CN110963984A - 一种呋喃二甲酰-聚羟基酸酯增塑剂及其应用 - Google Patents
一种呋喃二甲酰-聚羟基酸酯增塑剂及其应用 Download PDFInfo
- Publication number
- CN110963984A CN110963984A CN201911189792.0A CN201911189792A CN110963984A CN 110963984 A CN110963984 A CN 110963984A CN 201911189792 A CN201911189792 A CN 201911189792A CN 110963984 A CN110963984 A CN 110963984A
- Authority
- CN
- China
- Prior art keywords
- acid
- furan
- plasticizer
- dicarboxyl
- polyhydroxyalkanoate
- 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.)
- Granted
Links
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000004014 plasticizer Substances 0.000 title claims abstract description 67
- 150000002148 esters Chemical class 0.000 title claims abstract description 19
- 229920001273 Polyhydroxy acid Polymers 0.000 title abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical group OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 20
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 20
- 150000001261 hydroxy acids Chemical class 0.000 claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 6
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 3
- -1 coatings Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 31
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- 239000004800 polyvinyl chloride Substances 0.000 claims description 20
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 239000004626 polylactic acid Substances 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 4
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 4
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 4
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001944 Plastisol Polymers 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000976 ink Substances 0.000 claims description 3
- 239000004922 lacquer Substances 0.000 claims description 3
- 239000002649 leather substitute Substances 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 239000004999 plastisol Substances 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 claims description 2
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 claims description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 claims description 2
- NMRPBPVERJPACX-QMMMGPOBSA-N 3-Octanol Natural products CCCCC[C@@H](O)CC NMRPBPVERJPACX-QMMMGPOBSA-N 0.000 claims description 2
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 2
