CN110790981A - Pvc增塑剂及其制备方法 - Google Patents
Pvc增塑剂及其制备方法 Download PDFInfo
- Publication number
- CN110790981A CN110790981A CN201910709353.1A CN201910709353A CN110790981A CN 110790981 A CN110790981 A CN 110790981A CN 201910709353 A CN201910709353 A CN 201910709353A CN 110790981 A CN110790981 A CN 110790981A
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- composition
- acid
- less
- tofa
- 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
- 238000002360 preparation method Methods 0.000 title description 5
- 239000008037 PVC plasticizer Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 111
- 239000000194 fatty acid Substances 0.000 claims abstract description 71
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 70
- 229930195729 fatty acid Natural products 0.000 claims abstract description 70
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 70
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004014 plasticizer Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 24
- -1 acyl morpholine Chemical compound 0.000 claims abstract description 19
- 239000003784 tall oil Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 claims abstract description 11
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 7
- 239000008158 vegetable oil Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 29
- 239000004800 polyvinyl chloride Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 11
- 229960004488 linolenic acid Drugs 0.000 claims description 10
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 235000020778 linoleic acid Nutrition 0.000 claims description 7
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 7
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- XUBOMFCQGDBHNK-JTQLQIEISA-N (S)-gatifloxacin Chemical compound FC1=CC(C(C(C(O)=O)=CN2C3CC3)=O)=C2C(OC)=C1N1CCN[C@@H](C)C1 XUBOMFCQGDBHNK-JTQLQIEISA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 229960003923 gatifloxacin Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 claims description 2
- 238000007038 hydrochlorination reaction Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 230000004580 weight loss Effects 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 2
- QXJSBBXBKPUZAA-CMDGGOBGSA-N (e)-octadec-10-enoic acid Chemical compound CCCCCCC\C=C\CCCCCCCCC(O)=O QXJSBBXBKPUZAA-CMDGGOBGSA-N 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 44
- 229920000915 polyvinyl chloride Polymers 0.000 description 17
- 150000007513 acids Chemical class 0.000 description 13
- 150000002780 morpholines Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 11
