SE545575C2 - Pinene-based polymers, method for its preparation, and its use in a coating or barrier - Google Patents
Pinene-based polymers, method for its preparation, and its use in a coating or barrierInfo
- Publication number
- SE545575C2 SE545575C2 SE2150508A SE2150508A SE545575C2 SE 545575 C2 SE545575 C2 SE 545575C2 SE 2150508 A SE2150508 A SE 2150508A SE 2150508 A SE2150508 A SE 2150508A SE 545575 C2 SE545575 C2 SE 545575C2
- Authority
- SE
- Sweden
- Prior art keywords
- acid
- alkyl
- polymer
- hydroxyethyl
- alkenyl
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000004888 barrier function Effects 0.000 title claims abstract description 10
- 239000011248 coating agent Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical group 0.000 claims abstract description 4
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 15
- 150000005690 diesters Chemical class 0.000 claims description 14
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 claims description 11
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- -1 itaconic Chemical compound 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229960003505 mequinol Drugs 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 8
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 abstract 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 24
- 239000000178 monomer Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 229920001225 polyester resin Polymers 0.000 description 11
- 239000004645 polyester resin Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 229920013724 bio-based polymer Polymers 0.000 description 5
- 239000011436 cob Substances 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 241000779819 Syncarpia glomulifera Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011111 cardboard Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 239000001739 pinus spp. Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 229940036248 turpentine Drugs 0.000 description 3
- OMDMTHRBGUBUCO-IUCAKERBSA-N (1s,5s)-5-(2-hydroxypropan-2-yl)-2-methylcyclohex-2-en-1-ol Chemical compound CC1=CC[C@H](C(C)(C)O)C[C@@H]1O OMDMTHRBGUBUCO-IUCAKERBSA-N 0.000 description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 238000003820 Medium-pressure liquid chromatography Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100438619 Mus musculus Cpb2 gene Proteins 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940054192 micro-guard Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229960000230 sobrerol Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- OMDMTHRBGUBUCO-UHFFFAOYSA-N trans-sobrerol Natural products CC1=CCC(C(C)(C)O)CC1O OMDMTHRBGUBUCO-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/27—Polyhydroxylic alcohols containing saturated rings
- C07C31/272—Monocyclic
- C07C31/274—Monocyclic with a three to five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/28—Polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to a polymer comprising repeating units of formula (I)whereinA is selected from O, NR6, -C(O)-O- and C=O;B is selected from O, NR6, -O-C(O)-, C=O, and E-C(O)-X-C(O)-, wherein E is O or NR6; R1, R2, R3, R4, R5 and R6each independently are selected from H, C1-6 alkyl, halogenated C1-6 alkyl;X is selected from C1-6 alkyl, C2-6 alkenyl, which may be mono- or diunsaturated, C3-6 cycloalkyl, C3-6 cycloalkenyl, diamino- C2-6 alkyl, diamino- C2-6 alkenyl, and a 4- to 6-membered saturated or unsaturated ring optionally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsaturated ring is optionally substituted;and wherein any alkyl and alkenyl may be linear or branched and is optionally substituted with a halogen or an aromatic unit; andm is an integer between 10 and 10000,and a method for its preparation, as well as its use in coating, barrier, or moulding applications.
Description
The present inventíon relates to a polymer comprising repeating units of formula (I)
(I)
a method for its preparation, and its use in coating, barrier, or moulding applications.
TECHNICAL BACKGROUND
Today, the vast majority of all polymeric synthetic materials are fossil-based. As polymeric materials are essential for our daily life innovative technologies to generate sustainable biomaterials from renewable feedstocks are urgently needed. Paint and coating industries, as well as other chemical companies, seek to replace current petroleum-sourced products with renewable alternatives. Still, only a very small proportion of all synthetic polymers are generated from renewable resources. Growing plants only for bioplastíc production raises further environmental issues, e.g. the use of fertilizers and land redirected from food production (Tabone, M. D., et al., Environ. Sci. Technol. 44, 8264-8269 (2010)). Development of sustainable polymers towards a circular materials economy would thus be favoured by the use of already existing but
underutilized side streams in industrial processes.
