method for polymerization comprising contacting a monomer with a catalyst and an optional protic initiator to form a polymer via ring opening polymerization reaction of the monomer, wherein the monomer is a monomer of Formula I or Formula V :
- G 3 is O, S, or NR Z ;
- R x , R y and R z are each independently H or (Ci-Cs)alkyl
- n 0-20;
- each -(Ci-Cs)alkyl moiety is independently branched or unbranched, and each ring-embedded carbon independently has an optional -(Ci-Cs)alkyl substituent or phenyl substituent.
- the polymer is formed at a pressure of about 1 atm to about 10 atm and at a temperature of about 0 °C to about 100 °C. In other embodiments, the pressure is about 1 atmosphere to about 100 atmospheres. In yet other embodiments, the temperature is about -20 °C to about 200 °C.
- the catalyst is a metal-based catalyst or an organic catalyst.
- the organometallic catalyst comprises a nucleophile and a lanthanide metal or a transition metal.
- the organometallic catalyst is tris[N,N-bis(trimethylsilyl)amide]lanthanum(III),
- X is a donor solvent molecule
- the protic initiator is an alcohol, a thiol, or an amine. In other embodiments, the protic initiator is, for example, Ph 2 CHCH 2 OH, hexanol, dipropylamine, or a combination thereof.
- the described methods may further comprise a solvent, wherein the solvent is any effective solvent.
- the solvent can be a non-protic or protic solvent.
- the solvent can be, for example, but not limited to, dichloromethane (DCM), toluene, tetrahydrofuran, ether, xylene, or a combination of solvents.
- the disclosed method may not require a solvent (e.g., the reaction is performed“neat”).
- the monomer (M), catalyst (C), and initiator (I) are contacted at various ratios of M:C:I.
- the value of M in the ratio M:C:I can range from about 1 to about 100,000, about 10 to about 10,000, or about 100 to about 1000.
- the value of C in the ratio M:C:I can range from about 0.1 to about 1,000, about 0.5 to about 500, or about 1 to about 100.
- the value of I in the ratio M:C:I can range from about 0 to about 1,000, about 0 to about 100, or about 0 to about 10.
- the monomer is a monomer of Formula IVA or Formula IVB:
- n 1-20. In some various embodiments, n is 1- 6, n is 1-4, or n is 0-50. In some other embodiments, the monomer is a monomer of Formula IVC or Formula IVD:
- n 1-20.
- Various embodiments of the disclosed methods further comprise quenching the polymerization reaction to form a polymer.
- a protic source is used for quenching, such as, but not limited to, chloroform, an acid (e.g., HC1), or water.
- the monomer is a monomer of Formula IVA:
- n 1-20;
- the catalyst comprises a nucleophile (Q).
- polyester of Formula VI (or Formula VIB):
- Q is the nucleophile and R is H, or Q and R taken together form a cyclic polymer of Formula VI (or Formula VIB); and m is about 20 to about 10 10 .
- the monomer is a monomer of Formula
- n 1-20;
- the catalyst comprises a nucleophile (Q).
- polyester of Formula VII (or Formula VIIB):
- Q is the nucleophile and R is H, or Q and R taken together form a cyclic polymer of Formula VII (or Formula VIIB); and m is about 20 to about 10 10 .
- m is about 5 to about 10 8 , or about 10 7 , about 10 6 , about 10 5 , about 10 4 or about 10 3 .
- the polymer for example a polyester
- the disclosed methods further comprises contacting the polymerization reaction with a second monomer.
- the second monomer is a lactone or lactide.
- a block or random copolymer is formed by contacting the polymerization reaction with a second monomer.
- the polymer is recycled to the monomer by thermal depolymerization or chemical depolymerization.
- stoichiometric amounts of a polymer (e.g., a polyester) having a stereo-configuration formed from one enantiomer of the monomer, and a second polymer (e.g., a second polyester) having the opposite stereo-configuration formed from the other enantiomer of the monomer are co- crystallized to form a crystalline stereocomplex, wherein the crystalline stereocomplex has a higher melting temperature than said polymer (or polyester) having the stereo-configuration or opposite stereo-configuration.