- 235000021313 oleic acid Nutrition 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000007112 amidation reaction Methods 0.000 description 6
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 5
- 239000004808 2-ethylhexylester Substances 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 4
- 235000021322 Vaccenic acid Nutrition 0.000 description 4
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 4
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 3
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 3
- 240000002791 Brassica napus Species 0.000 description 3
- 235000006008 Brassica napus var napus Nutrition 0.000 description 3
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 3
- 244000188595 Brassica sinapistrum Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000020551 Helianthus annuus Species 0.000 description 3
- 235000003222 Helianthus annuus Nutrition 0.000 description 3
- 229920001944 Plastisol Polymers 0.000 description 3
- 230000009435 amidation Effects 0.000 description 3
- 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 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000004999 plastisol Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- ADHNUPOJJCKWRT-JLXBFWJWSA-N (2e,4e)-octadeca-2,4-dienoic acid Chemical compound CCCCCCCCCCCCC\C=C\C=C\C(O)=O ADHNUPOJJCKWRT-JLXBFWJWSA-N 0.000 description 1
- HXQHFNIKBKZGRP-URPRIDOGSA-N (5Z,9Z,12Z)-octadecatrienoic acid Chemical compound CCCCC\C=C/C\C=C/CC\C=C/CCCC(O)=O HXQHFNIKBKZGRP-URPRIDOGSA-N 0.000 description 1
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- HNVIQLPOGUDBSU-UHFFFAOYSA-N 2,6-dimethylmorpholine Chemical compound CC1CNCC(C)O1 HNVIQLPOGUDBSU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- LQMMFVPUIVBYII-UHFFFAOYSA-N 2-methylmorpholine Chemical compound CC1CNCCO1 LQMMFVPUIVBYII-UHFFFAOYSA-N 0.000 description 1
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 1
- SFWWGMKXCYLZEG-UHFFFAOYSA-N 3-methylmorpholine Chemical compound CC1COCCN1 SFWWGMKXCYLZEG-UHFFFAOYSA-N 0.000 description 1
- MLBYBBUZURKHAW-UHFFFAOYSA-N 4-epi-Palustrinsaeure Natural products CC12CCCC(C)(C(O)=O)C1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FXUKWLSZZHVEJD-UHFFFAOYSA-N C16:0-14-methyl Natural products CCC(C)CCCCCCCCCCCCC(O)=O FXUKWLSZZHVEJD-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical class O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- HXQHFNIKBKZGRP-UHFFFAOYSA-N Ranuncelin-saeure-methylester Natural products CCCCCC=CCC=CCCC=CCCCC(O)=O HXQHFNIKBKZGRP-UHFFFAOYSA-N 0.000 description 1
- 101100224410 Solanum tuberosum DPEP gene Proteins 0.000 description 1
