JP5531328B2 - Method for producing alkylene oxide adduct - Google Patents
Method for producing alkylene oxide adduct Download PDFInfo
- Publication number
- JP5531328B2 JP5531328B2 JP2008551130A JP2008551130A JP5531328B2 JP 5531328 B2 JP5531328 B2 JP 5531328B2 JP 2008551130 A JP2008551130 A JP 2008551130A JP 2008551130 A JP2008551130 A JP 2008551130A JP 5531328 B2 JP5531328 B2 JP 5531328B2
- Authority
- JP
- Japan
- Prior art keywords
- alkylene oxide
- acid
- crude product
- catalyst
- 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.)
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- 125000002947 alkylene group Chemical group 0.000 title claims description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 239000012043 crude product Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 24
- 239000011949 solid catalyst Substances 0.000 claims description 23
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 22
- 239000000194 fatty acid Substances 0.000 claims description 22
- 229930195729 fatty acid Natural products 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 238000007259 addition reaction Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000003054 catalyst Substances 0.000 description 58
- 238000010790 dilution Methods 0.000 description 26
- 239000012895 dilution Substances 0.000 description 26
- 239000002736 nonionic surfactant Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 229920001515 polyalkylene glycol Polymers 0.000 description 12
- -1 alcohols and amines Chemical class 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 238000010979 pH adjustment Methods 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229940087291 tridecyl alcohol Drugs 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- ACUZDYFTRHEKOS-SNVBAGLBSA-N 2-Decanol Natural products CCCCCCCC[C@@H](C)O ACUZDYFTRHEKOS-SNVBAGLBSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ACUZDYFTRHEKOS-UHFFFAOYSA-N decan-2-ol Chemical compound CCCCCCCCC(C)O ACUZDYFTRHEKOS-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- XSWSEQPWKOWORN-UHFFFAOYSA-N dodecan-2-ol Chemical compound CCCCCCCCCCC(C)O XSWSEQPWKOWORN-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
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- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
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- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920000768 polyamine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 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
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
Description
本発明は、触媒を容易に分離して除去することが可能な非イオン界面活性剤の製造方法に関する。 The present invention relates to a method for producing a nonionic surfactant capable of easily separating and removing a catalyst.
アルコール、アミンなど活性水素含有化合物や脂肪酸アルキルエステルへのアルキレンオキサイド付加物は、各種非イオン界面活性剤や、更に硫酸エステル化やカルボキシメチル化を行い対応するアニオン界面活性剤を製造する中間体や、その他各種溶剤、工業用製品の中間体等として有用である。アルキレンオキシド付加物の中でもポリオキシアルキレン型非イオン界面活性剤は、種々の疎水基に対し、親水基となるアルキレンオキシドの付加モル数を適宜調整することにより、親水性-疎水性バランス（ＨＬＢ）を任意にコントロールできるため特に有用であり、洗浄、乳化、分散といった各種用途に広く用いられている。
このアルキレンオキシド付加粗製物の調製において、アルキレンオキシド付加モル数分布の狭い反応物を得る方法として、アルコキシル化用固体触媒、特にアルカリ変性処理したアルコキシル化用固体触媒を使用する方法がある。固体触媒を使用する場合、触媒をろ過操作等により除去する必要があるが、前記固体触媒を使用した場合には反応液中にポリアルキレングリコール（例えばポリエチレングリコール）等の副反応物が生成するため、前記の用途に使用するためには副生する高分子量のポリアルキレングリコールも触媒とともにろ過操作等で除去することが必要となる。しかし、アルキレンオキシド付加粗製物中に高分子量ポリアルキレングリコールが存在すると一般に濾紙や濾布の目詰まりをおこし易く、その結果ろ過速度が遅くなり、工業的には多大なろ過設備が必要となる。
触媒の分離及び除去を効率よく行う方法として、凝集促進剤としてのアクリル系重合体と水とをアルキレンオキシド付加物に接触させ、副生するポリアルキレングリコールとアルコキシル化用固体触媒を分離して除去する方法が知られている（特許文献１）。しかしながら、この方法では、廃棄物の増加や、コスト増加などのデメリットがあり、また、高分子量ポリエチレングリコールの副生量の多い高付加モル体などの一部のアルキレンオキシド付加物に対しては、ろ過性が必ずしも十分ではない。Alkylene oxide adducts to active hydrogen-containing compounds such as alcohols and amines, and fatty acid alkyl esters include various nonionic surfactants, intermediates that produce corresponding anionic surfactants by sulfate esterification and carboxymethylation, It is useful as an intermediate for various other solvents and industrial products. Among the alkylene oxide adducts, polyoxyalkylene type nonionic surfactants have a hydrophilic-hydrophobic balance (HLB) by appropriately adjusting the number of moles of alkylene oxide added as a hydrophilic group for various hydrophobic groups. Is particularly useful because it can be controlled arbitrarily, and is widely used in various applications such as washing, emulsification, and dispersion.
In the preparation of this alkylene oxide addition crude product, as a method of obtaining a reaction product having a narrow distribution of alkylene oxide addition mole number, there is a method of using a solid catalyst for alkoxylation, particularly a solid catalyst for alkoxylation which has been subjected to alkali modification treatment. When a solid catalyst is used, it is necessary to remove the catalyst by a filtration operation or the like. However, when the solid catalyst is used, a side reaction product such as polyalkylene glycol (for example, polyethylene glycol) is generated in the reaction solution. In order to use it in the above-mentioned applications, it is necessary to remove the high-molecular-weight polyalkylene glycol by-produced together with the catalyst by a filtration operation or the like. However, if a high molecular weight polyalkylene glycol is present in an alkylene oxide-added crude product, filter paper and filter cloth are generally easily clogged. As a result, the filtration speed is slow, and a large amount of filtration equipment is required industrially.
As a method for efficiently separating and removing the catalyst, an acrylic polymer as an aggregation accelerator and water are brought into contact with an alkylene oxide adduct, and the polyalkylene glycol by-product and the solid catalyst for alkoxylation are separated and removed. A method is known (Patent Document 1). However, in this method, there are disadvantages such as an increase in waste and an increase in cost, and for some alkylene oxide adducts such as high addition moles having a high by-product amount of high molecular weight polyethylene glycol, Filterability is not always sufficient.
本発明は、触媒及びポリアルキレングリコールを容易に分離して除去することが可能なアルキレンオキシド付加物の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of the alkylene oxide adduct which can isolate | separate and remove a catalyst and polyalkylene glycol easily.
本発明は、アルコキシル化用固体触媒を使用して得たアルキレンオキシド付加粗製物のｐＨおよび水分量を調整することにより、前記粗製物のろ過性が向上し、触媒を容易に分離して除去することが可能となるとの知見に基づいてなされたものである。
すなわち、本発明は、
(a) アルコキシル化用固体触媒の存在下で、活性水素含有化合物および／または脂肪酸アルキルエステルにアルキレンオキシドを付加反応させてアルキレンオキシド付加粗製物を得る工程、
(b) 前記アルキレンオキシド付加粗製物に、２０℃における水への溶解度が１以上であって分子量４００以下の有機酸または２０℃における水への溶解度が１以上の無機酸を添加することによりｐＨを4.0〜8.0に、かつ、水分量を5質量%以上15質量%以下に調整する工程、
(c) 工程(b)のアルキレンオキシド付加粗製物からアルコキシル化用固体触媒を分離して除去する工程、
を含む、アルキレンオキシド付加物の製造方法を提供する。The present invention improves the filterability of the crude product by adjusting the pH and water content of the alkylene oxide-added crude product obtained using the alkoxylation solid catalyst, and the catalyst is easily separated and removed. It was made based on the knowledge that it would be possible.
That is, the present invention
(a) a step of adding an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of a solid catalyst for alkoxylation to obtain an alkylene oxide-added crude product,
(b) By adding an organic acid having a solubility in water at 20 ° C. of 1 or more and a molecular weight of 400 or less or an inorganic acid having a solubility in water at 20 ° C. of 1 or more to the alkylene oxide-added crude product. Adjusting the water content to 4.0 to 8.0 and the water content to 5% by mass or more and 15% by mass or less,
(c) a step of separating and removing the alkoxylation solid catalyst from the crude alkylene oxide addition product of step (b),
The manufacturing method of the alkylene oxide adduct containing this is provided.
また、本発明は、
(d) アルカリ変性処理を施したアルコキシル化用固体触媒の存在下で、脂肪酸アルキルエステルにアルキレンオキシドを付加反応させて非イオン界面活性剤粗製物を得る工程、
(e) 前記非イオン界面活性剤粗製物のｐＨを4.0〜8.0に、かつ、水分量を5質量%以上15質量%以下に調整する工程、
(f) 工程(e)の非イオン界面活性剤粗製物からアルコキシル化用固体触媒を分離して除去する工程、
を含む、非イオン界面活性剤の製造方法を提供する。The present invention also provides:
(d) a step of adding a fatty acid alkyl ester to an alkylene oxide in the presence of an alkali-modified solid catalyst for alkoxylation to obtain a crude nonionic surfactant,
(e) adjusting the pH of the nonionic surfactant crude product to 4.0 to 8.0, and adjusting the water content to 5 mass% or more and 15 mass% or less,
(f) a step of separating and removing the alkoxylation solid catalyst from the crude nonionic surfactant in step (e),
The manufacturing method of the nonionic surfactant containing this is provided.
本発明によれば、アルコキシル化用固体触媒を用いて得たアルキレンオキシド付加粗製物のｐＨ及び水分量を調整することにより、前記粗製物中から高分子量ポリアルキレングリコール等の副生成物とともに触媒をろ過操作等により容易に分離して除去することができる。また、高分子量ポリアルキレングリコールの副生量の多い高付加モル体においても良好なろ過性を得ることができる。そのため従来困難であった付加モル数分布が狭いアルキレンオキシド付加物の高付加モル体を工業的に妥当なコストで製造することが可能となる。 According to the present invention, by adjusting the pH and water content of the alkylene oxide-added crude product obtained using the alkoxylation solid catalyst, the catalyst is added together with by-products such as high molecular weight polyalkylene glycol from the crude product. It can be easily separated and removed by a filtration operation or the like. In addition, good filterability can be obtained even in a high addition molar body having a large amount of by-product of high molecular weight polyalkylene glycol. Therefore, it is possible to produce a high addition mole of an alkylene oxide adduct having a narrow addition mole number distribution, which has been conventionally difficult, at an industrially reasonable cost.
本発明の工程(a)では、アルコキシル化用固体触媒の存在下で、活性水素含有化合物および／または脂肪酸アルキルエステルにアルキレンオキシドを付加反応させてアルキレンオキシド付加粗製物を得る。また、本発明の工程(d)では、アルカリ変性処理を施したアルコキシル化用固体触媒の存在下で、脂肪酸アルキルエステルにアルキレンオキシドを付加反応させて非イオン界面活性剤粗製物を得る。
本発明に使用される「アルコキシル化用固体触媒」としては、例えば、金属イオン添加酸化マグネシウム（特公平６−１５０３８号公報、特開平７−２２７５４０号公報、同６−１９８１６９号公報、同６−１８２２０６号公報、同５−１７０６８８号公報）、焼成ハイドロタルサイト（特開平２−７１８４１号公報）、水酸化アルミニウム・マグネシウム焼成物（特願平７−９４４１７号公報、特開平８−２６８９１９号公報）等のＡｌ−Ｍｇ系複合酸化物触媒などのアルコキシル化触媒が挙げられる。また、上記触媒はアルカリ変性処理により表面改質していてもよい（特願平６−３３４７８１号公報、同６−３３４７８２号公報）。特に、脂肪酸アルキルエステルにアルキレンオキシドを付加する場合、アルカリ変性処理した触媒を使用して反応を行うと、残存未反応脂肪酸アルキルエステル量が少なく、アルキレンオキシド付加モル量が極めて狭い生成物を得ることが可能となる。本発明においては、水酸化アルミニウム・マグネシウム焼成物をアルカリ変性処理により表面改質した触媒が好ましい。In step (a) of the present invention, an alkylene oxide addition crude product is obtained by addition reaction of an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of a solid catalyst for alkoxylation. In the step (d) of the present invention, a crude nonionic surfactant is obtained by addition reaction of an alkylene oxide with a fatty acid alkyl ester in the presence of an alkali-modified solid catalyst for alkoxylation.
Examples of the “solid catalyst for alkoxylation” used in the present invention include, for example, magnesium ion-added magnesium oxide (JP-B-6-15038, JP-A-7-227540, JP-A-6-198169, No. 182206 and No. 5-170688), calcined hydrotalcite (Japanese Patent Laid-Open No. 2-71841), calcined aluminum hydroxide and magnesium (Japanese Patent Application No. 7-94417, Japanese Patent Laid-Open No. 8-268919) And alkoxylation catalysts such as Al—Mg based composite oxide catalysts. The catalyst may be surface-modified by alkali modification treatment (Japanese Patent Application Nos. 6-334781 and 6-334882). In particular, when adding an alkylene oxide to a fatty acid alkyl ester, if the reaction is carried out using an alkali-modified catalyst, a product with a small amount of residual unreacted fatty acid alkyl ester and a very narrow alkylene oxide addition molar amount can be obtained. Is possible. In the present invention, a catalyst obtained by surface modification of an aluminum hydroxide / magnesium fired product by alkali modification treatment is preferable.
前記水酸化アルミニウム・マグネシウム焼成物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開平８−２６８９１９号公報に記載のものなどが挙げられる。具体的には、下記式（Ｉ）で表される水酸化アルミニウムと水酸化マグネシウムとの共沈物であり、焼成によりアルミニウム−マグネシウム系複合金属酸化物触媒とすることができる。
ｎＭｇＯ・Ａｌ2Ｏ3・ｍＨ2Ｏ （Ｉ）
［前記式（Ｉ）中、ｎは特に制限はなく、目的に応じて適宜選択することができるが、２．５程度が好ましく、ｍは特に制限はなく、目的に応じて適宜選択することができる。］ ここで、前記焼成温度は、特に制限はなく、目的に応じて適宜選択することができるが、触媒活性発現と副生物の生成量抑制の点から、４００〜９５０℃が好ましく、４００〜９００℃がより好ましい。The calcined aluminum hydroxide / magnesium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those described in JP-A-8-268919. Specifically, it is a coprecipitate of aluminum hydroxide and magnesium hydroxide represented by the following formula (I), and can be made into an aluminum-magnesium composite metal oxide catalyst by firing.
nMgO.Al 2 O 3 .mH 2 O (I)
[In formula (I), n is not particularly limited and can be appropriately selected according to the purpose, but is preferably about 2.5, and m is not particularly limited and can be appropriately selected according to the purpose. it can. Here, the calcination temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 400 to 950 ° C., and preferably 400 to 900 from the viewpoint of the expression of catalytic activity and the suppression of the amount of by-products generated. ° C is more preferred.
また、前記水酸化アルミニウム・マグネシウム焼成物をアルカリ変性処理により表面改質した触媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前述の特願平６−３３４７８１号公報、同６−３３４７８２号公報に記載のものなどが挙げられる。具体的には、前記水酸化アルミニウム・マグネシウム焼成物を、金属水酸化物又は金属アルコキシドで表面改質して、改質焼成水酸化アルミナ・マグネシウム触媒とすることができる。前記金属水酸化物としては、アルカリ金属又はアルカリ土類金属の水酸化物が好ましく、中でも、水酸化ナトリウム、水酸化カリウムがより好ましい。前記金属アルコキシドとしては、アルカリ金属又はアルカリ土類金属のアルコキシドが好ましく、中でも、ナトリウムアルコキシド、カリウムアルコキシドがより好ましい。また、アルコキシドの炭素数は１〜４が好ましい。
なお、本発明におけるアルカリ変性処理は、例えば、触媒をアルカリ金属又はアルカリ土類金属の水酸化物またはアルコキシドで改質した後、反応用触媒として使用する方法や、アルコキシル化用反応器の中で、原料の脂肪酸アルキルエステルと金属水酸化物又は金属アルコキシドを混合し、原料中で触媒の改質をする方法などにより行うことができる。
すなわち、アルカリ変性処理は、触媒の調製時に行ってもよいし、付加反応の際にアルカリを添加することによって行ってもよい。The catalyst obtained by surface modification of the calcined aluminum hydroxide / magnesium by alkali modification treatment is not particularly limited and can be appropriately selected according to the purpose. For example, the above-mentioned Japanese Patent Application No. 6-334781 The thing of the gazette and 6-333482 gazette etc. are mentioned. Specifically, the above-mentioned calcined aluminum hydroxide / magnesium can be surface-modified with a metal hydroxide or a metal alkoxide to obtain a modified calcined alumina / magnesium hydroxide catalyst. As the metal hydroxide, alkali metal or alkaline earth metal hydroxide is preferable, and sodium hydroxide and potassium hydroxide are more preferable. The metal alkoxide is preferably an alkali metal or alkaline earth metal alkoxide, and more preferably sodium alkoxide or potassium alkoxide. Moreover, as for carbon number of an alkoxide, 1-4 are preferable.
The alkali modification treatment in the present invention is, for example, a method in which the catalyst is modified with an alkali metal or alkaline earth metal hydroxide or alkoxide and then used as a reaction catalyst, or in an alkoxylation reactor. The raw material fatty acid alkyl ester can be mixed with a metal hydroxide or metal alkoxide, and the catalyst can be modified in the raw material.
That is, the alkali modification treatment may be performed during the preparation of the catalyst, or may be performed by adding an alkali during the addition reaction.
前記触媒は、１種単独で使用してもよいし、２種以上を併用してもよい。触媒の粒子径に特に制限は無く、また、通常、アルキレンオキシド付加反応時には、例えば触媒粒子内部での反応熱の蓄積や高分子量副生物の生成、急激な圧力差の発生、撹拌翼等による機械的な剪断などによって触媒粒子が崩壊するため、触媒の粒子径は変動し得る。さらには、後述するように、触媒の活性を向上させるために反応混合物に多価アルコールを加えることにより触媒をさらに微細化する場合もある。従って、反応後の粗製物中に含まれる触媒の粒子径は、平均粒子径として例えば０．１μｍ〜５００μｍであり得る。また、前記触媒は、微細化が顕著に起こる点で、多孔質粒子であることが好ましく、また、比表面積が５０〜４００ｍ2／ｇであることが好ましい。
なお、本発明において、触媒の平均粒子径とは、レーザー光散乱式粒度分布測定装置 LA-920（HORIBA社製）を使用してアセトニトリルを分散媒として測定し、メジアン径として算出した値を意味する。
前記触媒の使用量としては、反応が適切に進行する量であれば、特に制限はなく、使用する触媒の活性等に応じて適宜選択することができるが、前記反応原料（脂肪酸アルキルエステルとアルキレンオキシド）の総質量に対し、０．０１〜５質量％が好ましく、０．０３〜１質量％がより好ましく、０．０５〜０．２質量％が特に好ましい。触媒の使用量を前記好ましい範囲とすることにより反応を適切に進行することができる。The said catalyst may be used individually by 1 type, and may use 2 or more types together. There is no particular limitation on the particle size of the catalyst, and usually during alkylene oxide addition reaction, for example, accumulation of reaction heat inside the catalyst particles, generation of high molecular weight by-products, generation of abrupt pressure difference, machinery using stirring blades, etc. The catalyst particle size may fluctuate because the catalyst particles collapse due to, for example, shearing. Furthermore, as will be described later, the catalyst may be further refined by adding a polyhydric alcohol to the reaction mixture in order to improve the activity of the catalyst. Therefore, the particle diameter of the catalyst contained in the crude product after the reaction can be, for example, 0.1 μm to 500 μm as the average particle diameter. In addition, the catalyst is preferably a porous particle from the viewpoint that refining occurs remarkably, and the specific surface area is preferably 50 to 400 m 2 / g.
In the present invention, the average particle diameter of the catalyst means a value calculated as a median diameter by measuring acetonitrile as a dispersion medium using a laser light scattering particle size distribution analyzer LA-920 (manufactured by HORIBA). To do.
The amount of the catalyst used is not particularly limited as long as the reaction proceeds appropriately, and can be appropriately selected according to the activity of the catalyst to be used. The reaction raw materials (fatty acid alkyl ester and alkylene) 0.01-5 mass% is preferable with respect to the gross mass of oxide), 0.03-1 mass% is more preferable, and 0.05-0.2 mass% is especially preferable. By making the usage-amount of a catalyst into the said preferable range, reaction can be advanced appropriately.
本発明において、活性水素含有化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アルコール類、アミン類、アミド類、フェノール類、チオール類などが挙げられる。これらの中でも、下記一般式（ＩＩ）で表されるアルコール類が、好ましい。
Ｒ１ＯＨ （ＩＩ）
［前記一般式（ＩＩ）中、Ｒ１は、特に制限はなく、得ようとする生成物に要求される性能等に応じて適宜選択することができ、例えば、アルキル基、アルケニル基などが挙げられる。前記アルキル基、アルケニル基は、直鎖であってもよいし、分岐鎖を有していてもよい。前記アルキル基、アルケニル基の炭素数も、特に制限はなく、目的に応じて適宜選択することができるが、１〜４０が好ましく、３〜３０が好ましく、６〜２２が特に好ましい。］
アルコール類の具体例としては、n-オクタノール、n-デカノール、n-ドデカノール、n-テトラデカノール、n-ヘキサデカノール、n-オクタデカノール、オレイルアルコール、エトコサノール、ベヘノール、ノナノール、ウンデカノール、トリデカノール等の炭素数８〜２２の飽和又は不飽和の直鎖アルキル基を有する高級脂肪族第一級アルコール、または、２−エチルヘキサノール、炭素数１６〜３６のゲルベ型アルコール等の分岐鎖アルキル第一級アルコール、及び、２−オクタノール、２−デカノール、２−ドデカノール等の第二級アルコール、更に、ベンジルアルコール等が挙げられる。
アミン類の具体例としては、オクチルアミン、ジオクチルアミン、ラウリルアミン、ジラウリルアミン、ステアリルアミン、ジステアリルアミン等の炭素数８〜２４の飽和又は不飽和アルキル基を有する第一級又は第二級アミン、また、エチレンジアミン、ジエチレントリアミン等のポリアミンなどが挙げられる。
アミド類の具体例としては、ラウリン酸モノエタノールアミド、ラウリン酸ジエタノールアミド等の炭素数１２〜１８のアルカノールアミドが挙げられる。
これらの活性水素含有化合物の中で炭素数８〜２２の直鎖または分岐の飽和又は不飽和のアルコールが好ましい。In the present invention, the active hydrogen-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols, amines, amides, phenols, and thiols. Among these, alcohols represented by the following general formula (II) are preferable.
R1OH (II)
[In general formula (II), R1 is not particularly limited and may be appropriately selected depending on the performance required for the product to be obtained. Examples thereof include an alkyl group and an alkenyl group. . The alkyl group and alkenyl group may be linear or branched. The number of carbon atoms of the alkyl group or alkenyl group is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 40, preferably 3 to 30, and particularly preferably 6 to 22. ]
Specific examples of alcohols include n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, oleyl alcohol, etcosanol, behenol, nonanol, undecanol, tridecanol. Branched aliphatic primary alcohols such as higher aliphatic primary alcohols having a saturated or unsaturated linear alkyl group having 8 to 22 carbon atoms, such as 2-ethylhexanol, Gerve type alcohol having 16 to 36 carbon atoms, etc. Examples include secondary alcohols such as secondary alcohols, 2-octanol, 2-decanol, and 2-dodecanol, and benzyl alcohol.
Specific examples of amines include primary or secondary having a saturated or unsaturated alkyl group having 8 to 24 carbon atoms such as octylamine, dioctylamine, laurylamine, dilaurylamine, stearylamine, distearylamine and the like. Examples include amines and polyamines such as ethylenediamine and diethylenetriamine.
Specific examples of amides include alkanolamides having 12 to 18 carbon atoms such as lauric acid monoethanolamide and lauric acid diethanolamide.
Among these active hydrogen-containing compounds, linear or branched saturated or unsaturated alcohols having 8 to 22 carbon atoms are preferable.
本発明において、脂肪酸アルキルエステルとしては、特に制限はなく、目的に応じて適宜選択することができる。前記脂肪酸エステルは一般式Ｒ1ＣＯＯＲ2で示され、ここで、式中、Ｒ1、Ｒ2は、アルキル基を意味するが、これは炭素鎖中に二重結合を含むいわゆるアルケニル基をも含む概念である。また、グリセリンの脂肪酸エステルであるトリグリセライドも含まれる。Ｒ1の炭素数は、例えば１〜４０が好ましく、３〜３０がより好ましく、５〜２１が特に好ましい。Ｒ2の炭素数は、例えば１〜３０が好ましく、１〜１０がより好ましく、１〜４が特に好ましい。脂肪酸アルキルエステルは、１種単独で使用してもよいし、２種以上を併用してもよい。
脂肪酸アルキルエステルの使用量は、特に制限はなく、得ようとする生成物量や、触媒や後述のアルキレンオキシドの使用量等に応じて、適宜選択することができる。In the present invention, the fatty acid alkyl ester is not particularly limited and may be appropriately selected depending on the purpose. The fatty acid ester is represented by the general formula R 1 COOR 2 , wherein R 1 and R 2 represent an alkyl group, which also has a so-called alkenyl group containing a double bond in the carbon chain. It is a concept that includes. Also included are triglycerides, which are fatty acid esters of glycerin. The number of carbon atoms in R 1, for example 1 to 40, more preferably 3 to 30, particularly preferably from 5 to 21. The number of carbon atoms of R 2 is, for example, preferably 1 to 30, more preferably 1 to 10, 1 to 4 are particularly preferred. Fatty acid alkyl ester may be used individually by 1 type, and may use 2 or more types together.
The amount of fatty acid alkyl ester used is not particularly limited, and can be appropriately selected according to the amount of product to be obtained, the amount of catalyst and the amount of alkylene oxide described below, and the like.
本発明において、アルキレンオキシドとしては、前記活性水素含有化合物および／または脂肪酸アルキルエステルと反応してアルキレンオキシド付加物が得られるものであれば、特に制限はなく、目的に応じて適宜選択することができるが、例えば炭素数２〜４のアルキレンオキシドが好ましい。具体的には、エチレンオキシド、プロピレンオキシド、ブチレンオキシドなどを使用し得、これらは一種又は二種以上の混合物として用いることができる。本発明では、活性水素含有化合物および／または脂肪酸アルキルエステル１モルあたり、１〜５０モルのアルキレンオキシドを付加させたものが好ましく、３〜３０モルのアルキレンオキシドを付加させたものがより好ましく、特に好ましくは５〜２０モルのアルキレンオキシドを付加したアルキレンオキシドである。また、非イオン界面活性剤としては、ＨＬＢ（グリフィン法）が３〜２０のものが好ましい。
前記アルキレンオキシドの使用量は特に制限はなく、使用する前記脂肪酸アルキルエステルの種類、得ようとする生成物に要求される性能等に応じて適宜選択することができるが、前記脂肪酸アルキルエステルの使用量１モルに対して、１〜５０モルが好ましく、３〜３０モルがより好ましく、５〜２０モルが特に好ましい。In the present invention, the alkylene oxide is not particularly limited as long as it can be reacted with the active hydrogen-containing compound and / or the fatty acid alkyl ester to obtain an alkylene oxide adduct, and can be appropriately selected according to the purpose. For example, an alkylene oxide having 2 to 4 carbon atoms is preferable. Specifically, ethylene oxide, propylene oxide, butylene oxide and the like can be used, and these can be used as one kind or a mixture of two or more kinds. In the present invention, it is preferable to add 1 to 50 mol of alkylene oxide per mol of active hydrogen-containing compound and / or fatty acid alkyl ester, more preferable to add 3 to 30 mol of alkylene oxide, particularly Preferably, it is an alkylene oxide to which 5 to 20 moles of alkylene oxide is added. Moreover, as a nonionic surfactant, the thing of 3-20 of HLB (Griffin method) is preferable.
The amount of the alkylene oxide used is not particularly limited and can be appropriately selected according to the type of the fatty acid alkyl ester used, the performance required for the product to be obtained, etc. 1-50 mol is preferable with respect to 1 mol of amounts, 3-30 mol is more preferable, and 5-20 mol is especially preferable.
本発明においては、工程(a)及び(d)の反応を、アルコキシル化用固体触媒及び多価アルコールの存在下で行ってもよい。多価アルコールを反応系に加えることにより、触媒が微細化し、その活性が向上するという効果が得られる。
前記多価アルコールとしては、水酸基を分子内に２基以上有し、かつ、前記触媒を微細化する効果が得られるものであれば特に制限はなく、例えば、前記脂肪酸アルキルエステルに乳化又は分散均一化できる化合物の中から目的に応じて適宜選択することができ、グリセリン、エチレングリコール、ジエチレングリコールなどが好ましく挙げられる。これらの中でも、グリセリンが特に好ましい。前記多価アルコールは、１種単独で使用してもよいし、２種以上を併用してもよい。
前記多価アルコールの使用量は、特に制限はなく、目的に応じて適宜選択することができるが、前記反応原料（活性水素含有化合物および／または脂肪酸アルキルエステルとアルキレンオキシド）の総質量に対し、０．０２〜０．５質量％が好ましく、０．０５〜０．２５質量％がより好ましい。また、前記触媒の質量に対し、１．０倍以上が好ましく、１．２５倍以上がより好ましい。多価アルコールの使用量を前記好ましい範囲とすることにより、触媒を速やかにかつ十分に微細化することが可能となる。In the present invention, the reactions of steps (a) and (d) may be performed in the presence of a solid catalyst for alkoxylation and a polyhydric alcohol. By adding a polyhydric alcohol to the reaction system, the effect of miniaturizing the catalyst and improving its activity can be obtained.
The polyhydric alcohol is not particularly limited as long as it has two or more hydroxyl groups in the molecule and the effect of refining the catalyst is obtained. For example, the fatty acid alkyl ester is uniformly emulsified or dispersed. Can be suitably selected from the compounds that can be converted according to the purpose, and preferred examples include glycerin, ethylene glycol, and diethylene glycol. Among these, glycerin is particularly preferable. The said polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.
The amount of the polyhydric alcohol used is not particularly limited and may be appropriately selected depending on the purpose. However, with respect to the total mass of the reaction raw materials (active hydrogen-containing compound and / or fatty acid alkyl ester and alkylene oxide), 0.02-0.5 mass% is preferable and 0.05-0.25 mass% is more preferable. Moreover, 1.0 times or more is preferable with respect to the mass of the said catalyst, and 1.25 times or more is more preferable. By making the usage-amount of a polyhydric alcohol into the said preferable range, it becomes possible to refine | miniaturize a catalyst rapidly and fully.
上記原料から、周知の操作手順及び反応条件によりアルキレンオキシド付加粗製物を容易に調製することができる。反応温度は８０〜２３０℃が好ましく、反応圧力は反応温度にもよるが０〜２MPa、好ましくは０．２〜０．８Mpaであり、必要により窒素希釈した条件下でアルキレンオキシドを付加反応させることもできる。上記反応は、たとえばオートクレーブ中に活性水素含有化合物および／または脂肪酸アルキルエステルとアルコキシル化用固体触媒とを仕込み、窒素雰囲気下で所定の温度、圧力条件下でアルキレンオキシドを導入して反応して得ることができる。 From the above raw materials, an alkylene oxide-added crude product can be easily prepared by well-known operating procedures and reaction conditions. The reaction temperature is preferably 80 to 230 ° C., and the reaction pressure is 0 to 2 MPa, preferably 0.2 to 0.8 MPa, although it depends on the reaction temperature. If necessary, the alkylene oxide is subjected to addition reaction under nitrogen diluted conditions. You can also. The above reaction is obtained, for example, by charging an active hydrogen-containing compound and / or fatty acid alkyl ester and a solid catalyst for alkoxylation into an autoclave and introducing alkylene oxide under a predetermined temperature and pressure under a nitrogen atmosphere. be able to.
本発明の工程(b)では、工程(a)で得たアルキレンオキシド付加粗製物に、２０℃における水への溶解度が１以上であって分子量４００以下の有機酸または２０℃における水への溶解度が１以上の無機酸を添加することにより、アルキレンオキシド付加粗製物のｐＨが4.0〜8.0に、かつ、水分量が5質量%以上15質量%以下に調整される。また、本発明の工程(e)では、工程(d)で得た非イオン界面活性剤粗製物のｐＨが4.0〜8.0に、かつ、水分量が5質量%以上15質量%以下に調整される。
ｐＨの調整は酸（ｐＨ調整剤）と水分をアルキレンオキシド付加粗製物または非イオン界面活性剤粗製物に添加することにより、前記アルキレンオキシド付加粗製物または非イオン界面活性剤粗製物のｐＨが4.0〜8.0、好ましくは5.0〜8.0、特に好ましくは約7.5に調整される。ｐＨが４より小さくなるとろ過後の液が白濁することがあり、これは、分子量１万以上２万未満程度のポリアルキレングリコールが残存するためであると考えられる。さらに、上記のようにｐＨの値が低いと触媒の金属分がろ過後の液に溶出してアルキレンオキシド付加物または非イオン界面活性剤に混入する場合があり、触媒の金属分が混入したアルキレンオキシド付加物または非イオン界面活性剤は、他成分と混合した組成物とする場合に、該他成分との相互作用により、沈殿を形成して外観を悪化させたり、該他成分の性能を低下させたりするという問題点を有する。また、ｐＨが８を超えるとろ過性が急激に低下する。
本発明の方法においてはｐＨ調整剤として酸が使用される。酸としては有機酸および無機酸を使用することができる。本発明で使用できる酸は２０℃における水への溶解度（水１００ｇに溶解し得る溶質の質量（ｇ））が１以上のものである。また、本発明における有機酸とは、分子量４００以下の有機酸を指す。ポリアクリル酸などポリマーの酸性化合物では、濾過性改善効果は小さく、また高分子化合物の添加は、製品の粘度上昇によるハンドリング性悪化や、製品中にポリマーが残存することによる低温での濁りの発生など液外観を損ねる原因となる。有機酸としては、例えば酢酸、プロピオン酸、酪酸、吉草酸、グリコール酸、乳酸、グリセリン酸、リンゴ酸、酒石酸、クエン酸、パラトルエンスルホン酸などの有機酸が好ましく使用される。また、無機酸として、例えば、ホウ酸、リン酸、塩酸、硫酸、硝酸などが使用される。
上記のうち、有機カルボン酸が無機酸等に比べて弱酸であるためｐＨの調整がしやすく、また触媒成分の溶出の問題も少ないために好ましい。特にｐＫａが２．５以上５．０以下の有機カルボン酸が好ましく使用される。ｐＫａが２．５より小さい強酸であると、十分に濾過性改善効果の得られる量を添加すると、触媒である複合金属酸化物の溶解が起き、マグネシウムやアルミニウムなどの触媒成分が製品に溶出する場合があるため、製品安定性や他の組成物との相互作用の点から問題となる場合がある。ｐＫａが５．０を超えると酸添加の効果が得られない場合がある。また中でも金属のキレート効果を有するヒドロキシカルボン酸がモル数当りの効果が大きいため、より好ましい。有機カルボン酸としては、特に酢酸、乳酸、リンゴ酸、クエン酸が好ましい。これらの酸は、一種単独で使用しても良いし、二種以上を併用しても良い。
なお、本発明におけるｐＨの値は、水分添加及び酸を添加したアルキレンオキシド付加物の一部をサンプリングし、アルキレンオキシド付加物濃度が5%となるように蒸留水により希釈した希釈物のｐＨを２５℃で測定することにより得られた値を意味する。なお、ｐＨの測定には例えば堀場製作所製のＨＯＲＩＢＡ Ｄ-５１ＳのｐＨメータを使用することができる。In the step (b) of the present invention, the alkylene oxide-added crude product obtained in the step (a) has an solubility in water at 20 ° C. of 1 or more and an organic acid having a molecular weight of 400 or less or solubility in water at 20 ° C. By adding one or more inorganic acids, the pH of the alkylene oxide-added crude product is adjusted to 4.0 to 8.0, and the water content is adjusted to 5% by mass or more and 15% by mass or less. Further, in the step (e) of the present invention, the pH of the crude nonionic surfactant obtained in the step (d) is adjusted to 4.0 to 8.0, and the water content is adjusted to 5% by mass or more and 15% by mass or less. .
The pH is adjusted by adding an acid (pH adjusting agent) and moisture to the alkylene oxide addition crude product or the nonionic surfactant crude product so that the pH of the alkylene oxide addition crude product or the nonionic surfactant crude product is 4.0. It is adjusted to ˜8.0, preferably 5.0 to 8.0, particularly preferably about 7.5. When the pH is less than 4, the liquid after filtration may become cloudy, which is considered to be because polyalkylene glycol having a molecular weight of about 10,000 to less than 20,000 remains. Furthermore, if the pH value is low as described above, the metal content of the catalyst may elute into the liquid after filtration and mix with the alkylene oxide adduct or the nonionic surfactant. Oxide adducts or nonionic surfactants, when mixed with other components, form precipitates that deteriorate the appearance or reduce the performance of the other components due to the interaction with the other components. Or have the problem of Moreover, if pH exceeds 8, filterability will fall rapidly.
In the method of the present invention, an acid is used as a pH adjuster. Organic acids and inorganic acids can be used as the acid. The acid that can be used in the present invention has a solubility in water at 20 ° C. (mass of solute that can be dissolved in 100 g of water (g)) of 1 or more. The organic acid in the present invention refers to an organic acid having a molecular weight of 400 or less. Polymeric compounds such as polyacrylic acid have little effect on improving filterability, and the addition of a high molecular weight compound causes deterioration of handling properties due to an increase in the viscosity of the product and generation of turbidity at low temperatures due to the polymer remaining in the product. It may cause damage to the liquid appearance. As the organic acid, for example, organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, glycolic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid, and paratoluenesulfonic acid are preferably used. Further, as the inorganic acid, for example, boric acid, phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid and the like are used.
Among the above, the organic carboxylic acid is preferable because it is a weak acid as compared with an inorganic acid or the like, so that the pH can be easily adjusted, and the problem of elution of the catalyst component is small. In particular, an organic carboxylic acid having a pKa of 2.5 to 5.0 is preferably used. If the pKa is a strong acid less than 2.5, the addition of an amount capable of sufficiently improving the filterability causes dissolution of the composite metal oxide, which is a catalyst, and catalyst components such as magnesium and aluminum are eluted into the product. In some cases, this may be problematic in terms of product stability and interaction with other compositions. If pKa exceeds 5.0, the effect of acid addition may not be obtained. Of these, hydroxycarboxylic acids having a metal chelating effect are more preferred because they have a large effect per mole. As the organic carboxylic acid, acetic acid, lactic acid, malic acid, and citric acid are particularly preferable. These acids may be used individually by 1 type, and may use 2 or more types together.
In the present invention, the pH value is obtained by sampling a part of the alkylene oxide adduct added with water and acid, and adjusting the pH of the diluted product with distilled water so that the alkylene oxide adduct concentration is 5%. It means a value obtained by measuring at 25 ° C. For the measurement of pH, for example, a HORIBA D-51S pH meter manufactured by HORIBA, Ltd. can be used.
また、水分量は、5質量%以上15質量%以下、好ましくは7質量%以上12質量%以下、特に好ましくは約10質量%に調整される。水分量が少なすぎるとろ過性の向上効果は得られないが、これは高分子量ポリアルキレングリコールの凝集が不足するためであると考えられる。また、水分量が多すぎるとポリアルキレングリコールが溶解し、白濁が起こる。
水分量調整の方法は特に限定されるものではないが、例えば蒸留水やイオン交換水を添加することにより行われる。本発明における水分量測定は、水分を添加した後（ｐＨ調整、ろ過助剤添加の前）若しくはろ過後の濾液を用いて、カールフィッシャー法により水分を測定することにより行われる。なお、カールフィッシャー水分計としては、例えば京都電子工業製のＫＥＭ ＭＫＣ-５０１を使用することができる。The water content is adjusted to 5 to 15% by mass, preferably 7 to 12% by mass, and particularly preferably about 10% by mass. If the amount of water is too small, the effect of improving the filterability cannot be obtained, but this is considered to be due to insufficient aggregation of the high molecular weight polyalkylene glycol. Moreover, when there is too much water content, polyalkylene glycol will melt | dissolve and white turbidity will arise.
The method for adjusting the amount of water is not particularly limited, and for example, it is performed by adding distilled water or ion exchange water. The water content in the present invention is measured by measuring the water content by the Karl Fischer method after adding water (before adjusting pH and adding filter aid) or using the filtrate after filtration. As the Karl Fischer moisture meter, for example, KEM MKC-501 manufactured by Kyoto Electronics Industry can be used.
本発明の工程(c)及び(f)では、それぞれ工程(b)及び(e)でｐＨおよび水分量を調整したアルキレンオキシド付加粗製物または非イオン界面活性剤粗製物からアルコキシル化用固体触媒を分離して除去する。ｐＨおよび水分量を調整することにより、アルキレンオキシド付加粗製物または非イオン界面活性剤粗製物に含まれる重量平均分子量２万以上の高分子量ポリエチレングリコールなどの副生成物を適度に凝集させることができると考えられ、従って、例えば周知の操作手順及びろ過条件でろ過することにより、前記高分子量ポリエチレングリコールとともに、アルコキシル化用固体触媒を容易に分離して除去することができる。更には、遠心分離により、例えばデカンター或いは遠心分離機などを用いて触媒を除去することも可能である。
濾紙として例えばセルロースとポリエステルの二層フィルター、金属メッシュ型フィルターなどを用いて、減圧又は加圧下、温度３５〜１００℃、特に４０〜８５℃の条件下でろ過するのが好ましい。
また、好ましくはろ過助剤を使用することでろ過性を向上させることができる。ろ過助剤としては、当業者に知られる任意のろ過助剤を用いることができるが、例えば、主成分であるＳｉＯ2を８０〜９５％含有する非結晶質ケイ酸のケイソウ土として、例えばラジオライト♯１００、ラジオライト♯２００、ラジオライト♯５００、ラジオライト♯６００、ラジオライト♯９００、ゼムライトスーパーＭ、ゼムライトスーパー1、ゼムライトスーパー５６、ゼムライトスーパー２、セライト５０１、セライト５０３、セライト５３５、セライト５４５、ハイフロスーパーセル、スタンダードスーパーセル、フィルターセル等が挙げられる。主成分であるＳｉＯ2を約７０％含有するケイ酸アルミニウムとして、例えば、トプコ♯３１、トプコ♯３４等が挙げられ、セルロース系ろ過助剤としてはＫＣフロック、ＳＷ４０、ＢＷ２０、ＢＷ４０、ＢＷ１００、ＢＷ２００、ＢＮＢ２０等が挙げられ、それぞれ単独又は２種以上の混合物として用いることができる。ろ過助剤の使用量は、粗製物に対して０．０５〜５質量％程度、特に０．１〜２質量％とすることが好ましい。
上記の方法を使用することにより、ろ過速度を向上させることができる。これは例えば、平均ろ過速度（１時間、１ｍ2当たり処理できる濾液の量[ｔ]）を測定することにより確認することができる。
本発明の方法によるろ過性向上効果は、従来より知られるポリアクリル酸、活性白土などに比べて顕著に向上し、またポリアルクリル酸ではろ過性向上のために添加量を増やすと、低温保存時の製品の外観に濁りが生じることがあるのに対し、そのような問題もなく、幅広い付加モル数に対して使用できる。
また、本発明の方法は、特にろ過が困難なアルキレンオキシド高付加モル体（平均付加モル数７モル以上、さらには９モル以上、特に１５モル以上）で重量平均分子量２万以上の高分子量ポリアルキレングリコール（副生物）を０．４質量％以上、さらには０．７以上、特には１％以上含むアルキレンオキシド付加物に対して適用したときに効果が大きい。さらには、触媒金属分の含有量の少ないアルキレンオキシド付加物を得ることが可能となる。In the steps (c) and (f) of the present invention, a solid catalyst for alkoxylation is prepared from the alkylene oxide-added crude product or the nonionic surfactant crude product whose pH and water content are adjusted in steps (b) and (e), respectively. Separate and remove. By adjusting the pH and water content, by-products such as high molecular weight polyethylene glycol having a weight average molecular weight of 20,000 or more contained in the crude alkylene oxide addition product or the crude nonionic surfactant can be appropriately aggregated. Therefore, the solid catalyst for alkoxylation can be easily separated and removed together with the high molecular weight polyethylene glycol by, for example, filtration under a well-known operation procedure and filtration conditions. Furthermore, the catalyst can be removed by centrifugation, for example, using a decanter or a centrifuge.
For example, it is preferable to use a two-layer filter of cellulose and polyester, a metal mesh type filter, or the like as filter paper, and filter under reduced pressure or increased pressure at a temperature of 35 to 100 ° C., particularly 40 to 85 ° C.
Moreover, preferably filterability can be improved by using a filter aid. As the filter aid, any filter aid known to those skilled in the art can be used. For example, as an amorphous siliceous diatomaceous earth containing 80 to 95% of SiO 2 as a main component, for example, radio Light # 100, Radio Light # 200, Radio Light # 500, Radio Light # 600, Radio Light # 900, Zem Light Super M, Zem Light Super 1, Zem Light Super 56, Zem Light Super 2, Celite 501, Celite 503, Examples thereof include Celite 535, Celite 545, Hyflo Supercell, Standard Supercell, and Filter Cell. Examples of the aluminum silicate containing about 70% of SiO 2 as the main component include Topco # 31, Topco # 34 and the like, and cellulose filter aids include KC Flock, SW40, BW20, BW40, BW100, and BW200. , BNB20, and the like, each of which can be used alone or as a mixture of two or more. The amount of the filter aid used is preferably about 0.05 to 5% by mass, particularly 0.1 to 2% by mass, based on the crude product.
By using the above method, the filtration rate can be improved. This can be confirmed, for example, by measuring the average filtration rate (the amount of filtrate [t] that can be treated per 1 m 2 per hour).
The filterability improving effect by the method of the present invention is remarkably improved as compared with conventionally known polyacrylic acid, activated clay, etc. In addition, when polyacrylic acid is added to increase the filterability, While the appearance of the product may become turbid, it can be used for a wide range of added moles without such problems.
In addition, the method of the present invention is a high molecular weight polyhydride having a weight average molecular weight of 20,000 or more with a high addition mole of alkylene oxide (average addition mole number of 7 moles or more, further 9 moles or more, especially 15 moles or more) that is particularly difficult to filter. The effect is great when applied to an alkylene oxide adduct containing alkylene glycol (by-product) of 0.4% by mass or more, further 0.7 or more, particularly 1% or more. Furthermore, it becomes possible to obtain an alkylene oxide adduct having a low content of catalytic metal.
以下、実施例及び比較例を挙げ、本発明を具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。
実施例においては以下の試薬を使用した。
各種酸： WAKO試薬特級
グリセリン： 精製グリセリン ライオンケミカル社製
ポリアクリル酸： 純正化学株式会社製 平均分子量９万
活性白土： ガレオンアースNV 水澤化学社製
酸性白土： ミズカエース＃600 水澤化学社製EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples at all.
In the examples, the following reagents were used.
Various acids: WAKO reagent special grade Glycerin: Purified glycerin manufactured by Lion Chemical Co., Ltd. Polyacrylic acid: Junsei Chemical Co., Ltd. average molecular weight 90,000 activated clay: Galeon Earth NV, manufactured by Mizusawa Chemical Co., Ltd. Acidic clay: Mizuka Ace # 600, manufactured by Mizusawa Chemical
実施例及び比較例のろ過性の評価は、平均ろ過速度を測定することにより行った。
平均ろ過速度は、１時間、１ｍ2当たり処理できる濾液の量[ｔ]を表す。
また、ろ過所要時間は、1ｔの反応粗製物を１ｍ3のろ過面積のろ過器で処理した場合の所要時間として求め、以下の評価基準に従って分類した。
◎：３０分以内
○：３０分超、１時間以内
□：１時間超、３時間以内
△：３時間超、５時間以内
×：５時間超The filterability of Examples and Comparative Examples was evaluated by measuring the average filtration rate.
The average filtration rate represents the amount [t] of the filtrate that can be treated per 1 m 2 for 1 hour.
The time required for filtration was determined as the time required for treating a 1 t reaction crude product with a filter having a filtration area of 1 m 3 and classified according to the following evaluation criteria.
◎: Within 30 minutes ○: Over 30 minutes, within 1 hour □: Over 1 hour, within 3 hours △: Over 3 hours, within 5 hours ×: Over 5 hours
また、白濁の程度を調べるための外観の評価は、吸光度計UV-2200（SHIMADZU社製）を用いて、70℃における480nmでの吸光度を測定し、以下の基準で評価した。
○ 0.1未満
△ 0.1以上0.3未満
× 0.3以上Further, the appearance for examining the degree of cloudiness was evaluated by measuring the absorbance at 480 nm at 70 ° C. using an absorptiometer UV-2200 (manufactured by SHIMADZU) and evaluating it according to the following criteria.
○ Less than 0.1 △ 0.1 or more but less than 0.3 × 0.3 or more
また、各反応の反応物中に含まれるポリアルキレングリコール量をゲルパーミエィションクロマトグラフィ（ＧＰＣ）法により測定し、質量％で示した。ポリアルキレングリコールの質量平均分子量は、ゲルパーミエーションクロマトグラフィーにより、ポリエチレングリコール標準試薬（ＧＬサイエンス社製）を基準とする値として求めた。
また、触媒金属分の含有量は以下の通り測定した。
試料を白金るつぼに秤量し、ガスバーナーで加熱炭化したのち電気炉（550℃・１２時間）で加熱灰化し、灰化物を硫酸、硝酸、フッ化水素酸および過塩素酸で加熱分解し、希硝酸で溶解して定容液とした。パーキンエルマー製 ICP発光分析装置 OPTIMA 4300DVを使用し、定容液をICP発光分析法でマグネシウム、アルミニウムを測定、試料中の含有量を求めた。Further, the amount of polyalkylene glycol contained in the reaction product of each reaction was measured by gel permeation chromatography (GPC) method and indicated by mass%. The mass average molecular weight of the polyalkylene glycol was determined by gel permeation chromatography as a value based on a polyethylene glycol standard reagent (manufactured by GL Science).
Further, the content of the catalyst metal was measured as follows.
A sample is weighed in a platinum crucible, heated and carbonized with a gas burner, then heated and ashed in an electric furnace (550 ° C, 12 hours), and the ash is pyrolyzed with sulfuric acid, nitric acid, hydrofluoric acid and perchloric acid. Dissolved with nitric acid to make a constant volume solution. Using an ICP emission analyzer OPTIMA 4300DV manufactured by PerkinElmer, magnesium and aluminum were measured with a constant volume solution by ICP emission spectrometry, and the content in the sample was determined.
１．酸（ｐＨ調整剤）の種類による影響
実施例１
(1) 触媒調製
２．５ＭｇＯ・Ａｌ2Ｏ3・ｍＨ2Ｏからなる化学組成の水酸化アルミニウム・マグネシウム（協和化学工業社製、キョーワード３００）を７５０℃で３時間焼成してマグネシウム・アルミニウム複合金属酸化物触媒粉末を得た。これに４０質量％水酸化カリウム水溶液を（触媒に対して水酸化カリウム純分で５質量％）噴霧し、乾燥させることにより、アルカリ変性処理を施した複合金属酸化物触媒を得た。なお、反応前の触媒平均粒子径は５０μｍであった。
(2) 反応粗製物
４リットル容オートクレーブ中にラウリン酸メチルエステル（ライオンケミカル製 パステルＭ１２）を４４０ｇ（２．０６モル）、前記アルカリ変性処理を施した複合金属酸化物触媒を１．８ｇ、多価アルコールとしてグリセリン２．２５ｇを仕込み、攪拌混合しながらオートクレーブ内を窒素置換した後、昇温して１００℃にて、減圧下（１．３３ｋＰａ以下）で３０分間、脱水を行った。次いで、１８０℃にて、圧力上限値を０．４９MPａとし、エチレンオキシド１３６１ｇ（３０．９モル）を導入した。更に０．５時間熟成を行った後、８０℃まで冷却して抜き出し、反応粗製物（アルキレンオキシド付加物）を得た。なお、反応後の触媒平均粒子径は１．０μｍであった。また、エチレンオキサイドの平均付加モル数は１５であった。
(3) ろ過
攪拌器と温調装置を備えた圧力容器に上記粗製物を４９５ｇ入れ、８０℃に加温した。
次いで、イオン交換水５５ｇ（水希釈物として水分１０％）加え、水希釈物を得た。得られた水希釈物に対して、ｐＨ（一部をサンプリングし、アルキレンオキシド付加物濃度が5%となるように蒸留水により希釈した希釈物のｐＨ）が７．６となるようにクエン酸を添加してｐＨ調整を行い、８０℃を維持したまま１５分間攪拌した。その後、ろ過助剤としてハイフロスーパーセルを１．４９ｇ（対粗製物０．３％；東京珪藻土工業(株)製）、ＫＣフロックＷ−５０（ｓ）を２．４８ｇ（対粗製物０．５％；日本製紙ケミカル(株)製）を添加し、１５分間攪拌した。次いで、ろ過助剤の入った水希釈物を１７０ｇとり、更にプレコート剤としてハイフロスーパーセルを０．２５ｇ（ろ過面積に対して０．２ｋｇ/ｍ2）、ＫＣフロックＷ−５０（ｓ）を１．２６ｇ(ろ過面積に対して１．０ｋｇ/ｍ2)を添加し、均一に分散させた後、プレコートを行った。プレコート終了後、本ろ過を行い、アルコキシル化触媒を濾別除去して精製品を得た。ろ過装置は、濾材がセルロースとポリエステルの二層フィルター、内径４．５ｃｍの加圧ろ過器（ADVANTEC社製）で温度８０℃、窒素圧０．２MPaで行った。1. Influence of the type of acid (pH adjuster)
Example 1
(1) Catalyst preparation Magnesium / aluminum was calcined at 750 ° C. for 3 hours with aluminum hydroxide / magnesium (Kyowa Chemical Industry Co., Ltd., Kyoward 300) having a chemical composition of 2.5MgO / Al 2 O 3 / mH 2 O. A composite metal oxide catalyst powder was obtained. This was sprayed with a 40% by mass aqueous potassium hydroxide solution (5% by mass in terms of pure potassium hydroxide with respect to the catalyst) and dried to obtain an alkali-modified composite metal oxide catalyst. In addition, the average particle diameter of the catalyst before the reaction was 50 μm.
(2) Crude reaction product In a 4 liter autoclave, 440 g (2.06 mol) of lauric acid methyl ester (Lion Chemical Pastel M12), 1.8 g of the composite metal oxide catalyst subjected to the alkali modification treatment, 2.25 g of glycerin was charged as a monohydric alcohol, and the interior of the autoclave was purged with nitrogen while stirring and mixing. Then, the temperature was raised and dehydration was performed at 100 ° C. under reduced pressure (1.33 kPa or less) for 30 minutes. Next, at 180 ° C., the pressure upper limit was set to 0.49 MPa, and 1361 g (30.9 mol) of ethylene oxide was introduced. After aging for 0.5 hour, the reaction mixture was cooled to 80 ° C. and extracted to obtain a crude reaction product (alkylene oxide adduct). The average catalyst particle size after the reaction was 1.0 μm. The average number of moles of ethylene oxide added was 15.
(3) Filtration 495 g of the crude product was put in a pressure vessel equipped with a stirrer and a temperature controller, and heated to 80 ° C.
Subsequently, 55 g of ion-exchanged water (water 10% as a water dilution) was added to obtain a water dilution. Citric acid so that the pH (diluted with distilled water so that the concentration of the alkylene oxide adduct was 5%) was 7.6 with respect to the obtained water dilution. Was added to adjust pH, and the mixture was stirred for 15 minutes while maintaining 80 ° C. Thereafter, 1.49 g of Hyflo Supercell (0.3% relative to the crude product; manufactured by Tokyo Diatomite Industries Co., Ltd.) and 2.48 g of KC Flock W-50 (s) as a filter aid (0.5% relative to the crude product). %; Manufactured by Nippon Paper Chemicals Co., Ltd.) and stirred for 15 minutes. Next, 170 g of a water dilution containing a filter aid was taken, and 0.25 g of Hyflo supercell (0.2 kg / m 2 with respect to the filtration area) as a precoat agent and 1 KC floc W-50 (s) were added. .26 g (1.0 kg / m 2 with respect to the filtration area) was added and dispersed uniformly, followed by precoating. After completion of the precoat, this filtration was performed, and the alkoxylation catalyst was removed by filtration to obtain a purified product. The filtration device was a pressure filter (made by ADVANTEC) with a two-layer filter made of cellulose and polyester and an inner diameter of 4.5 cm at a temperature of 80 ° C. and a nitrogen pressure of 0.2 MPa.
実施例２
ｐＨ調整にリンゴ酸を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを７．５に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
実施例３
ｐＨ調整に乳酸を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを７．５に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
実施例４
ｐＨ調整に酢酸を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを７．５に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
実施例５
アルキレンオキシド付加粗製物の水希釈物のｐＨを５．０に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
実施例６
アルキレンオキシド付加粗製物の水希釈物のｐＨを８．０に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。 Example 2
Malic acid was used for pH adjustment, and the same procedure as in Example 1 was performed except that the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 7.5. The same reaction crude product as in Example 1 was used.
Example 3
The same procedure as in Example 1 was performed except that lactic acid was used for pH adjustment, and the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 7.5. The same reaction crude product as in Example 1 was used.
Example 4
The same procedure as in Example 1 was performed except that acetic acid was used for pH adjustment, and the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 7.5. The same reaction crude product as in Example 1 was used.
Example 5
The same procedure as in Example 1 was performed except that the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 5.0. The same reaction crude product as in Example 1 was used.
Example 6
The same procedure as in Example 1 was performed except that the pH of the water dilution of the crude alkylene oxide addition product was adjusted to 8.0. The same reaction crude product as in Example 1 was used.
実施例７
ｐＨ調整に塩酸を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを５．０に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
実施例８
ｐＨ調整に硫酸を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを５．０に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
比較例１
ｐＨ調整にポリアクリル酸を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを６．５に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
比較例２
ｐＨ調整に活性白土を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを７．０に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
比較例３
ｐＨ調整に酸性白土を使用し、アルキレンオキシド付加粗製物の水希釈物のｐＨを８．０に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。 Example 7
It was carried out according to Example 1 except that hydrochloric acid was used for pH adjustment and the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 5.0. The same reaction crude product as in Example 1 was used.
Example 8
The same procedure as in Example 1 was performed except that sulfuric acid was used for pH adjustment, and the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 5.0. The same reaction crude product as in Example 1 was used.
Comparative Example 1
The same procedure as in Example 1 was performed except that polyacrylic acid was used for pH adjustment, and the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 6.5. The same reaction crude product as in Example 1 was used.
Comparative Example 2
This was carried out in the same manner as in Example 1 except that activated clay was used for pH adjustment, and that the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 7.0. The same reaction crude product as in Example 1 was used.
Comparative Example 3
It was carried out according to Example 1 except that acid clay was used for pH adjustment and the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 8.0. The same reaction crude product as in Example 1 was used.
２．ｐＨの影響
実施例９
アルキレンオキシド付加粗製物の水希釈物のｐＨを４．０に調整すること以外は実施例１に準じて行なった。
比較例４
アルキレンオキシド付加粗製物の水希釈物のｐＨを３．０に調整すること以外は実施例１に準じて行なった。
比較例５
アルキレンオキシド付加粗製物の水希釈物のｐＨを８．５に調整すること以外は実施例１に準じて行なった。
比較例６
ｐＨ調整を行なわないこと（ｐＨ＝９．０）以外は実施例１に準じて行なった。2. Effect of pH
Example 9
The same procedure as in Example 1 was performed except that the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 4.0.
Comparative Example 4
The same procedure as in Example 1 was conducted except that the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 3.0.
Comparative Example 5
The same procedure as in Example 1 was performed except that the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 8.5.
Comparative Example 6
The procedure was the same as in Example 1 except that the pH was not adjusted (pH = 9.0).
３．水分の影響
実施例１０
水希釈物として水分５％に調整すること以外は実施例１に準じて行なった。なお、反応粗製物は実施例１と同じものを使用した。
実施例１１
水希釈物として水分７％に調整すること以外は実施例１に準じて行なった。
実施例１２
水希釈物として水分１２％に調整すること以外は実施例１に準じて行なった。
実施例１３
水希釈物として水分１５％に調整すること以外は実施例１に準じて行なった。
比較例７
水希釈物として水分２％に調整すること以外は実施例１に準じて行なった。
比較例８
水希釈物として水分２０％に調整すること以外は実施例１に準じて行なった。3. Effect of moisture
Example 10
The same procedure as in Example 1 was performed except that the water dilution was adjusted to 5%. The same reaction crude product as in Example 1 was used.
Example 11
The same procedure as in Example 1 was performed except that the water dilution was adjusted to 7%.
Example 12
The same procedure as in Example 1 was performed except that the water dilution was adjusted to 12% water.
Example 13
This was carried out according to Example 1 except that the water dilution was adjusted to 15%.
Comparative Example 7
The same procedure as in Example 1 was performed except that the water dilution was adjusted to 2%.
Comparative Example 8
This was carried out according to Example 1 except that the water dilution was adjusted to 20% water.
４．アルキレンオキシド（ＡＯ）付加モル数（不純物ＰＡＧ量）の影響
実施例１４
ラウリン酸メチルエステルの量を２９２ｇ（１．３７モル）、エチレンオキシドの量を１５０６ｇ（３４．２モル）とした以外は実施例１と同じ触媒及び反応方式でアルキレンオキシドの付加反応を行った。ＡＯ平均付加モル数は２５であった。また、水希釈物として水分１２．５％に調整し、クエン酸でｐＨを７．６に調整した。
実施例１５
ラウリン酸メチルエステルの量を８８５ｇ（４．１４モル）、エチレンオキシドの量を９１３ｇ（２０．７モル）とした以外は実施例１と同じ触媒及び反応方式でアルキレンオキシドの付加反応を行った。ＡＯ平均付加モル数は５であった。また、水希釈物として水分７．５％に調整し、クエン酸でｐＨを７．６に調整した。
比較例９
ｐＨ調整を行なわないこと（ｐＨ＝９．０）以外は実施例１４に準じて行なった。
比較例１０
ｐＨ調整を行なわないこと（ｐＨ＝９．０）以外は実施例１５に準じて行なった。4). Effect of added number of moles of alkylene oxide (AO) (impurity PAG amount)
Example 14
The alkylene oxide addition reaction was carried out using the same catalyst and reaction method as in Example 1 except that the amount of lauric acid methyl ester was 292 g (1.37 mol) and the amount of ethylene oxide was 1506 g (34.2 mol). The average added mole number of AO was 25. Further, the water dilution was adjusted to 12.5%, and the pH was adjusted to 7.6 with citric acid.
Example 15
The addition reaction of alkylene oxide was carried out by the same catalyst and reaction method as in Example 1 except that the amount of lauric acid methyl ester was 885 g (4.14 mol) and the amount of ethylene oxide was 913 g (20.7 mol). The average added mole number of AO was 5. Further, the water was adjusted to 7.5% as a water dilution, and the pH was adjusted to 7.6 with citric acid.
Comparative Example 9
Example 14 was performed except that pH adjustment was not performed (pH = 9.0).
Comparative Example 10
Example 15 was performed except that pH adjustment was not performed (pH = 9.0).
５．その他要因の影響
実施例１６
アルキレンオキシド付加粗製物の原料としてSafol23を使用した。
(1) 触媒調製
硝酸マグネシウム６水和物６８．０３ｇ、硝酸アルミニウム９水和物４７．６９ｇ、及び硝酸マンガン６水和物２４．３３ｇを脱イオン水４５０ｇに溶解させた溶液と、炭酸ナトリウム１３．４７ｇを脱イオン水４５０ｇに溶解させた溶液とを、予め脱イオン水１８００ｇを仕込んだ触媒調製槽に、２NのNaOHによりｐＨを９、温度を４０℃に保ちながら１時間かけて滴下した。滴下終了後、更に１時間熟成させた。これをろ過した後、脱イオン水で洗浄し、噴霧乾燥して３０ｇの複合水酸化物を得た。この複合水酸化物を、窒素雰囲気下８００℃で３時間焼成して、Mg/Al/Mnの複合酸化物の固体触媒粒子を調製した。なお、反応前の触媒平均粒子径は５０μｍであった。
(2) 反応粗製物
４リットル容オートクレーブ中にドデシル・トリデシルアルコール（SASOL社製 Safol23）を４０７ｇ（２．１１モル）、前記複合金属酸化物触媒を１．８ｇ仕込み、攪拌混合しながらオートクレーブ内を窒素置換した後、昇温して１００℃にて、減圧下（１．３３ｋＰａ以下）で３０分間、脱水を行った。次いで、１８０℃にて、圧力上限値を０．４９MPａとし、エチレンオキサイド１３９３ｇ（３１．７モル）を導入した。更に０．７時間熟成を行った後、８０℃まで冷却して抜き出し、反応粗製物（アルキレンオキサイド付加物）を得た。なお、反応後の触媒平均粒子径は１０μｍであった。また、エチレンオキサイドの平均付加モル数は１５であった。
(3) ろ過速度等の測定は実施例１に準じて行った。5. Impact of other factors
Example 16
Safol23 was used as a raw material for the crude product of alkylene oxide addition.
(1) Catalyst preparation A solution of 68.03 g of magnesium nitrate hexahydrate, 47.69 g of aluminum nitrate nonahydrate, and 24.33 g of manganese nitrate hexahydrate in 450 g of deionized water, and sodium carbonate 13 A solution prepared by dissolving .47 g in 450 g of deionized water was dropped into a catalyst preparation tank in which 1800 g of deionized water had been previously charged over 2 hours while maintaining the pH at 9 and the temperature at 40 ° C. with 2N NaOH. After completion of dropping, the mixture was further aged for 1 hour. This was filtered, washed with deionized water, and spray-dried to obtain 30 g of composite hydroxide. The composite hydroxide was calcined at 800 ° C. for 3 hours in a nitrogen atmosphere to prepare Mg / Al / Mn composite oxide solid catalyst particles. In addition, the average particle diameter of the catalyst before the reaction was 50 μm.
(2) Crude reaction product In a 4-liter autoclave, 407 g (2.11 mol) of dodecyl tridecyl alcohol (SASOL Safol23) and 1.8 g of the composite metal oxide catalyst were charged, and the mixture was stirred and mixed in the autoclave. After replacing with nitrogen, the temperature was raised and dehydration was performed at 100 ° C. under reduced pressure (1.33 kPa or less) for 30 minutes. Next, at 180 ° C., the pressure upper limit was set to 0.49 MPa, and 1393 g (31.7 mol) of ethylene oxide was introduced. After further aging for 0.7 hours, the mixture was cooled to 80 ° C. and extracted to obtain a crude reaction product (alkylene oxide adduct). The average catalyst particle size after the reaction was 10 μm. The average number of moles of ethylene oxide added was 15.
(3) The filtration rate and the like were measured according to Example 1.
実施例１７
アルキレンオキシド付加粗製物の水希釈物のｐＨを５．０に調整すること以外は実施例１６に準じて行なった。
実施例１８
アルキレンオキシド付加粗製物の原料として、実施例１等で使用したラウリン酸メチルエステルを使用した。触媒はアルカリ変性をしたものを用い、グリセリンは添加しなかった。
比較例１１
ｐＨ調整を行なわないこと（ｐＨ＝８．５）以外は実施例１６に準じて行なった。 Example 17
The same procedure as in Example 16 was performed, except that the pH of the water dilution of the alkylene oxide-added crude product was adjusted to 5.0.
Example 18
The lauric acid methyl ester used in Example 1 etc. was used as a raw material for the alkylene oxide-added crude product. The catalyst used was alkali-modified and glycerin was not added.
Comparative Example 11
Example 16 was performed except that pH adjustment was not performed (pH = 8.5).
Claims (9)
(b) 前記アルキレンオキシド付加粗製物に、２０℃における水への溶解度が１以上であって分子量４００以下の有機酸または２０℃における水への溶解度が１以上の無機酸を添加することによりｐＨを4.0〜8.0に、かつ、水分量を5質量%以上15質量%以下に調整する工程、
(c) 工程(b)のアルキレンオキシド付加粗製物からアルコキシル化用固体触媒を分離して除去する工程、
を含む、アルキレンオキシド付加物の製造方法。(a) a step of adding an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of a solid catalyst for alkoxylation to obtain an alkylene oxide-added crude product,
(b) By adding an organic acid having a solubility in water at 20 ° C. of 1 or more and a molecular weight of 400 or less or an inorganic acid having a solubility in water at 20 ° C. of 1 or more to the alkylene oxide-added crude product. Adjusting the water content to 4.0 to 8.0 and the water content to 5% by mass or more and 15% by mass or less,
(c) a step of separating and removing the alkoxylation solid catalyst from the crude alkylene oxide addition product of step (b),
The manufacturing method of the alkylene oxide adduct containing this.
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| CA2776141A1 (en) * | 2009-10-02 | 2011-04-07 | Basf Se | Reduced-odor polyol composition and method of producing same |
| JP5711648B2 (en) * | 2011-11-16 | 2015-05-07 | ライオン株式会社 | Method for producing alkylene oxide adduct |
| JP6403325B2 (en) * | 2014-12-26 | 2018-10-10 | ライオン株式会社 | Process for producing fatty acid alkyl ester alkoxylate |
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| JPS56112931A (en) * | 1980-02-12 | 1981-09-05 | Sanyo Chem Ind Ltd | Polyol composition |
| JPH08268919A (en) * | 1995-03-28 | 1996-10-15 | Lion Corp | Production of alkylene oxide adduct to active hydrogen-containing compound |
| JPH09262456A (en) * | 1996-03-28 | 1997-10-07 | Lion Corp | Purifying method of nonionic surfactant |
| JP2005187415A (en) * | 2003-12-26 | 2005-07-14 | Lion Corp | Fatty acid polyoxyalkylenealkyl ether and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56112931A (en) * | 1980-02-12 | 1981-09-05 | Sanyo Chem Ind Ltd | Polyol composition |
| JPH08268919A (en) * | 1995-03-28 | 1996-10-15 | Lion Corp | Production of alkylene oxide adduct to active hydrogen-containing compound |
| JPH09262456A (en) * | 1996-03-28 | 1997-10-07 | Lion Corp | Purifying method of nonionic surfactant |
| JP2005187415A (en) * | 2003-12-26 | 2005-07-14 | Lion Corp | Fatty acid polyoxyalkylenealkyl ether and method for producing the same |
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| TWI659942B (en) * | 2014-04-24 | 2019-05-21 | 日商獅子股份有限公司 | Method for producing fatty acid alkyl ester alkoxylate |
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