CN103804436A - Solvent-removing method - Google Patents
Solvent-removing method Download PDFInfo
- Publication number
- CN103804436A CN103804436A CN201310534679.8A CN201310534679A CN103804436A CN 103804436 A CN103804436 A CN 103804436A CN 201310534679 A CN201310534679 A CN 201310534679A CN 103804436 A CN103804436 A CN 103804436A
- Authority
- CN
- China
- Prior art keywords
- solvent
- aromatic carboxylic
- carboxylic acid
- sucrose
- under reduced
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229930006000 Sucrose Natural products 0.000 claims abstract description 58
- 239000005720 sucrose Substances 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 48
- -1 sucrose aromatic carboxylic esters Chemical class 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 6
- 241001550224 Apha Species 0.000 claims description 5
- 238000004040 coloring Methods 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 20
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 19
- 239000003822 epoxy resin Substances 0.000 description 18
- 229920000647 polyepoxide Polymers 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 230000032050 esterification Effects 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- SYDJVRWZOWPNNO-UHFFFAOYSA-N sucrose-benzoate Natural products OCC1OC(OC2(COC(=O)c3ccccc3)OC(CO)C(O)C2O)C(O)C(O)C1O SYDJVRWZOWPNNO-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930182470 glycoside Natural products 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003445 sucroses Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- WASZXVMLVDQNDE-UHFFFAOYSA-N 3-[(3-aminopropyl)amino]-4-hydroxybenzoic acid Chemical compound NCCCNC=1C=C(C(=O)O)C=CC=1O WASZXVMLVDQNDE-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 108010067369 acetylpolyamine amidohydrolase Proteins 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention relates to a removing method of a solvent used for producing sucrose aromatic carboxylic esters. The method comprises the steps of using more than one pressure-reducing drying machine to enable the pressure in the drying machine and/or enable the heating temperature to have change of more than two stages; conducting a series of pressure-reducing and drying process on a mixture of the sucrose aromatic carboxylic esters and the solvent. The pressure in the drying machine of the first stage is below the atmospheric pressure, and the heating temperature is above 20 DEG C and below 250 DEG C. At the final stage, pressure in the drying machine is below 10kPa.abs, and the heating temperature is above 80 DEG C and below 250 DEG C. Through the removing method of the solvent, sucrose aromatic carboxylic esters with little coloring and little solvent residue can be obtained.
Description
Technical field
The present invention relates to obtain the method for removing of the solvent using in the sucrose aromatic carboxylic acid esters manufacture of the considerably less sucrose aromatic carboxylic acid esters of the remaining quantity of non-coloring almost and solvent.
Background technology
Sucrose aromatic carboxylic acid esters is the useful compound that a class can be used in various industrial fields.For example, as modifier, for improving forming process and the physical property of the noncrystalline resins such as ABS resin, polyvinyl chloride (PVC) RESINS, epoxy resin, unsaturated polyester, or for improving flexibility, the shock resistance of crystallized polyurethane resin; Or as the additive of optical thin film for improving the wet fastness etc. of optical thin film.The manufacture of sucrose aromatic carboxylic acid esters is normally for example by the esterification between sucrose and aromatic carboxylic acid, and after carrying out required refining step as required, then the solvent of using except dereaction with in refining is implemented (patent documentation 1).
Removing conventionally of related solvents undertaken by distillation, but because sucrose aromatic carboxylic acid esters is sucrose derivative, therefore, there will be because heating and cause easily painted problem.In patent documentation 2, record in the manufacture of alkyl glycoside, use film-type vaporizer point two stages from the mixture because of the residual alcohol of unreacted and alkyl glycoside to remove the method for desolventizing, but because sucrose aromatic carboxylic acid is more easily more painted than alkyl glycoside, therefore the method is difficult to state with non-coloring almost except desolventizing.
Formerly technical literature
Patent documentation
Patent documentation 1: Japanese kokai publication sho 52-95625 communique
Patent documentation 2: the special public table 5-500508 communique of Japan
Summary of the invention
The problem that invention will solve
The object of the invention is to, the method for removing of the solvent using in the manufacture of sucrose aromatic carboxylic acid esters of the considerably less sucrose aromatic carboxylic acid esters of a kind of remaining quantity that can easily obtain non-coloring almost and solvent is provided.