- MWGSSMAHEZDRQP-UHFFFAOYSA-N [hydroxy(phenyl)phosphoryl]oxy-phenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)OP(O)(=O)C1=CC=CC=C1 MWGSSMAHEZDRQP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940108924 conjugated linoleic acid Drugs 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- AZSFNUJOCKMOGB-UHFFFAOYSA-N cyclotriphosphoric acid Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- GGIGNDWYMFQYKS-UHFFFAOYSA-N docosa-11,14-dienoic acid Chemical compound CCCCCCCC=CCC=CCCCCCCCCCC(=O)O GGIGNDWYMFQYKS-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000005481 linolenic acid group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
Classifications
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
-
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
公开了一种不含邻苯二甲酸酯且颜色浅的增塑的PVC组合物。所述组合物包含酰替吗啉增塑剂，其由选自妥尔油脂肪酸、由其衍生的妥尔油脂肪酸单体及其混合物的脂肪酸制备。所述脂肪酸的总碳足迹为从植物油中获得的脂肪酸的总碳足迹的<95％。酰替吗啉由妥尔油脂肪酸和吗啉在催化剂存在下反应制备。
Description
技术领域
本发明涉及聚氯乙烯(PVC)增塑剂组合物，其衍生自具有低碳足迹的脂肪酸，例如妥尔油脂肪酸，以及制备所述组合物的方法。
背景技术
将增塑剂添加到材料中以改变其物理性能，增加可塑性(即材料在外力作用下的不可逆变形)，或增加流动性。商用增塑剂通常基于不可再生的石油化学原料，如邻苯二甲酸、对苯二甲酸或苯甲酸。增塑剂通常分为邻苯二甲酸酯和非邻苯二甲酸酯增塑剂。对于一些现有技术的增塑剂，例如DEHP(邻苯二甲酸二(2-乙基己基)酯)，所述组合物的增塑功效好，但迁移速率太高而不能用于高温应用。基于石油化学的非邻苯二甲酸酯增塑剂TOTM(偏苯三酸三辛酯)具有相对低的迁移速率，适用于高温应用，但塑化功效差。
环状单酰胺，例如衍生自吡咯烷酮的那些，已用作增塑剂。已经开发了几类生物增塑剂，如癸二酸酯类、柠檬酸酯类、琥珀酸酯类、异山梨醇酯类和衍生自蓖麻油、环氧化大豆油等的增塑剂。此类生物增塑剂为酯，且通常不提供最佳的PVC相容性。此外，其可能由于扩散泄漏而导致不良的性能。
仍然需要具有低碳足迹、不含邻苯二甲酸酯、具有均衡良好增塑功效和低迁移倾向的改善性能的增塑的PVC聚合物组合物。
发明概述
本发明的一个方面为包含吗啉化合物和脂肪酸的反应产物的脂肪酸酰替吗啉(morpholide)组合物，其中脂肪酸的总碳足迹为从植物油中获得的脂肪酸的总碳足迹的<95％，或者低碳足迹为小于约500g CO2/kg脂肪酸，或小于约200g CO2/kg脂肪酸。
本发明的另一方面为酰替吗啉组合物，其为吗啉化合物和脂肪酸的反应产物，其中脂肪酸选自妥尔油脂肪酸(TOFA)、由其衍生的妥尔油脂肪酸单体(TOFA单体)、及其混合物；其中脂肪酸包含20-55wt％的油酸、20-55wt％的亚油酸和任选地至多15wt％的亚麻酸。脂肪酸的总碳足迹为从植物油中获得的脂肪酸的总碳足迹的<95％，或者平均碳足迹为小于500g CO2当量/kg脂肪酸。酰替吗啉组合物的加德纳色度(纯)为小于约3。
在另一方面，本发明提供一种聚合物组合物，其包含聚合物，例如聚氯乙烯(PVC)，以及用作增塑剂的上述酰替吗啉组合物。
本发明的另一方面为制备不含邻苯二甲酸酯的增塑的PVC组合物的方法，包括将上述酰替吗啉组合物与PVC和一种或多种聚合物稳定剂和抗氧化剂共混和配混。
在又一方面，公开了一种制备不含邻苯二甲酸酯的增塑剂组合物的方法。所述方法包括形成包含吗啉化合物、催化剂和脂肪酸的混合物，其中脂肪酸选自TOFA、由其衍生的TOFA单体、及其混合物。脂肪酸包含约20-55wt％的油酸、约20-55wt％的亚油酸和任选地至多15wt％的亚麻酸；并且脂肪酸的总碳足迹为从植物油中获得的脂肪酸的总碳足迹的<95％，或者平均碳足迹为小于500g CO2当量/kg脂肪酸。
发明详述
除非另有说明，否则以下术语具有以下含义。
“不含邻苯二甲酸酯”是指没有故意添加邻苯二甲酸酯。
“碳足迹”是指由产品、工艺或事件直接或间接引起的总温室气体排放。碳足迹可以碳氧化物当量(吨)来度量。
“低碳足迹”或“减少的碳足迹”是指替代产品、工艺或事件的碳足迹的<95％或<92％或<90％或<80％或<70％或<50％或<30％或<20％。例如，与替代品相比，妥尔油脂肪酸(TOFA)具有减少的碳足迹，这取决于来源，例如，与替代大豆油相比，TOFA的排放可为10％(https://www.forchem.com/forchem/low_carbon_solutions)，或者比用大豆、向日葵、油菜籽和油酸混合物制成的植物油替代品低至少五倍(http://www.kraton.com/products/ pdf/Oleochemicals_web_final.pdf)。
“低碳足迹”脂肪酸是指平均碳足迹为小于500g CO2当量/kg脂肪酸，优选为小于200gCO2当量/kg脂肪酸的脂肪酸。
“渗出”用于聚合物组合物(尤其是PVC组合物)中包括的增塑剂组分。该术语表示增塑剂组分与聚合物基质(例如PVC)的相容性的度量。增塑剂的渗出可通过在两张纸巾之间放置薄膜样品来评估。然后将组合的体系(样品+纸)在室温下储存48小时。在此期间后纸的重量的增加给出了增塑剂渗出的度量。