- 229940006015 4-hydroxybutyric acid Drugs 0.000 claims description 2
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 claims description 2
- YDCRNMJQROAWFT-UHFFFAOYSA-N 5-hydroxyhexanoic acid Chemical compound CC(O)CCCC(O)=O YDCRNMJQROAWFT-UHFFFAOYSA-N 0.000 claims description 2
- PHOJOSOUIAQEDH-UHFFFAOYSA-N 5-hydroxypentanoic acid Chemical compound OCCCCC(O)=O PHOJOSOUIAQEDH-UHFFFAOYSA-N 0.000 claims description 2
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- ABIKNKURIGPIRJ-UHFFFAOYSA-N DL-4-hydroxy caproic acid Chemical compound CCC(O)CCC(O)=O ABIKNKURIGPIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000004811 fluoropolymer Substances 0.000 claims description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 18
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 18
- 238000005886 esterification reaction Methods 0.000 description 16
- 230000032050 esterification Effects 0.000 description 15
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 14
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 13
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- BMBDJILYIZBBMQ-UHFFFAOYSA-N furan-2,3-dicarbonyl chloride Chemical compound ClC(=O)C=1C=COC=1C(Cl)=O BMBDJILYIZBBMQ-UHFFFAOYSA-N 0.000 description 9
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 8
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 8
- 125000005498 phthalate group Chemical class 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229940116333 ethyl lactate Drugs 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 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
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HRELNAWNYHNHHO-UHFFFAOYSA-N bis(7-methyloctyl) benzene-1,2-dicarboxylate cyclohexane Chemical compound C1CCCCC1.C(CCCCCC(C)C)OC(C=1C(C(=O)OCCCCCCC(C)C)=CC=CC1)=O HRELNAWNYHNHHO-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 230000004102 tricarboxylic acid cycle Effects 0.000 description 2
- OZZQHCBFUVFZGT-UHFFFAOYSA-N 2-(2-hydroxypropanoyloxy)propanoic acid Chemical compound CC(O)C(=O)OC(C)C(O)=O OZZQHCBFUVFZGT-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GQIDSVPVVYHXAP-UHFFFAOYSA-N dihexyl decanedioate Chemical compound CCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC GQIDSVPVVYHXAP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001779 embryotoxic effect Effects 0.000 description 1
