JPH06166644A - Mixed alcohol for plasticizer and plasticizer production by using the alcohol - Google Patents
Mixed alcohol for plasticizer and plasticizer production by using the alcoholInfo
- Publication number
- JPH06166644A JPH06166644A JP4349703A JP34970392A JPH06166644A JP H06166644 A JPH06166644 A JP H06166644A JP 4349703 A JP4349703 A JP 4349703A JP 34970392 A JP34970392 A JP 34970392A JP H06166644 A JPH06166644 A JP H06166644A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- plasticizer
- mixed
- alcohol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004014 plasticizer Substances 0.000 title claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title description 13
- 239000000203 mixture Substances 0.000 claims abstract description 65
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- JILNFHMXFBDGGA-UHFFFAOYSA-N 2-ethyl-2-methylheptan-1-ol Chemical compound CCCCCC(C)(CC)CO JILNFHMXFBDGGA-UHFFFAOYSA-N 0.000 claims abstract description 3
- AOWJVNTZMBKLQO-UHFFFAOYSA-N 2-propan-2-ylheptan-1-ol Chemical compound CCCCCC(CO)C(C)C AOWJVNTZMBKLQO-UHFFFAOYSA-N 0.000 claims abstract description 3
- VZXWJVFQXZUFQS-UHFFFAOYSA-N 4-methyl-2-propylhexan-1-ol Chemical compound CCCC(CO)CC(C)CC VZXWJVFQXZUFQS-UHFFFAOYSA-N 0.000 claims abstract description 3
- QEVWDMOIPOLQBL-UHFFFAOYSA-N 5-methyl-2-propylhexan-1-ol Chemical compound CCCC(CO)CCC(C)C QEVWDMOIPOLQBL-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000005886 esterification reaction Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 136
- 150000001299 aldehydes Chemical class 0.000 description 43
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 42
- 239000007789 gas Substances 0.000 description 36
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 34
- 230000000704 physical effect Effects 0.000 description 34
- 239000000047 product Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 32
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 30
- 239000002994 raw material Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 150000001336 alkenes Chemical class 0.000 description 27
- 238000005984 hydrogenation reaction Methods 0.000 description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 24
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 22
- 238000005882 aldol condensation reaction Methods 0.000 description 21
- 238000007037 hydroformylation reaction Methods 0.000 description 21
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 20
- 238000003965 capillary gas chromatography Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 19
- 230000008859 change Effects 0.000 description 19
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 18
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 description 17
- 238000005292 vacuum distillation Methods 0.000 description 15
- 239000003446 ligand Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 11
- 239000001273 butane Substances 0.000 description 11
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 239000001282 iso-butane Substances 0.000 description 11
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 11
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910052703 rhodium Inorganic materials 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000001893 (2R)-2-methylbutanal Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- -1 phthalic acid diester Chemical class 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical group CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229940067597 azelate Drugs 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 229940116351 sebacate Drugs 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 4
- 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 4
- CRFFZGAVKNNBKJ-UHFFFAOYSA-N chembl45367 Chemical compound CCCOC1=CC=C(NS(C)(=O)=O)C=C1C(NC1=O)=NC2=C1C(C)=NN2C CRFFZGAVKNNBKJ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 4
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 3
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000005591 trimellitate group Chemical group 0.000 description 3
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ONUFRYFLRFLSOM-UHFFFAOYSA-N lead;octadecanoic acid Chemical compound [Pb].CCCCCCCCCCCCCCCCCC(O)=O ONUFRYFLRFLSOM-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- DHPXCZQIGRUZAY-UHFFFAOYSA-N 2-ethyl-2,4-dimethylhexan-1-ol Chemical compound CCC(C)CC(C)(CC)CO DHPXCZQIGRUZAY-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- TVDUZVIJAUNRRO-UHFFFAOYSA-N 4,4-dimethyl-2-propylpentan-1-ol Chemical compound CCCC(CO)CC(C)(C)C TVDUZVIJAUNRRO-UHFFFAOYSA-N 0.000 description 1
- VHGVOODVCUKVCL-UHFFFAOYSA-N 4-methyl-2-propan-2-ylhexan-1-ol Chemical compound CCC(C)CC(CO)C(C)C VHGVOODVCUKVCL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920006266 Vinyl film Polymers 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
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- 239000012670 alkaline solution Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 238000004523 catalytic cracking Methods 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
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- DTDMYWXTWWFLGJ-UHFFFAOYSA-N decan-4-ol Chemical compound CCCCCCC(O)CCC DTDMYWXTWWFLGJ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は特定の組成を有する炭素
数１０の可塑剤用混合アルコール及び該可塑剤用混合ア
ルコールとカルボン酸またはカルボン酸無水物とをエス
テル化反応させることによって得られる可塑剤に関す
る。フタル酸ジエステル、アジピン酸ジエステルに代表
される可塑剤は、主として塩化ビニル系樹脂用可塑剤と
して利用されている。The present invention relates to a mixed alcohol having a specific composition for a plasticizer having 10 carbon atoms and a plastic obtained by the esterification reaction of the mixed alcohol for a plasticizer with a carboxylic acid or a carboxylic acid anhydride. Regarding agents. The plasticizer represented by phthalic acid diester and adipic acid diester is mainly used as a plasticizer for vinyl chloride resin.
【０００２】[0002]
【従来の技術】従来、炭素数１０のアルコールであるデ
カノールは、炭化水素油の熱分解または接触分解によっ
て得られる炭素数４の留分（以下、ＢＢ留分という）を
ヒドロホルミル化反応させてバレルアルデヒド類を製造
し、次いでこれをアルドール縮合反応させてデセナール
類を製造し、更にこれを水素添加反応させることにより
製造される。ＢＢ留分中のブテンとしては、１−ブテ
ン、２−ブテン、イソブテンの３種類がある。従って、
これをヒドロホルミル化して得られる炭素数５のアルデ
ヒドはｎ−バレルアルデヒド、２−メチルブチルアルデ
ヒド、３−メチルブチルアルデヒド及びピバルアルデヒ
ドの混合物となる。2. Description of the Related Art Conventionally, decanol, which is an alcohol having 10 carbon atoms, is subjected to hydroformylation reaction of a fraction having 4 carbon atoms (hereinafter referred to as BB fraction) obtained by thermal decomposition or catalytic cracking of hydrocarbon oil, and then barreled. It is produced by producing an aldehyde, then subjecting this to an aldol condensation reaction to produce decenals, and further subjecting this to a hydrogenation reaction. There are three types of butene in the BB fraction, 1-butene, 2-butene and isobutene. Therefore,
The aldehyde having 5 carbon atoms obtained by hydroformylating this is a mixture of n-valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde and pivalaldehyde.
【０００３】従って、ＢＢ留分のヒドロホルミル化によ
り得られるバレルアルデヒド類の縮合生成物及びデカノ
ール製品は一般に多種類の構造異性体の混合物となる。
ブテン類のオキソ反応について、フォン ベルンハルト
らのヘミカ−ツワイツング（Ｃｈｅｍｉｋｅｒ−Ｚｅｉ
ｔｕｎｇ）９９ イヤ−ルガンク（Ｊａｈｒｇａｎｇ）
（１９７５），ｌｌ号，Ｐ４５２−４５８や特開昭５５
−１２７３３５号などには、通常のヒドロホルミル化条
件でバレルアルデヒドを製造できること、また、ｎ−バ
レルアルデヒドをより高収率で得るためのヒドロホルミ
ル化条件などが記載されている。Therefore, the condensation products of valeraldehydes obtained by hydroformylation of the BB fraction and decanol products are generally mixtures of various structural isomers.
Regarding the oxo reaction of butenes, Chemiker-Zeiting of von Bernhard et al.
tung) 99 Earl Gang (Jahrangang)
(1975), No. 11, P452-458 and JP-A-55.
No. 127335 and the like describe that valeraldehyde can be produced under usual hydroformylation conditions, and hydroformylation conditions for obtaining n-valeraldehyde in a higher yield.
【０００４】また、ＥＰ特許第２１３６３９号、特表昭
６１−５０１２６８号、米国特許第４６６８６５１号、
特公昭５８−５７４１３号には、ロジウム錯体触媒存在
下、配位子としてポリホスファイトまたはトリフェニル
ホスフィンを用いることによってブテン類をヒドロホル
ミル化して種々のＣ５アルデヒドを製造するための適当
なポリホスファイトの構造式とヒドロホルミル化条件と
が記載されている。Further, EP Patent No. 213639, Japanese Patent Publication No. 61-501268, US Pat. No. 4,668,651,
JP-B-58-57413 discloses a suitable polyphosphite for producing various C5 aldehydes by hydroformylating butenes by using polyphosphite or triphenylphosphine as a ligand in the presence of a rhodium complex catalyst. And the hydroformylation conditions are described.
【０００５】また特開昭５８−２０６５３７号には、ブ
テン類から可塑剤性能の良いデカノールを製造するため
に、２−プロピルヘプタノールを主成分とするアルコー
ル中のｎ−バレルアルデヒドと２−置換アルデヒドとの
クロスアルドール生成物から誘導されるアルコールの量
を生成物の２０％以下にするためのバレルアルデヒドの
組成と縮合条件とが記載されている。Further, in JP-A-58-206537, in order to produce decanol having good plasticizer performance from butenes, n-valeraldehyde and 2-substitution in alcohol containing 2-propylheptanol as a main component. The composition of valeraldehyde and the condensation conditions to bring the amount of alcohol derived from the cross aldol product with the aldehyde to 20% or less of the product are described.
【０００６】米国特許第２９２１０８９号、同第３１２
１０５１号には、ｎ−バレルアルデヒドの縮合生成物か
ら誘導される２−プロピルヘプタノール及びｎ−バレル
アルデヒドと２−メチルブチルアルデヒドとのクロスア
ルドール生成物から誘導されるデカノールについて記載
されており、縮合反応及び水素添加反応は通常の方法で
よいこと、２−プロピルヘプタノールはフタル酸ジ−２
−プロピルヘプチルあるいはアジピン酸ジ−２−プロピ
ルヘプチルのエステルにすると優れた性能を示す可塑剤
になること、またクロスアルドール生成物から誘導され
るデカノールを用いた可塑剤は、可塑剤性能が２−プロ
ピルヘプタノールを使用した場合に比べて劣るものの、
２−プロピルヘプタノールとの十数％までの混合物とし
て使うならば性能はそれほど劣らぬことなどが記載され
ている。US Pat. Nos. 2921089 and 312
No. 1051 describes 2-propylheptanol derived from a condensation product of n-valeraldehyde and decanol derived from a cross aldol product of n-valeraldehyde and 2-methylbutyraldehyde, The condensation reaction and the hydrogenation reaction may be carried out by ordinary methods.
-Propylheptyl or an ester of di-2-propylheptyl adipate results in a plasticizer having excellent performance, and a plasticizer using decanol derived from a cross aldol product has a plasticizer performance of 2- Although inferior to using propylheptanol,
It is described that the performance is not so inferior when it is used as a mixture with 2-propylheptanol up to 10% or more.
【０００７】また特開平２−１９６７４１号や特開平２
−２０９８３８号には、ブテン類を用いてオキソ反応に
より、ｎ−バレルアルデヒド、２−メチルブチルアルデ
ヒド、３−メチルブチルアルデヒド及びピバルアルデヒ
ドの４種のアルデヒド混合物を製造し、この混合物を単
離することなくアルドール縮合反応、それに続く水素添
加反応を経て炭素数１０の可塑剤用混合アルコールを製
造する方法および該混合アルコールを用いてフタル酸ジ
エステルとした可塑剤が開示されている。Further, JP-A-2-196741 and JP-A-2-196741
No. 209838 discloses an oxo reaction using butenes to produce a mixture of four aldehydes of n-valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde and pivalaldehyde, and the mixture is isolated. A method for producing a mixed alcohol for a plasticizer having 10 carbon atoms through an aldol condensation reaction followed by a hydrogenation reaction without performing the above, and a plasticizer made into a phthalic acid diester using the mixed alcohol are disclosed.
【０００８】そして、村井孝一編著、「可塑剤−その理
論と応用」、幸書房（１９７３）刊には、可塑剤分子中
アルコール部分の炭素分岐度が大きいと電気絶縁性、耐
油性、耐移行性及び耐汚染性は向上するが、耐寒性、可
塑化効率、熱安定性、耐候性及び耐揮発性は低下すると
記載されている。[0008] And Koichi Murai, "Plasticizer-Theory and Application", published by Koshobo (1973), shows that when the carbon branching degree of the alcohol portion in the plasticizer molecule is large, electrical insulation, oil resistance, and migration resistance are high. It is described that although the resistance and stain resistance are improved, the cold resistance, plasticizing efficiency, thermal stability, weather resistance and volatility resistance are decreased.
【０００９】しかしながら、特開平２−１９６７４１号
公報および特開平２−２０９８３８号公報に開示の如き
ｎ−バレルアルデヒド、２−メチルブチルアルデヒド、
３−メチルブチルアルデヒドおよびピバルアルデヒドの
４種類のアルデヒドを含む混合物を用いてアルド−ル縮
合反応を行い、次いで水素添加反応して得られるデカノ
−ルは分岐度の大きいデカノ−ル成分即ちｎ−バレルア
ルデヒドとピバルアルデヒドとの反応に由来するデカノ
−ルを含んだ混合アルコ−ルとなる。かかる分岐度の大
きいアルコ−ルを含む混合アルコ−ルを用いた可塑剤は
電気絶縁性、耐油性、耐移行性および耐汚染性は向上す
るが、耐寒性、可塑化効率、熱安定性、耐候性および耐
揮発性が低下することが知られている。また、ピバルア
ルデヒドはα位に活性水素を持たないことから、次工程
のアルド−ル縮合反応工程で反応性が極めて悪く、未反
応ピバルアルデヒドが多量に残存することになり、これ
の除去が必要となり、経済的に極めて不利となるといっ
た問題点を有している。しかるに該ピバルアルデヒドを
含まないアルデヒド類を製造する為には、原料オレフィ
ンガスとして１−ブテンのみからなるガスもしくはイソ
ブテンを完全に除去した１−ブテン、２−ブテンからな
る混合ガスを用いてヒドロホルミル化反応を行えばよい
が、かかるガスを得る為には多くの精製分離工程を経て
原料ガスを精製することが必要であり、工業的に経済的
でないといった問題点がある。However, n-valeraldehyde, 2-methylbutyraldehyde, as disclosed in JP-A-2-196741 and JP-A-2-209838,
The decanol obtained by carrying out an aldol condensation reaction using a mixture containing four types of aldehydes of 3-methylbutyraldehyde and pivalaldehyde, and then hydrogenating the decanol component having a large branching degree, that is, n A mixed alcohol containing decanol derived from the reaction of valeraldehyde and pivalaldehyde. A plasticizer using a mixed alcohol containing an alcohol having a large degree of branching has improved electric insulation, oil resistance, migration resistance and stain resistance, but cold resistance, plasticization efficiency, thermal stability, It is known that weather resistance and volatility resistance decrease. Further, since pivalaldehyde does not have active hydrogen at the α-position, the reactivity is extremely poor in the subsequent aldol condensation reaction step, and a large amount of unreacted pivalaldehyde remains. Is required, which is extremely disadvantageous economically. However, in order to produce the aldehydes containing no pivalaldehyde, hydroformyl is used as a starting olefin gas using a gas consisting of only 1-butene or a mixed gas consisting of 1-butene and 2-butene from which isobutene is completely removed. However, in order to obtain such a gas, it is necessary to purify the raw material gas through many purification and separation steps, which is a problem in that it is not industrially economical.