Solve the means of problem
The inventor etc. conduct in-depth research for solving above-mentioned problem, found that: in the case of using more than one vacuum drying apparatus to carry out drying under reduced pressure, carry out a succession of operation of drying under reduced pressure by making pressure in moisture eliminator and/or Heating temperature that more than two stages variation at least occur, and make the moisture eliminator internal pressure of first stage below normal atmosphere, and be heated temperature and maintain within the limits prescribed, make the moisture eliminator internal pressure of terminal stage below 10kPaabs, and be heated temperature and maintain within the limits prescribed, almost can suppress thus painted completely and can make the remaining quantity of solvent few.It is further completed to the present invention after research repeatedly.
, the present invention relates to a kind of method of removing of solvent, the solvent that it uses for removing the manufacture of sucrose aromatic carboxylic acid esters, comprise and use an above vacuum drying apparatus to make pressure and/or Heating temperature in moisture eliminator that variations more than two stages at least occur, the mixture that contains sucrose aromatic carboxylic acid esters and above-mentioned solvent is carried out to a succession of drying under reduced pressure operation of drying under reduced pressure, the moisture eliminator internal pressure of the first stage of this drying under reduced pressure operation is below normal atmosphere, and its Heating temperature is more than 20 ℃, below 250 ℃, the moisture eliminator internal pressure of the terminal stage of this drying under reduced pressure operation is below 10kPaabs, and its Heating temperature is more than 80 ℃, below 250 ℃.
Above-mentioned a succession of drying under reduced pressure operation, preferably includes any number of stages in 2～9 stages.
The content of the sucrose aromatic carboxylic acid esters in said mixture is preferably 10～80 % by weight.
In addition, the invention still further relates to a kind of sucrose aromatic carboxylic acid esters obtaining by the above-mentioned solvent method of removing, its APHA is below 40, and the remaining quantity of solvent is below 3000ppm.
Embodiment
Below each integrant of the present invention is described.
Target product
In the present invention, sucrose aromatic carboxylic acid esters refers to the ester that sucrose and aromatic carboxylic acid form, and as this aromatic carboxylic acid, for example, can enumerate the aromatic series monocarboxylic acid shown in following general formula (I),
In formula, R
1～R
5independent separately, expression is selected from the group of hydrogen atom, alkyl and alkoxyl group.
The form and aspect of target product of the present invention are, the numerical value (Hazen colourity: APHA) of APHA standardized solution is below 40, and the remaining quantity of solvent is below 3000ppm.
In sucrose aromatic carboxylic acid esters of the present invention, the mean value (hereinafter referred to as " average esterification degree ") of the esterification ratio of the alcohol moiety of sucrose is not particularly limited, in the situation that easy the to be painted average esterification degree of sucrose aromatic carboxylic acid esters is below 6.0, be particularly suitable for adopting the method for removing of solvent of the present invention.
In aromatic series monocarboxylic acid (I), R
1～R
5independent separately, be preferably respectively hydrogen atom or alkyl, be all more preferably the phenylformic acid of hydrogen atom, or one of them position is alkyl, all the other carboxylic acids that are hydrogen atom, are preferably R
3for alkyl, all the other carboxylic acids that are hydrogen atom.
As alkyl, can enumerate the alkyl of carbonatoms 1～20.Wherein, be preferably the alkyl of carbonatoms 1～5, more preferably methyl, ethyl, propyl group or sec.-propyl.As alkoxyl group, can enumerate the alkoxyl group of carbonatoms 1～20, be wherein preferably the alkoxyl group of carbonatoms 1～5, more preferably methoxyl group, oxyethyl group, propoxy-or isopropoxy.
Drying under reduced pressure operation
Drying under reduced pressure operation of the present invention comprises that the vacuum drying apparatus more than using makes pressure and/or Heating temperature in moisture eliminator that variations more than two stages at least occur, the mixture of the solvent using in the manufacture that contains sucrose aromatic carboxylic acid esters and this sucrose aromatic carboxylic acid is carried out to a succession of operation of drying under reduced pressure, the moisture eliminator internal pressure of the drying under reduced pressure operation of first stage is below normal atmosphere, and its Heating temperature is more than 20 ℃, below 250 ℃, the moisture eliminator internal pressure of the drying under reduced pressure operation of terminal stage is below 10kPaabs, and its Heating temperature is more than 80 ℃, below 250 ℃.