- 231100000238 embryotoxicity Toxicity 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 231100000386 immunotoxicity Toxicity 0.000 description 1
- 230000007688 immunotoxicity Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- CTJJGIVJOBVMEO-UHFFFAOYSA-N tetraoctyl benzene-1,2,4,5-tetracarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC(C(=O)OCCCCCCCC)=C(C(=O)OCCCCCCCC)C=C1C(=O)OCCCCCCCC CTJJGIVJOBVMEO-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种呋喃二甲酰‑聚羟基酸酯增塑剂及其应用。该呋喃二甲酰‑聚羟基酸酯增塑剂由三部分组成:呋喃二甲酸部分、由羟基酸低聚化形成的聚酯部分和末端封端醇部分。该增塑剂可以应用在聚合物增塑方面,特别在PVC中表现出良好的相容性和增塑效率。同时,该增塑剂所需原料来源均可来源于生物质,具有较好的可再生性。
Description
技术领域
本发明涉及一种新型的增塑剂:呋喃二甲酰-聚羟基酸酯,特别是涉及呋喃二甲酰-聚羟基酸酯的结构、合成和在聚合物增塑方面的应用。
背景技术
在我国增塑剂的产品结构中,邻苯二甲酸酯类使用量最多。近年来,人们发现邻苯二甲酸酯类在环境中稳定持久,不仅能造成环境污染,如果渗入食物中还可能危害人体健康。有动物实验研究表明,邻苯二甲酸酯类具有生殖发育毒性,免疫毒性,胚胎毒性,肝脏毒性及致癌性等。尽管国际上对于邻苯二甲酸酯类是否致癌到仍争论不休,但对邻苯二甲酸酯类存在潜在的致癌危险,国际上已开始采取相应的措施,限制邻苯二甲酸酯类的使用范围。目前,美国环境保护总局根据国家癌症研究所的研究结果,已经停止了6种邻苯二甲酸脂类的工业生产;瑞士政府决定在儿童玩具中禁止使用邻苯二甲酸酯类;德国已在与人体、卫生食品相关的所有塑料制品中禁止使用邻苯二甲酸酯类;在日本,邻苯二甲酸酯类作为塑料助剂仅限于在工业塑料制品中应用。全球已加快了无毒增塑剂产品的研发,先后开发了柠檬酸酯类、环氧大豆油、偏苯三酸酯类、均苯四酸四辛酯、癸二酸二正己酯、1,2-环己烷二酸酯等一系列环保无毒增塑剂。但这些增塑剂总存在有成本过高、与PVC相容性差等各种各样的缺陷,造成现在增塑剂市场仍然以邻苯二甲酸酯类占有巨大市场。
2,5-呋喃二甲酸(FDCA)是一种从生物质获取的、同样具有与邻苯二甲酸相似的芳环和二酸结构的化合物,由其形成的酯具有与邻苯二甲酸相似的增塑能力。各大化工公司均在呋喃二甲酸酯作为增塑剂方面进行了研究,例如:赢创奥克森诺有限责任公司开发了一系列呋喃二甲酸酯作为增塑剂,包括呋喃二甲酸的C11-C13二烷基酯(CN201280009803.2)、呋喃二甲酸戊酯(CN201280010193.8)和呋喃二甲酸庚酯(CN201280010195.7)。这些呋喃二甲酸酯表现出良好的PVC增塑性能,不仅能够替代邻苯二甲酸酯类增塑剂,甚至在一些指标上优于邻苯二甲酸酯类增塑剂。陶氏环球也开发了2,5-呋喃二甲酸二烷基酯增塑剂(CN201480030067.8、CN201480028778.1),此类增塑的聚合物组合物可以用于形成各种制品,如涂布导体。The Dow Chemical Company的Chaudhary也报道了呋喃二甲酸酯与环氧脂肪酸酯混合用于PVC的增塑,表现出比邻苯二甲酸酯类增塑剂更优的增塑效率(J.Appl.Polym.Sci.2015,132,42382)。南京工业大学的曹飞也公开了一种制备浅色的2,5-呋喃二甲酸二酯的方法(CN201610165975.9),该2,5-呋喃二甲酸二酯也可以应用于PVC的增塑。
同时,呋喃二甲酸能够通过体内三羧酸循环(TCA)代谢,与邻苯二甲酸不可降解相比具有极大的优势。2014年欧盟食品安全局就2,5-呋喃二甲酸用于食品接触材料的安全性评估发布意见认为:呋喃二甲酸在人体不会产生积累风险,对消费者不构成威胁。这些均表明FDCA酯作为一种绿色无毒增塑剂,具有可替代PEAs的潜力。
虽然呋喃二甲酸酯作为增塑剂在增塑PVC方面已经表现出良好的效果,但仍然存在有以下一些问题:大多数呋喃二甲酸酯是固体(少量混合醇表现为液体),在使用过程中多有不便;呋喃二甲酸酯的分子量较小,容易从增塑的聚合物中迁移出来;呋喃二甲酸仅含有两个羧基,不能提供更多的酯键来提高增塑剂与聚合物的粘附力。因此现有的呋喃二甲酸酯增塑剂还需要进一步优化改进。
发明内容
本发明主要涉及一种新型的增塑剂--呋喃二甲酰-聚羟基酸酯,特别是涉及呋喃二甲酰-聚羟基酸酯的结构、合成和在聚合物增塑方面的应用。
该呋喃二甲酰-聚羟基酸酯结构包括三部分:呋喃二甲酸部分、由羟基酸低聚化形成的聚酯部分和聚酯末端封端醇部分。
在呋喃二甲酰-聚羟基酸酯类化合物中,羟基酸部分可以是羟基乙酸、2-羟基丙酸、3-羟基丙酸、2-羟基丁酸、3-羟基丁酸、4-羟基丁酸、2-羟基戊酸、3-羟基戊酸、4-羟基戊酸、5-羟基戊酸、2-羟基己酸、3-羟基己酸、4-羟基己酸、5-羟基己酸、6-羟基己酸等;低聚化羟基酸的聚合度是2-10。