粘度根据ASTM D2196用21号锭子测定。
“酸值”(或“中和值”或“酸度”)是指通过ASTM D465-05(2010)测试方法测定的酸值，并且表示为中和1g本文所公开的酰替吗啉组合物所需氢氧化钾(KOH)的量，单位为mg。
“胺值”(或“胺数”)是指碱度等于1g本文所公开的酰替吗啉组合物的碱度当量的氢氧化钾(KOH)的毫克数。其可通过以稀盐酸于异丙醇溶剂中滴定酰替吗啉样品的溶液来比色测定。
拉伸强度和伸长率是根据ASTM D882-12测试方法测量。硬度是根据ASTM D2240-15测试方法测量。黄度指数(YI)是根据ASTM E313-15e1测试方法测量。
本发明涉及衍生自具有低碳足迹的脂肪酸的酰替吗啉组合物的制备和用途。此类脂肪酸具有植物酸(例如大豆酸、棕榈酸、向日葵酸和花生酸)的一小部分碳足迹。
本发明还涉及由TOFA、由其衍生的TOFA单体或其混合物制备的酰替吗啉组合物的制备和用作增塑剂的用途，当掺入聚合物例如PVC中时具有良好增塑功效和最小迁移率的平衡性能。
妥尔油脂肪酸(TOFA)：TOFA为具有一个或多个羧酸基团的TOFA馏分组分，该羧酸基团与吗啉化合物进行酰胺化反应形成酰胺键。
在一个实施方案中，TOFA含有超过80wt％的C18羧酸。在另一个实施方案中，TOFA包含C18长链羧酸，其包含一个或多个碳-碳双键，以及相对低的浊点和倾点。C18长链羧酸的实例包括硬脂酸(C18饱和羧酸)、油酸(C18单不饱和羧酸)、亚油酸(C18二不饱和羧酸)和α-亚麻酸(C18三不饱和羧酸)。TOFA还可含有极少量(<0.5wt％)的棕榈酸(C16饱和羧酸)和碳原子数大于18的饱和及不饱和羧酸。
在一个实施方案中，羧酸包括但不限于碳链长度为16-20的羧酸，例如棕榈酸、硬脂酸、油酸、亚油酸、反油酸、α-亚麻酸、花生酸、14-甲基十六烷酸、十八碳二烯酸、11,14-二十二碳二烯酸、顺式-5,顺式-11,顺式-14-二十碳三烯酸、8(9),15-异海松二烯-18-酸、2α-[2'(间-异丙基苯基)乙基]-1β,3α-二甲基环己烷羧酸、8(9),15-海松二烯-18-酸、2β-[2'(间-异丙基苯基)乙基]-1β/3α-二甲基环己烷羧酸、8(14),15-海松二烯-18-酸)、7(8)/15-海松二烯-18-酸、8,13-二烯-18-枞酸、长叶松酸、7,15-异海松二烯-18-酸、异海松酸、二氢枞酸、枞酸、8,11,13-二烯-18-枞酸和8(14)，13(15)-二烯-18-枞酸。
在另一个实施方案中，羧酸包括不同量的其他植物酸，例如，菜籽油酸(canolaacids)、蓖麻酸、椰子酸、棉籽酸、亚麻酸、花生酸、菜籽酸(低芥酸)、菜籽酸(高芥酸)、红花酸、大豆酸和向日葵酸。
在一个实施方案中，TOFA包含20-55wt％的油酸、20-55wt％的亚油酸和任选至多15wt％的亚麻酸。在另一个实施方案中，通过ACQM 022测试方法测定，TOFA任选地包含至多15wt％的α-亚麻酸和松油酸的总和，和1-4wt％的饱和脂肪酸。在另一个实施方案中，TOFA包含0.1-5wt％的C-20树脂酸。在一个实施方案中，TOFA的油酸水平为32wt％,共轭亚油酸和亚油酸(也称为(9Z，12Z)-十八碳-9,12-二烯酸)的总含量为50wt％,α-亚麻酸的含量为12wt％,饱和脂肪酸的含量为2％，酸值为197mg KOH/g(AQCM 001)，碘值为154cg I/g(AQCM009)，以及倾点为-15℃(AQCM 060)。在另一个实施方案中，TOFA的酸值为194mg KOH/g，碘值为125cg I/g，颜色为4.5加德纳(纯)(AQCM 002)。在又一个实施方案中，TOFA的酸值为196mg KOH/g，碘值为125cg I/g，颜色为3.0加德纳(纯)。在又一个实施方案中，TOFA组分的特征在于具有减少的足迹，即总碳足迹为从植物油中获得的脂肪酸的总碳足迹的<95％。
妥尔油馏分主要含有TOFA。适于制备酰替吗啉衍生物的TOFA可通过精炼粗妥尔油等级获得。在一个实施方案中，通过ACQM 060测试方法测定，TOFA馏分的倾点(℃)为-35℃至30℃。在另一个实施方案中，TOFA馏分的倾点(℃)为-25℃至15℃。在又一个实施方案中，TOFA馏分的倾点为-15℃。
在另一个实施方案中，TOFA衍生的化学组合物，例如妥尔油脂肪酸单体(也称为“TOFA单体”)也用于制备酰替吗啉组合物。TOFA单体存在于在TOFA的酸性粘土催化的聚合过程中形成的单体馏分中。在此通常在高温下进行的聚合过程中，烯属脂肪酸进行各种化学反应，包括异构化和分子间加成反应，形成二聚和聚合脂肪酸的混合物，以及单体脂肪酸的独特混合物。通过分离方法(例如蒸馏)将单体脂肪酸馏分与聚合产物分离，并且单体脂肪酸馏分在本领域中通常称为“单体”或“单体酸”或“单体脂肪酸”(CAS登记号68955-98-6)。
TOFA单体通常为支链、芳族、环状和直链脂肪酸的混合物，其可为饱和的或不饱和的，其中不饱和脂肪酸中的烯属双键可具有顺式或反式构型。TOFA单体中的主要酸为所谓的“异油酸”，其实际上为直链、支链和环状C-18单不饱和脂肪酸的混合物。在一个实施例中，TOFA单体含有饱和及不饱和C-18脂肪酸，其中异油酸作为主要组分存在，多不饱和脂肪酸以低水平存在。此外，实例TOFA单体的酸值为174mg KOH/g(AQCM 001)，加德纳色度(纯)为6.1(AQCM 002)，碘值为75cg I/g(AQCM 009)。
在一些实施方案中，TOFA单体为化学改性TOFA，例如异油酸，以及其精制或氢化馏分，例如异硬脂酸和相关的支化、饱和或部分饱和的C-18羧酸组合物。在一个实施方案中，TOFA单体为支链和直链脂肪酸的混合物，其在TOFA的二聚反应过程中形成并从所得反应混合物中获得。在另一个实施方案中，TOFA单体酸含有饱和及不饱和C-18脂肪酸，其中支链异油酸构成主要部分，并且几乎不含多不饱和脂肪酸。
碘值通常用于表示油、脂肪或蜡的不饱和度。TOFA或TOFA单体组分的碘值(每克TOFA碘的厘克数)为60-180、110-170或125-155cg I/g TOFA，根据ACQM 009测定。
吗啉组分：为了形成酰替吗啉组合物，使用吗啉化合物与TOFA反应。在一个实施方案中，使用吗啉(O(CH2CH2)2NH)。在另一个实施方案中，吗啉化合物选自吗啉、2-甲基吗啉、2,6-二甲基吗啉、2,2-二甲基吗啉、3-甲基吗啉或其混合物。
吗啉可通过用硫酸使二乙醇胺脱水来制备。另一种方法包括在催化剂如雷尼镍的存在下使二甘醇与氨反应。
任选组分：在一个实施方案中，形成酰替吗啉组合物的反应混合物还包含含松香的物质，例如妥尔油松香、脂松香或其组合，其量小于15wt％(相对于酰替吗啉增塑剂组合物的总重量)。含松香的物质的非限制性实例包括得自Kraton Corporation的SYLVAROSTM产品。
酰替吗啉组合物可进一步包含清除剂，例如酸清除剂，例如取代或未取代的缩水甘油酯。清除剂减少了发色体的形成。
TOFA酰替吗啉的改性形式：低碳足迹脂肪酸酰替吗啉(包括TOFA酰替吗啉组合物)可具有不同量的残余不饱和度，其主要来源于不饱和脂肪酸组分，例如油酸、亚油酸和亚麻酸。可使用各种化学转化部分或完全除去这些不饱和位点，以提供几乎没有残留不饱和度的酰替吗啉。实例包括但不限于环氧化、氢化、氯化、溴化、氢氯化和氢溴化。部分或完全除去不饱和度改善了酰替吗啉的热稳定性并且还降低了产物的颜色。掺入此改性酰替吗啉的增塑剂组合物可具有甚至更浅的颜色或可具有更高的热稳定性，用于制备颜色浅的增塑剂聚合物组合物，例如增塑的PVC组合物。
制备酰替吗啉组合物的方法：酰替吗啉组合物可在酰胺化反应中制备，其中吗啉或取代的吗啉与脂肪酸反应，同时除去水。可使用本领域已知的任何酰胺化催化剂。酸催化剂通常用于辅助正向反应。实例包括磷酸，例如正磷酸(H3PO4)、偏磷酸(HPO3)、亚磷酸(H3PO3)和次磷酸(H3PO2)。其他类型的亚磷酸，例如焦磷酸(H4P2O7)、三磷酸(H5P3O10)和三偏磷酸(H3P3O9)也可用作催化剂。在一个实施方案中，使用次磷酸作为形成酰替吗啉组合物的催化剂。酰胺化催化剂的其他实例还包括磷酸、2-(2'-吡啶基)乙基膦酸(PEPA)及其二乙酯(DPEP)、次磷酸钠、苯基膦酸酐、苯基膦酸、苯基次膦酸、芳基硼酸和其他含硼化学品、路易斯酸如FeCl3，脱水剂如分子筛、鏻盐和碳二亚胺。
通过将反应混合物加热至形成酰替吗啉组合物所需的温度来进行酰胺化反应。在一个实施方案中，反应温度高于200℃。在酰胺化反应过程中水作为副产物形成，并且优选在反应过程中作为蒸气除去，例如通过惰性气体(如氮气)流吹扫。在产物分离步骤之前或之后，含有酰替吗啉产物的反应混合物可用清除剂如缩水甘油酯处理。通过蒸馏实现产物分离，例如，刮膜蒸发和短程蒸馏。可向分离的产物中添加抗氧化剂，以稳定其防止氧化分解。
酰替吗啉也可通过其他方法合成，例如通过使TOFA的羧酸衍生物与吗啉化合物反应。例如，酯，例如TOFA的甲基或低级烷基酯可在催化剂存在下与吗啉化合物反应。TOFA的酰氯衍生物可在有机胺存在下与吗啉反应，该有机胺充当碱。或者，衍生自TOFA的酸酐可与胺反应以产生酰替吗啉组合物。
如上所述制备的酰替吗啉组合物仍可含有TOFA中存在的残余不饱和度或低碳足迹脂肪酸。可使用上文所述的方法部分或完全除去此不饱和度。
包含上述酰替吗啉组合物的增塑剂组合物可基于吗啉组分和/或TOFA组分的结构变化含有一种或多种类型的酰替吗啉。酰替吗啉结构中的酰基包含18-碳酰基。在一个实施方案中，增塑剂组合物包含由吗啉与TOFA反应得到的酰替吗啉组合物。在另一个实施方案中，增塑剂组合物包含酰替吗啉组合物，其由吗啉化合物与2种或更多种不同的TOFA单体反应得到。在又一个实施方案中，增塑剂组合物包含酰替吗啉组合物，其由吗啉和一种或多种取代的吗啉化合物与TOFA反应得到。在又一个实施方案中，增塑剂组合物包含酰替吗啉组合物，其由吗啉和一种或多种取代的吗啉化合物与TOFA和一种或多种TOFA单体反应得到。
酰替吗啉组合物和酰替吗啉增塑剂组合物的性能：通过所述方法制备的酰替吗啉组合物(和由其得到的增塑剂组合物)的加德纳色度(纯)为<5或<3或<2。
酰替吗啉组合物的酸值为小于12mg KOH/g，或小于9mg KOH/g，或小于5mg KOH/g，或小于3mg KOH/g。酰替吗啉的胺值为<6mg KOH/g，或<4mg KOH/g，或<2mg KOH/g，或<1mg KOH/g。
衍生自碳足迹小于500g CO2当量/kg脂肪酸的脂肪酸的酰替吗啉(包括TOFA酰替吗啉)具有低泄漏倾向；和当包含在聚合物组合物中时具有低渗出倾向。这使得其可用于制备聚合物组合物，例如包含PVC和/或氯乙烯-乙酸乙烯酯共聚物树脂的聚合物组合物。在此类体系中，增塑剂的特征在于与PVC和/或氯乙烯-乙酸乙烯酯共聚物树脂基本相容。
工业实用性：TOFA基酰替吗啉增塑剂可用于建筑应用，例如管道和型材应用，例如门和窗户。其还可用于制造瓶子、非食品包装和卡片(例如银行或会员卡)。其他应用包括管道、电缆绝缘、仿皮革、标牌、留声机唱片、地板、充气产品、玩具、以及许多用于替代橡胶的应用。
TOFA基酰替吗啉增塑剂可通过本领域已知的方法包括在PVC组合物中，例如增塑溶胶法、干混、配混和挤出。干混在混合设备如带式混合器或高速混合器中进行。在一个实施方案中，TOFA基酰替吗啉增塑剂的加入量为10-90phr(相对于每100重量份PVC树脂的重量份数)，在另一个实施方案中为10-60phr。首先将适量的PVC和其它所需的固体成分混合在一起，然后在搅拌下将液体增塑剂加入混合物中。在一个实例中，然后将干混料加工并挤出或模塑成最终应用。
在各实施方案中，增塑的PVC组合物在70℃下老化7天后的黄度指数(ΔE)为3或更低。
实施例
以下实施例旨在是非限制性的。
实施例1(E-1)：酰替吗啉组合物由包含73.4wt％的TOFA(包含45-50wt％的油酸和40-45wt％的亚油酸)、1wt％的催化剂(次磷酸)和25.6wt％的吗啉的反应混合物制备。