In the present invention, " moisture eliminator internal pressure " refers to the pressure of gas phase in vacuum drying apparatus, and this moisture eliminator internal pressure can pass through ordinary method, and for example, the pressure warning unit etc. that is connected setting with this gas phase is measured.Manometric setting position does not limit, and as long as being for example connected with the gas phase in vacuum drying apparatus, for example, can being arranged on and drawing in the vapor pipe of vacuum drying apparatus." Heating temperature " refers to the temperature of the big envelope at vacuum drying apparatus for heating said mixture or mobile thermal medium (hot water, steam, wet goods), the electric heater etc. of coil pipe.
About said mixture, the solvent using in manufacture refer to ester described later synthetic in ester manufacture and/or refining in the solvent that uses.In addition, more than the concentration of the sucrose aromatic carboxylic acid esters in this mixture is preferably 10 % by weight, more preferably more than 30 % by weight.When this concentration is during lower than 10 % by weight, industrial efficiency is low.On the other hand, this concentration is preferably below 80 % by weight, more preferably below 50 % by weight.In the time that this concentration exceedes 80 % by weight, viscosity is very high, is difficult to be applicable to vacuum drying apparatus.
Vacuum drying apparatus in the present invention is not particularly limited, can carry out drying under reduced pressure as long as being maintained in moisture eliminator internal pressure and Heating temperature under the condition of specified pressure and specified temperature, machinery or the utensil with such function all can be used in object of the present invention.As the concrete example of vacuum drying apparatus of the present invention, can enumerate the intermittent apparatus such as such as steel basin, the continuous equipments such as flasher, thin-film evaporator, revolver drier, forcing machine, belt dryer etc.
In this manual, " drying under reduced pressure of one-phase " refers under the condition of utilizing a vacuum drying apparatus moisture eliminator internal pressure and Heating temperature to be maintained to specified pressure and specified temperature and carries out drying under reduced pressure.Wherein, " vacuum drying apparatus " is except representing single vacuum drying apparatus, for example shown in certain forcing machine, vacuum drying apparatus internal separation is being become to plural region, the in the situation that of can distinguishing setting pressure and temperature in each region, divide and also can represent " vacuum drying apparatus " of the present invention by this region.
Therefore, two a succession of drying under reduced pressure more than stage also can carry out at least one drying under reduced pressure more than stage by equipment of independent use, or implement with two above equipment.For example, can implement by making pressure in moisture eliminator and/or Heating temperature that two variations more than stage occur in an equipment.In this case, preferably there is variations more than at least two stages in the pressure in moisture eliminator and/or Heating temperature, as long as can reach such condition, the pressure in moisture eliminator and Heating temperature do not change and also can in the continuous plural stage.At this, " a succession of " means other operation of not introducing during drying under reduced pressure beyond drying under reduced pressure (for example, refining step etc.).
In drying under reduced pressure, " pressure and/or Heating temperature in moisture eliminator are changed " refers to " pressure " and/or " temperature " " discontinuous variation ".
Consider the quality of target product and for obtaining the efficiency of this target product, number of stages is preferably the arbitrary number in 2～9 numbers of stages.
< pressure >
In the present invention,, below normal atmosphere, be preferably below 80kPaabs as the moisture eliminator internal pressure in the drying under reduced pressure operation of first stage, more preferably below 60kPaabs.In the time exceeding normal atmosphere, become too high for the required Heating temperature of desolventizing, therefore exist easily painted tendency of sucrose aromatic carboxylic acid esters.On the other hand, this pressure preferably more than 3kPaabs, more preferably more than 4kPaabs.When lower than 3kPaabs, be easy to because rinsing or the spittle causes producing inaccessible.In addition, this moisture eliminator internal pressure is preferably the moisture eliminator internal pressure higher than terminal stage.
The moisture eliminator internal pressure of the drying under reduced pressure operation of terminal stage, below 10kPaabs, is preferably below 2kPaabs, more preferably below 0.6kPaabs.In the time exceeding 10kPa, likely there is being difficult to fully reducing remaining solvent, or because improving temperature so that the easy painted situation of sucrose aromatic carboxylic acid esters.On the other hand, as the lower value of this pressure, be not particularly limited, it is more low better to be within the bounds of possibility preferably.
< temperature >
In the present invention, the Heating temperature in the drying under reduced pressure operation of first stage is 20～250 ℃.In the time exceeding 250 ℃, likely cannot suppress painted; On the other hand, when lower than 20 ℃, be likely difficult to fully reduce residual solvent.In order to address the above problem, for example, need to make moisture eliminator internal pressure is very high vacuum tightness, likely causes cost of equipment to increase.As the higher limit of Heating temperature, be preferably below 220 ℃, more preferably below 200 ℃.As the lower value of this temperature, be preferably more than 130 ℃, more preferably more than 140 ℃.
On the other hand, the Heating temperature in the drying under reduced pressure operation of terminal stage is 80～250 ℃.In the time exceeding 250 ℃, likely cannot suppress painted; On the other hand, when lower than 80 ℃, be likely difficult to fully reduce residual solvent.As the higher limit of Heating temperature, be preferably below 200 ℃, more preferably below 190 ℃.As the lower value of this temperature, be preferably more than 130 ℃, more preferably more than 160 ℃.
Moisture eliminator internal pressure and the Heating temperature in the intermediate stage between first stage and terminal stage can suitably be set in the scope of above-mentioned pressure and temperature.But, not only in this intermediate stage, in main drying under reduced pressure operation, also there is the larger situation of the higher painted trend of temperature, therefore, also need the pressure and temperature with reference to first stage employing, and the predetermined pressure and temperature adopting of terminal stage suitably determines.
Ester is synthetic
In the present invention, can make sucrose and aromatic carboxylic acid carry out esterification by ordinary method as the sucrose aromatic carboxylic acid esters of the raw material of above-mentioned drying under reduced pressure operation manufactures.This esterification is according to the manufacture method of the sucrose benzoate of recording in No. 40-5688, No. 61-4839, Japanese kokai publication sho for example, Japanese Patent Publication, by making the muriate of sucrose and aromatic carboxylic acid react to carry out.
For example, in the case of the method for recording for No. 61-4839 according to Japanese kokai publication sho is carried out, the muriate of sucrose and aromatic carboxylic acid, in the mixed solution of hydrophilic organic solvent and water, reacts under the existence of basic cpd.
As hydrophilic organic solvent, for example, can be suitable for the ketone series solvents such as acetone, butanone, pimelinketone; The ether such as diox, tetrahydrofuran (THF) series solvent; The ester series solvents such as methyl acetate; Any in the alcohol series solvents such as the trimethyl carbinol.These solvents both can be used alone and also can two or more mixing use.
As basic cpd, for example, can enumerate sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, ammonia, Trimethylamine 99, triethylamine etc.
The mixture ratio of hydrophilic organic solvent and water is preferably and makes the water ratio of the even liquid layer being made up of both is 7～80%.Why like this, although be because these hydrophilic organic solvents can will dissolve as the muriate of raw material one side's aromatic carboxylic acid and as the crude ester of resultant, but only can not dissolve the sucrose as raw material the opposing party completely with this hydrophilic organic solvent, or see to be dissolved to from the angle of reaction efficiency and cannot be used for practical degree, and by this hydrophilic organic solvent is mixed with the water as the good solvent of sucrose, just can dissolve and be enough to make the sucrose of this mixing solutions for practical degree.
Therefore, by utilizing the such character of hydrophilic organic solvent, can control the muriatic speed of response of sucrose and aromatic carboxylic acid, result just can be manufactured corresponding to the muriatic mixed volume (mol ratio) of sucrose/aromatic carboxylic acid ratio and/or the different crude ester of average ester exchange degree of low permutoid.For example, by making the muriatic mixed volume of aromatic carboxylic acid more with respect to the mixed volume of sucrose, can obtain thus the thick ester body that ratio is relatively less or average ester exchange degree is relatively large of low permutoid, on the contrary, by making the muriatic mixed volume of aromatic carboxylic acid less with respect to the mixed volume of sucrose, the relatively many or relatively little thick ester body of average ester exchange degree of the ratio that can obtain low permutoid.