在呋喃二甲酰-聚羟基酸酯类化合物中,聚酯末端封端醇可以是甲醇、乙醇、丙醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、异戊醇、1-己醇、2-己醇、3-己醇、异己醇、1-辛醇、2-辛醇、3-辛醇、异辛醇、庚醇、壬醇、癸醇、十二醇、十四醇、十六醇、十八醇等。
呋喃二甲酰-聚羟基酸酯类化合物合成步骤分为三步:
(1)羟基酸低聚化,在低聚化过程中,可根据后续应用要求调节低聚化的程度,一般控制聚合度在2-10左右,低聚化的聚羟基酸不需要分离,直接用于后一步的酯化;
(2)前一步制备低聚羟基酸末端带有羧基,不利于作为增塑剂使用,需要采用醇进行封端酯化;酯化过程可以加入酯化催化剂促进反应过程,酯化催化剂可以是无机酸、有机酸、固体酸等,同时,在酯化过程中低聚羟基酸可能进一步低聚化;
(3)低聚羟基酸酯仍然存在一个末端羟基,可以与呋喃二甲酸或其酰氯、酸酐衍生物进行酯化反应形成目标产物:呋喃二甲酰-聚羟基酸酯(I)。
常用增塑剂的结构可分为三部分:(1)直链/支链烷烃结构,用于撑开聚合物分子,提高聚合物分子的可移动性;(2)酯键,与聚合物中氢键相结合,提高增塑剂与聚合物的粘附力;(3)芳环,用于增强增塑剂与聚合物的相容性。但除了芳环外,其他两部分在各种增塑剂中均存在。呋喃二甲酸酯类增塑剂满足了以上的三部分结构要求,需要解决的是降低其熔点、降低迁移率和增强粘附力。因此我们设计了一种新型的呋喃二甲酰-聚羟基酸酯类化合物(I)。该类化合物具有更多的酯键,增强了增塑剂与聚合物的粘附力;提高了呋喃二甲酸酯类化合物的分子量,降低挥发性、迁移性,耐抽出,能较长久的保留于被增塑的制品中;羟基酸和封端醇的结构可变性较大,呋喃二甲酰-聚羟基酸酯类化合物的分子量、化学结构均可调节,可根据不同的聚合物开发相应的增剂。
呋喃二甲酰-聚羟基酸酯类化合物增塑剂可以单独使用,也可以与其他增塑剂混合形成组合物使用。
该类呋喃二甲酰-聚羟基酸酯增塑剂或与其他增塑剂混合形成组合物,主要应用于聚合物增塑,包括:塑料、橡胶、粘合剂、密封材料、涂料、漆料、油漆、增塑溶胶、合成革、油墨中的应用。
这些聚合物包括:聚氯乙烯、聚丙烯酸酯、氟聚合物、聚乙烯醇、苯乙烯聚合物、聚烯烃、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚酰胺、聚乙二醇、聚氨酯、聚乳酸、聚羟基丁酸、聚酯、淀粉、纤维素及其衍生物、橡胶,以及以所述聚合物或其单体的混合物或共聚物。
呋喃二甲酰-聚羟基酸酯增塑剂或与其他增塑剂混合形成组合物在聚合物中的用量为:每100份聚合物中添加2-200质量份的呋喃二甲酰-聚羟基酸酯增塑剂。
有益效果:本发明制备了一类呋喃二甲酰-聚羟基酸酯化合物,该类化合物可以用于聚合物的增塑,表现出比邻苯二甲酸酯类增塑剂更低的迁移率和更高的增塑效率。同时,该增塑剂所需原料来源均可来源于生物质,具有较好的可再生性。
附图说明
图1呋喃二甲酰-乳酸丁酯的核磁氢谱;
图2呋喃二甲酰-二聚乳酸丁酯的红外光谱;
图3呋喃二甲酰-二聚乳酸丁酯的核磁氢谱;
图4呋喃二甲酰-乙醇酸丁酯的红外谱图;
图5呋喃二甲酰-聚羟基酸酯的DMA检测;
图6呋喃二甲酰-聚羟基酸酯的迁移率检测。
具体实施方式
根据下述实施例,可以更好地理解本发明。然而,实施例所描述的内容仅用于说明本发明,而不应当也不会限制权利要求书中所详细描述的本发明。
实施例1:呋喃二甲酰-乳酸丁酯的制备
反应路线如下:
酰氯法:
式1酰氯法呋喃二甲酰-乳酸丁酯的制备
呋喃二甲酰氯的制备:可参照《有机合成实验手册》中关于酰氯制备的方法,也可以参考专利CN201280009803.2、CN201610165975.9中公开的方法制备。
聚乳酸单封端醚制备:乳酸丁酯可从市面上购买,也可以参考专利CN201710531866.9、CN201610546423.2中公开的方法制备。
呋喃二甲酰-乳酰-丁酯:将乳酸丁酯与呋喃二甲酰氯按照摩尔比2:1.1的比例添加到三口烧瓶中,通过测定酸值确认反应进程。反应结束后,用氢氧化钠溶液洗去多余的未反应的呋喃二甲酰氯和单酯。得到纯品呋喃二甲酰-乳酸丁酯。
直接酯化法:
式2直接酯化法呋喃二甲酰-乳酸丁酯的制备
将乳酸丁酯与呋喃二甲酸按照摩尔比2:1.1的比例添加到三口烧瓶中,加入酯化催化剂对甲苯磺酸,160℃反应。通过测定酸值确认反应进程。反应结束后,用氢氧化钠溶液洗去多余的未反应的呋喃二甲酸和单酯。得到纯品呋喃二甲酰-乳酸丁酯。核磁氢谱如图1所示,0.9ppm处是丁醇上甲基,1.5ppm附近代表丁醇上靠近末端甲基的两个亚甲基以及乳酸上甲基,4.0-4.5ppm是丁醇上靠近酯键的亚甲基,5.0-5.5ppm是乳酸上的次甲基,7.5ppm附近代表呋喃上的H。
实施例2:呋喃二甲酰-二聚乳酸丁醇酯的制备
反应路线如下:
式3酰氯法呋喃二甲酰-二聚乳酸丁酯的制备
(1)二聚乳酸:在三口烧瓶中加入36.0g(0.4mol)乳酸,设置油浴温度130℃,水泵持续抽负压下(-0.1MPa)进行反应,反应两个小时左右得到乳酸二聚体,具体通过测定酸值确定聚合度。
(2)二聚乳酸丁醇酯:反应(1)结束后,撤掉真空,装备分水器和冷凝管,向三口烧瓶中投入22.2g丁醇(摩尔比,酸/醇=1:1.5),催化剂0.77g(0.005mol)对甲苯磺酸(反应物摩尔量的1%)和5.5mL(反应物质量10%)对二甲苯为带水剂,设置油浴温度160℃,加热回流分水至酸值不再降低为反应终点;原位-0.1MPa减压蒸馏,去除对二甲苯和剩余丁醇,得到聚乳酸丁醇酯。