【００１０】[0010]
【発明が解決しようとする課題】本発明者らは、デカノ
−ル混合物を用いて塩化ビニル樹脂組成物用可塑剤を製
造するに際し、特定の範囲のデカノール組成を有する混
合アルコ−ルを使用すれば塩化ビニル樹脂組成物として
最良の物性を与える可塑剤になることを見い出し、提案
した（特願平４−４８１０６号）が、さらに鋭意研究を
進めた結果、次のような事実を見い出した。即ち、以下
に示す組成を持った混合デカノールをカルボン酸無水物
もしくはカルボン酸とエステル化反応させ、カルボン酸
ジエステルとした可塑剤が、これらを用いて塩化ビニル
樹脂組成物とすると、上述の特願平４−４８１０６号に
記載した範囲の組成を有するデカノール混合物から得ら
れる可塑剤を用いた塩化ビニル樹脂組成物に比べて、耐
寒性（低温柔軟性）、耐油性、耐水性及び耐揮発性（加
熱老化性）などの物性は実用上、何ら問題なく、しかも
電気絶縁性が極めて優れた組成物を与える可塑剤にな
り、しかもかかる混合アルコ−ルは、用いる原料オレフ
ィンガスを多くの精製分離工程で精製しなくてもよく、
工業的に経済的な原料オレフィンガスを使用して得られ
るこを見い出し、この知見に基づき本発明を完成した。DISCLOSURE OF THE INVENTION The present inventors have prepared a plasticizer for a vinyl chloride resin composition using a decanol mixture by using a mixed alcohol having a decanol composition within a specific range. For example, the inventors have found that the plasticizer gives the best physical properties as a vinyl chloride resin composition and proposed it (Japanese Patent Application No. 4-48106), but as a result of further intensive research, the following facts were found. That is, if a mixed decanol having the composition shown below is subjected to an esterification reaction with a carboxylic acid anhydride or a carboxylic acid to form a carboxylic acid diester as a plasticizer into a vinyl chloride resin composition, the above-mentioned Japanese Patent Application Cold resistance (low temperature flexibility), oil resistance, water resistance and volatility resistance (compared to a vinyl chloride resin composition using a plasticizer obtained from a decanol mixture having a composition in the range described in JP-A-4-48106) ( Physical properties such as heat aging) are practically no problems, and become a plasticizer that gives a composition with extremely excellent electrical insulation properties. Moreover, such mixed alcohols are used in many purification and separation processes for the raw olefin gas used. Need not be refined with
They have found that they can be obtained by using industrially economical raw material olefin gas, and completed the present invention based on this finding.
【００１１】 ２ＰＨＯ ：８１重量％以上９
５重量％未満 ４ＭＰＨＯと５ＭＰＨＯを合わせて：５．０重量％を越
え１８重量％以下 ＭＥＨＯとＩＰＨＯを合わせて ：１．０重量％以下 但し、２ＰＨＯは２−プロピル−１−ヘプタノールを、
４ＭＰＨＯは４−メチル−２−プロピル−１−ヘキサノ
ール、ＭＥＨＯは２−メチル−２−エチル−１−ヘプタ
ノール、５ＭＰＨＯは５−メチル−２−プロピル−１−
ヘキサノール、ＩＰＨＯは２−イソプロピル−１−ヘプ
タノールをそれぞれ表す。2PHO: 81% by weight or more 9
Less than 5% by weight 4MPHO and 5MPHO combined: more than 5.0% by weight and 18% by weight or less MEHO and IPHO combined: 1.0% by weight or less However, 2PHO is 2-propyl-1-heptanol,
4MPHO is 4-methyl-2-propyl-1-hexanol, MEHO is 2-methyl-2-ethyl-1-heptanol, 5MPHO is 5-methyl-2-propyl-1-.
Hexanol and IPHO represent 2-isopropyl-1-heptanol, respectively.
【００１２】以上の記述から明らかなように、本発明の
目的は耐揮発性、耐寒性、耐油性、耐水性及び電気特性
に優れた可塑剤性能を与える炭素数１０の可塑剤用混合
アルコール及び該混合アルコールを用いた上述のような
性能を有する可塑剤を提供することにある。かかる可塑
剤は例えば塩化ビニル樹脂に配合され、多種多様な用途
に使用可能であり、例えば、一般フィルム、シート、農
業用ビニールフイルム、建材、レザー、電線被覆、押出
成形品、履物、ゾルなどに使用される。As is clear from the above description, the object of the present invention is to prepare a mixed alcohol for a plasticizer having 10 carbon atoms, which gives a plasticizer performance excellent in volatility, cold resistance, oil resistance, water resistance and electric characteristics. An object of the present invention is to provide a plasticizer using the mixed alcohol and having the above-mentioned properties. Such a plasticizer is blended with, for example, a vinyl chloride resin and can be used in a wide variety of applications, for example, in general films, sheets, agricultural vinyl films, building materials, leather, wire coatings, extruded products, footwear, sols, etc. used.
【００１３】[0013]
【課題を解決するための手段】本発明は次の構成を有す
る。 （１）炭素数１０のアルコールとカルボン酸またはカル
ボン酸無水物とをエステル化反応させることによって可
塑剤用エステルを製造するにあたり、該エステル化反応
に供するアルコールの組成が以下で示されることを特徴
とする可塑剤用混合アルコール ２ＰＨＯ ：８１重量％以上９
５重量％未満 ４ＭＰＨＯと５ＭＰＨＯを合わせて：５．０重量％を越
え１８重量％以下 ＭＥＨＯとＩＰＨＯを合わせて ：１．０重量％以下 （２）上記（１）項記載の可塑剤用混合アルコールとカ
ルボン酸またはカルボン酸無水物とをエステル化反応さ
せることによって得られる可塑剤。 （３）カルボン酸またはカルボン酸無水物がフタル酸、
フタル酸無水物、アジピン酸、アゼライン酸、セバシン
酸、トリメリット酸、トリメリット酸無水物、ピロメリ
ット酸またはピロメリット酸無水物である上記（２）項
記載の可塑剤。The present invention has the following configuration. (1) When an ester for a plasticizer is produced by subjecting an alcohol having 10 carbon atoms to an esterification reaction of a carboxylic acid or a carboxylic acid anhydride, the composition of the alcohol to be subjected to the esterification reaction is shown below. And mixed alcohol for plasticizer 2PHO: 81% by weight or more 9
Less than 5% by weight 4MPHO and 5MPHO combined: more than 5.0% by weight and 18% by weight or less MEHO and IPHO combined: 1.0% by weight or less (2) Mixed alcohol for plasticizer according to the above item (1) A plasticizer obtained by subjecting a carboxylic acid or a carboxylic anhydride to an esterification reaction. (3) The carboxylic acid or carboxylic acid anhydride is phthalic acid,
The plasticizer according to the above item (2), which is phthalic anhydride, adipic acid, azelaic acid, sebacic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid or pyromellitic anhydride.
【００１４】本発明における可塑剤用混合アルコールは
その組成が指定した範囲であれば、その製造方法を選ぶ
ものではなく、例えば原料オレフィンガスとして、イソ
ブテンを０．１〜１０重量％できれば０．５〜５重量％
含有する１−ブテン、２−ブテンおよびイソブテンの混
合物を原料オレフィンガスとして用い、ロジウム錯体触
媒の存在下、配位子としてビスホスファイトまたはポリ
ホスファイトを用い、反応圧力常圧〜３００ｋｇ／ｃｍ
2Ｇ、反応温度５０〜１５０℃、Ｈ2／ＣＯモル比０．５
〜１０、触媒濃度数ｐｐｍ〜数重量％、配位子は触媒に
対するモル比で通常１〜１０００の条件でヒドロホルミ
ル化することにより、ピバルアルデヒドをほとんど含ま
ないｎ−バレルアルデヒドと２−メチルブチルアルデヒ
ドおよび３−メチルブチルアルデヒドのほぼ３成分から
なる炭素数５の混合アルデヒドを得、ついで、通常のア
ルドール縮合反応条件下、該アルデヒド生成物をアルド
ール縮合反応せしめ炭素数１０のアルケナール生成物を
得、引続き通常の水添反応条件下、２ＰＨＯ、４ＭＰＨ
Ｏ、５ＭＰＨＯ、ＭＥＨＯ及びＩＰＨＯのアルコール混
合物を得る方法でもよく、蒸留により該組成を得る方法
や、２ＰＨＯ、４ＭＰＨＯ、５ＭＰＨＯ、ＭＥＨＯもし
くはＩＰＨＯをそれぞれ別個に調製し該アルコール混合
物の組成を与えるように混合する方法によっても何ら不
都合を生じるものではない。The mixed alcohol for a plasticizer according to the present invention does not have any manufacturing method selected as long as its composition is within the specified range. For example, if the raw material olefin gas is 0.1 to 10% by weight of isobutene, 0.5 is possible. ~ 5% by weight
A mixture of 1-butene, 2-butene and isobutene contained is used as a raw material olefin gas, bisphosphite or polyphosphite is used as a ligand in the presence of a rhodium complex catalyst, and the reaction pressure is normal pressure to 300 kg / cm.
2 G, reaction temperature 50 to 150 ° C., H 2 / CO molar ratio 0.5
-10, a catalyst concentration of several ppm to several wt%, and the ligand is hydroformylated under a condition of a molar ratio to the catalyst of usually 1 to 1000, whereby n-valeraldehyde and 2-methylbutylaldehyde containing almost no pivalaldehyde are contained. A mixed aldehyde having almost 5 components of aldehyde and 3-methylbutyraldehyde and having 5 carbon atoms is obtained, and then the aldehyde product is aldol-condensed to obtain an alkenal product having 10 carbon atoms. , 2PHO, 4MPH under normal hydrogenation reaction conditions
A method of obtaining an alcohol mixture of O, 5MPHO, MEHO and IPHO may be used, and a method of obtaining the composition by distillation, or 2PHO, 4MPHO, 5MPHO, MEHO or IPHO may be separately prepared and mixed to give a composition of the alcohol mixture. The method does not cause any inconvenience.
【００１５】上述のアルドール縮合反応は通常の触媒を
用い、反応は温度約２０℃〜約２５０℃、好ましくは６
０℃〜２００℃の攪拌条件下で行う。反応圧力は、減圧
から加圧までの広範囲の圧力下で行うことができる。好
ましくは、０．９Ｋｇ／ｃｍ2Ａ〜１５Ｋｇ／ｃｍ2Ａで
行う。反応は還流で行ってもよい。触媒は、水酸化ナト
リウムや水酸化カリウム、シアン化ナトリウム、シアン
化カリウムのような強アルカリ触媒でも、トリメチルア
ミン、ジメチルアミン、トリエチルアミンのような弱ア
ルカリ触媒でもよい。アルカリ水溶液濃度は約１〜２０
重量％の範囲で、アルカリ水溶液量は反応アルデヒド量
に対して、０．１〜１０倍、好ましくは、０．５〜３倍
で行う。反応は目的の転化率を得る時間で終えることが
できるが、時間は数分〜約５時間で完結する。反応は連
続式でも回分式でも可能である。The aldol condensation reaction described above uses a conventional catalyst, and the reaction temperature is about 20 ° C to about 250 ° C, preferably 6 ° C.
It is performed under stirring conditions of 0 ° C to 200 ° C. The reaction pressure can be under a wide range of pressure from reduced pressure to increased pressure. Preferably carried out in 0.9Kg / cm 2 A~15Kg / cm 2 A. The reaction may be carried out at reflux. The catalyst may be a strong alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium cyanide or potassium cyanide, or a weak alkali catalyst such as trimethylamine, dimethylamine or triethylamine. Alkaline solution concentration is about 1-20
The amount of the alkaline aqueous solution is 0.1 to 10 times, preferably 0.5 to 3 times the amount of the reaction aldehyde in the range of wt%. The reaction can be completed in a time to obtain a desired conversion rate, but the time is completed in a few minutes to about 5 hours. The reaction can be carried out continuously or batchwise.
【００１６】反応終了後、反応液を油水分離したのち、
油層をそのままもしくは蒸留して炭素数１０のアルケナ
ールを得る。また、該アルケナ−ルの水素添加反応は、
Ｎｉ、Ｃｕ、Ｃｒ、Ｐｄ等の通常の水素添加触媒によ
り、反応圧力は常圧〜３００Ｋｇ／ｃｍ2Ｇ、好ましく
は２０〜１５０Ｋｇ／ｃｍ2Ｇ、温度は３０〜３００
℃、好ましくは１００〜２００℃の条件で水素添加反応
が行われる。水素添加反応により、不飽和炭素結合及び
アルデヒドの還元を行わせる。水素添加反応は粉末触媒
使用の懸濁方式あるいは成型触媒使用の固定床方式いず
れでもよく、さらに、連続式でも回分式でもよい。得れ
れた水素添加生成物は、通常の蒸留により精製すると目
的組成の炭素数１０の混合アルコールが得られる。After completion of the reaction, the reaction solution is separated into oil and water,
The oil layer is directly or distilled to obtain an alkenal having 10 carbon atoms. In addition, the hydrogenation reaction of the alkenal
The reaction pressure is normal pressure to 300 Kg / cm 2 G, preferably 20 to 150 Kg / cm 2 G, and the temperature is 30 to 300 with a normal hydrogenation catalyst such as Ni, Cu, Cr and Pd.
The hydrogenation reaction is carried out at a temperature of 100 ° C, preferably 100 to 200 ° C. The hydrogenation reaction causes reduction of unsaturated carbon bonds and aldehydes. The hydrogenation reaction may be either a suspension system using a powder catalyst or a fixed bed system using a molded catalyst, and may be a continuous system or a batch system. The obtained hydrogenation product is purified by ordinary distillation to obtain a mixed alcohol having a target composition of 10 carbon atoms.