As the method for reaction, can adopt and sucrose and aromatic carboxylic acid muriate are dissolved or be suspended in the mixed solution that hydrophilic organic solvent and water form, drip the method with aromatic carboxylic acid muriate equivalent or slightly excessive basic cpd; Or make sucrose and basic cpd dissolve or be suspended in mixed solution, drip the muriatic method of aromatic carboxylic acid; Or make sucrose dissolved or be suspended in mixed solution, simultaneously or alternately drip the method for aromatic carboxylic acid muriate and basic cpd.
Temperature of reaction can adopt-15 ℃～100 ℃, more preferably-10 ℃～30 ℃.In addition, after all reaction raw materials dropwise, in order to promote to have reacted, also can heat at high-temperature area.
Preferably the pH value in reaction is remained to weakly alkaline.On the other hand, under strong basicity environment, for example, according to temperature of reaction etc. pH be 13 with first-class environment under, because the hydrolytic side reactions of aromatic carboxylic acid is remarkable, be therefore preferably under the environment of for example pH8～13 and react.
As the reaction times, be not particularly limited, fully react and finish between raw material as long as can make.The concrete time is depended on starting compound amount and various condition, conventionally carries out about 1 hour enough.
After reaction, will after reaction mixture sat, remove isolated water layer, can obtain thus the mixture of the solvent that the ester of sucrose aromatic carboxylic acid and this carboxylic acid uses in synthetic.In addition, this mixture can utilize water or other refining solvent of using as required, utilizes single to clean or repeatedly cleans and refine.As can be used in such solvent in refining, can enumerate the organic solvents such as toluene, o-Xylol, m-xylene.These are refining can use separately with solvent, also can two or more mixing uses.
On the other hand, in the case of the method for recording for No. 40-5688 according to Japanese Patent Publication, esterification also can not used above-mentioned hydrophilic organic solvent, but implement with other solvent,, can implement with the one or more kinds of organic solvents that are selected from aromatic hydrocarbon or substituted aroma hydrocarbon, chlorinated aliphatic hydrocarbon, lower aliphatic ether.At this, as aromatic hydrocarbon or substituted aroma hydrocarbon, can enumerate benzene,toluene,xylene, ethylbenzene, chlorobenzene, toluene(mono)chloride etc.; As chlorinated aliphatic hydrocarbon, can enumerate methylene dichloride, chloroform, tetracol phenixin, tetrachloroethane etc.; As lower aliphatic ether, can enumerate diethyl ether, diisopropyl ether etc.These solvents can use separately, also can two or more mixing use.
As temperature of reaction, can adopt-15 ℃～50 ℃, as the reaction times, depend on various conditions, conventionally carry out about 3 hours enough.
Other condition with record based on above-mentioned Japanese kokai publication sho 61-4839 communique method time described in identical.
Modifier
Sucrose aromatic carboxylic acid esters of the present invention as modifier of great use, as the resin that adds ester class of the present invention, except the noncrystalline resins such as ABS resin, polyvinyl chloride (PVC) RESINS, epoxy resin, unsaturated polyester, can enumerate the crystalline resins such as crystallized polyurethane resin etc.Adding the combination of sucrose aromatic carboxylic acid esters of the present invention in resin and resin to can suitably select respectively according to purposes.
As ABS resin, be not particularly limited, for example, can enumerate and make vinyl cyanide, vinylbenzene, alpha-methyl styrene, methyl methacrylate etc. and polyhutadiene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, chlorinatedpolyethylene, as methyl acrylate, ethyl propenoate, propylene base system rubber and the vinyl cyanide such as butyl acrylate, vinylbenzene, vinylformic acid, acrylamide, the rubbery polymer graft polymerizations such as the multipolymer of 2-chloroethyl vinyl ether etc. and the resin that obtains, can also enumerate vinyl cyanide-Polybutadiene-styrene is graft copolymer etc.ABS resin can be used, or two or more may be used separately.