- the disclosed polyester is prepared according to the methods described herein, wherein the polyester is a polyester of Formula VI. In other various embodiments, the disclosed polyester is prepared according to the method described herein, wherein the polyester is a polyester of Formula VII.
- n number-average molecular weight up to only 6.2 kg/mol [by gel permeation chromatography (GPC)] or 2.6 kg/mol [by nuclear magnetic resonance (NMR)].
- Ml Quantitative conversion of Ml was achieved even with common anionic initiators such as potassium /ert-butoxide and TBD (l,5,7-triazabicyclo[4.4.0]dec-5-ene), but the product was not that of a polymer; instead, Ml was isomerized under the basic conditions to its cis isomer, which is nonpolymerizable, as verified by its independent synthesis and subsequent polymerization surveys with different catalysts and conditions (Table 2). To overcome this isomerization issue, we used a coordinative-insertion ROP catalyst,
- Lai exhibited high selectivity and activity toward the ROP to afford poly- M1 [P(M1)], achieving greater than 80% conversion with 0.2 or 0.1 mole % (mol %) catalyst loading.
- PhiCHCThO was further confirmed by matrix-assisted laser desorption/ionization-time-of- flight mass spectroscopy (MALDI-TOF MS) of a low-molecular weight sample.
- MALDI-TOF MS matrix-assisted laser desorption/ionization-time-of- flight mass spectroscopy
- thermogravimetric analysis TGA in terms of onset decomposition temperature 7d (defined by the temperature of 5% weight loss) and maximum decomposition
- Tmax values were similar (390° versus 394°C).
- the Td and / ' max of /-P(M1) were 115° and l76°C higher, respectively, than those of the linear PGBL (obtained with
- the Td (344°C) of the physical blend of 1 : 1 P[(T?)-Ml]-P[(ri)-Ml] was found to be about 17 to 21 °C higher than those of the respective enantiomeric polymers (Figure 17), whereas the / ' max values varied only slightly (Figure 2B).
- the circular monomer-polymer-monomer cycle was examined through three consecutive polymerization-depolymerization cycles on a multigram scale.
- recovered Ml can be directly repolymerized without a decrease in the subsequent monomer conversion and polymer quality.
- DSC Differential scanning calorimetry
- P[(7?)-M1] or P[fV)-M l] is readily soluble in common polar organic solvents such as CHCh, CH2CI2, and A/A'-di methyl form a ide (DMF)
- .sc-P(Ml) is only partially soluble in CHCh and insoluble in CH2CI2, tetrahydrofuran, and DMF.
- the above corroborative evidence showed that a nanocrystalline stereocomplex formed between the two enantiomeric P(M1) polymers and that such a stereocomplex exhibited markedly enhanced crystallinity, crystallization rate, and solvent resistance over those of the parent enantiomers.
- thermomechanical spectra of .sc-P(M l) ( Figure 4A) and rac-P(Ml) ( Figure 22) show that, at room temperature (the glassy state), both .sc-P(M l) and rac -P(M1) exhibited high storage modulus ( E ) values, although E (1.58 ⁇ 0.44 GPa) of .ve-P(Ml) was somewhat higher than that (1.47 ⁇ 0.25 GPa) of rac -P(M1).
- angular frequency (w) dependencies of the dynamic storage or elastic modulus (GO and loss or viscous modulus (G") of rac-P(Ml) and .s -P(M l) were characterized at six different temperatures (165°, 175°, 185°, 195°, 205°, and 2l5°C) in the linear viscoelastic regime (1.0% strain) established by the strain sweeps at 2l5°C.
- the data obtained from frequency sweep experiments at each temperature were compiled to generate a master curve reported as a time-temperature superposition curve at reference temperature 2l5°C
- Monomers Two classes of ring-fused GBL monomers with /ra//.s-fusing of five, six, and seven-membered rings to the GBL ring at 3,4 -( ⁇ 3 ⁇ 4 b) and 4,5-(or b ⁇ -positions (Scheme 1). Note that these structures also include their respective enantiomers and they can exist in racemic forms as well. In addition, monomers with a four-membered ring fused to the GBL ring are also possible. Furthermore, trans-di substituted GBL derivatives represent an extreme ring-fused structure when the fused ring is very large. These types of /raws-fusing to the parent GBL ring increase the ring strain of GBL, thus rending such monomers readily polymerizable, even under ambient conditions (room temperature, 1 atm).