【００１７】前述のような３種のアルデヒド混合物を用
いてアルド−ル縮合反応、水素添加反応により得られる
デカノールは理論上次の９種類の混合アルコ−ルにな
る。即ち、ｎ−バレルアルデヒドとｎ−バレルアルデヒ
ドとの縮合反応に由来した生成物として２ＰＨＯ、ｎ−
バレルアルデヒドと２−メチルブチルアルデヒドとの反
応に由来した生成物として４ＭＰＨＯ及びＭＥＨＯ、２
−メチルブチルアルデヒドと２−メチルブチルアルデヒ
ドとの反応に由来した生成物として２、４−ジメチル−
２−エチル−１−ヘキサノールがある。ｎ−バレルアル
デヒドと３−メチルブチルアルデヒドとの反応に由来し
た生成物として５ＭＰＨＯ及びＩＰＨＯ、３−メチルブ
チルアルデヒドと３−メチルブチルアルデヒドとの反応
に由来した生成物として５−メチル−２−イソプロピル
−１−ヘキサノールがある。２−メチルブチルアルデヒ
ドと３−メチルブチルアルデヒドとの反応に由来した生
成物として２、４−ジメチル−２−エチル−１−ヘキサ
ノール、４−メチル−２−イソプロピル−１−ヘキサノ
ールがある。しかしながら、原料オレフィンガスとし
て、上述の如きイソブテンを０．１〜１０重量％含有す
る１−ブテン、２−ブテンおよびイソブテンから主とし
てなる混合オレフィンンガスを用い、上述のようなヒド
ロホルミル化反応条件で生成する混合アルデヒドをアル
ド−ル縮合反応、ついで水素添加反応して得られる混合
デカノ−ルは２ＰＨＯ、４ＭＰＨＯ，ＭＥＨＯ，５ＭＰ
ＨＯ、ＩＰＨＯのほぼ５成分であり、他の成分はほとん
ど含まれない。Decanol obtained by an aldol condensation reaction and a hydrogenation reaction using the above-mentioned three kinds of aldehyde mixtures theoretically becomes the following nine kinds of mixed alcohols. That is, as a product derived from the condensation reaction of n-valeraldehyde and n-valeraldehyde, 2PHO, n-
4MPHO and MEHO as products derived from the reaction of valeraldehyde and 2-methylbutyraldehyde, 2
-2,4-dimethyl-as a product derived from the reaction of methylbutyraldehyde and 2-methylbutyraldehyde
There is 2-ethyl-1-hexanol. 5MPHO and IPHO as products derived from the reaction of n-valeraldehyde and 3-methylbutyraldehyde, and 5-methyl-2-isopropyl as products derived from the reaction of 3-methylbutyraldehyde and 3-methylbutyraldehyde There is -1-hexanol. The products derived from the reaction of 2-methylbutyraldehyde and 3-methylbutyraldehyde include 2,4-dimethyl-2-ethyl-1-hexanol and 4-methyl-2-isopropyl-1-hexanol. However, a mixed olefin gas mainly containing 1-butene, 2-butene and isobutene containing 0.1 to 10% by weight of isobutene as described above is used as a raw material olefin gas, and is produced under the hydroformylation reaction conditions as described above. The mixed decanol obtained by subjecting the mixed aldehyde to an aldehyde condensation reaction and then a hydrogenation reaction is 2PHO, 4MPHO, MEHO, 5MP.
HO and IPHO are almost 5 components, and other components are hardly contained.
【００１８】上記のようにして得られる混合アルコール
はついで常法によりチタン、銅などの金属触媒や硫酸、
パラトルエンスルホン酸などの酸触媒などの存在下もし
くは無触媒において、無水フタル酸、アジピン酸などと
エステル化反応させて、フタル酸ジエステル、アジピン
酸ジエステルなどの可塑剤とし、また、無水トリメリッ
ト酸、無水ピロメリット酸などの芳香族カルボン酸、ア
ゼライン酸、セバシン酸などの脂肪族二塩基酸とのエス
テル化反応によってそれぞれ対応する可塑剤とする。The mixed alcohol obtained as described above is then mixed with a metal catalyst such as titanium or copper or sulfuric acid by a conventional method.
In the presence or absence of an acid catalyst such as paratoluene sulfonic acid, or in the absence of a catalyst, it is esterified with phthalic anhydride, adipic acid, etc. to form a plasticizer such as phthalic acid diester, adipic acid diester. , An aromatic carboxylic acid such as pyromellitic dianhydride, and an aliphatic dibasic acid such as azelaic acid and sebacic acid to form corresponding plasticizers.
【００１９】本発明における塩化ビニル樹脂とは、ポリ
塩化ビニル及び塩化ビニルコポリマーであり、塩化ビニ
ルコポリマーとは塩化ビニルを主体としこれと他のモノ
マー、例えばエチレン、プロピレン、酢酸ビニル、アル
キルビニルエーテル、アクリル酸エステル、メタクリル
酸エステル等とのコポリマーが挙げられるが、本発明は
上記の樹脂の種類に制限されるものではない。The vinyl chloride resin in the present invention is polyvinyl chloride and vinyl chloride copolymer, and the vinyl chloride copolymer mainly comprises vinyl chloride and other monomers such as ethylene, propylene, vinyl acetate, alkyl vinyl ether, and acrylic. Examples thereof include copolymers with acid esters, methacrylic acid esters and the like, but the present invention is not limited to the types of the above resins.
【００２０】[0020]
【実施例】以下、実施例に基づき本発明を詳細説明す
る。また、以下の実施例における物性値は下記の試験方
法によった。 〔比重〕ＡＳＴＭ Ｄ ７９２に準じた。 〔引張試験〕ＪＩＳ Ｋ ６７２３に準じて、引っ張り
強さ、伸び、１００％モジュラスを測定した。EXAMPLES The present invention will be described in detail below based on examples. Moreover, the physical property values in the following examples were based on the following test methods. [Specific gravity] According to ASTM D792. [Tensile Test] Tensile strength, elongation and 100% modulus were measured according to JIS K 6723.
【００２１】〔加熱減量〕フタレート、アジペート、セ
バケート、アゼレート系の評価に使用した。ＪＩＳ Ｋ
６７２３の引張り試験片を温度８７℃のオーブン中で
１４４時間加熱し、加熱減量を測定する。加熱減量は次
の式により求めた。 加熱減量＝（Ｗ1−Ｗ2）／Ｗ1×１００ ここに、Ｗ1は加熱前の試験片の重量（ｇ）を、Ｗ2は加
熱後の試験片の重量（ｇ）を表す。 〔加熱減量（高温）〕トリメリテート系可塑剤の評価に
使用した。ＪＩＳ Ｋ ６７２３の引っ張り試験片を温
度１３６℃のオーブン中で１６８時間加熱し、加熱減量
を測定する。加熱減量は次の式により求めた。 加熱減量＝（Ｗ1−Ｗ2）／Ｗ1×１００ ここに、Ｗ1は加熱前の試験片の重量（ｇ）を、Ｗ2は加
熱後の試験片の重量（ｇ）を表す。[Heating Loss] Used for evaluation of phthalate, adipate, sebacate, and azelate systems. JIS K
The 6723 tensile test piece is heated in an oven at a temperature of 87 ° C. for 144 hours, and the loss on heating is measured. The heating loss was calculated by the following formula. Heating loss = (W 1 −W 2 ) / W 1 × 100 Here, W 1 represents the weight (g) of the test piece before heating, and W 2 represents the weight (g) of the test piece after heating. [Heating loss (high temperature)] Used for evaluation of trimellitate plasticizer. The tensile test piece of JIS K 6723 is heated in an oven at a temperature of 136 ° C. for 168 hours, and the heating loss is measured. The heating loss was calculated by the following formula. Heating loss = (W 1 −W 2 ) / W 1 × 100 Here, W 1 represents the weight (g) of the test piece before heating, and W 2 represents the weight (g) of the test piece after heating.
【００２２】〔柔軟温度〕ＪＩＳ Ｋ ６７４５に準じ
た。 〔体積固有抵抗〕ＪＩＳ Ｋ ６７２３に準じ、恒温槽
の温度を３０℃で測定した。 〔耐油性試験重量変化率〕ＪＩＳ Ｋ ６７２３の引っ
張り試験片を温度９０℃の１種２号絶縁油（ＪＩＳ Ｃ
２３２０）中に４時間浸漬し、重量変化率を測定す
る。重量変化率は次の式により求めた。 重量変化率＝（Ｗ2−Ｗ1）／Ｗ1×１００ ここに、Ｗ1は試験前の試験片の重量（ｇ）を、Ｗ2は試
験後の試験片の重量（ｇ）を表す。[Flexible temperature] According to JIS K 6745. [Volume Specific Resistance] The temperature of the constant temperature bath was measured at 30 ° C. according to JIS K 6723. [Oil resistance test weight change rate] A tensile test piece according to JIS K 6723 was used as a type 1 No. 2 insulating oil (JIS C
2320) and immersed for 4 hours, and the weight change rate is measured. The weight change rate was calculated by the following formula. Weight change rate = (W 2 −W 1 ) / W 1 × 100 Here, W 1 represents the weight (g) of the test piece before the test, and W 2 represents the weight (g) of the test piece after the test.
【００２３】〔耐水性試験重量変化率〕ＪＩＳ Ｋ ７
１１３の２号試験片を１００℃の温水中に４８時間浸漬
し、重量変化率を測定する。重量変化率については次の
式により求めた。 重量変化率＝（Ｗ2−Ｗ1）／Ｗ1×１００ ここに、Ｗ1は試験前の試験片の重量（ｇ）を、Ｗ2は試
験後の試験片の重量（ｇ）を表す。 〔硬さ〕ＪＩＳ Ｋ ６３０１に準じスプリング式硬さ
試験機Ａ型を使用した。[Rate of Weight Change in Water Resistance Test] JIS K 7
The No. 2 test piece of No. 113 is immersed in warm water of 100 ° C. for 48 hours, and the weight change rate is measured. The weight change rate was calculated by the following formula. Weight change rate = (W 2 −W 1 ) / W 1 × 100 Here, W 1 represents the weight (g) of the test piece before the test, and W 2 represents the weight (g) of the test piece after the test. [Hardness] According to JIS K 6301, a spring type hardness tester A type was used.
【００２４】また、本発明における炭素数１０のアルコ
ールの組成分析はキャピラリーガスクロ分析で行った。
このガスクロ分析条件を示す。 分析機：ＧＣ−１４Ａ（島津製作所製） カラム名：キャピラリー Ｇ−１００（化学品検査協会
製） カラム詳細：長さ４０ｍ、内径１．２ｍｍ、膜厚１μｍ 検出器：ＦＩＤ カラム温度：１１０℃ 注入口温度：２００℃ 検出器温度：２００℃ キャリア：ヘリウムガス ２０ｍｌ／ｍｉｎ 計算法：内部標準法 内部標準用試料：４−ヘプタノン（チッソ（株）製：Ｃ
Ｓ−７）The composition analysis of the alcohol having 10 carbon atoms in the present invention was carried out by capillary gas chromatography analysis.
The gas chromatography analysis conditions are shown below. Analyzer: GC-14A (manufactured by Shimadzu Corporation) Column name: Capillary G-100 (manufactured by Chemicals Inspection Association) Column details: Length 40 m, inner diameter 1.2 mm, film thickness 1 μm Detector: FID Column temperature: 110 ° C Note Inlet temperature: 200 ° C. Detector temperature: 200 ° C. Carrier: Helium gas 20 ml / min Calculation method: Internal standard method Sample for internal standard: 4-heptanone (manufactured by Chisso Corporation: C
S-7)
【００２５】なお、以下の比較例におけるフタル酸ジオ
クチル（ＤＯＰ）はチッソ株式会社製造の製品、フタル
酸ジイソノニル（ＤＩＮＰ）、フタル酸ジイソデシル
（ＤＩＤＰ）は積水化学株式会社の製品を使用した。Dioctyl phthalate (DOP) used in the following comparative examples was a product manufactured by Chisso Corporation, and diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP) were products manufactured by Sekisui Chemical Co., Ltd.
【００２６】実施例１ ２ＰＨＯを９４．５重量％、４ＭＰＨＯを５．１重量
％、５ＭＰＨＯを０．２５重量％、ＭＥＨＯを０．１１
重量％およびＩＰＨＯを０．０２９重量％を含む混合ア
ルコール（１）は以下の方法で製造した。Example 1 94.5% by weight of 2PHO, 5.1% by weight of 4MPHO, 0.25% by weight of 5MPHO and 0.11 of MEHO
A mixed alcohol (1) containing 1% by weight and 0.029% by weight of IPHO was produced by the following method.
【００２７】（１）ヒドロホルミル化反応 溶媒の２，２，４−トリメチル−１，３−ペンタンジオ
ールモノイソブチレートに、ロジウムジカルボニルアセ
チルアセトネ−ト（金属ロジウムとして約２５０ｐｐｍ
になる量）および下記化１で示されるビスホスファイト
配位子（ロジウム１モル当量当たり約８，５モル当量、
溶液中約２重量％）を溶解した溶液２０ミリリットルを
窒素置換したガラス反応装置に入れ、下記の条件でヒド
ロホルミル化反応を行った。(1) Hydroformylation reaction Rhodium dicarbonyl acetylacetonate (about 250 ppm as metal rhodium) was added to 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as a solvent.
And a bisphosphite ligand represented by the following chemical formula 1 (about 8.5 molar equivalents per 1 molar equivalent of rhodium,
Twenty milliliters of a solution in which about 2% by weight of the solution) was placed in a glass reactor replaced with nitrogen, and a hydroformylation reaction was carried out under the following conditions.
【化１】 [Chemical 1]
【００２８】原料オレフィンガスは以下の組成のスペン
トスペントＢＢ留分を使用した。 １−ブテン ４７重量％ シス−２−ブテン ２０重量％ トランス−２−ブテン １５重量％ イソブテン ０．３重量％ ブタン １３重量％ イソブタン １重量％ 全ガス圧約１１Ｋｇ／ｃｍ2Ｇ、水素、一酸化炭素及び
１−ブテンの分圧はそれぞれ４．４Ｋｇ／ｃｍ2Ａ、
２．１Ｋｇ／ｃｍ2Ａ及び０．２１Ｋｇ／ｃｍ2Ａ、残り
は窒素及びアルデヒドにおいて実施した。供給ガス（一
酸化炭素、水素、１−ブテン、窒素）の流量を個々に流
量計で調節し、反応温度は７１℃で行った。生成したＣ
５アルデヒドをキャピラリーガスクロマトグラフィーに
よって分析した結果、ｎ−バレルアルデヒド（以下、ｎ
ＶＬＡという）と２−メチルブチルアルデヒド（以下、
２ＭＢＡという）と３−メチルブチルアルデヒド（以
下、３ＭＢＡという）との生成比は１８．２：１：０．
０２９であった。なお、ピバルアルデヒド（以下、ＰＶ
Ａという）は確認されなかった。As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 47% by weight cis-2-butene 20% by weight trans-2-butene 15% by weight isobutene 0.3% by weight butane 13% by weight isobutane 1% by weight Total gas pressure about 11 kg / cm 2 G, hydrogen, carbon monoxide And the partial pressure of 1-butene is 4.4 Kg / cm 2 A, respectively.
2.1 Kg / cm 2 A and 0.21 Kg / cm 2 A, the rest was carried out in nitrogen and aldehyde. The flow rates of the feed gases (carbon monoxide, hydrogen, 1-butene, nitrogen) were individually adjusted with a flow meter, and the reaction temperature was 71 ° C. Generated C
As a result of analyzing 5 aldehydes by capillary gas chromatography, n-valeraldehyde (hereinafter, n
VLA and 2-methylbutyraldehyde (hereinafter,
2MBA) and 3-methylbutyraldehyde (hereinafter, referred to as 3MBA) production ratio is 18.2: 1: 0.
It was 029. In addition, pivalaldehyde (hereinafter, PV
(A) was not confirmed.