Terpenes is a large class of small-molecule hydrocarbons that are produced predominantly by plants and constitute one of the most diversified families of natural products (Oldfield, E. & Lin, F.-Y. Angew. Chemie Int. Ed. 51, 1124-1137 (2012)) with a broad variety of structural and functional properties. One major source of terpenes is turpentine, a pine-tree resin emanating from the paper and pulping industry. The main
component of turpentine is oi-pinene, which has a bicyclic unsaturated structure that
has been shown to react cationically. However, the steric hindrance of the trisubstituted double bond poses an issue to the production of high molecular weight polymers (Lomelí-Rodriguez, M., et al., Polymers (Basel). 10, 600 (2018)). Lanteri et al. (Front. Chem. 8, 85 (2020)) studied the use of terpene-based diols as monomers for polyester synthesis by using the photo oxidized product ofcitronellol as comonomer together with butanediol and dimethyl succinate. Firdaus et al. (Macromolecules 44, 7253-7262 (2011)) studied the use of functionalized, limonene-based monomers bearing both, ester and alcohol functionality. lshmuratov, G. Y., et al., (Chem. Nat. Compd. 53, 63-(2017)) have reported the use of ozone for the cleavage of the alpha pine double bond.
Thus, achieving appropriate functionalization of inert metabolites to afford activated monomers compatible with desired polymerization type and provision of scalable synthesis of bio-based materials With tuneable properties are problems that need to be
solved.
SUMMARY OF THE INVENTION
lt is an object of the present ínvention to provide a bio-based polymer, such as a polyester resin, a polyamide resin, or a polyurethane resin, with tailored properties based on terpene derived monomers solely or in combination with dicarboxylic acid or
a diester thereof, §__§§_.__and the use of said bío-based polymer as coating
and green barriers.
A further object is to provide a method for preparing a bio-based polymer, such as a
polyester, polyamide or polyurethane resin from a terpene-derived monomer solely or
in combination with a dicarboxylic acid or diester thereof_,.__¿<_>_-_;j¿ -
A still further object is to provide a coating comprising the bio-based polymer resin.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 presents lH-NMR spectra of polyesters.
Figure 2 presents molecular weight distribution curves.
Figure 3 presents TGA thermograms for (a) polyester resins and (b) cured polyester coatings.
Figure 4 presents DSC thermograms for (a) polyester resins and (b) cured polyester
coatings.
DETAILED DESCRIPTION OF THE INVENTION
ln a first aspect the present invention relates to a polymer comprising repeating units of
R4 Aíyeïïïs / \
RZ Rß
formula (I)
(I)
wherein
A is selected from O, NRG, -C(O)-O- and C=O;
B is selected from O, NRG, -O-C(O)-, C=O, and E-C(O)-X-C(O)-, wherein E is O or NRG; Rl, RZ, R3, R4, RS and R6 each independently are selected from H, C1-6 alkyl, and halogenated C1.6 alkyl;
X is selected from C1-e alkyl, C24; alkenyl, which may be mono- or diunsaturated, C36 cycloalkyl, C36 cycloalkenyl, diamino- CH alkyl, diamino- CH alkenyl, and a 4- to 6- membered saturated or unsaturated ring optionally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsaturated ring is optionally substituted; and
wherein any alkyl and alkenyl may be linear or branched and is optionally substituted with a halogen or an aromatic unit; and
m is an integer between 10 and
Preferably, A and E each independently are selected from O and NR6. Also preferably, B is E-C(O)-X-C(O)-.
ln one embodiment, the polymer of the present invention comprises repeating units of
formula (ll)
H2 RB” (n)
wherein
A and E each independently are selected from O and NRG;
Rl, RZ, R3, R4, R5 and Re each independently are selected from H, C1-e alkyl, halogenated C14; alkyl;
X is selected from C14 alkyl, Cz-v alkenyl, which may be mono- or diunsaturated, Ca-a cycloalkyl, C34; cycloalkenyl, diamino- C24; alkyl, diamino- C24; alkenyl, and a 4- to 6- membered saturated or unsaturated ring optíonally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsatu rated ring is optionally substituted; and
wherein any alkyl and alkenyl may be linear or branched and is optionally su bstituted with a halogen or an aromatic unit; and
m is an ínteger from 10 to
Preferably, in any one of the formulas (I) and (ll) above, Rl, Rz and R3 are each independently methyl. Preferably, X is selected from ethyl, propyl, butyl, ethenyl, propenyl, butenyl, butadienyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, imidazolyl, pyrazolyl, furyl, thienyl, pyridyl, pyrazinyl, pyranyl, and phenyl. More preferably, X is ethenyl, 2- propenyl, or furyl. ln some embodiments m is an integer from 10 to 1000, or fromto
The polymer according to the present invention may be a polyester, a polyamide a polyurethane or a polyester resin. Preferably, the polymer is a polyester, or a polyester
resin. ln one aspect, the polymer according to the present invention may be obtained
by polycondensation or polyadduct formation of at least two different monomers, characterized in that a first monomer is 1-(1'-hydroxyethy|)-3-(2"-hydroxyethyl)-2,2- dimethylcyclobutane (HHDC) and that a second monomer is selected from at least one of a dicarboxylic acid, an anhydride or a diester thereof, and an isocyanate. Preferably, the second monomer is a dicarboxylic acid or a diester thereof. Preferably, the dicarboxylic acid or a diester thereof is selected from any one of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aspartic acid, itaconic acid, maleic acid, 2,5-furan dicarboxylic acid, dimethyl maleate (DMM), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA), and mixtures thereof. More preferably, the dicarboxylic acid or a diester thereof is selected from dimethyl maleate (DMM), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA). Preferred isocyanates are selected from methylenebis(pheny| isocyanate)
(MDI), toluene diisocyanate (TDI), and hexamethylene diisocyanate (HDI).
In a further aspect the present invention relates to a method for preparing a polymer of
formula (I) by reacting 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2- dimethylcyclobutane (HHDC) with a dicarboxylic acid, an anhydride or a diester thereof, or an isocyanate. Preferably, the method for preparing a polymer is made by reacting 1- (1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC) with a dicarboxylic acid, or an anhydride or a diester thereof. The reaction may be made by polycondensation. In one embodiment the dicarboxylic acid or diester thereof used in the method for preparing the polymer is selected from itaconic, maleic acid, 2,5-furan dicarboxylic acid, dimethyl maleate (DMM), dimethyl itaconate (DMI), and dimethyl
furandicarboxylate (DM-FDCA), and mixtures thereof.
The method according to the present invention may comprise a step of mixing the 1-(1'- hydroxyethy|)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HH DC) with a dicarboxylic acid, or an anhydride or a diester thereof, or an isocyanate to obtain a mixture. In one embodiment, a polymerisation inhibitor is added to the mixture, such as a radical
inhibitor, preferably a phenolic radical inhibitor, such as mequinol. ln a further
embodiment, a catalyst is added to the mixture. The catalyst may provide for a more rapid polymerization. The method according to the present invention may also comprise a step of heating the mixture to obtain a polyester resin. Heating may provide for
improved solubility of reagents or a higher reaction rate, or both.
The polymer obtained by the method of the invention may further be cured to obtain a cross-linked polymer, such as a cross-linked polyester. Thus, the method according to the present invention may further comprise a step of curing the polymer to obtain a cross-linked polymer. Curing of the polymer may be obtained by UV, preferably using cross-linkers, such as multifunctional thiols, such as trimethylolpropane tris(3- mercaptopropionate) (TMTP). The polymer can also be cured together with solvents,
including styrene, methyl methacrylate, and Sobrerol methacrylate.
The monomer 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane used in the method according to the present invention may be obtained by oxidative cleavage of the double bond in oL-pinene, such as by using ozone, to obtain the cx-pinene-ozonide
followed by reduction, such as by using sodium borohydride.
A yet further aspect of the present invention is the use of an oL-pinene derived monomer, such as 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC), for the preparation ofa polymer, such as a polyester, a polyester resin, a polyurethane or a polyurethane resin. As presented herein, HHDC provides a bio-based renewable polyol in polyurethane or polyester resin synthesis resulting in a fully amorphous polyester or polyurethane with increased thermal stability, when co-polymerized with a dicarboxylic acid or diester thereof, or an isocyanate including itaconic, maleic acid and 2,5-furan dicarboxylic acid. Thus, the present invention enables synthesis of a variety of biobased polyesters and polyurethanes by reacting HHDC with different diacids or isocyanides or isocyanates. The present invention thus enables the synthesis of fully biobased polymers
by using biobased comonomers like furan-, itaconic- or maleic-based substrates. By
addition of further types of monomers to the polymerization system, the properties of
the polymer may be further tailored.
The polymer according to the present invention can be efficiently produced from a- pinene derived from turpentine. The cyclic structure of oL-pinene enables the preparation of polymers With an extent of rings in the backbone, which allows for beneficial structural and thermal properties of the generated materials. Thus, the present invention enables use ofabundant renewable building blocks in industrial waste streams to generate polymers with industrially appealing properties, such as appealing
glass-transition temperatures and hydrophobicities.
One application of the present invention is in formulations based on curing of the polymer. Such formulations could be used as coatings; barriers, preferably against oxygen and moisture; consumer, marine and automotive articles; as well as in sheet moulding and bulk moulding composites. Thus, in a further aspect, the present invention also relates to coatings, barriers, sheet moulding and bulk moulding composites comprising a polymer according to the present invention. Preferably, the present invention relates to coatings or barriers comprising a polymer according to the present
invention.
Thus, in a further aspect, the present invention relates to the use of a polymer according to the present invention, such as in a coating, in a barrier, in sheet moulding or in bulk
moulding composites.
The present invention thus enables fully bio-based coatings exhibiting properties similar to petroleum-based counterparts. Further, through the recycling of waste streams within the pulp and paper industry, the present invention also provides a cost-effective way for pulp and paper mills to upcycle their waste and use it directly as part of the
protectíve paper coatings, such as cardboard and food packaging with green barriers.
The invention will now be described by the following examples which do not limit the invention in any respect. All cited documents and references mentioned herein are
incorporated by reference in their entireties.
EXAMPLES
EXAMPLESynthesis of 1-(1'-hydroxyethyl)-3-( "-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC)
A solution of d-pinene (50 g, 367 mmol) in MeOH (100 ml) and CHZCIZ (400 ml) was stirred at -76 °C, purged with an 03/02 mixture (200 l/h, 290 mA) until 1 equivalent (367 mmol) of O; was absorbed (indicated by colour change). The reaction was afterwards purged with oxygen, treated with NaBH4 (42.4 g, 1.12 mol) and stirred for 4 h at room temperature. Afterwards 5M hydrochloric acid was added until the pH reached 1 (about 130 ml). The organic layer was separated, and the aqueous layer was washed three times with ethyl acetate. The organic layers were combined, dried over |VlgSO4 and concentrated under reduced pressure. The crude product was purified using column chromatography resulting in the diol as transparent oil with a yield of 65% (240 mmol,
41g).
EXAMPLESynthesis of polyester resins by polycondensation
Four different polyester compositions were prepared by charging 2.5 g of HHDC monomer (prepared according to Example 1), dimethyl maleate (DMM), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA) into a round bottom flask (25 ml) according to ratios seen in Table 1 along with 2-3 ml of p-xylene and optionally a radical inhibitor, mequinol (5 wt% of total monomer weight). The reaction vessel was connected to a Dean-Stark setup and lowered into an oil bath at 160°C. Reaction was started with injection of catalyst Ti(OBu)4 (7 mol% of total monomer amount). The attached solvent trap was filled with p-xylene. The reaction Was stopped once SEC- analysis showed molecular weights in the range of 4k-8k Da. The resulting polymer was
precipitated twice in ice-cold methanol and dried under vacuum.
EXAMPLECuring of HHDC-based polyester coatings
HHDC-based polymers (prepared in accordance with Example 2), trimethylolpropane tris(3-mercaptopropionate) (thiol agent TMTP) (1:1 molar ratio of thiol to unsaturations), UV-curing agent lrgacure 651 (1 wt% of resin weight) and solvent butyl acetate (40 wt% of resin weight) were mixed and then poured on to substrate using a box applicator (150 um). For producing free standing film, an additional droplet of releasing agent silicone was added to the wet resin mixture. Coatings were subjected to UV-light until FT-IR showed a significant decrease in the signal originating from C=C at 1600-1680 cm*1. Successful crosslinking was further corroborated by the fact that the films were insoluble in chloroform and EtOAc, two solvents that solubilizes the uncured
polyesters.
Characterization
instrumentation and methods
GC-MS (Shimadzu, GCMS-QP2010 Ultra) was performed on an Rxi®-5ms (30 m, 0.25 mm [inner diameter], 0.25 um [film thickness], RESTEK). The temperature program was set at 70 °C, before increasing to 300 °C with a rate of 20 °C/min and finally increased to 350 °C with a rate of 5 °C/min before holding at 350 °C for 10 min. For MPLC, a Biotage lsolera Four system equipped with a UV detector and Biotage KP-Sil SNAP Cartridge columns was used. 1H (400 MHz) and BC (100 MHz) NMR spectra were recorded with a Bruker Avance AI\/I 400 instrument. The signal of the deuterated solvent CDCI; (ó'= 7.26 ppm47) was used as reference. For SEC, a TOSOH EcoSEC HLC-8320G PC system was used equipped with an EcoSEC RI detector and three PSS PFG 5 um columns (microguard, 100 Å, and 300 Å). Poly(methy| methacrylate) (PMMA) standards were used for calibration
and toluene was used as internal standard.
DSC was performed using a Mettler Toledo DSC 820 module. Samples (5-10 mg) were
prepared in 100 uL aluminium crucibles. The samples were subjected to heating from
to 170 °C (or 160 °C), then cooled to -60 °C, and then heated again to 170 °C (or 160 °C) at a heating/cooling rate of 10 “C/min under nitrogen flow (50 mL/min). The data obtained from the second heating was used for analyses. For TGA, a Mettler Toledo TGA/DSC1 instrument was used. Samples (5-7 ug) were prepared in 70 uL alumina crucibles and heated from 40 to 700 °C at a heating rate of 10 °C/min under a nitrogen
flow (50 mL/min).
FTIR was performed on a Perkín-Elmer Spectrum 100 FT-IR instrument equipped with a single reflection ATR system and a MIR-TGS detector using a MKII Golden Gate (Graseby Specac Ltd, Kent, England). Spectra were recorded over the range 4000-600 cm'1 and
based on 16 scans at an average 4.0 cmil resolution.
Cobb method for determining water absorptiveness of carton coated With biobased coatings. Coated carton, ICG 280 for Cobb-testing was acquired by Iggesund Paperboard. Cobb-setup was made with inspiration from the official ISO-535 since a proper setup was not available. lnstead ofa metal cylinder with clamping potential, a rubber cylinder with an inner diameter of 3.3 cm was used. lnstead of clamping, a circular metal weight was used to fixate the cylinder. To determine baseline absorptiveness, three pieces of untreated carton where subjected to Cobbno-test. Another three-set of UV-treated carton was also subjected to Cobb test to account for substrate effects on absorptiveness post curing. Lastly all four HHDC-based polyester resins were coated onto the carton and cut into three samples of each. Samples plates with a diameter 2 5 cm. Besides these ad-hoc solutions, testing procedure follows as described by ISO- standard. Absorptiveness, A is calculated by the following expression. F is the inverse of
the surface area in the unit m
A I F(mwet _ mdry) Contact angle measurements to determine wettability of the four terpene-based
polyester coatings, untreated carton, and UV-treated carton (ICG 280, Iggesund
Paperboard). Coated substrates used were same as for the Cobb-test. Three droplets of
about 10-15 ml of each sample were measured. Contact angle of left and right side where averaged and then combined into a total average for all three droplets.
Measurements were made with an OCA20 (Data Physics).
Dynamical mechanical analysis (DMA) experiments were performed with a DMA Q80O from TA Instruments equipped with a tensile fixture. Samples of prepared coating a geometry of 30-5-0.07 mm3 strips fixated with 16-18 mm between anchoring points. Samples are in itially cooled down to -100°C by nítrogen cooling. Then heated with a rate of 5°C/min up to 180°C while subdued to an oscillating axial stress to the sample to induce a periodic pre-determined strain of 7% at frequency 1 Hz. Glass-transition temperatures are reported as the temperature correspondíng to the maximum value of
the resulting tan-ö curve.
Composition
The composition of the copolymers prepared according to Example 2 was determined by IH NMR. Respective lH-NMR spectra of the synthesized polymers are displayed in Figure 1. The molecular weights were calculated by the ratio of signals within the polymers 7.2 > ö > 4 ppm to signals stemming from end groups 4 > ö > 3.5 ppm. The ratio was further multiplíed by the mass of the repeating units for respective polymer to
determine molecular weights. The results are presented in Ta bleTableSample Mmwmegs Reaction Charged Ratio A:Btot coïzrlšgïign (Å,B,B*)a ' *= ID t|me [h] (B+B Btot) (A _ B _ B*) m] 16 HHDC, DIVIIVI 7 1.01I1 49.8 350.2 18 HHDC, Dl\/|| 39 1.02I1 50.9 149.1 HHDC D|\/|l\/| 20 ' ' 7 1.023 0.5 0.5 50.62 23.13 26.3 DM-FDcA ( + ) 21 HHDC, own, _ _ _ DM_FDCA 16 1.02 . (0.5+0.5) 50.1 . 23.9 .a) A=HHDC, B=DMM or DMI, B*=DM-FDCA
The polymers were further characterized by SEC to study the molecular structure, while thermal degradation was studied using thermal gravimetric analysis (TGA). Glass transition temperatures were analyzed using differential scanning calorimetry (DSC) and DIVIA (dynamic mechanical analysis). The results are presented in Table 2. Molecular
weight distribution curves are shown in Figure 2 of the four polyester compositions.
Thermal characterization of uncured polyesters
Thermal characterization of polymers prepared according to Example 2 is shown in figure 3(a) and 4(a). The TGA thermograms presented in Figure 3(a) show two step degradation profile for all synthesized HHDC based polyesters. A partial decomposition around l00-150°C causes between 4 and 15% mass reduction. Full decomposition starts at 240-250°C for the polyesters containing FDCA, while the itaconate and maleate polyesters have slightly better thermal resistance, decomposing closer to 300°C. Decomposition temperatures (Td-5%) ofthe four polyesters are reported in Table 2. The DSC thermograms are shown in figure 4(a) and extracted values are summarized in Ta ble 2. The polymers pHHDC-DMM and pHHDC-DMI possess glass transition temperatures below room temperature while the polymers containing FDCA display values slightly above. ltaconate-based polymers tend to have slightly lower Tg compared to the maleate based materials. One more carbon in the itaconate compared with the maleate
residue facilitates chain movement, thus contributing to lower the Tg, and the endo-double bond of the maleate residues further impairs chain movement due to the spz- hybridization. FDCA-moieties tend to significantly increase Tg. DSC shows no exothermic
crystallization trend indicating all polyesters being fully amorphous.
TableSample lH-NMR Mn D DSC Tg TGA Td ID Mn [g/mol] [g/mol] (Mw/Mn) [°C] [°C] 16 6384 4453 2.3 17.0 274.8 18 8445 7734 3.0 13.6 258.5 20 6105 4405 1.9 42.3 153.0 21 6242 4248 2.9 32.5 125.Thermal characterization of cured polyesters
The four polyester coatings prepared according to Example 3, were characterized by TG- analysis and DSC to determine their thermal properties (Table 3). The TGA and DSC thermograms are presented in Figures 3(b) and 4(b), respectively. DSC-derived Tg - values are higher for all four materials compared to uncured polyesters due to the introduced cross-linkages, hindering coordinated chain movement. The two coatings containing FDCA have less amounts of unsaturated groups and thus shows decrease in Tg for the respective materials. Td-5% obtained from TG analysis are quite similar for all four materials being around 270°C. Tensile analysis is conducted by dynamical mechanical analysis (DMA) showing a storage mod uli around 2 GPa for all four materials
at temperatures below the softening temperature (Ty).
Cobb test and contact analysis
To test the materials as protective coatings for paper applications, thin ”10 um films were coated on industrial used paper (|CG280; ZSOg/mz, Iggesund Paper Board) and cured. Results of the Cobb test are all average absorptiveness (A) based on three measurements of each sample (Table 3). To evaluate the obtained values, non-coated carton samples were measured (non-treated and UV-treated). UV irradiated carton had the highest average A-value of 51 [g/mg] while non-treated cardboard had 37 [g/m3]. A
significant decrease of water absorptiveness is experienced with all coating resins. Everso slightly does the two coatings with itaconate-moieties excel with absorptiveness below 2 [g/mgl. For comparison, disposable food service items coated with biobased polymers should have a Cobb-value smaller than 25 [g/m3].Contact angle of untreated card board was 72°. The contact angles of the two references after UV- and heat treatment were 52° and 81°, respectively. lt shows that UV irradiation
has a negative impact on the paper material inherent properties.
Table 3 sample ID Dsoc rg Tafi rd c? cobzgzzo
Monomers (A,B) l C] l C] I] f] non-treated _ _ _ 72 37 UV-treated _ _ _ 52 51 16 TMTP HHDc, DMM 62 270 72 2.7 18 TMTP HHDc, Dmi ss 274 ss 1.1 20 TMTP HHDc, DMM, FDcA 47 265 62 2.1 21 TMTP HHDc, Dmi, FocA 62 267 92 1.14
Claims (1)
1. A polymer comprising repeating units of formula (I) A R R wherein A is selected from O, NRG, -C(O)-O- and C=O; B is selected from O, NRG, -O-C(O)-, C=O, and E-C(O)-X-C(O)-, wherein E is O or NRG; Rl, RZ, R3, R4, R5 and R6 each independently are selected from H, C14; alkyl, halogenated C14; alkyl; X is selected from 01-7 alkyl, CN alkenyl, which may be mono- or diunsaturated, C34; cycloalkyl, C34; cycloalkenyl, diamino- C24; alkyl, diamino- C24; alkenyl, and a 4- to 6-membered saturated or unsaturated ring optionally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsaturated ring is optionally substituted; and wherein any alkyl and alkenyl may be linear or branched and is optionally substituted with a halogen or an aromatic unit; and m is an integer from 10 to polymer according to claim 1, wherein B is E-C(O)-X-C(O)-, wherein E is O or NRG. A method for preparing the polymer according to claim 1 by reacting 1- (1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC) with a dicarboxylic acid, an anhydride or a diester thereof, or hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC) with a dicarboxylic acid or a diester thereof to obtain a mixture. The method according to claim wherein the dicarboxylic acid or diester is selected from malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aspartic acid, itaconic, maleic acid, 2,5- furan dicarboxylic acid, dimethyl maleate (DI\/|I\/|), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA), and mixtures thereof. wherein the mixture The method according to any one of claims tol ...I may further comprise a polymerisation inhibitor, preferably a phenolic radica| inhibitor, such as mequinol. Use of a polymer according to any one of claims 1 to fåïš, in a coating or barrier.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE2150508A SE545575C2 (en) | 2021-04-22 | 2021-04-22 | Pinene-based polymers, method for its preparation, and its use in a coating or barrier |
| PCT/EP2022/060778 WO2022223825A1 (en) | 2021-04-22 | 2022-04-22 | Pinene-based polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE2150508A SE545575C2 (en) | 2021-04-22 | 2021-04-22 | Pinene-based polymers, method for its preparation, and its use in a coating or barrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| SE2150508A1 SE2150508A1 (en) | 2022-10-23 |
| SE545575C2 true SE545575C2 (en) | 2023-10-24 |
Family
ID=81842047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE2150508A SE545575C2 (en) | 2021-04-22 | 2021-04-22 | Pinene-based polymers, method for its preparation, and its use in a coating or barrier |
Country Status (2)
| Country | Link |
|---|---|
| SE (1) | SE545575C2 (en) |
| WO (1) | WO2022223825A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170101488A1 (en) * | 2015-10-08 | 2017-04-13 | Northwestern University | Apopinene as a Biorenewable Monomer for Ring-Opening Metathesis Polymerization |
| US20190002387A1 (en) * | 2017-06-30 | 2019-01-03 | The University Of North Dakota | Cyclobutane-1, 3-diacid building blocks |
| US20190106383A1 (en) * | 2017-10-06 | 2019-04-11 | International Business Machines Corporation | Pinene-derived diisocyanates |
| WO2020168177A1 (en) * | 2019-02-14 | 2020-08-20 | University Of Florida Research Foundation | Methods and compositions for biorenewable polyesters derived from camphoric acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK3158017T3 (en) * | 2014-06-20 | 2018-04-03 | Dsm Ip Assets Bv | RESIN, COMPOSITION AND APPLICATION |
-
2021
- 2021-04-22 SE SE2150508A patent/SE545575C2/en unknown
-
2022
- 2022-04-22 WO PCT/EP2022/060778 patent/WO2022223825A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170101488A1 (en) * | 2015-10-08 | 2017-04-13 | Northwestern University | Apopinene as a Biorenewable Monomer for Ring-Opening Metathesis Polymerization |
| US20190002387A1 (en) * | 2017-06-30 | 2019-01-03 | The University Of North Dakota | Cyclobutane-1, 3-diacid building blocks |
| US20190106383A1 (en) * | 2017-10-06 | 2019-04-11 | International Business Machines Corporation | Pinene-derived diisocyanates |
| WO2020168177A1 (en) * | 2019-02-14 | 2020-08-20 | University Of Florida Research Foundation | Methods and compositions for biorenewable polyesters derived from camphoric acid |
Non-Patent Citations (1)
| Title |
|---|
| STAMM, A ET AL "A Retro-biosynthesis-Based Route to Generate Pinene-Derived Polyesters", ChemBioChem, 2019, Vol. 20, p. 1664-1671 * |
Also Published As
| Publication number | Publication date |
|---|---|
| SE2150508A1 (en) | 2022-10-23 |
| WO2022223825A1 (en) | 2022-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gerbase et al. | Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil | |
| Montarnal et al. | Epoxy‐based networks combining chemical and supramolecular hydrogen‐bonding crosslinks | |
| Yang et al. | Study on the synthesis of bio-based epoxy curing agent derived from myrcene and castor oil and the properties of the cured products | |
| Gimenez et al. | Modification of poly (vinyl alcohol) with acid chlorides and crosslinking with difunctional hardeners | |
| Karayannidis et al. | Alkyd resins derived from glycolized waste poly (ethylene terephthalate) | |
| Wang et al. | Investigation of non-isocyanate urethane dimethacrylate reactive diluents for UV-curable polyurethane coatings | |
| Gioia et al. | Sustainable polyesters for powder coating applications from recycled PET, isosorbide and succinic acid | |
| US4020125A (en) | Thermosetting resin | |
| Costa et al. | Soybean and coconut oil based unsaturated polyester resins: Thermomechanical characterization | |
| Del Rio et al. | Biobased polyurethanes from polyether polyols obtained by ionic‐coordinative polymerization of epoxidized methyl oleate | |
| US4220563A (en) | Heat-curable and solvent-soluble ester group-containing polymer compositions and process for their preparation | |
| Di Mauro et al. | Building thermally and chemically reversible covalent bonds in vegetable oil based epoxy thermosets. Influence of epoxy–hardener ratio in promoting recyclability | |
| Bai et al. | Vanillin derived a carbonate dialdehyde and a carbonate diol: Novel platform monomers for sustainable polymers synthesis | |
| US6288208B1 (en) | Highly branched oligomers, process for their preparation and applications thereof | |
| Jahandideh et al. | Synthesis, characterization and curing optimization of a biobased thermosetting resin from xylitol and lactic acid | |
| Jahandideh et al. | Synthesis and characterization of novel star-shaped itaconic acid based thermosetting resins | |
| Taşdelen-Yücedağ et al. | Preparation of oil-modified polycaprolactone and its further modification with benzoxazine for coating purposes | |
| Fu et al. | Green preparation of robust hydrophobic bio-based epoxy resin with low dielectric constant | |
| EP2166030A1 (en) | Re-mouldable cross-linked resin, a composition, a substituted furan, and processes for preparing the same | |
| JPH10508655A (en) | Crosslinked resin | |
| CN112920393B (en) | Synthesis method and application of unsaturated polyester modified asparagus resin | |
| SE545575C2 (en) | Pinene-based polymers, method for its preparation, and its use in a coating or barrier | |
| JP2000502115A (en) | Uses of reactive prepolymer organic compounds | |
| Chen et al. | Mimosa tannin based NIPU wood adhesive with significant substitution of hexamethylenediamine using polyethyleneimine | |
| US5914385A (en) | Polyimide resin composition and method for producing prepreg and paint and method for curing resin using the same |