将TOFA和次磷酸(催化剂)在装有冷凝器装置(以收集作为冷凝物的副产物水)的反应烧瓶中合并。用氮气吹扫反应烧瓶30分钟以除去氧气后，将混合物以100℃/小时的速率加热至210℃。然后在100分钟时间内以0.3wt％的比率在表面下加入吗啉。在加入所有吗啉后，将温度保持在210℃，同时通过对反应混合物的等分试样进行取样，并使用滴定技术测量其酸值和胺值来监测反应过程。当酸值小于或等于9mg KOH/g时，将反应混合物用氮气鼓泡1小时，冷却至70℃，并用1wt％的缩水甘油酯处理并搅拌1小时。接下来，将反应混合物置于刮膜蒸发器中并在100-300毫巴(1×104-3×104帕斯卡)的压力下加热至220℃。收集纯的酰替吗啉组合物作为头部馏分，在氮气保护下冷却至环境温度，并倒入储存容器中。向其中加入1wt％的抗氧化剂并搅拌直至产生均匀的液体。将最终产物在室温下储存在密封容器中。该产物的加德纳色度(纯)为0.9，酸值为5.6mg KOH/g，胺值为0.0mg KOH/g，在30℃下的粘度为40cPs。
实施例(CE-2，E-2，CE-3，E-3)：使用实施例1的TOFA酰替吗啉，现有技术的PVC增塑剂(TOTM和DOTP)，和表1中所示的其他组分制备PVC制剂。在175-205℃的温度下加工混合物。
表1
然后将所得PVC化合物压塑成测试板，然后测试其性能。表2示出增塑的PVC组合物的性能。根据ASTM D638收集拉伸强度和伸长率数据。CIEL*a*b*用于PVC板的颜色测量，其中L*表示亮度，a*表示绿-红色成分，b*表示蓝-黄色组分。ΔE为两种颜色之间的差异，其根据以下等式计算：
在表2中，实施例组合物E-2的初始ΔE是老化前实施例和比较例之间的颜色差异，给定样品的老化ΔE是在相同样品老化之前和之后测量的色差。
表2
如上所示，与具有TOTM或DOTP的组合物(CE-2和CE-3)相比，PVC组合物E-2和E-3使用35wt％的较少增塑剂。此外，增塑的组合物E-2和E-3的伸长率和拉伸强度分别与包含TOTM和DOTP的对比组合物CE-2和CE-3所示的伸长率和拉伸强度相当。
无填料的实施例：表3示出几种无填料的制剂。在Brabender上制备组合物，压塑成测试板，然后测试肖氏A硬度。结果表明，TOFA酰替吗啉在宽制剂范围内是比DOTP更有效的增塑剂。
表3
| CE-4 | E-4 | CE-5 | E-5 | CE-6 | E-6 | |
| PVC | 100 | 100 | 100 | 100 | 100 | 100 |
| DOTP | 80 | 60 | 40 | |||
| TOFA酰替吗啉 | 80 | 60 | 40 | |||
| 添加剂(wt％) | 约1％ | 约1％ | 约1％ | 约1％ | 约1％ | 约1％ |
| 肖氏A硬度 | 65 | 62 | 77 | 72 | 88 | 81 |
实施例-增塑溶胶制剂：含有乳液PVC的增塑溶胶组合物如表4所示配制，然后流延和干燥。然后从流延板上切下测试板，并测试其性能。与表4中所示的传统邻苯二甲酸酯PVC相比，TOFA酰替吗啉再次显示出更好的增塑剂功效。
表4
实施例-熔合速率：使用Brabender在180℃和50rpm下配制表5中列出的组合物，然后根据ASTM D-2538评定熔合速率。如表5所示，TOFA酰替吗啉不仅具有更好的增塑功效，而且具有更快的融合速率。
表5
| CE-8 | E-8 | |
| CaCO3(wt％) | 54％ | 54％ |
| DOTP(phr) | 58 | - |
| TOFA酰替吗啉(phr) | - | 45 |
| 其他添加剂(wt％) | 约1％ | 约1％ |
| 熔合时间(sec) | 48 | 34 |
| 硬度(肖氏A) | 93.8 | 93.7 |
| 拉伸强度(psi) | 1,325 | 1,405 |
| 伸长率％ | 143 | 166 |
| 撕裂强度k lb/in | 0.21 | 0.23 |
| 重量损失(70℃ 7天) | 0.25 | 0.22 |
Claims (15)
1.一种酰替吗啉组合物，其包含吗啉化合物和脂肪酸的反应产物，其中所述脂肪酸选自妥尔油脂肪酸、由其衍生的妥尔油脂肪酸单体、及其混合物；
其中所述脂肪酸包含20-55wt％的油酸和20-55wt％的亚油酸，和任选的0-15wt％的亚麻酸；
其中所述脂肪酸的总碳足迹为从植物油中获得的脂肪酸的总碳足迹的<95％；和
其中所述酰替吗啉组合物的加德纳色度(纯)为小于3。
2.根据权利要求1所述的酰替吗啉组合物，其中所述脂肪酸的平均碳足迹为小于500gCO2当量/kg脂肪酸。
3.根据权利要求1所述的酰替吗啉组合物，其中所述酰替吗啉组合物的酸值为小于12mg KOH/g，胺值为小于1mg KOH/g。
4.根据权利要求1所述的酰替吗啉组合物，其中所述脂肪酸为妥尔油脂肪酸单体，且其中所述妥尔油脂肪酸单体包括异油酸。
5.一种增塑的聚氯乙烯(PVC)组合物，其包含根据权利要求1-4中任一项所述的酰替吗啉组合物。
6.根据权利要求5所述的增塑的聚氯乙烯(PVC)组合物，其在渗出试验中48小时后的重量损失小于1％，且在70℃老化7天后黄度指数ΔE为等于或小于3。
7.一种制备不含邻苯二甲酸酯的增塑的聚氯乙烯(PVC)组合物的方法，其包括将权利要求1-4中任一项所述的酰替吗啉组合物与增塑的PVC以及一种或多种聚合物稳定剂和抗氧化剂共混并配混。
8.一种制备酰替吗啉组合物的方法，其包括：
形成包含吗啉化合物、催化剂和脂肪酸的混合物，其中所述脂肪酸选自妥尔油脂肪酸、由其衍生的妥尔油脂肪酸单体、及其混合物；所述脂肪酸包含20-55wt％的油酸、20-55wt％的亚油酸和任选的0-15wt％的亚麻酸；和所述脂肪酸的总碳足迹为从植物油中获得的脂肪酸的总碳足迹的<95％；和
分离所述酰替吗啉组合物；
其中所述酰替吗啉组合物的加德纳色度(纯)为小于3。
9.根据权利要求8所述的方法，其中所述脂肪酸的平均碳足迹为小于500g CO2当量/kg脂肪酸。
10.根据权利要求9所述的方法，其中所述催化剂为次磷酸。
11.根据权利要求8所述的方法，还包括向所分离的酰替吗啉组合物中加入清除剂，其中所述清除剂为取代或未取代的缩水甘油酯。
12.根据权利要求8所述的方法，还包括降低残余不饱和度的步骤，其选自环氧化、氢化、溴化、氯化、氢氯化和氢溴化。