- polymers Upon polymerization, these two classes of ring-fused GBL monomers can lead to either linear or cyclic polymers structures, or both, depending the catalysts/initiators used and reaction conditions employed (Scheme 2).
- the resulting polyesters exhibit high thermal stability, with degradation temperature typically above 300 °C, and high molecular weight up to 390 kg/mol; they can also be selectively recycled back to monomers under heating and/or catalytic conditions.
- Copolymers can also be produced by copolymerizing one such ring-fused GBL monomer with another, or such a ring-fused GBL with other common lactones such the parent GBL, b-butyrolactone, d-valerolactone, e-caprolactone, lactide, glycolide, etc.
- the ROP is typically carried out under solvent-free conditions (i.e., bulk polymerization), or in solution (e.g., in toluene), at room temperature in the presence of catalyst.
- Suitable ROP catalysts can also be grouped into four classes:
- lanthanide also referred to as rare-earth metal
- transition-metal transition-metal
- main-group organic catalysts
- the metal center is typically protected by one or more bulky mono-dentate or polydentate organic ligands such as a tetradentate amino-alkoxy-bis(phenoxy) ligand.
- Organic catalysts are those strong organic bases or nucleophiles, such as
- TBD triazabicyclodecene
- Basic catalysts can be grouped into two general classes: strong organic bases and inorganic bases. They can be used alone but are often used in combination with a protic initiator.
- Organic catalysts include strong organic bases, especially polyaminophosphazene superbases such as l-/er/-butyl-4,4,4- tri s(di methyl a i no)-2,2-bis[tri s(dimethylami no)-phosphoranylidenami ho]-2l 5 ,4l 5 - catenadi(phosphazene) (3 ⁇ 4u-P4); guanidines such as l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), proazaphosphatranes (cyclic azaphosphines), and cyclopropenimine superbases, including the following catalysts.
- Anonic versions of organic catalysts/initiators such as urea or thiourea anions can also be used.
- the above catalysts for polymerization and other compounds can also be used as catalysts for depolymerization to recover the monomer back.
- Typical initiators include protic compounds such as alcohols (ROH), di-alcohols (HO- R-OH), polyols (compounds containing more than two OH groups, or sugars; amines (RNH2, R2NH); thiols (RSH), where R is alkyl, aryl, substituted alkyl, or substituted aryl, or deprotonated monomers.
- ROH alcohols
- HO- R-OH di-alcohols
- polyols compounds containing more than two OH groups, or sugars
- RNH2, R2NH amines
- thiols R is alkyl, aryl, substituted alkyl, or substituted aryl, or deprotonated monomers.
- the polymer has enhanced thermostability and can be repeatedly and quantitatively recycled back to its monomer by thermolysis or chemolysis. Mixing of the two enantiomers of the polymer generates a highly crystalline supramolecular stereocomplex.
- the invention also relates to methods of making the compounds and compositions of the invention.
- the compounds and compositions can be prepared by any of the applicable techniques of organic synthesis, for example, the techniques described herein. Many such techniques are well known in the art. However, many of the known techniques are elaborated in Compendium of Organic Synthetic Methods (John Wiley & Sons, New York), Vol. 1, Ian T. Harrison and Shuyen Harrison, 1971; Vol. 2, Ian T. Harrison and Shuyen Harrison, 1974; Vol. 3, Louis S. Hegedus and Leroy Wade, 1977; Vol. 4, Leroy G. Wade, Jr., 1980; Vol. 5, Leroy G. Wade, Jr., 1984; and Vol. 6, Michael B.
- reaction conditions such as temperature, reaction time, solvents, work up procedures, and the like, will be those common in the art for the particular reaction to be performed.
- the cited reference material, together with material cited therein, contains detailed descriptions of such conditions.
- the temperatures will be -l00°C to 200°C
- solvents will be aprotic or protic depending on the conditions required
- reaction times will be 1 minute to 10 days.
- Work-up typically consists of quenching any unreacted reagents followed by partition between a water / organic layer system (extraction) and separation of the layer containing the product.