Be not particularly limited as polyvinyl chloride (PVC) RESINS, for example, can enumerate vinyl chloride homo resin, chlorinated vinyl chloride resin, as vinyl-acetic ester-vinyl chloride copolymer, ethylene-vinyl chloride copolymer etc. can be with more than one random copolymerization in all monomers of vinyl chloride monomer copolymerization or block copolymerization and the functional group such as chlorinated ethylene copolymer resins or hydroxyl graft on above-mentioned resin and resin and functional group be combined with reactive compounds reaction grafting and the polyvinyl chloride (PVC) RESINS that obtains etc.Polyvinyl chloride (PVC) RESINS can be used, or two or more may be used separately.
Be not particularly limited as epoxy resin, for example can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol lacquer resins type epoxy resin, alkylphenol lacquer resins type epoxy resin, the aralkyl-type epoxy resin such as phenol xenyl aralkyl epoxy resin, bisphenol-type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, phenols and the epoxide of condenses of aromatic aldehyde with phenol hydroxyl, triglycidyl isocyanurate, alicyclic epoxy resin etc.Epoxy resin can be used, or two or more may be used separately.
As unsaturated polyester resin, be not particularly limited, for example, can enumerate by α the addition reaction of β-ethylene series unsaturated dicarboxylic acid or its acid anhydrides and alcohol or the unsaturated polyester resin that dehydration condensation is synthesized into.In addition, can also and use Dicyclopentadiene (DCPD) with saturated dicarboxylic acid, aromatic binary carboxylic acid or their acid anhydrides or carboxylic acid reaction etc.As α, β-ethylene series unsaturated dicarboxylic acid example, for example, can enumerate the acid anhydrides of toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid and these di-carboxylic acid.As can with these α, the di-carboxylic acid example of β-ethylene series unsaturated dicarboxylic acid use, for example, can enumerate hexanodioic acid, sebacic acid, succsinic acid, Tetra hydro Phthalic anhydride, phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid etc.Wherein, preferably also use fumaric acid as α, β-ethylene series unsaturated dicarboxylic acid and m-phthalic acid are as di-carboxylic acid.Unsaturated polyester resin can be used, or two or more may be used separately.
As crystalline polyester resin, be not particularly limited, for example can enumerate polyethylene terephthalate, poly--1,4-butylene terephthalate, poly--2,6-naphthalic acid second diester, poly terephthalic acid hexamethylene dimethyl ester, poly--Isosorbide-5-Nitrae-Ding phenylbenzene-4,4 '-dicarboxylic esters, polyoxyethylene benzoic ether, poly--1, the crystallinity polyester such as 3-terephthalic acid propylene diester, the poly-own diester of-1,6-terephthalic acid.Wherein, preferred polyethylene terephthalate, poly--Isosorbide-5-Nitrae-butylene terephthalate, poly--NDA second diester.Crystalline polyester resin can be used separately a kind, also can be used together two or more.
It should be noted that, in these resins, can add as required the various additives such as impact-resistance modified dose, stablizer, lubrication prescription, weighting agent, pigment, whipping agent, ultra-violet stabilizer.
Mixing ratio when sucrose aromatic carboxylic acid esters of the present invention is used as modifier in resin is to be preferably 1～40 part with respect to 100 parts of resins, more preferably 1～30 part.When lower than 1 part, likely cannot realize target performance; In the time exceeding 40 parts, because long-term preservation waited the possibility raising that causes draining (bleed out).
It should be noted that, although be not intended to be limited to theoretical value, but in the present invention, in the time of solvent drying under reduced pressure, in the lower first stage of the concentration of sucrose aromatic carboxylic acid esters, by moisture eliminator internal pressure is remained on to high value, can prevent the bumping of the mixture that contains sucrose aromatic carboxylic acid esters and solvent, and pass through by heating and temperature control within the limits prescribed, can prevent the painted of sucrose aromatic carboxylic acid esters, and become higher terminal stage in the concentration of sucrose aromatic carboxylic acid esters after this, by moisture eliminator internal pressure is set in to lower value, improve the efficiency of drying under reduced pressure, thus, can provide to have concurrently and suppress the method for removing painted and solvent that raise the efficiency.