【００２９】（２）アルドール縮合反応 磁気式攪拌機、ジムロート型凝縮器、熱電対温度計及び
滴下装置を装着した２リットル四つ口フラスコに（１）
で得られたＣ５アルデヒド溶液（ｎＶＬＡ：９４．６重
量％、２ＭＢＡ：５．２重量％、３ＭＢＡ：０．２重量
％）３５１．１ｇを仕込み攪拌した。１．２５重量％Ｎ
ａＯＨ水溶液３５５．６ｇを調製し、これをフラスコ中
に２５℃にて滴下した。６０分後に滴下を終了し、この
時の系内温度は６０℃であった。この後加熱を開始し、
８５℃に達してから４時間そのまま攪拌を続けた。次
に、室温まで冷却した後攪拌を止め、油水分離し２９
２．０ｇ（水分０．５３重量％）の油層を得た。(2) Aldol condensation reaction In a 2-liter four-necked flask equipped with a magnetic stirrer, Dimroth condenser, thermocouple thermometer and dropping device (1)
351.1 g of the C5 aldehyde solution (nVLA: 94.6% by weight, 2MBA: 5.2% by weight, 3MBA: 0.2% by weight) obtained in the above was charged and stirred. 1.25 wt% N
355.6 g of an aOH aqueous solution was prepared, and this was added dropwise to the flask at 25 ° C. The dropping was completed after 60 minutes, and the temperature in the system at this time was 60 ° C. After this start heating,
After reaching 85 ° C., the stirring was continued for 4 hours. Next, after cooling to room temperature, stirring was stopped, oil and water were separated, and 29
An oil layer of 2.0 g (water content 0.53% by weight) was obtained.
【００３０】（３）水素添加反応 磁気式攪拌機、水素調圧器及び熱電対温度計を装着した
３リットルステンレススチールオートクレーブに窒素雰
囲気下、（２）と同様に調製したアルドール縮合液の油
層１６０２．５ｇ及び触媒としてラネーニッケル８０．
４ｇを仕込んだ。系内を水素で３回置換した後、水素圧
力を５０Ｋｇ／ｃｍ2Ｇに設定し、５００ｒｐｍで攪拌
した。それと同時に、電気炉を加熱し昇温を開始したと
ころ、系内温度が９５℃付近から水素吸収が始まり、そ
の後３．５時間水素吸収が継続した（その間の最高到達
温度は１６５℃であった）。水素吸収が停止してから更
に２時間、１３０から１４８℃で攪拌を続けた後加熱を
停止した。(3) Hydrogenation reaction In a 3 liter stainless steel autoclave equipped with a magnetic stirrer, hydrogen pressure regulator and thermocouple thermometer, under nitrogen atmosphere, 1602.5 g of an oil layer of an aldol condensation liquid prepared in the same manner as in (2). And Raney nickel 80.
4g was charged. After the system was replaced with hydrogen three times, the hydrogen pressure was set to 50 Kg / cm 2 G and the mixture was stirred at 500 rpm. At the same time, when the electric furnace was heated and the temperature started to rise, hydrogen absorption started at a system temperature of around 95 ° C and continued for 3.5 hours thereafter (the maximum temperature reached during that time was 165 ° C). ). After the hydrogen absorption was stopped, the stirring was continued at 130 to 148 ° C. for another 2 hours, and then the heating was stopped.
【００３１】一晩放置後、メンブランフィルターを用い
て触媒を濾別したところ、１６１６．３ｇの油層を得
た。この油層を減圧にて単蒸留を行い、高沸分を取り除
いた。留出分キャピラリーガスクロマトグラフィーにて
分析した結果、以下の組成の混合デカノ−ル（１）であ
ることがわかった。 ２ＰＨＯ ９４．５重量％ ４ＭＰＨＯ ５．１重量％ ５ＭＰＨＯ ０．２５重量％ ＭＥＨＯ ０．１１重量％ ＩＰＨＯ ０．０２９重量％After standing overnight, the catalyst was filtered off with a membrane filter to obtain an oil layer of 1616.3 g. This oil layer was subjected to simple distillation under reduced pressure to remove high boiling components. As a result of analysis by distillate capillary gas chromatography, it was found to be a mixed decanol (1) having the following composition. 2PHO 94.5% by weight 4MPHO 5.1% by weight 5MPHO 0.25% by weight MEHO 0.11% by weight IPHO 0.029% by weight
【００３２】さらに、該混合デカノ−ル（１）を使用し
て、フタレート可塑剤（エステル化）の製造及び物性評
価のための軟質塩化ビニル製シートの製造は次の方法で
行った。 （４）エステル化反応 ３００リットルＳＵＳ反応器に、原料として無水フタル
酸６２ｋｇ及び上記の混合アルコ−ル（１）１６３ｋｇ
を窒素雰囲気下仕込んだ。この溶液を攪拌しながら加熱
し反応液温度が６０℃になったところで触媒であるテト
ライソプロポキシチタンの２５重量％デカノール溶液１
０５１ｇを加えた後、さらに２２０℃まで昇温した。生
成水は反応器に取り付けた油水分離器を用いて系外に除
去し、未反応アルコールは系内に戻した。反応液温度が
２２０℃に到達してから１時間毎にサンプリングを実施
し、酸価が０．３以下になったところ（約５時間後）で
加熱を停止し、通常の中和、水洗、減圧蒸留及び後処理
操作を経た後、目的物である混合フタレート（以下、Ｄ
ＸＰ−１という。）１７４．６ｋｇを得た。この時の酸
価は０．０２２、残アルコール分は１００ｐｐｍ以下、
水分０．０５重量％であった。Further, using the mixed decanol (1), a phthalate plasticizer (esterification) was produced and a soft vinyl chloride sheet for physical property evaluation was produced by the following method. (4) Esterification reaction In a 300-liter SUS reactor, 62 kg of phthalic anhydride as a raw material and 163 kg of the above-mentioned mixed alcohol (1)
Was charged under a nitrogen atmosphere. This solution was heated with stirring, and when the temperature of the reaction solution reached 60 ° C., a 25 wt% decanol solution of tetraisopropoxytitanium as a catalyst 1
After adding 051 g, the temperature was further raised to 220 ° C. The produced water was removed to the outside of the system using an oil-water separator attached to the reactor, and the unreacted alcohol was returned to the inside of the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C., heating was stopped when the acid value became 0.3 or less (after about 5 hours), normal neutralization, washing with water, After the distillation under reduced pressure and the post-treatment operation, mixed phthalate (hereinafter referred to as D
It is called XP-1. ) 174.6 kg was obtained. At this time, the acid value is 0.022, the residual alcohol content is 100 ppm or less,
The water content was 0.05% by weight.
【００３３】（５）シート化 平均重合度１０３０のポリ塩化ビニル（チッソ（株）；
ＳＬ）１００重量部に対し、ＤＸＰ−１を５０重量部、
三塩基性硫酸鉛を４重量部、ステアリン酸鉛を１重量部
配合し、これを１７５℃の試験ロールにて５分間混練
し、厚さ１．３ｍｍのシートを作成した。更に、これを
１８５℃にて２分間予熱した後、３分間１５０ｋｇ／ｃ
ｍ2の圧力にて加圧し厚さ１ｍｍのシートを作成し、こ
れを用いて引っ張り試験、加熱重量変化率、耐油性試験
重量変化率、耐水性試験重量変化率、柔軟温度、硬さの
測定を行った。(5) Sheeting Polyvinyl chloride having an average degree of polymerization of 1030 (Chisso Corporation;
SL) 100 parts by weight, DXP-1 50 parts by weight,
4 parts by weight of tribasic lead sulfate and 1 part by weight of lead stearate were mixed and kneaded with a test roll at 175 ° C. for 5 minutes to prepare a sheet having a thickness of 1.3 mm. Furthermore, after preheating this at 185 ° C. for 2 minutes, 150 kg / c for 3 minutes
A sheet with a thickness of 1 mm is prepared by pressurizing at a pressure of m 2 and using this, tensile test, heating weight change rate, oil resistance test weight change rate, water resistance test weight change rate, flexible temperature, hardness measurement I went.
【００３４】平均重合度１０３０のポリ塩化ビニル（チ
ッソ（株）；ＳＬ）１００重量部に対し、ＤＸＰ−１を
５０重量部、クレーを１５重量部、三塩基性硫酸鉛を４
重量部配合し、これを１６５℃の試験ロールにて５分間
混練し、厚さ１．３ｍｍのシートを作成した。更に、こ
れを１７０℃にて３分間予熱した後、２分間１５０ｋｇ
／ｃｍ2の圧力にて加圧し厚さ１ｍｍのシートを作成
し、これを用いて体積固有抵抗の測定を行った。これら
の結果を表−１に示す。50 parts by weight of DXP-1, 15 parts by weight of clay and 4 parts by weight of tribasic lead sulfate per 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1030 (Chisso Corporation; SL).
Parts by weight were blended, and this was kneaded with a test roll at 165 ° C. for 5 minutes to prepare a sheet having a thickness of 1.3 mm. Furthermore, after preheating this at 170 ° C for 3 minutes, 150 kg for 2 minutes
A sheet having a thickness of 1 mm was prepared by pressurizing at a pressure of / cm 2 , and the volume resistivity was measured using the sheet. The results are shown in Table-1.
【００３５】実施例２ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ４２重量％ シス−２−ブテン ２２重量％ トランス−２−ブテン １８重量％ イソブテン １重量％ ブタン １４重量％ イソブタン １重量％ 上記組成の原料オレフィンガスを用いる以外は実施例１
の（１）に準拠してヒドロホルミル化反応を行った。そ
の結果、生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと
３ＭＢＡの生成比が１７．３：１：０．２０であること
がわかった。なお、ＰＶＡは確認されなかった。Example 2 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 42% by weight cis-2-butene 22% by weight trans-2-butene 18% by weight isobutene 1% by weight butane 14% by weight isobutane 1% by weight Example 1 except that a raw material olefin gas having the above composition was used
The hydroformylation reaction was performed according to (1). As a result, it was found that the production ratio of nVLA, 2MBA and 3MBA in the produced C5 aldehyde was 17.3: 1: 0.20. No PVA was confirmed.
【００３６】アルドール縮合は、実施例１の（２）に準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：９３．５重量
％、２ＭＢＡ：５．４重量％、３ＭＢＡ：１．１重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。生成した混合デカノール
（２）をキャピラリーガスクロマトグラフィーにて分析
した結果、以下の組成であった。 ２ＰＨＯ ９３．２重量％ ４ＭＰＨＯ ５．６重量％ ５ＭＰＨＯ ０．９４重量％ ＭＥＨＯ ０．１３重量％ ＩＰＨＯ ０．１０重量％ 該混合デカノ−ル（２）１６３ｋｇを使用した以外は、
実施例１の（４）に準拠してエステル化反応を行い、１
７３．３ｋｇの目的物（以下ＤＸＰ−２という）を得
た。実施例１の（５）に準拠して得たシートの諸物性測
定結果を表−１に示す。The aldol condensation was carried out using a C5 aldehyde solution (nVLA: 93.5% by weight, 2MBA: 5.4% by weight, 3MBA: 1.1% by weight) according to Example 1 (2). The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (2) by capillary gas chromatography, the following composition was obtained. 2PHO 93.2 wt% 4MPHO 5.6 wt% 5MPHO 0.94 wt% MEHO 0.13 wt% IPHO 0.10 wt% except that 163 kg of the mixed decanol (2) was used.
The esterification reaction is carried out according to (4) of Example 1 and
73.3 kg of the desired product (hereinafter referred to as DXP-2) was obtained. Table 1 shows the results of measuring the physical properties of the sheet obtained in accordance with (5) of Example 1.
【００３７】実施例３ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ４０重量％ シス−２−ブテン ２０重量％ トランス−２−ブテン １７重量％ イソブテン ２重量％ ブタン １４重量％ イソブタン １重量％ 上記組成の原料オレフィンガスを使用する以外は実施例
１の（１）に準拠してヒドロホルミル化を行った。生成
Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと３ＭＢＡの生
成比が１７．４：１：０．４３であることがわかった。
なお、ＰＶＡは確認されなかった。Example 3 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 40% by weight cis-2-butene 20% by weight trans-2-butene 17% by weight isobutene 2% by weight butane 14% by weight isobutane 1% by weight In the same manner as in Example 1 except that the raw material olefin gas having the above composition was used ( Hydroformylation was performed according to 1). It was found that the production ratio of nVLA, 2MBA and 3MBA in the produced C5 aldehyde was 17.4: 1: 0.43.
No PVA was confirmed.
【００３８】アルドール縮合は、実施例１の（２）に準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：９２．３重量
％、２ＭＢＡ：５．３重量％、３ＭＢＡ：２．３重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。生成した混合デカノール
（３）をキャピラリーガスクロマトグラフィーにて分析
した結果、以下の組成であった。 ２ＰＨＯ ８９．８重量％ ４ＭＰＨＯ ５．５重量％ ５ＭＰＨＯ ４．１重量％ ＭＥＨＯ ０．１２重量％ ＩＰＨＯ ０．４６重量％ 該混合デカノ−ル（３）１６３ｋｇを使用した以外は、
実施例１の（４）に準拠してエステル化反応を行い、１
７３．６ｋｇの目的物（以下ＤＸＰ−３という）を得
た。また、実施例１の（５）に準拠して得たシートの諸
物性測定結果を表−１に示す。The aldol condensation was carried out using a C5 aldehyde solution (nVLA: 92.3% by weight, 2MBA: 5.3% by weight, 3MBA: 2.3% by weight) in accordance with Example 1 (2). The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (3) by capillary gas chromatography, the following composition was obtained. 2PHO 89.8% by weight 4MPHO 5.5% by weight 5MPHO 4.1% by weight MEHO 0.12% by weight IPHO 0.46% by weight Except that 163 kg of the mixed decanol (3) was used,
The esterification reaction is carried out according to (4) of Example 1 and
73.6 kg of the desired product (hereinafter referred to as DXP-3) was obtained. In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００３９】実施例４ 配位子として下記化２で示されるビスホスファイト化合
物（配位子とロジウムのモル比は９．２）を使用した以
外は実施例１の（１）に準拠してヒドロホルミル化反応
を行った。Example 4 In accordance with (1) of Example 1 except that the bisphosphite compound represented by the following chemical formula 2 was used as the ligand (the molar ratio of the ligand and rhodium was 9.2). A hydroformylation reaction was performed.
【化２】 生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと３ＭＢＡ
の生成比が９．７：１：０．０３２であることがわかっ
た。なお、ＰＶＡは確認されなかった。[Chemical 2] NVLA, 2MBA and 3MBA in the produced C5 aldehyde
Was found to be 9.7: 1: 0.032. No PVA was confirmed.