- Oxidation and reduction reactions are typically carried out at temperatures near room temperature (about 20 °C), although for metal hydride reductions frequently the temperature is reduced to 0 °C to -100 °C. Heating can also be used when appropriate.
- Solvents are typically aprotic for reductions and may be either protic or aprotic for oxidations. Reaction times are adjusted to achieve desired conversions.
- Condensation reactions are typically carried out at temperatures near room temperature, although for non-equilibrating, kinetically controlled condensations reduced temperatures (0 °C to -100 °C) are also common.
- Solvents can be either protic (common in equilibrating reactions) or aprotic (common in kinetically controlled reactions).
- Standard synthetic techniques such as azeotropic removal of reaction by-products and use of anhydrous reaction conditions (e.g. inert gas environments) are common in the art and will be applied when applicable.
- protecting group refers to any group which, for example, when bound to a hydroxy or other heteroatom prevents undesired reactions from occurring at this group and which can be removed by conventional chemical or enzymatic steps to reestablish the hydroxyl group.
- Suitable hydroxyl protecting groups are known to those skilled in the art and disclosed in more detail in T.W. Greene, Protecting Groups In Organic Synthesis ; Wiley: New York, 1981 (“Greene”) and the references cited therein, and Kocienski, Philip J.; Protecting Groups (Georg Thieme Verlag Stuttgart, New York, 1994), both of which are incorporated herein by reference.
- l,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), 2,2- diphenylethanol, diphenylmethanol and triphenylmethanol were purchased from Aldrich Chemical Co., which were purified by dissolving in toluene over CaEh, filtering after stirring overnight, and removing the solvent.
- Benzyl alcohol and 1, 8-diazabicyclo[5.4.0]undec-7-ene (DBU) were purchased from Fisher Scientific Co. and Aldrich Chemical Co. respectively, which were purified by distillation over CaEh and stored over activated Davison 4 A molecular sieves.
- Tetradentate amino-bisphenolate yttrium alkyl complex (Yl) and 2,6- diisopropylphenyl substituted /3-diiminate zinc isopropoxide complex [(BDI)ZnO'Pr] (Znl) were prepared according to available procedures (Scheme 5).
- the GPC instrument consisted of an Agilent HPLC system equipped with one guard column and two PLgel 5 pm mixed-C gel permeation columns and coupled with a Wyatt DAWN HELEOS II multi (18)- angle light scattering detector and a Wyatt Optilab TrEX dRI detector; the analysis was performed at 40 °C using chloroform as the eluent at a flow rate of 1.0 mL/min, using Wyatt ASTRA 7.1.2 molecular weight characterization software.
- the refractive index increments (d «/dc) of the linear and cyclic P(M1) were determined to be 0.0764 ⁇ 0.0014 mL/g and 0.0814 ⁇ 0.0030 mL/g, respectively, obtained by batch experiments using Wyatt Optilab TrEX dRI detector and calculated using ASTRA software. Polymer solutions were prepared in chloroform and injected into dRI detector by Harvard Apparatus pump 11 at a flow rate of 0.25 mL/min. A series of known concentrations were injected and the change in refractive index was measured to obtain a plot of change in refractive index versus change in concentration ranging from 0.4 to 2.0 mg/mL. The slope from a linear fitting of the data was the &nl&c of the polymer.
- the isolated low molecular weight samples were analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS); the experiment was performed on an Ultraflex MALDI-TOF mass spectrometer (Bruker Daltonics) operated in positive ion, reflector mode using a Nd: YAG laser at 355 nm and 25 kV accelerating voltage.
- a thin layer of a 1% Nal solution was first deposited on the target plate, followed by 0.6 pl of both sample and matrix (DHB, 20mg/mL in MeOH, 10% AAC).
- DHB 20mg/mL in MeOH, 10% AAC
- External calibration was done using a peptide calibration mixture (4 to 6 peptides) on a spot adjacent to the sample.
- the raw data was processed in the FlexAnalysis software (version 2.4, Bruker Daltonics).
- FT-IR Fourier transform infrared
- T m and 7 glass-transition temperature of purified and thoroughly dried polymer samples were measured by differential scanning calorimetry (DSC) on an Auto Q20, TA Instrument. All T m and 7 values were obtained from a second scan after the thermal history was removed from the first scan. The second heating rate was 10 °C/min and cooling rate was 10 °C/min.