13.一种酰替吗啉组合物，其为吗啉和脂肪酸的反应产物，其中所述脂肪酸的碳足迹为小于500g CO2当量/kg脂肪酸。
14.一种增塑剂组合物，其包含根据权利要求13所述的酰替吗啉组合物。
15.一种增塑的聚氯乙烯(PVC)组合物，其包含根据权利要求14所述的增塑剂组合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201862714055P | 2018-08-02 | 2018-08-02 | |
| US62/714,055 | 2018-08-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110790981A true CN110790981A (zh) | 2020-02-14 |
| CN110790981B CN110790981B (zh) | 2024-01-12 |
Family
ID=67303396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910709353.1A Active CN110790981B (zh) | 2018-08-02 | 2019-08-02 | Pvc增塑剂及其制备方法 |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US11279813B2 (zh) |
| EP (1) | EP3604418A1 (zh) |
| JP (1) | JP7410663B2 (zh) |
| CN (1) | CN110790981B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3291629A (en) * | 1962-01-15 | 1966-12-13 | Frank C Magne | Morpholides of a mixture of epoxidized, saturated, and monounsaturated fatty acids |
| US3301798A (en) * | 1963-04-16 | 1967-01-31 | Vanderbilt Co R T | Polyvinyl chloride foam |
| CN101686935A (zh) * | 2007-07-03 | 2010-03-31 | 佐治亚-太平洋化工品有限公司 | 马来化脂肪酸的化学改性 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2541584A (en) | 1947-06-11 | 1951-02-13 | Nat Aluminate Corp | N-acylated piperazines |
| US3250635A (en) | 1963-02-19 | 1966-05-10 | Frank C Magne | Vinyl chloride polymers plasticized with mixed morpholides of dimerized fatty acids |
| US3519661A (en) | 1964-08-26 | 1970-07-07 | Us Agriculture | N,n-disubstituted amides |
| US3385813A (en) | 1966-07-20 | 1968-05-28 | Agriculture Usa | Vinyl chloride polymers plasticized with morpholides |
| JP4250815B2 (ja) | 1999-07-27 | 2009-04-08 | 堺化学工業株式会社 | 塩素含有樹脂用安定剤滑剤固体組成物とそれを含む塩素含有樹脂組成物 |
| US7411012B2 (en) | 2005-11-14 | 2008-08-12 | Isp Investments Inc. | Plasticized PVC compositions |
| US9346939B2 (en) | 2013-11-01 | 2016-05-24 | Galata Chemicals Llc | Flexible PVC compounds having a low metals content |
| CN106661419A (zh) | 2014-06-16 | 2017-05-10 | 英格维蒂南卡罗来纳有限责任公司 | 用于粘合剂组合物改性的复合聚合物材料和相关的制造方法 |
| US10927234B2 (en) * | 2018-01-17 | 2021-02-23 | Kraton Polymers U.S. Llc | PVC plasticizers and methods for making thereof |
-
2019
- 2019-07-15 EP EP19186376.0A patent/EP3604418A1/en active Pending
- 2019-07-18 US US16/515,498 patent/US11279813B2/en active Active
- 2019-07-18 JP JP2019132505A patent/JP7410663B2/ja active Active
- 2019-08-02 CN CN201910709353.1A patent/CN110790981B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3291629A (en) * | 1962-01-15 | 1966-12-13 | Frank C Magne | Morpholides of a mixture of epoxidized, saturated, and monounsaturated fatty acids |
| US3301798A (en) * | 1963-04-16 | 1967-01-31 | Vanderbilt Co R T | Polyvinyl chloride foam |