(3)呋喃二甲酰-二聚乳酸丁醇酯:反应(2)结束后,设置油浴80℃,继续加入19.3g(0.1mol)呋喃二甲酰氯,在氮气保护下反应,尾气用饱和NaOH溶液吸收,当反应液澄清,反应体系不再产气即可停止反应,所得产物即为呋喃二甲酰-聚乳酸丁醇酯,红外光谱图如图2所示,1747cm-1处为酯键中碳氧双键C=O的伸缩振动峰,1278、1224、1132cm-1为酯键中C-O-C不对称伸缩振动峰,可以确定产物中有酯键结构的形成;1582、1458、1380cm-1处为呋喃环骨架C=C双键的伸缩振动峰,3127cm-1处是呋喃环C-H键伸缩振动峰,表明产物中存在呋喃环结构;
核磁氢谱如图3所示,0.9ppm处是丁醇上甲基,1.5ppm附近代表丁醇上靠近末端甲基的两个亚甲基以及乳酸上甲基,4.0-4.5ppm是丁醇上靠近酯键的亚甲基,5.0-5.5ppm是乳酸上的次甲基,7.5ppm附近代表呋喃上的H。
实施例3:呋喃二甲酰-乙醇酸丁酯的制备
反应路线如下:
酰氯法:
式4酰氯法制备呋喃二甲酰-乙醇酸丁酯
呋喃二甲酰氯的制备:可参照《有机合成实验手册》中关于酰氯制备的方法,也可以参考专利CN201280009803.2、CN201610165975.9中公开的方法制备。
乙醇酸丁酯的制备:乙醇酸丁酯可从市面上购买,也可以参考专利CN109550507A中公开的方法制备。
呋喃二甲酰-乙醇酸丁酯:将乙醇酸丁酯与呋喃二甲酰氯按照摩尔比2:1.1的比例添加到三口烧瓶中,通过测定酸值确认反应进程。反应结束后,用氢氧化钠溶液洗去多余的未反应的呋喃二甲酰氯和单酯。得到纯品呋喃二甲酰-乙醇酸丁酯。
直接酯化法:
式5直接酯化法制备呋喃二甲酰-乙醇酸丁酯
呋喃二甲酰-乙醇酸丁酯:将乙醇酸丁酯与呋喃二甲酸按照摩尔比2:1.1的比例添加到三口烧瓶中,加入酯化催化剂对甲苯磺酸,160℃反应。通过测定酸值确认反应进程。反应结束后,用氢氧化钠溶液洗去多余的未反应的呋喃二甲酸和单酯。得到纯品呋喃二甲酰-乙醇酸丁酯。
实施例4:呋喃二甲酰-乳酸乙酯的制备
酰氯法:
式6酰氯法呋喃二甲酰-乳酸乙酯的制备
呋喃二甲酰氯的制备:可参照《有机合成实验手册》中关于酰氯制备的方法,也可以参考专利CN201280009803.2、CN201610165975.9中公开的方法制备。
乳酸乙酯制备:乳酸乙酯可从市面上购买,也可以参考专利CN109438228A中公开的方法制备。
呋喃二甲酰-乳酸乙酯:将乳酸乙酯与呋喃二甲酰氯按照摩尔比2:1.1的比例添加到三口烧瓶中,通过测定酸值确认反应进程。反应结束后,用氢氧化钠溶液洗去多余的未反应的呋喃二甲酰氯和单酯。得到纯品呋喃二甲酰-乳酸乙酯。
直接酯化法:
式7直接酯化法呋喃二甲酰-乳酸乙酯的制备
呋喃二甲酰-乳酸乙酯:将乳酸乙酯与呋喃二甲酸按照摩尔比2:1.1的比例添加到三口烧瓶中,加入酯化催化剂对甲苯磺酸,160℃反应。通过测定酸值确认反应进程。反应结束后,用氢氧化钠溶液洗去多余的未反应的呋喃二甲酸和单酯。得到纯品呋喃二甲酰-乳酸乙酯。
实施例5:呋喃二甲酰-聚羟基醇酸酯与PVC的相容性以邻苯二甲酸二辛酯(DOP)为对照,采用水价法评价呋喃二甲酰-乳酸丁酯、呋喃二甲酰-乙醇酸丁酯、呋喃二甲酰-二聚乳酸丁酯与PVC的相容性,具体实验流程如下:
水价法:称取增塑剂2.5克,加入25毫升丙酮,待完全相溶呈透明状态后,采用蒸馏水进行滴定,开始出现混浊时即为滴定终点,读取蒸馏水耗用毫升数蒸馏水耗用量越多,表明增塑剂与PVC树脂相容性越好。
实验结果见表1
表1水价法表征增塑剂相容性
增塑剂名称 | 消耗蒸馏水量(g) |
邻苯二甲酸二辛酯 | 4.24 |
呋喃二甲酰-乳酸丁酯 | 4.88 |
呋喃二甲酰-乙醇酸丁酯 | 6.25 |
呋喃二甲酰-二聚乳酸丁酯 | 4.6 |
实验结果表明:呋喃二甲酰-乳酸丁酯、呋喃二甲酰-乙醇酸丁酯、呋喃二甲酰-二聚乳酸丁酯所需水量均大于DOP,表明呋喃二甲酸-聚乙/丙二醇醚酯类增塑剂与PVC树脂相容性更好。
实施例6:呋喃二甲酰-羟基酸酯增塑PVC
取250g PVC,加15g钙锌稳定剂,加分别加入50%(w/w)的呋喃二甲酰-乳酸丁酯、呋喃二甲酰-乙醇酸丁酯等呋喃二甲酰-聚羟基酸酯增塑剂,以及传统增塑剂邻苯二甲酸二辛酯(DOP)和新型无毒增塑剂环己烷1,2-二甲酸二异壬基酯(DINCH)。经密炼机(XSS-300)密炼,平板硫化机(XLB-Q350.350.2)180℃热压5min、室温冷压10min处理后制的150*150*4mm样板,按照国标GB/T 1040将制备的样板切割制备用于性能测试的样条。以不加增塑剂和加入同样添加量的DOP为增塑剂为对照组。对于测定增塑剂迁移率的样品,则采用1mm厚模板压制。
实施例7:呋喃二甲酰-聚羟基酸酯增塑PVC的力学性能通过测试呋喃二甲酰-聚羟基酸酯增塑剂增塑PVC的力学性能可以有效表明其增塑性能。
样条制备:采用实施例6制备的增塑PVC板子,切割成符合力学性能标准要求的样条。如,拉伸实验实验样条尺寸为150×10×4mm。
力学性能测试:拉伸性能测试在万能试验机(UTM-1422)上进行测试速率为50mm/min,测试温度为室温,测试数据取五个平行样的平均值。
具体结果见表2:
表2呋喃二甲酰-聚羟基酸酯增塑剂的力学性能比较