In this manual, while there is " part " separately, represent " weight part "." toluene " amount in sucrose aromatic carboxylic acid esters is the value of obtaining by gas-chromatography (GC)." average esterification degree " in sucrose aromatic carboxylic acid esters be by proton magnetic resonance (PMR) (
1the value of H-NMR) trying to achieve.
According to the method for removing of solvent of the present invention, can obtain also little sucrose aromatic carboxylic acid esters of less painted and residual solvent amount.More specifically, for example can obtain painted below APHA40, the sucrose aromatic carboxylic acid esters of residual solvent amount below 3000ppm.
Embodiment
Describe the present invention in detail based on embodiment below, but the invention is not restricted to this.
Synthesizing of Production Example 1(sucrose benzoate)
At the 20m that possesses anchor shape blade, resistance bulb, cooler condenser, big envelope
3steel basin in add 28.7 parts of sucrose, 10265.4 parts of dissolvings of water, then add 880.8 parts of 24% aqueous sodium hydroxide solutions, make secondary refrigerant in big envelope flow, liquid temperature is cooled to 1 ℃.Then in groove, add 649.0 parts of 187.2 parts of toluene, Benzoyl chlorides successively.Liquid temperature is remained on below 5 ℃, continue to stir 2 hours, complete thus reaction.Then stop stirring, leave standstill approximately 1 hour, separate and remove water, obtain thus sucrose benzoate solution (solids component 80%).The average esterification degree of this sucrose benzoate passes through
1h-NMR obtains, and its value is 5.5.
Embodiment 1～14 and comparative example 1～4
The equipment using in drying under reduced pressure
Forcing machine 1: twin screw extruder 1, screw diameter 25mm
Forcing machine 2: twin screw extruder 2, screw diameter 90mm
Thin-film evaporator: heat transfer area 0.5m
2
Flasher: the flasher of flash vaporization kettle capacity 200L, heating tube heat transfer area 0.8m
2(preheating use)
Rotating drum dryer: double drum dryer, heat transfer area 0.2m
2, diameter of cylinder 200mm, steel basin: capacity 5m
3steel basin, there is anchor shape blade
Drying under reduced pressure
As required, regulate the solids component amount of the sucrose benzoate solution of Production Example 1 gained, then according to the condition described in table 1～5, this specified amount is carried out to drying under reduced pressure, except desolventizing." processing flow " in each table refers to the flow (kg/hr) of the handled thing (drying under reduced pressure sucrose benzoate solution after treatment) in the situation that uses continous way vacuum drying apparatus.
The measurement of solvent remaining quantity
According to following condition, utilize gas-chromatography (GC) to measure the residual toluene amount of each sample of the sucrose benzoate obtaining as mentioned above.
The condition of GC
Each sample of the sucrose benzoate obtaining is as mentioned above dissolved in orthodichlorobenzene, according to internal standard method, the residual toluene amount under following measuring condition is carried out quantitatively.
Spectrum post: SE-30(Chromosorb WAW DHCS)
Solvent: orthodichlorobenzene
Internal standard: n-dodecane
Inlet temperature: 250 ℃
Column temperature: 80 ℃ (4 minutes) → 150 ℃ (16 ℃/min)
Form and aspect are evaluated
Each sample of the sucrose benzoate obtaining is as mentioned above dissolved in to toluene, the solution that formation concentration is 50%, the method for recording according to JIS K2421 is judged its form and aspect., being recorded in situation about with the naked eye comparing judges as the numerical value (Hazen chromatic number: APAH) of the APHA standardized solution of each sample of identical form and aspect.
More than the results are shown in each table.
Table 1
Table 2
Table 3
Table 4
Table 5
* " the moisture eliminator internal pressure " of comparative example 3 refers to the pressure in last hour that in drying under reduced pressure operation (omnidistance 10 hours), pressure is minimum.
As mentioned above, embodiments of the invention 1～14 can obtain residual solvent amount and the of the present invention target product of form and aspect in specialized range, and the comparative example 1 that Heating temperature is high, the comparative example 2 that the moisture eliminator internal pressure of terminal stage is high, the comparative example 3 of single phase processing and the low comparative example 4 of Heating temperature of terminal stage all can not obtain target product of the present invention.