| CN101686935A (zh) * | 2007-07-03 | 2010-03-31 | 佐治亚-太平洋化工品有限公司 | 马来化脂肪酸的化学改性 |
| CN102513024A (zh) * | 2007-07-03 | 2012-06-27 | 佐治亚-太平洋化工品有限公司 | 马来化脂肪酸的化学改性 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110790981B (zh) | 2024-01-12 |
| EP3604418A1 (en) | 2020-02-05 |
| JP2020019946A (ja) | 2020-02-06 |
| JP7410663B2 (ja) | 2024-01-10 |
| US11279813B2 (en) | 2022-03-22 |
| US20200040160A1 (en) | 2020-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9388292B2 (en) | Primary PVC plasticizers derived from vegetable oils, process for obtaining primary PVC plasticizers derived from vegetable oils and plasticized PVC composition | |
| US20100010127A1 (en) | Oleochemical Plasticizers with Thermal and Ultraviolet Radiation Stabilizing Activity for PVC Molding Resins and Process for Obtaining Thereof | |
| US10844194B2 (en) | Plasticizer composition and resin composition including same | |
| Nihul et al. | Epoxidized rice bran oil (ERBO) as a plasticizer for poly (vinyl chloride)(PVC) | |
| US20090149585A1 (en) | Primary pvc plasticizers derived from vegetable oils, process for obtaining primary pvc plasticizers derived from vegetable oils and plasticized pvc composition | |
| US8865936B2 (en) | Vegetal oil derivatives | |
| KR101913877B1 (ko) | 복합 올리고머 구조체 | |
| TWI805879B (zh) | 塑化劑組成物及含彼之樹脂組成物 | |
| WO2013119402A1 (en) | Plasticizer compositions and methods for making plasticizer compositions | |
| US10927234B2 (en) | PVC plasticizers and methods for making thereof | |
| CN110790981B (zh) | Pvc增塑剂及其制备方法 | |
| CN107531937A (zh) | 增塑剂组合物、树脂组合物及其制备方法 | |
| US10113051B2 (en) | Epoxy estolide fatty acid alkyl esters useful as biorenewable plasticizers | |
| US20190002681A1 (en) | Phthalate-free, epoxidized plasticizer compositions comprising fatty acid esters and bio-based oils, and methods of making the same | |
| JP2023531628A (ja) | ジアミド、官能化ポリマーおよびワックスに基づくレオロジー添加剤 | |
| JP6178310B2 (ja) | エポキシ化天然脂肪および油由来の色度低減エポキシ化エステル | |
| CN106795273B (zh) | 增塑剂组合物以及制备增塑剂组合物的方法 | |
| JP2704273B2 (ja) | ゴム用軟化剤 | |
| US11421098B2 (en) | Use of a depleted epoxidized fatty acid ester mixture as plasticizer in halogenated resins | |
| EP3687984B1 (en) | Process for preparing mixtures of epoxidized fatty acid esters | |
| Stolp | Development Of Biobased Plasticizers From Vegetable Oils For Poly (Vinyl Chloride), PVC | |
| JPH0725951B2 (ja) | ゴム用軟化剤 | |
| JP2020019946A5 (zh) | ||
| Sadieva et al. | New composite materials based on polyvinyl chloride | |
| WO2023114821A1 (en) | Bio-based plasticizers |
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 |