- Decomposition onset temperatures ( 7 0 nsct) and maximum rate decomposition temperatures (7 ' max) of the polymers were measured by thermal gravimetric analysis (TGA) on a Q50 TGA Analyzer, TA Instrument. Polymer samples were heated from ambient temperatures to 700 °C at a heating rate of 10 °C/min. Values of 7 max were obtained from derivative (wt %/°C) vs. temperature (°C), while 7 onset values (initial and end temperatures) were obtained from wt % vs. temperature (°C) plots.
- Film specimens suitable for dynamic mechanical analysis were prepared via solvent-casting of concentrated polymer solutions in chloroform at 30-50 °C.
- the .s -P(M l ) films were afforded by combining the isolated ( R )- and (ri)-chiral polymer materials P[(77)- Ml] and P[fV)-M 1 ] in solution and stirred to generate the stereocomplex.
- the rac -P(M1) solutions were solvated directly for casting.
- Polymer solutions were solvent-cast using a syringe into PTFE molds and left to dry gradually at room temperature in open air. Upon slow solvent evaporation of chloroform, typically after 24 - 72 h, the films were extensively dried overnight in a vacuum oven up to 100 °C and stored at room temperature prior to analysis.
- Storage modulus (77), loss modulus (A"), and tan d (77777) were measured by DMA on a Q800 DMA Analyzer (TA Instruments) in a tension film mode at a maximum strain of 0.05% and a frequency of 1 Hz (complying with strain-sweep and frequency-sweep linearity analysis performed prior to sample testing).
- Specimens for analysis were generated via solvent-casting of polymer materials in chloroform into PTFE molds (approx. 35 x 15 x 1.5 mm), dried, and cut down to a standard width (13 mm).
- Specimen length (5 - 10 mm) and thickness (0.10 - 0.30 mm) were measured for normalization of data by Q-series measurement software (TA Instruments). Test specimens were mounted to screw-tight grips (maximum 2 N). The samples were heated from -50 °C to 250 °C at a heating rate of 3 °C min -1 . Glass transition temperature (T g ) was calculated as the peak maxima of the tan d curve. Samples were tested to the point of yield (amplitude of displacement > 20 mm) with measurements repeated for 3 specimens, the values reported are averaged from the measured data.
- Tensile stress/strain testing was performed by an Instron 4442 universal testing system (50 N load cell) on dog-bone-shaped test specimens (ASTM D638 standard; Type V) prepared via slow-solvent evaporation. Concentrated polymer and stereocomplex solutions in chloroform were solvent cast into PTFE molds (approx. 73 x 54 x 7 mm), thoroughly dried, and cut using an ASTM D638-5-IMP cutting die (Qualitest) to standard dimensions.
- Thickness (0.10 - 0.40 mm) and grip length (25-26 mm) were measured for normalization of data by the Bluehill measurement software (Instron).
- Test specimens were affixed into the pneumatic grip (maximum 2 kN) frame at 30 psi (N2).
- Tensile stress and strain were measured to the point of material break at a grip extension speed of 5.0 mm/min at room temperature, with the measurements repeated for 4-6 specimens and the values reported are averaged from the measured data.
- isolated polymer materials rac-P(Ml) and .s -P(M l) were compression-molded using a Carver Bench Top Laboratory Press (Model 4386) equipped with a two-column hydraulic unit (Carver, Model 3912, maximum force 24000 psi).
- Oscillating frequency sweeps were then performed in a logarithmic fashion (5 points per decade) within the linear viscoelastic region (1.0% strain) from 0.1 to 100 and 500 rad so under continuous direct oscillation and a pre-analysis soak time of 5 min to allow for specimen thermostatization.
- the frequency sweep measurements were performed at 165, 175, 185, 195, 205, and 215 °C and the data compiled to a master curve reported as a time-temperature superposition curve at reference temperature 215 °C.
- reaction solution was cooled to 0 °C and quenched by addition of 4.0 M HC1 (10 mL) and diluted with water (20 mL). The mixture was extracted with Et 2 0 (3 x 100 mL). The combined organic layers were washed with brine and dried over anhydrous NaiSOr, filtrated, and concentrated in vacuo. The crude products were used directly for the next step directly.