【００４０】アルドール縮合は、実施例１の（２）と準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：９０．３重量
％、２ＭＢＡ：９．３重量％、３ＭＢＡ：０．３重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。生成した混合デカノール
（４）をキャピラリーガスクロマトグラフィーにて分析
した結果、以下の組成であった。 ２ＰＨＯ ８９．６重量％ ４ＭＰＨＯ ９．９重量％ ５ＭＰＨＯ ０．２６重量％ ＭＥＨＯ ０．１８重量％ ＩＰＨＯ ０．０３７重量％ 該混合デカノ−ル（４）１６３ｋｇを使用した以外は、
実施例１の（４）に準拠してエステル化反応を行い、１
７３．４ｋｇの目的物（以下ＤＸＰ−４という）を得
た。また、実施例１の（５）に準拠して得たシートの諸
物性測定結果を表−１に示す。The aldol condensation was carried out by using a C5 aldehyde solution (nVLA: 90.3% by weight, 2MBA: 9.3% by weight, 3MBA: 0.3% by weight) according to Example 1 (2). The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (4) by capillary gas chromatography, the following composition was obtained. 2PHO 89.6% by weight 4MPHO 9.9% by weight 5MPHO 0.26% by weight MEHO 0.18% by weight IPHO 0.037% by weight Other than using 163 kg of the mixed decanol (4),
The esterification reaction is carried out according to (4) of Example 1 and
73.4 kg of the desired product (hereinafter referred to as DXP-4) was obtained. In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００４１】実施例５ 配位子として下記化３で示されるビスホスファイト化合
物（配位子とロジウムのモル比は４．１）を使用した以
外は実施例１の（１）に準拠してヒドロホルミル化反応
を行った。Example 5 In accordance with (1) of Example 1 except that the bisphosphite compound represented by the following chemical formula 3 (the molar ratio of the ligand and rhodium was 4.1) was used as the ligand. A hydroformylation reaction was performed.
【化３】 生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと３ＭＢＡ
の生成比が５．４：１：０．０１９であることがわかっ
た。なお、ＰＶＡは確認されなかった。[Chemical 3] NVLA, 2MBA and 3MBA in the produced C5 aldehyde
Was found to be 5.4: 1: 0.019. No PVA was confirmed.
【００４２】アルドール縮合は、実施例１の（２）と準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：８４．１重量
％、２ＭＢＡ：１５．５重量％、３ＭＢＡ：０．３重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。生成した混合デカノール
（５）をキャピラリーガスクロマトグラフィーにて分析
した結果、以下の組成であった。 ２ＰＨＯ ８４．６重量％ ４ＭＰＨＯ １４．８重量％ ５ＭＰＨＯ ０．３８重量％ ＭＥＨＯ ０．１６重量％ ＩＰＨＯ ０．０３９重量％ 該混合デカノ−ル（５）１６３ｋｇを使用した以外は、
実施例１の（４）に準拠してエステル化反応を行い、１
７３．２ｋｇの目的物（以下ＤＸＰ−５という）を得
た。また、実施例１の（５）に準拠して得たシートの諸
物性測定結果を表−１に示す。The aldol condensation is carried out by using a C5 aldehyde solution (nVLA: 84.1% by weight, 2MBA: 15.5% by weight, 3MBA: 0.3% by weight) in accordance with (2) of Example 1. The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (5) by capillary gas chromatography, the following composition was obtained. 2PHO 84.6% by weight 4MPHO 14.8% by weight 5MPHO 0.38% by weight MEHO 0.16% by weight IPHO 0.039% by weight except that 163 kg of the mixed decanol (5) was used.
The esterification reaction is carried out according to (4) of Example 1 and
73.2 kg of the desired product (hereinafter referred to as DXP-5) was obtained. In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００４３】実施例６ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ３５重量％ シス−２−ブテン ２３重量％ トランス−２−ブテン １９重量％ イソブテン ０．１重量％ ブタン １３重量％ イソブタン ２重量％ 上記組成の原料オレフィンガスを使用する以外は実施例
１の（１）に準拠してヒドロホルミル化反応を行った。
生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと３ＭＢＡ
の生成比が５．１：１：０．０９０であることがわかっ
た。なお、ＰＶＡは確認されなかった。Example 6 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 35% by weight cis-2-butene 23% by weight trans-2-butene 19% by weight isobutene 0.1% by weight butane 13% by weight isobutane 2% by weight Example 1 except that the raw material olefin gas having the above composition is used The hydroformylation reaction was performed according to (1).
NVLA, 2MBA and 3MBA in the produced C5 aldehyde
Was found to be 5.1: 1: 0.090. No PVA was confirmed.
【００４４】アルドール縮合は、実施例１の（２）に準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：８３．３重量
％、２ＭＢＡ：１６．５重量％、３ＭＢＡ：０．２重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。生成した混合デカノール
（６）をキャピラリーガスクロマトグラフィーにて分析
した結果、以下の組成であった。 ２ＰＨＯ ８２．２重量％ ４ＭＰＨＯ １６．９重量％ ５ＭＰＨＯ ０．２８重量％ ＭＥＨＯ ０．４９重量％ ＩＰＨＯ ０．０２１重量％ 該混合デカノ−ル（６）１６３ｋｇを使用した以外は、
実施例１の（４）に準拠してエステル化反応を行い、１
７３．５ｋｇの目的物（以下ＤＸＰ−６という）を得
た。また、実施例１の（５）に準拠して得たシートの諸
物性測定結果を表−１に示す。The aldol condensation was carried out by using a C5 aldehyde solution (nVLA: 83.3% by weight, 2MBA: 16.5% by weight, 3MBA: 0.2% by weight) in accordance with (2) of Example 1. The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (6) by capillary gas chromatography, the following composition was obtained. 2PHO 82.2 wt% 4MPHO 16.9 wt% 5MPHO 0.28 wt% MEHO 0.49 wt% IPHO 0.021 wt% except that 163 kg of the mixed decanol (6) was used.
The esterification reaction is carried out according to (4) of Example 1 and
73.5 kg of the desired product (hereinafter referred to as DXP-6) was obtained. In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００４５】実施例７ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ４７重量％ シス−２−ブテン ２０重量％ トランス−２−ブテン １５重量％ イソブテン ０．３重量％ ブタン １３重量％ イソブタン １重量％ 上記組成の原料オレフィンガスを使用し、配位子は実施
例５で用いたビスホスファイト化合物を使用した以外は
実施例１の（１）に準拠してヒドロホルミル化反応を行
った。生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと３
ＭＢＡの生成比が５．４：１：０．０１９であることが
わかった。なお、ＰＶＡは確認されなかった。Example 7 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 47% by weight cis-2-butene 20% by weight trans-2-butene 15% by weight isobutene 0.3% by weight butane 13% by weight isobutane 1% by weight The raw material olefin gas having the above composition is used, and the ligand is A hydroformylation reaction was carried out in the same manner as in Example 1 (1) except that the bisphosphite compound used in Example 5 was used. NVLA, 2MBA and 3 in the produced C5 aldehyde
It was found that the production ratio of MBA was 5.4: 1: 0.019. No PVA was confirmed.
【００４６】アルドール縮合は、実施例１の（２）と準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：８４．１重量
％、２ＭＢＡ：１５．５重量％、３ＭＢＡ：０．３重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。生成した混合デカノール
（７）をキャピラリーガスクロマトグラフィーにて分析
した結果、以下の組成であった。 ２ＰＨＯ ８４．６重量％ ４ＭＰＨＯ １４．８重量％ ５ＭＰＨＯ ０．３８重量％ ＭＥＨＯ ０．１６重量％ ＩＰＨＯ ０．０３９重量％ 該混合デカノ−ル（７）１６３ｋｇを使用した以外は、
実施例１の（４）に準拠してエステル化反応を行い、１
７３．２ｋｇの目的物（以下ＤＸＰ−７という）を得
た。また、実施例１の（５）に準拠して得たシートの諸
物性測定結果を表−１に示す。The aldol condensation was carried out using a C5 aldehyde solution (nVLA: 84.1% by weight, 2MBA: 15.5% by weight, 3MBA: 0.3% by weight) in accordance with the procedure (2) of Example 1. The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (7) by capillary gas chromatography, the following composition was obtained. 2PHO 84.6% by weight 4MPHO 14.8% by weight 5MPHO 0.38% by weight MEHO 0.16% by weight IPHO 0.039% by weight Except that 163 kg of the mixed decanol (7) was used,
The esterification reaction is carried out according to (4) of Example 1 and
73.2 kg of the desired product (hereinafter referred to as DXP-7) was obtained. In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００４７】実施例８ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ４７重量％ シス−２−ブテン ２０重量％ トランス−２−ブテン １５重量％ イソブテン ０．０１重量％以
下 ブタン １２重量％ イソブタン １重量％ 上記組成の原料オレフィンガスを使用する以外は実施例
１の（１）に準拠してヒドロホルミル化反応を行った。
生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡの生成比が
１９．０：１であることがわかった。なお、３ＭＢＡと
ＰＶＡは確認されなかった。Example 8 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 47% by weight cis-2-butene 20% by weight trans-2-butene 15% by weight Isobutene 0.01% by weight or less Butane 12% by weight Isobutane 1% by weight Examples other than using the raw material olefin gas having the above composition The hydroformylation reaction was performed according to (1) of 1.
It was found that the production ratio of nVLA and 2MBA in the produced C5 aldehyde was 19.0: 1. In addition, 3MBA and PVA were not confirmed.
【００４８】アルドール縮合は、実施例１の（２）に準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：９５．０重量
％、２ＭＢＡ：５．０重量％）を用いて行い、水素添加
反応及び減圧蒸留は実施例１の（３）に準拠して行っ
た。 生成した混合デカノール（８）をキャピラリーガ
スクロマトグラフィーにて分析した結果、以下の組成で
あった。 ２ＰＨＯ ９４．６重量％ ４ＭＰＨＯ ５．３重量％ ＭＥＨＯ ０．１０重量％ 該混合デカノ−ル（８）１６３ｋｇを使用した以外は、
実施例１の（４）に準拠してエステル化反応を行い、１
７３．３ｋｇの目的物（以下ＤＸＰ−８という）を得
た。また、実施例１の（５）に準拠して得たシートの諸
物性測定結果を表−１に示す。Aldol condensation was carried out using a C5 aldehyde solution (nVLA: 95.0% by weight, 2MBA: 5.0% by weight) in accordance with Example 1 (2), and hydrogenation reaction and vacuum distillation were carried out. It carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (8) by capillary gas chromatography, the following composition was obtained. 2PHO 94.6% by weight 4MPHO 5.3% by weight MEHO 0.10% by weight, except that 163 kg of the mixed decanol (8) was used.
The esterification reaction is carried out according to (4) of Example 1 and
73.3 kg of the desired product (hereinafter referred to as DXP-8) was obtained. In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００４９】実施例９ ＤＸＰ−１、５０重量部をＤＸＰ−１、７０重量部に変
更した以外は、実施例１の（５）に準拠して、シートを
作成し、シート物性を評価した。諸物性測定結果を表−
１に示す。Example 9 A sheet was prepared in accordance with (5) of Example 1 except that 50 parts by weight of DXP-1 was changed to 70 parts by weight of DXP-1, and the physical properties of the sheet were evaluated. Table of measurement results of various physical properties
Shown in 1.
【００５０】実施例１０ ＤＸＰ−１、５０重量部をＤＸＰ−１、１００重量部に
変更した以外は、実施例１の（５）に準拠して、シート
を作成し、シート物性を評価した。諸物性測定結果を表
−１に示す。Example 10 A sheet was prepared and the physical properties of the sheet were evaluated in accordance with (5) of Example 1 except that 50 parts by weight of DXP-1 was changed to 100 parts by weight of DXP-1. The results of measuring various physical properties are shown in Table 1.
【００５１】比較例１ 実施例８に準拠して調製した水素添加反応後の油層を２
５段オルダーショウ蒸留装置を用いて減圧蒸留した。た
だし、塔頂温が１０４．３℃／１５ｍｍＨｇから１０６
℃／１７ｍｍＨｇの留出分であった。これをキャピラリ
ーガスクロマトグラフィーにて分析した結果、２ＰＨＯ
として９８．１重量％、ＭＰＨＯとして１．１重量％、
ＭＥＨＯとして０．６２重量％を含む混合デカノ−ル
（９）であることがわかった。該混合デカノール（９）
１６３ｋｇを使用した以外は、実施例１の（４）に準拠
してエステル化反応を行い、１７２．９ｋｇの目的物
（以下ＤＸＰ−９という）を得た。また、該ＤＸＰ−９
を用いて実施例１の（５）に準拠してシ−トを作成し、
得られたシートの諸物性測定結果を表−１に示す。Comparative Example 1 Two oil layers were prepared according to Example 8 after the hydrogenation reaction.
Vacuum distillation was carried out using a 5-stage Oldershaw distillation apparatus. However, the tower top temperature is 104.3 ° C / 15 mmHg to 106
It was a distillate fraction of ° C / 17 mmHg. As a result of analyzing this by capillary gas chromatography, 2PHO
As 98.1% by weight, as MPHO 1.1% by weight,
It was found to be a mixed decanol (9) containing 0.62% by weight as MEHO. The mixed decanol (9)
The esterification reaction was performed according to (4) of Example 1 except that 163 kg was used to obtain 172.9 kg of the target product (hereinafter referred to as DXP-9). Also, the DXP-9
Is used to prepare a sheet in accordance with (5) of Example 1,
Table 1 shows the results of measuring various physical properties of the obtained sheet.
【００５２】比較例２ ロジウムジカルボニルアセチルアセトネート、ビスホス
ファイト配位子（配位子とロジウムとのモル比は８．
６）及び溶媒としてのバレルアルデヒド三量体からなる
溶液約１５ミリリットル（約１４ｇ、ロジウムが該溶液
中２５０ｐｐｍ、ビスホスファイト配位子が該溶液中２
重量％）を磁気攪拌式１００ミリリットルの窒素置換し
たステンレス製反応装置に仕込み、７０℃に加熱した。
この反応装置を０．３５Ｋｇ／ｃｍ2Ｇの減圧にし、１
−ブテン２５ミリリットル（２５Ｋｇ／ｃｍ2Ａ）を導
入した。次に、一酸化炭素及び水素｛全圧７Ｋｇ／ｃｍ
2Ａ、ＣＯ（モル）：Ｈ2（モル）＝１：２｝を導入し、
１−ブテンのヒドロホルミル化反応を行った。生成した
Ｃ５アルデヒドをキャピラリーガスクロマトグラフィー
によって分析した結果、ｎＶＬＡと２ＭＢＡとの生成比
は５０．５：１であった。次いで、得られたアルデヒド
混合物を用いて実施例１の（２）に準拠してアルドール
縮合し、実施例１の（３）に準拠して水素添加反応を行
った後の油層を２５段オルダーショウ蒸留装置を用いて
減圧蒸留した。ただし、塔頂温が１１２℃から１１３℃
／２０ｍｍＨｇの留出分であった。これをキャピラリー
ガスクロマトグラフィーにて分析した結果、２ＰＨＯと
して９９．７重量％、ＭＰＨＯとして０．２重量％を含
む混合デカノ−ル（１０）であることがわかった。Comparative Example 2 Rhodium dicarbonyl acetylacetonate, bisphosphite ligand (molar ratio of ligand to rhodium is 8.
6) and valeraldehyde trimer as a solvent in about 15 ml of a solution (about 14 g, rhodium 250 ppm in the solution, bisphosphite ligand 2 in the solution).
% By weight) was charged in a magnetic stirring type 100 ml stainless steel reactor substituted with nitrogen and heated to 70 ° C.