由呋喃二甲酰-乳酸丁酯和呋喃二甲酰-乙醇酸丁酯增塑PVC和DOP增塑PVC的力学性能对比可知:在相同增塑剂添加量下,呋喃二甲酰-乳酸丁酯和呋喃二甲酰-乙醇酸丁酯增塑的PVC拥有不弱于DOP增塑的PVC断裂伸长率,且远高于DINCH增塑的PVC,表明呋喃二甲酰-聚羟基酸酯的增塑效率与DOP相似,且增塑效率高于DINCH。
实施例8:呋喃二甲酰-聚羟基酸酯增塑PVC的热学性能采用动态热机械分析(DMA)检测考察呋喃二甲酰-乳酸丁酯(FDCA-LA)、呋喃二甲酰-乙醇酸丁酯(FDCA-GA)、呋喃二甲酰-二聚乳酸丁酯(FDCA-DLA)等增塑PVC的玻璃化转变温度Tg。
实验方案:采用DMA-Q800动态热机械分析仪。取增塑剂增塑的PVC样条(L×W×H=60mm×10mm×4mm)固定于三点弯曲夹具上,氮气氛围,以3℃/min的速率从-50℃升到100℃,采样频率1Hz。DMA检测结果见图5,增塑后PVC的玻璃化转变温度总结见表3。
表3增塑PVC的玻璃化转变温度Tg
增塑剂种类 | 玻璃化转变温度T<sub>g</sub>(℃) |
DOP | 39.20 |
DINCH | 12.11 |
呋喃二甲酰-乳酸丁酯 | 33.57 |
呋喃二甲酰-乙醇酸丁酯 | 17.38 |
呋喃二甲酰-二聚乳酸丁酯 | 6.74 |
文献可知,由50%DOP增塑PVC的玻璃化转变温度为39.20℃。而添加相同添加量下DINCH增塑PVC的玻璃化转变温度为12.11℃,呋喃二甲酰-乳酸丁酯增塑PVC的玻璃化转变温度为33.57℃,呋喃二甲酰-乙醇酸丁酯增塑PVC的玻璃化转变温度为17.38℃,呋喃二甲酰-二聚乳酸丁酯增塑PVC的玻璃化转变温度为6.74℃。玻璃化温度的降低表明加入呋喃二甲酰-聚羟基酸酯后都起到了明显的增塑效果,其中呋喃二甲酰-二聚乳酸丁酯增塑PVC的玻璃化转变温度还低于DINCH增塑PVC的玻璃化转变温度,表现出更佳的增塑效果。
实施例9:呋喃二甲酰–聚羟基酸酯的迁移率
采用失重法测定增塑剂的迁移率。选择有机溶剂(本实验用正己烷)为抽提溶剂,取一定质量1mm厚度的、呋喃二甲酰-乳酸丁酯(FDCA-LA)、呋喃二甲酰-乙醇酸丁酯(FDCA-GA)、邻苯二甲酸二辛酯(DOP)和环己烷1,2-二甲酸二异壬基酯(DINCH)增塑PVC切片置于室温有机溶剂中72h,滤出烘干,计算前后质量差值确定增塑剂的迁移率。
由图6中数据可知,DOP和DINCH在正己烷中的迁移量在24小时内就达到40%以上,且随着时间的延长,DOP和DINCH的迁移量趋于平缓;而相较于DOP和DINCH,呋喃二甲酰-乳酸丁酯和呋喃二甲酰-乙醇酸丁酯在168小时内的迁移量在10%以下,表明呋喃二甲酰-聚羟基酸酯在正己烷中的抗迁移能力要远高于DOP和DINCH。
Claims (10)
1.一种呋喃二甲酰-聚羟基酸酯增塑剂。
2.根据权利要求1所述的一种呋喃二甲酰-聚羟基酸酯增塑剂,其特征在于,所述的呋喃二甲酸酯包括三部分:呋喃二甲酸部分、由羟基酸低聚化形成的聚酯部分和聚酯末端封端醇部分。
3.根据权利要求2所述的一种呋喃二甲酰-聚羟基酸酯增塑剂,其特征在于,所述的羟基酸可以是羟基乙酸、2-羟基丙酸、3-羟基丙酸、2-羟基丁酸、3-羟基丁酸、4-羟基丁酸、2-羟基戊酸、3-羟基戊酸、4-羟基戊酸、5-羟基戊酸、2-羟基己酸、3-羟基己酸、4-羟基己酸、5-羟基己酸、6-羟基己酸;低聚化羟基酸的聚合度是2-10。
4.根据权利要求2所述的一种呋喃二甲酰-聚羟基酸酯增塑剂,其特征在于,所述的聚酯末端封端醇可以是甲醇、乙醇、丙醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、异戊醇、1-己醇、2-己醇、3-己醇、异己醇、1-辛醇、2-辛醇、3-辛醇、异辛醇、庚醇、壬醇、癸醇、十二醇、十四醇、十六醇、十八醇。
5.根据权利要求1或2所述的一种呋喃二甲酰-聚羟基酸酯,其特征在于,所述的呋喃二甲酰-聚羟基酸酯合成方法包括:(1)羟基酸低聚化;(2)低聚羟基酸与封端醇进行酯化;(3)呋喃二甲酸或其酰氯、酸酐衍生物与低聚羟基酸酯进行酯化。
6.增塑剂或增塑剂组合物,其特征在于,包含权利要求1-4中任一项的至少一种呋喃二甲酰-低聚羟基酸酯。
7.权利要求1至4中任意一项所述的一种呋喃二甲酰-聚羟基酸酯增塑剂在聚合物增塑中的应用,包括:塑料、橡胶、粘合剂、密封材料、涂料、漆料、油漆、增塑溶胶、合成革、油墨中的应用。
8.权利要求6所述的增塑剂或增塑剂组合物在聚合物增塑中的应用,包括:塑料、橡胶、粘合剂、密封材料、涂料、漆料、油漆、增塑溶胶、合成革、油墨中的应用。
9.根据权利要求7或8所述的应用,其特征在于,所述的聚合物选自:聚氯乙烯、聚丙烯酸酯、氟聚合物、聚乙烯醇、苯乙烯聚合物、聚烯烃、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚酰胺、聚乙二醇、聚氨酯、聚乳酸、聚羟基丁酸、聚酯、淀粉、纤维素及其衍生物、橡胶,以及以所述聚合物或其单体的混合物或共聚物。
10.根据权利要求7或8所述的应用,其特征在于,每100份聚合物中添加2-200质量份的呋喃二甲酰-聚羟基酸酯增塑剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911189792.0A CN110963984B (zh) | 2019-11-28 | 2019-11-28 | 一种呋喃二甲酰-聚羟基酸酯增塑剂及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911189792.0A CN110963984B (zh) | 2019-11-28 | 2019-11-28 | 一种呋喃二甲酰-聚羟基酸酯增塑剂及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110963984A true CN110963984A (zh) | 2020-04-07 |