- reaction solution was cooled to 0 °C and quenched by addition of 4 M HC1 (10 mL) and diluted with water (20 mL). The mixture was extracted with Et 2 0 (3 x 100 mL). The combined organic layers were washed with brine and dried over anhydrous Na 2 S0 4 , filtrated, and concentrated in vacuo. The crude products were used directly for the next step directly.
- amide-a acid-a To a solution of NaOH (4.0 g, 10 mol) in 40 mL of a 3 : 1 mixture of ethanokwater was added amide-a (1.6 g, 5.1 mmol). The reaction mixture was heated to 110 °C for 48 h and then cooled to 0 °C. The reaction mixture was treated with dilute HC1 to adjust the PH ⁇ 7 and concentrated in vacuo. The remaining solution was extracted with 4 x 200 mL of Et 2 0. The combined organic layers were washed with 200 mL of brine and dried over anhydrous NaiSOi, filtrated, and concentrated in vacuo.
- an NMR tube was charged with Y1 (7.4 mg, 9.8 pmol), and 0.3 mL of toluene-i3 ⁇ 4.
- the NMR tube was sealed with a Precision Seal rubber septum cap and taken out of the glovebox and immersed in a cooling bath at -78 °C.
- the equilibrium monomer concentration, [Ml] eq obtained by plotting [Ml] as a function time until the monomer concentration reached a constant, was measured to be 0.4154, 0.3316, 0.2679, and 0.2248 M for -25 °C, -30 °C, -35 °C, and -40 °C, respectively.
- Polymerizations were performed in 5 mL glass reactors inside the glovebox for ambient temperature ( ⁇ 25 °C) runs, or in 25 mL Schlenk flasks interfaced to a dual-manifold Schlenk line with an external temperature bath for runs at other temperatures.
- catalyst was added to the vigorously stirred monomer.
- the polymerization was quenched by addition of 3 mL HCCb acidified with HC1 (5%). The quenched mixture was precipitated into 100 mL of cold methanol, filtered, washed with methanol to remove any unreacted monomer, and dried in a vacuum oven at 50 °C to a constant weight (see Table 3 and Figures 5-12).
- Stereocomplexes were prepared from a mixture of isotactic (A’)-polymer and (S)- polymer in a 1 : 1 molar ratio (approximately 300 mg total).
- the solid polymer sample was dissolved in CHCb (20 mg mL -1 ), filtered through a plastic frit (0.45 pm pore size nylon filter), and allowed to evaporate slowly and undisturbed for 3-7 days.
- the obtained crystalline solid was collected and dried in a vacuum oven at 60 °C to a constant weight.
- a sealed tube containing 40 mg of the purified P(3,4-T6GBL) sample (free of catalyst residue) under an argon atmosphere was heated at 300 °C (for the linear polymer) for 1 h or at 300 °C (for the cyclic polymer) for 24 h. After cooling, a colorless liquid was formed and confirmed to be the cleanly and quantitatively recycled monomer 3,4-T6GBL by 3 ⁇ 4 NMR analysis (see Figures 19 and 20).
- e-CL e-caprolactone
- the molar composition of the diblock copolymer (57 mol % e-CL ) measured by 3 ⁇ 4 NMR was close to the calculated ratio (56 mol % e-CL) based on the monomer conversion data.
- the well-defined diblock copolymer structure was also confirmed by 13 C NMR analysis, which showed the presence of only two types of carbonyl resonances attributed to homo-sequences of e-CL and 4,5-T6GBL units of copolymer P(4, 5 -T6GBL)-/>-PCL.
- the thermal property of the diblock copolymer was analyzed by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA).
- the second heating scan DSC curve of P(4,5-T6GBL)-Z>-PCL (57 mol % f.-CL) showed only one melting-transition temperature (7 in) of 51 °C, while the glass-transition temperature (7 g ) typically at 72 °C attributed to homopolymer P(4,5-T6GBL) was not observed, which further demonstrated the diblock copolymer formation.
- TGA and DTG (derivative thermogravimetry) curves of P(4,5- T6GBL)-/>-PCL displayed two degradation steps; 7d (onset degradation temperature, defined by the temperature of 5% weight loss) of 318 °C and 7 ' max (maximum degradation
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