The reactor was evacuated to 0.35 Kg / cm 2 G and 1
25 ml of butene (25 Kg / cm 2 A) were introduced. Next, carbon monoxide and hydrogen (total pressure 7 Kg / cm
2 A, CO (mol): H 2 (mol) = 1: 2} is introduced,
A hydroformylation reaction of 1-butene was performed. As a result of analyzing the produced C5 aldehyde by capillary gas chromatography, the production ratio of nVLA and 2MBA was 50.5: 1. Then, the obtained aldehyde mixture was subjected to aldol condensation according to Example 1 (2), and the oil layer after hydrogenation reaction according to Example 1 (3) was subjected to 25-stage Oldershaw distillation. It was distilled under reduced pressure using an apparatus. However, the tower top temperature is 112 ° C to 113 ° C
It was a distillate of / 20 mmHg. As a result of analysis by capillary gas chromatography, it was found to be a mixed decanol (10) containing 99.7% by weight of 2PHO and 0.2% by weight of MPHO.
【００５３】該混合デカノ−ル（１０）１６３ｋｇを使
用した以外は、実施例１の（４）に準拠してエステル化
反応を行い、１７０．８ｋｇの目的物（以下、ＤＰＨＰ
という）を得た。また、該ＤＰＨＰを用いて実施例１の
（５）に準拠してシ−トを作成し、得られたシートの諸
物性測定結果を表−１に示す。The esterification reaction was carried out according to (4) of Example 1 except that 163 kg of the mixed decanol (10) was used, and 170.8 kg of the desired product (hereinafter referred to as DPHP) was used.
I got). Further, a sheet was prepared using the DPHP in accordance with (5) of Example 1, and the results of measuring the physical properties of the obtained sheet are shown in Table 1.
【００５４】比較例３ 溶媒のキシレンに、ロジウムジカルボニルアセチルアセ
トネ−ト（金属ロジウムとして約３００ｐｐｍになる
量）およびトリフェニルホスフィン（溶媒中３０重量
％）を溶解した溶液２０ミリリットルを窒素置換したガ
ラス反応装置に入れ、下記の条件でヒドロホルミル化反
応を行った。Comparative Example 3 20 ml of a solution prepared by dissolving rhodium dicarbonylacetylacetonate (amount of metal rhodium of about 300 ppm) and triphenylphosphine (30% by weight in a solvent) in xylene as a solvent was replaced with nitrogen. It was placed in a glass reactor and a hydroformylation reaction was carried out under the following conditions.
【００５５】原料オレフィンガスとして以下の組成のス
ペントスペントＢＢ留分を使用した。 １−ブテン ４５重量％ シス−２−ブテン １４重量％ トランス−２−ブテン １０重量％ イソブテン ４重量％ ブタン １４重量％ イソブタン １重量％ 全ガス圧約１１Ｋｇ／ｃｍ2Ｇ、水素、一酸化炭素及び
ＢＢ留分の分圧はそれぞれ４．４Ｋｇ／ｃｍ2Ａ、２．
１Ｋｇ／ｃｍ2Ａ及び０．２１Ｋｇ／ｃｍ2Ａ、残りは窒
素及びアルデヒドにおいて実施した。供給ガス（一酸化
炭素、水素、１−ブテン、窒素）の流量を個々に流量計
で調節し、反応温度は７１℃で行った。生成したＣ５ア
ルデヒドをキャピラリーガスクロマトグラフィーによっ
て分析した結果、ｎＶＬＡと２ＭＢＡと３ＭＢＡとＰＶ
Ａの生成比は２．２：１：０．０８３：０．１０であっ
た。As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 45% by weight cis-2-butene 14% by weight trans-2-butene 10% by weight isobutene 4% by weight butane 14% by weight isobutane 1% by weight Total gas pressure about 11 kg / cm 2 G, hydrogen, carbon monoxide and BB The partial pressures of the distillates are 4.4 kg / cm 2 A and 2.
1 kg / cm 2 A and 0.21Kg / cm 2 A, the rest were carried out in nitrogen and aldehyde. The flow rates of the feed gases (carbon monoxide, hydrogen, 1-butene, nitrogen) were individually adjusted with a flow meter, and the reaction temperature was 71 ° C. The generated C5 aldehyde was analyzed by capillary gas chromatography and found to be nVLA, 2MBA, 3MBA and PV
The production ratio of A was 2.2: 1: 0.083: 0.10.
【００５６】アルドール縮合、水素添加反応及び減圧蒸
留は実施例１の（２）、（３）に準拠して行った。生成
した混合デカノール（１１）をキャピラリーガスクロマ
トグラフィーにて分析した結果、以下の組成であること
がわかった。 ２ＰＨＯ ６１．６重量％ ４ＭＰＨＯ ２８．９重量％ ５ＭＰＨＯ ４．０重量％ ＭＥＨＯ ０．５９重量％ ＩＰＨＯ ０．３３重量％ ＤＭＰＰＯ ３．１重量％ ここで、ＤＭＰＰＯは４、４−ジメチル−２−プロピル
−１−ペンタノ−ル（以下、ＤＭＰＰＯという。）を示
す。該混合デカノール（１１）１６３ｋｇを使用した以
外は、実施例１の（４）に準拠してエステル化反応を行
い、１７６．０ｋｇの目的物（以下ＤＸＰ−１０とい
う）を得た。また、実施例１の（５）に準拠してシ−ト
を作成し、得られたシートの諸物性測定結果を表−１に
示す。The aldol condensation, hydrogenation reaction and vacuum distillation were carried out according to (2) and (3) of Example 1. As a result of analyzing the produced mixed decanol (11) by capillary gas chromatography, it was found to have the following composition. 2PHO 61.6 wt% 4MPHO 28.9 wt% 5MPHO 4.0 wt% MEHO 0.59 wt% IPHO 0.33 wt% DMPPO 3.1 wt% where DMPPO is 4,4-dimethyl-2-propyl -1-Pentanol (hereinafter referred to as DMPPO) is shown. The esterification reaction was carried out according to (4) of Example 1 except that 163 kg of the mixed decanol (11) was used to obtain 176.0 kg of the desired product (hereinafter referred to as DXP-10). In addition, a sheet was prepared in accordance with (5) of Example 1, and the results of measuring the physical properties of the obtained sheet are shown in Table-1.
【００５７】比較例４ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ５０重量％ シス−２−ブテン １１重量％ トランス−２−ブテン １０重量％ イソブテン １重量％ ブタン １４重量％ イソブタン １重量％ 原料オレフィンガスを上述の組成に変更して比較例６に
準拠してヒドロホルミル化反応を行った。生成したＣ５
アルデヒドをキャピラリーガスクロマトグラフィーによ
って分析した結果、ｎＶＬＡと２ＭＢＡと３ＭＢＡとピ
バルアルデヒドの生成比は５．１：１：０．０４５：
０．０６２であった。Comparative Example 4 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 50% by weight cis-2-butene 11% by weight trans-2-butene 10% by weight isobutene 1% by weight butane 14% by weight isobutane 1% by weight Based on Comparative Example 6, the raw material olefin gas was changed to the above composition. Then, the hydroformylation reaction was carried out. Generated C5
As a result of analyzing the aldehyde by capillary gas chromatography, the production ratio of nVLA, 2MBA, 3MBA and pivalaldehyde was 5.1: 1: 0.045:
It was 0.062.
【００５８】アルドール縮合、水素添加反応及び減圧蒸
留は実施例１の（２）、（３）に準拠して行った。生成
した混合デカノール（１２）をキャピラリーガスクロマ
トグラフィーにて分析した結果、以下の組成であること
がわかった。 ２ＰＨＯ ７７．１重量％ ４ＭＰＨＯ １６．５重量％ ５ＭＰＨＯ ３．１重量％ ＭＥＨＯ ０．５０重量％ ＩＰＨＯ ０．３６重量％ ＤＭＰＰＯ １．７重量％ 該混合デカノール（１２）１６３ｋｇを使用した以外
は、実施例１の（４）に準拠してエステル化反応を行
い、１７６．０ｋｇの目的物（以下ＤＸＰ−１１とい
う）を得た。また、実施例１の（５）に準拠してシ−ト
を作成し、得られたシートの諸物性測定結果を表−１に
示す。The aldol condensation, hydrogenation reaction and vacuum distillation were carried out according to (2) and (3) of Example 1. As a result of analyzing the produced mixed decanol (12) by capillary gas chromatography, it was found that it had the following composition. 2PHO 77.1 wt% 4MPHO 16.5 wt% 5MPHO 3.1 wt% MEHO 0.50 wt% IPHO 0.36 wt% DMPPO 1.7 wt% Implemented except that 163 kg of the mixed decanol (12) was used. The esterification reaction was performed according to (4) of Example 1 to obtain 176.0 kg of the target product (hereinafter referred to as DXP-11). In addition, a sheet was prepared in accordance with (5) of Example 1, and the results of measuring the physical properties of the obtained sheet are shown in Table-1.
【００５９】比較例５ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ３０重量％ シス−２−ブテン ２３重量％ トランス−２−ブテン ２２重量％ イソブテン １重量％ ブタン １２重量％ イソブタン １重量％ 上記の組成の原料オレフィンガスを使用し、配位子は実
施例５で用いたビスホスファイト化合物を使用した以外
は実施例１の（１）に準拠してヒドロホルミル化反応を
行った。生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと
３ＭＢＡの生成比が４．７：１：０．１１であることが
わかった。なお、ＰＶＡは確認されなかった。Comparative Example 5 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 30% by weight cis-2-butene 23% by weight trans-2-butene 22% by weight isobutene 1% by weight butane 12% by weight isobutane 1% by weight Using the raw material olefin gas having the above composition, the ligand is used. The hydroformylation reaction was carried out in the same manner as in Example 1 (1) except that the bisphosphite compound used in Example 5 was used. It was found that the production ratio of nVLA, 2MBA and 3MBA in the produced C5 aldehyde was 4.7: 1: 0.11. No PVA was confirmed.
【００６０】アルドール縮合は、実施例１の（２）に準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：８１．０重量
％、２ＭＢＡ：１７．１重量％、３ＭＢＡ：１．８重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。生成した混合デカノール
（１３）をキャピラリーガスクロマトグラフィーにて分
析した結果、以下の組成であった。 ２ＰＨＯ ７７．８重量％ ４ＭＰＨＯ １７．０重量％ ５ＭＰＨＯ ３．２重量％ ＭＥＨＯ ０．５４重量％ ＩＰＨＯ ０．３８重量％ 該混合デカノ−ル（１３）１６３ｋｇを使用した以外
は、実施例１の（４）に準拠してエステル化反応を行
い、１７３．２ｋｇの目的物（以下ＤＸＰ−１２とい
う）を得た。また、実施例１の（５）に準拠して得たシ
ートの諸物性測定結果を表−１に示す。The aldol condensation was carried out using a C5 aldehyde solution (nVLA: 81.0% by weight, 2MBA: 17.1% by weight, 3MBA: 1.8% by weight) according to Example 1 (2). The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. As a result of analyzing the produced mixed decanol (13) by capillary gas chromatography, the following composition was obtained. 2PHO 77.8 wt% 4MPHO 17.0 wt% 5MPHO 3.2 wt% MEHO 0.54 wt% IPHO 0.38 wt% Except that 163 kg of the mixed decanol (13) was used ( The esterification reaction was carried out according to 4) to obtain 173.2 kg of the desired product (hereinafter referred to as DXP-12). In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００６１】比較例６ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ２７重量％ シス−２−ブテン ２４重量％ トランス−２−ブテン ２３重量％ イソブテン ０．１重量％ ブタン １２重量％ イソブタン １重量％ 上記の組成の原料オレフィンガスを使用し、配位子は実
施例５で用いたビスホスファイト化合物を使用した以外
は実施例１の（１）に準拠してヒドロホルミル化反応を
行った。生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと
３ＭＢＡの生成比が４．５：１：０．０１１であること
がわかった。なお、ＰＶＡは確認されなかった。Comparative Example 6 As a raw material olefin gas, a spent spent BB fraction having the following composition was used. 1-butene 27% by weight cis-2-butene 24% by weight trans-2-butene 23% by weight isobutene 0.1% by weight butane 12% by weight isobutane 1% by weight A raw material olefin gas having the above composition is used to prepare a ligand. Was subjected to the hydroformylation reaction according to Example 1 (1) except that the bisphosphite compound used in Example 5 was used. It was found that the production ratio of nVLA, 2MBA and 3MBA in the produced C5 aldehyde was 4.5: 1: 0.011. No PVA was confirmed.
【００６２】アルドール縮合は、実施例１の（２）に準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：８１．８重量
％、２ＭＢＡ：１８．２重量％、３ＭＢＡ：０．２重量
％）を用いて行い、水素添加反応及び実施例１の（３）
に準拠して行った。さらに、２５段オルダーショウで減
圧蒸留を行った。留出した混合デカノール（１４）をキ
ャピラリーガスクロマトグラフィーにて分析した結果、
以下の組成であった。 ２ＰＨＯ ８０．６重量％ ４ＭＰＨＯ １６．２重量％ ５ＭＰＨＯ ０．２９重量％ ＭＥＨＯ １．５重量％ ＩＰＨＯ ０．０１１重量％ 該混合デカノ−ル（１４）１６３ｋｇを使用した以外
は、実施例１の（４）に準拠してエステル化反応を行
い、１７３．０ｋｇの目的物（以下ＤＸＰ−１３とい
う）を得た。また、実施例１の（５）に準拠して得たシ
ートの諸物性測定結果を表−１に示す。The aldol condensation was carried out by using a C5 aldehyde solution (nVLA: 81.8% by weight, 2MBA: 18.2% by weight, 3MBA: 0.2% by weight) according to Example 1 (2). , Hydrogenation reaction and (3) of Example 1
It was done according to. Further, vacuum distillation was performed using a 25-stage Oldershaw. As a result of analyzing the distilled mixed decanol (14) by capillary gas chromatography,
It had the following composition. 2PHO 80.6% by weight 4MPHO 16.2% by weight 5MPHO 0.29% by weight MEHO 1.5% by weight IPHO 0.011% by weight In the same manner as in Example 1 except that 163 kg of the mixed decanol (14) was used. The esterification reaction was carried out according to 4) to obtain 173.0 kg of the desired product (hereinafter referred to as DXP-13). In addition, Table 1 shows the results of measuring various physical properties of the sheet obtained in accordance with (5) of Example 1.
【００６３】比較例７ 原料オレフィンガスとして以下の組成のスペントスペン
トＢＢ留分を使用した。 １−ブテン ４２重量％ シス−２−ブテン ２１重量％ トランス−２−ブテン １６重量％ イソブテン ７重量％ ブタン １３重量％ イソブタン １重量％ 上記組成の原料オレフィンガスを使用する以外は実施例
１の（１）に準拠してヒドロホルミル化反応を行った。
生成Ｃ５アルデヒド中のｎＶＬＡと２ＭＢＡと３ＭＢＡ
の生成比が８２．４：１：１．５であることがわかっ
た。なお、ＰＶＡは確認されなかった。Comparative Example 7 Spent spent BB fraction having the following composition was used as a raw material olefin gas. 1-butene 42% by weight cis-2-butene 21% by weight trans-2-butene 16% by weight isobutene 7% by weight butane 13% by weight isobutane 1% by weight In the same manner as in Example 1 except that the raw material olefin gas having the above composition was used ( The hydroformylation reaction was carried out according to 1).
NVLA, 2MBA and 3MBA in the produced C5 aldehyde
Was found to be 82.4: 1: 1.5. No PVA was confirmed.