CN110963984B CN110963984B (zh) | 2023-03-28 |
Family
ID=70031955
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911189792.0A Active CN110963984B (zh) | 2019-11-28 | 2019-11-28 | 一种呋喃二甲酰-聚羟基酸酯增塑剂及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110963984B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114479042A (zh) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | 一种封端改性的聚羟基脂肪酸酯及其制备方法和其薄膜 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103201328A (zh) * | 2010-08-23 | 2013-07-10 | 佩什托普公司 | 非-邻苯二甲酸型增塑剂 |
US20150094491A1 (en) * | 2012-05-24 | 2015-04-02 | Purac Biochem Bv | Carboxylic acid recovery from magnesium carboxylate mixture |
CN105555854A (zh) * | 2013-09-12 | 2016-05-04 | 3M创新有限公司 | 增塑性聚合物组合物 |
CN107573496A (zh) * | 2017-08-10 | 2018-01-12 | 中国科学院宁波材料技术与工程研究所 | 一种含有苯并恶嗪结构的呋喃二甲酸聚酯及其制备方法和应用 |
CN109796626A (zh) * | 2019-01-22 | 2019-05-24 | 南京工业大学 | 一种呋喃二甲酸-聚乙/丙二醇醚酯增塑剂及其应用 |
-
2019
- 2019-11-28 CN CN201911189792.0A patent/CN110963984B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103201328A (zh) * | 2010-08-23 | 2013-07-10 | 佩什托普公司 | 非-邻苯二甲酸型增塑剂 |
US20150094491A1 (en) * | 2012-05-24 | 2015-04-02 | Purac Biochem Bv | Carboxylic acid recovery from magnesium carboxylate mixture |
CN105555854A (zh) * | 2013-09-12 | 2016-05-04 | 3M创新有限公司 | 增塑性聚合物组合物 |
CN107573496A (zh) * | 2017-08-10 | 2018-01-12 | 中国科学院宁波材料技术与工程研究所 | 一种含有苯并恶嗪结构的呋喃二甲酸聚酯及其制备方法和应用 |
CN109796626A (zh) * | 2019-01-22 | 2019-05-24 | 南京工业大学 | 一种呋喃二甲酸-聚乙/丙二醇醚酯增塑剂及其应用 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114479042A (zh) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | 一种封端改性的聚羟基脂肪酸酯及其制备方法和其薄膜 |
Also Published As
Publication number | Publication date |
---|---|
CN110963984B (zh) | 2023-03-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Jia et al. | Green plasticizers derived from soybean oil for poly (vinyl chloride) as a renewable resource material | |
KR101718568B1 (ko) | 이소데칸올을 포함하는 2,5-푸란 디카르복실레이트 및 그의 용도 | |
Omrani et al. | Synthesis of a bio-based plasticizer from oleic acid and its evaluation in PVC formulations | |
Tan et al. | Design and synthesis of ethoxylated esters derived from waste frying oil as anti-ultraviolet and efficient primary plasticizers for poly (vinyl chloride) | |