Industrial applicability
Sucrose aromatic carboxylic acid esters of the present invention is the useful compound that can be used in various industrial fields, for example, as modifier, for improving forming process and the physical property of the noncrystalline resins such as ABS resin, polyvinyl chloride (PVC) RESINS, epoxy resin, unsaturated polyester, or for improving flexibility, the shock resistance of crystallized polyurethane resin, or as the additive of optical thin film for improving the wet fastness of optical thin film.
Above, describe the present invention in detail, but can increase various changes and correction under the premise without departing from the spirit and scope of the present invention with reference to specific embodiment, this is self-evident to those skilled in the art.
The Japanese patent application (Japanese Patent Application 2012-243049) that the application proposed based on November 2nd, 2012, its content is incorporated in this as reference.
Claims (4)
1. the method for removing of solvent, the solvent that the method is used for removing the manufacture of sucrose aromatic carboxylic acid esters, is characterized in that,
Comprise and use an above vacuum drying apparatus to make pressure and/or Heating temperature in moisture eliminator that variations more than two stages at least occur, the mixture that contains sucrose aromatic carboxylic acid esters and described solvent is carried out to a succession of drying under reduced pressure operation of drying under reduced pressure,
The moisture eliminator internal pressure of the first stage of described drying under reduced pressure operation is below normal atmosphere, and Heating temperature is more than 20 ℃, below 250 ℃,
The moisture eliminator internal pressure of the terminal stage of described drying under reduced pressure operation is below 10kPaabs, and Heating temperature is more than 80 ℃, below 250 ℃.
2. the method for removing of solvent as claimed in claim 1, is characterized in that, described a succession of drying under reduced pressure operation comprises any number of stages in 2～9 stages.
3. the method for removing of solvent as claimed in claim 1 or 2, is characterized in that, the content of the sucrose aromatic carboxylic acid esters in described mixture is 10～80 % by weight.
4. a sucrose aromatic carboxylic acid esters, is characterized in that, obtains by the method for removing of the solvent described in any one in claim 1～3, and APHA value is below 40, and the remaining quantity of solvent is below 3000ppm.
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| WO2015020073A1 (en) * | 2013-08-09 | 2015-02-12 | 第一工業製薬株式会社 | Method for producing sucrose fatty acid ester |
| JP2016141667A (en) * | 2015-02-04 | 2016-08-08 | 第一工業製薬株式会社 | Method for producing sucrose fatty acid ester |
| JP2016141668A (en) * | 2015-02-04 | 2016-08-08 | 第一工業製薬株式会社 | Method for producing sucrose fatty acid ester |
| JP6612543B2 (en) * | 2015-07-13 | 2019-11-27 | 第一工業製薬株式会社 | Resin film |
| KR20200060811A (en) | 2018-11-23 | 2020-06-02 | 주식회사 바우테크 | Heat exchanger for devolatilizing twin screw compounding extruder |
| CN112457356A (en) * | 2020-11-30 | 2021-03-09 | 安徽金禾实业股份有限公司 | Method for removing ethyl ester from secondary esterified crude product in sucralose production |
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- 2013-11-01 CN CN201310534679.8A patent/CN103804436B/en active Active
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2016
- 2016-07-25 KR KR1020160094427A patent/KR20160095651A/en not_active Application Discontinuation
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| CN102836087A (en) * | 2011-06-20 | 2012-12-26 | 第一工业制药株式会社 | Sucrose benzoate composition and production method thereof |
| CN103254254A (en) * | 2012-02-21 | 2013-08-21 | 第一工业制药株式会社 | Sucrose aromatic monocarboxylic acid ester |
| JP2013170148A (en) * | 2012-02-21 | 2013-09-02 | Dai Ichi Kogyo Seiyaku Co Ltd | Sucrose aromatic monocarboxylate |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2014091705A (en) | 2014-05-19 |
| KR20160095651A (en) | 2016-08-11 |
| KR20140057181A (en) | 2014-05-12 |
| JP6109531B2 (en) | 2017-04-05 |
| CN103804436B (en) | 2016-07-06 |
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