【００６４】アルドール縮合は、実施例１の（２）に準
拠してＣ５アルデヒド溶液（ｎＶＬＡ：８７．５重量
％、２ＭＢＡ：５．１重量％、３ＭＢＡ：７．４重量
％）を用いて行い、水素添加反応及び減圧蒸留は実施例
１の（３）に準拠して行った。 生成した混合デカノー
ル（１５）をキャピラリーガスクロマトグラフィーにて
分析した結果、以下の組成であった。 ２ＰＨＯ ８４．１重量％ ４ＭＰＨＯ ４．９重量％ ５ＭＰＨＯ １２．６重量％ ＭＥＨＯ ０．１０重量％ ＩＰＨＯ １．５重量％ 該混合デカノ−ル（１５）１６３ｋｇを使用した以外
は、実施例１の（４）に準拠してエステル化反応を行
い、１７３．３ｋｇの目的物（以下ＤＸＰ−１４とい
う）を得た。また、実施例１の（５）に準拠してシ−ト
を作成し、得られたシートの諸物性測定結果を表−１に
示す。The aldol condensation was carried out by using a C5 aldehyde solution (nVLA: 87.5% by weight, 2MBA: 5.1% by weight, 3MBA: 7.4% by weight) in accordance with (2) of Example 1. The hydrogenation reaction and vacuum distillation were carried out according to (3) of Example 1. The composition of the produced mixed decanol (15) was analyzed by capillary gas chromatography, and the composition was as follows. 2PHO 84.1% by weight 4MPHO 4.9% by weight 5MPHO 12.6% by weight MEHO 0.10% by weight IPHO 1.5% by weight IPHO 1.5% by weight In the same manner as in Example 1 except that 163 kg of the mixed decanol (15) was used. The esterification reaction was carried out according to 4) to obtain 173.3 kg of the desired product (hereinafter referred to as DXP-14). In addition, a sheet was prepared in accordance with (5) of Example 1, and the results of measuring the physical properties of the obtained sheet are shown in Table-1.
【００６５】比較例８ フタル酸ジ−２−エチルヘキシル（ＤＯＰ：チッソ
（株）製造品）を使用した以外は、実施例１の（５）に
準拠してシートを作成した。諸物性測定結果を表−１に
示す。Comparative Example 8 A sheet was prepared according to (5) of Example 1 except that di-2-ethylhexyl phthalate (DOP: manufactured by Chisso Corporation) was used. The results of measuring various physical properties are shown in Table 1.
【００６６】比較例９ フタル酸ジイソノニル（ＤＩＮＰ：積水化学（株）製造
品）を使用した以外は、実施例１の（５）に準拠してシ
ートを作成した。諸物性測定結果を表−１に示す。Comparative Example 9 A sheet was prepared according to (5) of Example 1 except that diisononyl phthalate (DINP: manufactured by Sekisui Chemical Co., Ltd.) was used. The results of measuring various physical properties are shown in Table 1.
【００６７】比較例１０ フタル酸ジイソデシル（ＤＩＤＰ：積水化学（株）製造
品）を使用した以外は、実施例１の（５）に準拠してシ
ートを作成した。諸物性測定結果を表−１に示す。Comparative Example 10 A sheet was prepared according to (5) of Example 1 except that diisodecyl phthalate (DIDP: manufactured by Sekisui Chemical Co., Ltd.) was used. The results of measuring various physical properties are shown in Table 1.
【００６７】[0067]
【表１】 [Table 1]
【００６８】実施例１１ ２リットルガラス四つ口フラスコに、原料としてアジピ
ン酸４３８．３ｇ及び混合デカノール（１）１１３８．
３ｇを窒素雰囲気下仕込んだ。この溶液を攪拌しながら
加熱し反応液温度が１７３℃になったところで触媒であ
るテトライソプロポキシチタン１．８ｇを加えた後、さ
らに２２０℃まで昇温した。生成水は反応器に取り付け
た油水分離器を用いて系外に除去し、未反応アルコール
は系内に戻した。反応液温度が２２０℃に到達してから
１時間毎にサンプリングを実施し、酸価が０．１以下に
なったところ（約３．５時間後）で加熱を停止し、通常
の中和、水洗、減圧蒸留（９０℃／５０ｍｍＨｇ〜２１
０．５℃／１．５ｍｍＨｇの留分をカット）及び後処理
操作を経た後、目的物である混合アジペート（以下、Ｄ
ＸＡという）１１３０．１ｇを得た。この時の酸価は
０．０２３、残アルコール分は１００ｐｐｍ以下、水分
０．０４重量％であった。Example 11 In a 2 liter glass four-necked flask, adipic acid 438.3 g and mixed decanol (1) 1138.
3 g was charged under a nitrogen atmosphere. This solution was heated with stirring, and when the temperature of the reaction solution reached 173 ° C., 1.8 g of tetraisopropoxytitanium as a catalyst was added, and then the temperature was further raised to 220 ° C. The produced water was removed to the outside of the system using an oil-water separator attached to the reactor, and the unreacted alcohol was returned to the inside of the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C., heating was stopped when the acid value became 0.1 or less (after about 3.5 hours), and normal neutralization, Washing with water, distillation under reduced pressure (90 ° C / 50 mmHg-21
After undergoing a 0.5 ° C./1.5 mmHg fraction cut) and a post-treatment operation, the target adipate mixture (hereinafter, D
There was obtained 1130.1 g of XA). At this time, the acid value was 0.023, the residual alcohol content was 100 ppm or less, and the water content was 0.04% by weight.
【００６９】次に、平均重合度１０３０のポリ塩化ビニ
ル（チッソ（株）；ＳＬ）１００重量部に対し、ＤＸＡ
４０重量部、カルシウム−亜鉛系安定剤２重量部を配合
し、これを１７０℃の試験ロールにて５分間混練し、厚
さ１．３ｍｍのシートを作成した。更に、これを１８０
℃にて４分間予熱した後、２分間１８０ｋｇ／ｃｍ2の
圧力にて加圧、３分間１８０ｋｇ／ｃｍ2の圧力にて冷
却し、厚さ１ｍｍのシートを作成し、これを用いて比
重、加熱重量変化率、耐油性試験重量変化率、柔軟温
度、硬さの測定を行った。測定結果を表−２に示す。Next, DXA was added to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1030 (Chisso Corporation; SL).
40 parts by weight and 2 parts by weight of calcium-zinc stabilizer were mixed and kneaded for 5 minutes with a test roll at 170 ° C. to prepare a sheet having a thickness of 1.3 mm. In addition, 180
After preheating at 4 ° C for 4 minutes, pressurizing at a pressure of 180 kg / cm 2 for 2 minutes and cooling at a pressure of 180 kg / cm 2 for 3 minutes to prepare a sheet having a thickness of 1 mm, and using this, specific gravity, The heating weight change rate, oil resistance test weight change rate, softening temperature, and hardness were measured. The measurement results are shown in Table-2.
【００７０】比較例１１ ２ＰＨＯ高純度品（混合デカノ−ル（１０））１１３
８．３ｇを使用した以外は、実施例１１に準拠してアジ
ペートを製造し１１３２．８ｇのジ−２−プロピルヘプ
チルアジペート（以下、ＤＰＨＡという）を得た。さら
に、実施例１１に準拠してシートにし、同様な測定を行
った。諸物性測定結果を表−２に示す。Comparative Example 11 2PHO high-purity product (mixed decanol (10)) 113
Adipate was produced according to Example 11 except that 8.3 g was used to obtain 112.8 g of di-2-propylheptyl adipate (hereinafter referred to as DPHA). Further, a sheet was formed according to Example 11, and the same measurement was performed. The results of measuring various physical properties are shown in Table 2.
【００７１】比較例１２ 市販のジ−２−エチルヘキシルアジペート（チッソ
（株）製；ＤＯＡ）を使用して、実施例１１に準拠して
シートにし、同様な試験を行った。諸物性測定結果を表
−２に示す。Comparative Example 12 Using commercially available di-2-ethylhexyl adipate (manufactured by Chisso Corporation; DOA), a sheet was prepared according to Example 11, and the same test was conducted. The results of measuring various physical properties are shown in Table 2.
【００７２】実施例１２ ２リットルガラス四つ口フラスコに、原料として試薬の
無水トリメリット酸（和光純薬工業（株）製）３８４．
２ｇ及び混合デカノール（１）１１３８．３ｇを窒素雰
囲気下仕込んだ。この溶液を攪拌しながら加熱し反応液
温度が１７３℃になったところで触媒であるテトライソ
プロポキシチタン１．８ｇを加えた後、さらに２２０℃
まで昇温した。生成水は反応器に取り付けた油水分離器
を用いて系外に除去し、未反応アルコールは系内に戻し
た。反応液温度が２２０℃に到達してから１時間毎にサ
ンプリングを実施し、酸価が０．１以下になったところ
（約２．５時間後）で加熱を停止し、通常の中和、水
洗、減圧蒸留（８０℃／２０ｍｍＨｇ〜２２０℃／０．
５ｍｍＨｇの留分をカット）及び後処理操作を経た後、
目的物である混合トリメリテート（以下、ＴＸＴＭとい
う）１１６４．９ｇを得た。この時の酸価は０．０２
５、残アルコール分は１６０ｐｐｍ、水分０．０２重量
％であった。Example 12 A 2-liter glass four-necked flask was charged with a reagent, trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 384.
2g and 1138.3g of mixed decanol (1) were charged under a nitrogen atmosphere. This solution was heated with stirring, and when the reaction solution temperature reached 173 ° C., 1.8 g of tetraisopropoxytitanium as a catalyst was added, and then 220 ° C.
The temperature was raised to. The produced water was removed to the outside of the system using an oil-water separator attached to the reactor, and the unreacted alcohol was returned to the inside of the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C., and when the acid value became 0.1 or less (after about 2.5 hours), heating was stopped and normal neutralization, Washing with water, vacuum distillation (80 ° C / 20 mmHg to 220 ° C / 0.
After cutting 5 mmHg fraction) and post-treatment operations,
1164.9 g of mixed trimellitate (hereinafter referred to as TXTM), which is the target substance, was obtained. The acid value at this time is 0.02
5. The residual alcohol content was 160 ppm and the water content was 0.02% by weight.
【００７３】次に、平均重合度１０３０のポリ塩化ビニ
ル（チッソ（株）；ＳＬ）１００重量部に対し、ＴＸＴ
Ｍ５０重量部、三塩基性硫酸鉛４重量部、ステアリン酸
鉛１重量部を配合し、これを１７０℃の試験ロールにて
５分間混練し、厚さ１．３ｍｍのシートを作成した。更
に、これを１８０℃にて４分間予熱した後、２分間１８
０ｋｇ／ｃｍ2の圧力にて加圧、３分間１８０ｋｇ／ｃ
ｍ2の圧力にて冷却し、厚さ１ｍｍのシートを作成し、
これを用いて比重、加熱重量変化率、耐油性試験重量変
化率、柔軟温度、硬さの測定を行った。測定結果を表−
３に示す。Next, TXT was added to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1030 (Chisso Corporation; SL).
50 parts by weight of M, 4 parts by weight of tribasic lead sulfate and 1 part by weight of lead stearate were mixed and kneaded with a test roll at 170 ° C. for 5 minutes to prepare a sheet having a thickness of 1.3 mm. Furthermore, after preheating this at 180 ° C. for 4 minutes, it is heated for 2 minutes 18
Pressurized at a pressure of 0 kg / cm 2 for 3 minutes 180 kg / c
Cool at a pressure of m 2 to make a sheet with a thickness of 1 mm,
Using this, specific gravity, heating weight change rate, oil resistance test weight change rate, softening temperature, and hardness were measured. Table of measurement results
3 shows.
【００７４】比較例１３ ２ＰＨＯ高純度品（混合デカノ−ル（１０））１１３
８．９ｇを使用した以外は、実施例１２に準拠してエス
テル化反応を行い、１１６５．７ｇのトリ−２−プロピ
ルヘプチルトリメリテート（以下、ＴＰＨＴＭという）
を得た。さらに、実施例１２に準拠してシートにし、シ
−トの諸物性を測定した。諸物性測定結果を表−３に示
す。Comparative Example 13 2PHO High Purity Product (Mixed Decanol (10)) 113
The esterification reaction was carried out according to Example 12 except that 8.9 g was used, and 1165.7 g of tri-2-propylheptyl trimellitate (hereinafter referred to as TPHTM) was used.
Got Further, a sheet was formed according to Example 12, and various physical properties of the sheet were measured. The results of measuring various physical properties are shown in Table 3.
【００７５】比較例１４ 市販のトリ−２−エチルヘキシルトリメリテート（チッ
ソ（株）製；ＴＯＴＭ）を使用して、実施例１２に準拠
してシートにし、同様な試験を行った。諸物性測定結果
を表−３に示す。Comparative Example 14 Using commercially available tri-2-ethylhexyl trimellitate (manufactured by Chisso Corporation; TOTM), a sheet was prepared in accordance with Example 12, and the same test was conducted. The results of measuring various physical properties are shown in Table 3.
【００７６】[0076]
【表２】 [Table 2]
【００７７】実施例１３ ２リットルガラス四つ口フラスコに、原料として試薬の
セバシン酸（和光純薬工業（株）製）５０５．７ｇ及び
混合デカノ−ル（１）９４９．２ｇを窒素雰囲気下仕込
んだ。この溶液を攪拌しながら加熱し反応液温度が１７
３℃になったところで触媒であるテトライソプロポキシ
チタン１．８ｇを加えた後、さらに２２０℃まで昇温し
た。生成水は反応器に取り付けた油水分離器を用いて系
外に除去し、未反応アルコールは系内に戻した。反応液
温度が２２０℃に到達してから１時間毎にサンプリング
を実施し、酸価が０．１以下になったところ（約２．５
時間後）で加熱を停止し、通常の中和、水洗、減圧蒸留
（９０℃／２０ｍｍＨｇ〜２００℃／０．５ｍｍＨｇの
留分をカット）及び後処理操作を経た後、目的物である
混合セバケート（以下、ＤＸＳという）１１２７．４ｇ
を得た。この時の酸価は０．０３０、残アルコール分は
１００ｐｐｍ以下、水分０．０３重量％であった。Example 13 A 2-liter glass four-necked flask was charged with 505.7 g of the reagent sebacic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 949.2 g of mixed decanol (1) as a raw material under a nitrogen atmosphere. It is. This solution is heated with stirring to bring the reaction solution temperature to 17
When the temperature reached 3 ° C, 1.8 g of tetraisopropoxytitanium as a catalyst was added, and the temperature was further raised to 220 ° C. The produced water was removed to the outside of the system using an oil-water separator attached to the reactor, and the unreacted alcohol was returned to the inside of the system. Sampling was conducted every hour after the temperature of the reaction solution reached 220 ° C, and when the acid value became 0.1 or less (about 2.5
After a lapse of time), heating is stopped, normal neutralization, washing with water, vacuum distillation (cutting a fraction of 90 ° C./20 mmHg to 200 ° C./0.5 mmHg) and a post-treatment operation are performed, and then the target mixture sebacate is obtained. (Hereinafter referred to as DXS) 1127.4 g
Got At this time, the acid value was 0.030, the residual alcohol content was 100 ppm or less, and the water content was 0.03% by weight.
【００７８】次に、平均重合度１０３０のポリ塩化ビニ
ル（チッソ（株）；ＳＬ）１００重量部に対し、ＤＸＳ
５０重量部、カルシウム−亜鉛系安定剤２重量部を配合
し、これを１７０℃の試験ロールにて５分間混練し、厚
さ１．３ｍｍのシートを作成した。更に、これを１８０
℃にて４分間予熱した後、２分間１８０ｋｇ／ｃｍ2の
圧力にて加圧、３分間１８０ｋｇ／ｃｍ2の圧力にて冷
却し、厚さ１ｍｍのシートを作成し、これを用いて比
重、加熱重量変化率、耐油性試験重量変化率、柔軟温
度、硬さの測定を行った。測定結果を表−４に示す。Then, DXS was added to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1030 (Chisso Corporation; SL).
50 parts by weight and 2 parts by weight of a calcium-zinc stabilizer were mixed, and this was kneaded with a test roll at 170 ° C. for 5 minutes to prepare a sheet having a thickness of 1.3 mm. In addition, 180
After preheating at 4 ° C for 4 minutes, pressurizing at a pressure of 180 kg / cm 2 for 2 minutes and cooling at a pressure of 180 kg / cm 2 for 3 minutes to prepare a sheet having a thickness of 1 mm, and using this, specific gravity, The heating weight change rate, oil resistance test weight change rate, softening temperature, and hardness were measured. The measurement results are shown in Table-4.
【００７９】比較例１５ ２ＰＨＯ高純度品（混合デカノ−ル（１０））８４１．
３ｇを使用した以外は、実施例１３に準拠してセバケー
トを製造し１１２２．５ｇのジ−２−プロピルヘプチル
セバケート（以下、ＤＰＨＳという）を得た。さらに、
実施例１３に準拠してシートにし、同様な測定を行っ
た。諸物性測定結果を表−４に示す。Comparative Example 15 2PHO high-purity product (mixed decanol (10)) 841.
Sebacate was produced according to Example 13 except that 3 g was used to obtain 1122.5 g of di-2-propylheptyl sebacate (hereinafter referred to as DPHS). further,
A sheet was formed according to Example 13, and the same measurement was performed. The results of measuring various physical properties are shown in Table 4.
【００８０】比較例１６ 市販の２−エチルヘキサノール（チッソ（株）；ＯＡ）
８４１．３ｇを使用した以外は、実施例１３に準拠して
セバケートを製造し１０２３．６ｇのジ−２−エチルヘ
キシルセバケート（以下、ＤＯＳという）を得た。さら
に、同様にシートにし、同様な測定を行った。諸物性測
定結果を表−４に示す。Comparative Example 16 Commercially available 2-ethylhexanol (Chisso Corporation; OA)
Sebacate was produced according to Example 13 except that 841.3 g was used to obtain 1023.6 g of di-2-ethylhexyl sebacate (hereinafter referred to as DOS). Further, a sheet was similarly formed and the same measurement was performed. The results of measuring various physical properties are shown in Table 4.
【００８１】実施例１４ ２リットルガラス四つ口フラスコに、原料として試薬の
アゼライン酸（和光純薬工業（株）製）４７０．６ｇ及
び混合デカノール（１）９４９．２ｇを窒素雰囲気下で
仕込んだ。この溶液を攪拌しながら加熱し反応液温度が
１７３℃になったところで触媒であるテトライソプロポ
キシチタン１．８ｇを加えた後、さらに２２０℃まで昇
温した。生成水は反応器に取り付けた油水分離器を用い
て系外に除去し、未反応アルコールは系内に戻した。反
応液温度が２２０℃に到達してから１時間毎にサンプリ
ングを実施し、酸価が０．１以下になったところ（約
２．５時間後）で加熱を停止し、通常の中和、水洗、減
圧蒸留（９０℃／２０ｍｍＨｇ〜２００℃／０．５ｍｍ
Ｈｇの留分をカット）及び後処理操作を経た後、目的物
である混合アゼレート（以下、ＤＸＺという）１０７
９．０ｇを得た。この時の酸価は０．０３８、残アルコ
ール分は１００ｐｐｍ以下、水分０．０４重量％であっ
た。Example 14 A 2-liter glass four-necked flask was charged with 470.6 g of azelaic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a raw material and 949.2 g of mixed decanol (1) as a raw material under a nitrogen atmosphere. . This solution was heated with stirring, and when the temperature of the reaction solution reached 173 ° C., 1.8 g of tetraisopropoxytitanium as a catalyst was added, and then the temperature was further raised to 220 ° C. The produced water was removed to the outside of the system using an oil-water separator attached to the reactor, and the unreacted alcohol was returned to the inside of the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C., and when the acid value became 0.1 or less (after about 2.5 hours), heating was stopped and normal neutralization, Washing with water, distillation under reduced pressure (90 ° C / 20mmHg-200 ° C / 0.5mm
After the Hg fraction is cut) and a post-treatment operation is performed, the target mixed azelate (hereinafter referred to as DXZ) 107
9.0 g was obtained. At this time, the acid value was 0.038, the residual alcohol content was 100 ppm or less, and the water content was 0.04% by weight.
【００８２】次に、平均重合度１０３０のポリ塩化ビニ
ル（チッソ（株）；ＳＬ）１００重量部に対し、ＤＸＺ
５０重量部、カルシウム−亜鉛系安定剤３重量部を配合
し、これを１７０℃の試験ロールにて５分間混練し、厚
さ１．３ｍｍのシートを作成した。更に、これを１８０
℃にて４分間予熱した後、２分間１８０ｋｇ／ｃｍ2の
圧力にて加圧、３分間１８０ｋｇ／ｃｍ2の圧力にて冷
却し、厚さ１ｍｍのシートを作成し、これを用いて比
重、加熱重量変化率、耐油性試験重量変化率、柔軟温
度、硬さの測定を行った。測定結果を表−５に示す。Next, DXZ was added to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1030 (Chisso Corporation; SL).
50 parts by weight and 3 parts by weight of a calcium-zinc stabilizer were mixed and kneaded with a test roll at 170 ° C. for 5 minutes to prepare a sheet having a thickness of 1.3 mm. In addition, 180
After preheating at 4 ° C for 4 minutes, pressurizing at a pressure of 180 kg / cm 2 for 2 minutes and cooling at a pressure of 180 kg / cm 2 for 3 minutes to prepare a sheet having a thickness of 1 mm, and using this, specific gravity, The heating weight change rate, oil resistance test weight change rate, softening temperature, and hardness were measured. The measurement results are shown in Table-5.
【００８３】比較例１７ ２ＰＨＯ高純度品（混合デカノ−ル（１０））９４９．
３ｇを使用した以外は、実施例１４に準拠してアゼレー
トを製造し１０７４．１ｇのジ−２−プロピルヘプチル
アゼレート（以下、ＤＰＨＺという）を得た。さらに、
実施例１４に準拠してシートにし、同様な測定を行っ
た。諸物性測定結果を表−５に示す。Comparative Example 17 2PHO high purity product (mixed decanol (10)) 949.
Azelate was produced according to Example 14 except that 3 g was used to obtain 1074.1 g of di-2-propylheptyl azelate (hereinafter referred to as DPHZ). further,
A sheet was formed according to Example 14, and the same measurement was performed. The results of measuring various physical properties are shown in Table-5.
【００８４】比較例１８ 市販の２−エチルヘキサノール（チッソ（株）；ＯＡ）
８４１．１ｇを使用した以外は、実施例１４に準拠して
アゼレートを製造し１００４．９ｇのジ−２−エチルヘ
キシルアゼレート（以下、ＤＯＺという）を得た。さら
に、同様にシートにし、同様な測定を行った。諸物性測
定結果を表−５に示す。Comparative Example 18 Commercially available 2-ethylhexanol (Chisso Corporation; OA)
Azelate was produced according to Example 14 except that 841.1 g was used to obtain 1004.9 g of di-2-ethylhexyl azelate (hereinafter referred to as DOZ). Further, a sheet was similarly formed and the same measurement was performed. The results of measuring various physical properties are shown in Table-5.
【００８５】[0085]
【表３】 [Table 3]
【００８６】[0086]
【発明の効果】本発明の組成を有する可塑剤用混合アル
コールを用いて得られる可塑剤は該可塑剤を塩化ビニル
樹脂に配合すると、耐熱性（加熱老化性）、耐油性及び
耐寒性（低温柔軟性）が大幅に改良され、かつ電気特性
に優れた塩化ビニル樹脂組成物が得られる優れた可塑剤
であり、本発明の混合アルコールは上記の優れた可塑剤
を与える可塑剤用混合アルコールである。The plasticizer obtained by using the mixed alcohol for a plasticizer having the composition of the present invention has a heat resistance (heat aging resistance), an oil resistance and a cold resistance (low temperature) when the plasticizer is blended with a vinyl chloride resin. (Flexibility) is significantly improved, and a vinyl chloride resin composition having excellent electrical properties is obtained, which is an excellent plasticizer. The mixed alcohol of the present invention is a mixed alcohol for a plasticizer that gives the above excellent plasticizer. is there.
Claims (3)
たはカルボン酸無水物とをエステル化反応させることに
よって可塑剤用エステルを製造するにあたり、該エステ
ル化反応に供するアルコールの組成が以下で示すことを
特徴とする可塑剤用混合アルコール（但し、２ＰＨＯは
２−プロピル−１−ヘプタノールを、４ＭＰＨＯは４−
メチル−２−プロピル−１−ヘキサノール、ＭＥＨＯは
２−メチル−２−エチル−１−ヘプタノール、５ＭＰＨ
Ｏは５−メチル−２−プロピル−１−ヘキサノール、Ｉ
ＰＨＯは２−イソプロピル−１−ヘプタノールをそれぞ
れ表す。）。 ２ＰＨＯ ：８１重量％以上９
５重量％未満 ４ＭＰＨＯと５ＭＰＨＯを合わせて：５．０重量％を越
え１８重量％以下 ＭＥＨＯとＩＰＨＯを合わせて ：１．０重量％以下1. When producing an ester for a plasticizer by subjecting an alcohol having 10 carbon atoms to a carboxylic acid or a carboxylic acid anhydride to perform an esterification reaction, the composition of the alcohol to be subjected to the esterification reaction is shown below. Characteristic mixed alcohols for plasticizers (however, 2PHO is 2-propyl-1-heptanol and 4MPHO is 4-
Methyl-2-propyl-1-hexanol, MEHO is 2-methyl-2-ethyl-1-heptanol, 5MPH
O is 5-methyl-2-propyl-1-hexanol, I
PHO represents 2-isopropyl-1-heptanol, respectively. ). 2PHO: 81% by weight or more 9
Less than 5 wt% 4MPHO and 5MPHO combined: over 5.0wt% and 18wt% or less MEHO and IPHO combined: 1.0wt% or less
とカルボン酸またはカルボン酸無水物とをエステル化反
応させることによって得られる可塑剤。2. A plasticizer obtained by subjecting the mixed alcohol for plasticizer according to claim 1 to an esterification reaction with a carboxylic acid or a carboxylic acid anhydride.
タル酸、フタル酸無水物、アジピン酸、アゼライン酸、
セバシン酸、トリメリット酸、トリメリット酸無水物、
ピロメリット酸またはピロメリット酸無水物である請求
項２記載の可塑剤。3. The carboxylic acid or carboxylic anhydride is phthalic acid, phthalic anhydride, adipic acid, azelaic acid,
Sebacic acid, trimellitic acid, trimellitic anhydride,
The plasticizer according to claim 2, which is pyromellitic acid or pyromellitic anhydride.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4349703A JPH06166644A (en) | 1992-12-01 | 1992-12-01 | Mixed alcohol for plasticizer and plasticizer production by using the alcohol |
| TW082100285A TW353094B (en) | 1992-02-04 | 1993-01-18 | Mixed alcohol and plasticizers prepared therefrom |
| KR1019930001523A KR960001888B1 (en) | 1992-02-04 | 1993-02-04 | Mixed alcohol for plasticizer and plasticizer production by using |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4349703A JPH06166644A (en) | 1992-12-01 | 1992-12-01 | Mixed alcohol for plasticizer and plasticizer production by using the alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06166644A true JPH06166644A (en) | 1994-06-14 |
Family
ID=18405538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4349703A Pending JPH06166644A (en) | 1992-02-04 | 1992-12-01 | Mixed alcohol for plasticizer and plasticizer production by using the alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06166644A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998038152A1 (en) * | 1997-02-28 | 1998-09-03 | New Japan Chemical Co., Ltd. | p-HYDROXYBENZOIC ESTERS, PLASTICIZER CONTAINING THE SAME, POLYAMIDE RESIN COMPOSITION, AND MOLDED OBJECTS |
| JP2010526772A (en) * | 2007-04-26 | 2010-08-05 | コグニス・アイピー・マネージメント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Cosmetic composition containing an ester of 2-propylheptanol |
| WO2014005932A1 (en) * | 2012-07-06 | 2014-01-09 | Basf Se | The use of carboxylic acid esters as lubricants |
| WO2019171890A1 (en) * | 2018-03-08 | 2019-09-12 | 花王株式会社 | Plasticizer for halogen resins |
| US10811165B2 (en) | 2014-12-05 | 2020-10-20 | Kuraray Co., Ltd. | Insulation material |
-
1992
- 1992-12-01 JP JP4349703A patent/JPH06166644A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998038152A1 (en) * | 1997-02-28 | 1998-09-03 | New Japan Chemical Co., Ltd. | p-HYDROXYBENZOIC ESTERS, PLASTICIZER CONTAINING THE SAME, POLYAMIDE RESIN COMPOSITION, AND MOLDED OBJECTS |
| US6348563B1 (en) * | 1997-02-28 | 2002-02-19 | New Japan Chemical Co., Ltd. | p-hydroxybenzoic esters, plasticizer containing the same, polyamide resin composition and molded articles |
| JP2010526772A (en) * | 2007-04-26 | 2010-08-05 | コグニス・アイピー・マネージメント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Cosmetic composition containing an ester of 2-propylheptanol |
| WO2014005932A1 (en) * | 2012-07-06 | 2014-01-09 | Basf Se | The use of carboxylic acid esters as lubricants |
| US9708564B2 (en) | 2012-07-06 | 2017-07-18 | Basf Se | Use of carboxylic acid esters as lubricants |
| US10811165B2 (en) | 2014-12-05 | 2020-10-20 | Kuraray Co., Ltd. | Insulation material |
| WO2019171890A1 (en) * | 2018-03-08 | 2019-09-12 | 花王株式会社 | Plasticizer for halogen resins |
| JP2019156907A (en) * | 2018-03-08 | 2019-09-19 | 花王株式会社 | Plasticizer for halogen-based resin |
| CN111819233A (en) * | 2018-03-08 | 2020-10-23 | 花王株式会社 | Plasticizer for halogen resin |
| CN111819233B (en) * | 2018-03-08 | 2022-03-15 | 花王株式会社 | Plasticizer for halogen resin |
| US11945932B2 (en) | 2018-03-08 | 2024-04-02 | Kao Corporation | Plasticizer for halogen resins |
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