Liu et al. | An efficient cold-resistant strategy: synthesis and application of green cold-resistant bio-based plasticizer for poly (vinyl chloride) | |
CN110078902B (zh) | 一种乙二醇聚酯增塑剂的合成方法 | |
Feng et al. | Synthesis and application of high-stability bio-based plasticizer derived from ricinoleic acid | |
US8530558B2 (en) | Plasticizers comprising poly(trimethylene ether) glycol esters | |
Langer et al. | Application of waste poly (ethylene terephthalate) in the synthesis of new oligomeric plasticizers | |
Gao et al. | Synthesis and properties of a bio-based PVC plasticizer derived from lactic acid | |
He et al. | Designing anti-migration furan-based plasticizers and their plasticization properties in poly (vinyl chloride) blends | |
US20130228097A1 (en) | Bio-renewable plasticizers derived from vegetable oil | |
CN110642719A (zh) | 一种苹果酸基环保增塑剂的制备方法及其应用 | |
EP2831065B1 (en) | Compositions containing tetrahydrofurfuryl and/or alkyl-substituted tetrahydrofurfuryl esters of citric acid | |
CN110963984B (zh) | 一种呋喃二甲酰-聚羟基酸酯增塑剂及其应用 | |
Jia et al. | A novel biobased polyester plasticizer prepared from palm oil and its plasticizing effect on poly (vinyl chloride) | |
CN107176910B (zh) | 一种乙酰化柠檬酸脂肪酸酯增塑剂及其制备方法和应用 | |
Han et al. | Effects of modified tributyl citrate as a novel environmentally friendly plasticizer on the mechanical property and migration stability of soft polyvinyl chloride | |
CN116425766A (zh) | 一种环氧异山梨醇酯增塑剂及其制备方法 | |
Lu et al. | A multifunctional lactic acid based plasticizer used for plasticizing PVC and PLA: Endowing PLA elastic restore capability | |
Feng et al. | Ricinoleic acid-based plasticizer with excellent optical properties for PVC polymers | |
Tan et al. | Direct transformation of fatty acid-derived monomers from dimer acid manufacturing into valuable bio-plasticizers with high plasticization and compatibilization | |
Li et al. | Development and characterization of ricinoleic acid-based sulfhydryl thiol and ethyl cellulose blended membranes | |
Lu et al. | A highly stable bio-based plasticizer constructed from renewable acids for plasticizing and enhancing the optical properties of poly (vinyl chloride) | |
CN109796626A (zh) | 一种呋喃二甲酸-聚乙/丙二醇醚酯增塑剂及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |