JPH0137381B2 - - Google Patents
Info
- Publication number
- JPH0137381B2 JPH0137381B2 JP58227016A JP22701683A JPH0137381B2 JP H0137381 B2 JPH0137381 B2 JP H0137381B2 JP 58227016 A JP58227016 A JP 58227016A JP 22701683 A JP22701683 A JP 22701683A JP H0137381 B2 JPH0137381 B2 JP H0137381B2
- Authority
- JP
- Japan
- Prior art keywords
- atom
- reaction
- heteropolyacids
- heteropolyacid
- group
- 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.)
- Expired
Links
- -1 alkylene glycol monoalkyl ether Chemical class 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000011964 heteropoly acid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001983 dialkylethers Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000008043 acidic salts Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical group [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- PDDXOPNEMCREGN-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O PDDXOPNEMCREGN-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はモノ及び／又はポリアルキレングリコ
ール（以下、アルキレングリコール類と略す。）
のジアルキルエーテルの製法に関し、更に詳しく
はアルキレングリコール類のモノアルキルエーテ
ルのみを原料とし、特定のヘテロポリ酸及び／又
はこれらの酸性塩（以下ヘテロポリ酸類と略記す
る。）を触媒として、アルキレングリコール類の
ジアルキルエーテルを製造する方法に関する。
本発明者らは、以前本発明方法に用いるものと
同種のヘテロポリ酸類を触媒としエーテル基含有
化合物と水酸基含有化合物とを反応させ別種のエ
ーテル基含有化合物を製造する方法を提案した
（特願昭57−193522号）が、更に詳細に検討した
ところ、アルキレングリコール類のモノアルキル
エーテルの如く、同一分子中にエーテル基と水酸
基両者が存在する化合物のみを原料として用いて
も、ヘテロポリ酸類を触媒として存在させれば、
上記化合物の分子間でいわゆる不均化反応が起
り、アルキレングリコール類のジアルキルエーテ
ルが効率よく生成することを見出した。
すなわち、本発明は下記一般式〔〕
R1−Ｏ−〔R2O−〕oＨ ……〔〕
ここにR1は炭素数１〜４のアルキル基であり、
ヘテロ原子又はヘテロ原子を含む置換基で置換さ
れたものを含む。R2は炭素数２〜４のアルキレ
ン基であり、ヘテロ原子又はヘテロ原子を含む置
換基で置換されたものを含む。ｎは１又は２なる
正数であり、くり返し単位数を示す。
にて示されるアルキレングリコール類のモノアル
キルエーテルを特定のヘテロポリ酸類の存在下に
加熱することを特徴とする下記一般式〔〕
R1−Ｏ−〔R2O−〕oR1 ……〔〕
ここにR1，R2及びｎについては一般式［］
に示されるものと同じである。
にて示されるアルキレングリコールジアルキルエ
ーテルの製造方法である。
本発明方法に用いられる原料は前述の如く、一
般式〔〕にて示されるアルキレングリコール類
のモノアルキルエーテルのみである。前述のR1
は炭素数１〜４のアルキル基であり、これらのア
ルキル基がヘテロ原子あるいはヘテロ原子を含む
置換基で置換されたものも包含する。これらの具
体例としては、メチル基、エチル基、iso−プロ
ピル基、ｎ−プロピル基、ｎ−ブチル基、sec−
ブチル基、tert−ブチル基等これらアルキル基の
水素原子がハンゲン原子等で置換されたハロアル
キル基等を例示することが出来る。
R2の具体例としてはエチレン基、プロピレン
基、ブチレン基を例示出来、これらの水素原子が
ハロゲン原子、ハロアルキル基等で置換されたも
のも含まれる。
本発明方法に於て、触媒として用いられるヘテ
ロポリ酸類の中心原子と配位原子の比は１：６〜
１：12であり、これらヘテロポリ酸類を構成する
中心原子として、ホウ素、ケイ素、リン、クロ
ム、ゲルマニウム、チタン、マンガン、鉄、コバ
ルト、砒素等を例示出来る。これら中心原子に酸
素を共有して縮合配位する酸基の配位原子として
は、モリブデン、タングステン、バナジウム、ニ
オブ等かあるいはこれらの混合物を例示出来る。
前記ヘテロポリ酸の酸性塩としては、該酸のブロ
トンの一部分を金属カチオンで置換した金属塩あ
るいはアンモニア、アミン等の有機塩基で中和し
た塩が用いられる。金属カチオンとしては、例え
ばアルカリ金属、アルカリ土類金属、銅、銀、コ
バルト、ニツケル、亜鉛、カドミウム、アルミニ
ウム、スズ、マンガン等の金属カチオンを例示出
来るが、これらの塩のうち、金属塩が本発明方法
に好ましく使用される。
前述の如く例示したヘテロポリ酸類のうち、本
発明方法に好ましく使用されるものは、前述した
中心原子と配位原子の比が１：12のものであり、
具体例としては、ドデカモリブドリン酸、ドデカ
モリブドケイ酸、ドデカモリブドチタン酸、ドデ
カモリブド砒酸、ドデカモリブドゲルマニウム
酸、ドデカタングストリン酸、ドデカタングスト
ケイ酸、ドデカタングストホウ酸、ドデカタング
ストチタン酸、ドデカタングスト砒酸、ドデカタ
ングスト鉄酸、ドデカタングストコバルト酸、ド
デカタングストモリブドリン酸、ドデカモリブド
バナドリン酸、ドデカモリブドバナドケイ酸及び
ドデカタングストバナドケイ酸等のヘテロポリ
酸、並びにドデカモリブドケイ酸２ナトリウム、
ドデカタングストケイ酸１カルシウム、ドデカモ
リブドリン酸１銅、ドデカモリブドリン酸２マン
ガン等のヘテロポリ酸の酸性塩をあげることが出
来る。
更に、これら例示化合物のうちで、中心原子が
ホウ素、ケイ素、リン、ゲルマニウムのいずれか
の原子であり、配位原子がモリブテン、タングス
テンのいずれかの原子であるヘテロポリ酸の酸性
モノナトリウム塩、あるいは酸性モノマンガン塩
が特に好ましい。
ヘテロポリ酸類が本発明方法に必須の触媒であ
るが、これらは通常の構造水の他に、多量の結晶
水を有している。この結晶水量の変動が一般に触
媒活性に影響を示すことが多いが、本発明方法に
おいて触媒として用いる場合にはこの変動はあま
り影響がないだけでなく、他に広範囲な量の水分
も許容される。
以上述べた如き原料及び触媒を用いて、本発明
方法を実施するに当つては、まず使用する触媒の
含水量を公知の方法によつて調整する。このヘテ
ロポリ酸類の使用形態は反応方式、反応液の後処
理、回収再使用等を考慮して種々考えられるが、
例えばそのまま原料へ加えるとか、シリカ、アル
ミナ、活性炭等に担持させたりして使用すること
が出来る。次にヘテロポリ酸類の存在下、本発明
方法の反応を行う。反応方式は連続式又は回分式
のいずれも使用されうるし、又液相に於ても、気
相に於ても可能であり、更にヘテロポリ酸類を担
持させて使用出来ることを考慮すれば、固定床方
式で行えば有利となる。
本発明の方法を行うに当り、原料の溶解、混
合、反応熱の除去等に必要ならば、不活性の溶媒
を使用することが出来、この不活性溶媒としてジ
クロルメタン、ニトロメタン、クロルベンゼン、
ベンゼン、酢酸エチル、ジオキサン等を例示出来
る。また、本発明の方法の実施に際し、安全性、
触媒活性の維持、異常反応の防止を考慮すれば、
反応系を窒素、ヘリウム等の不活性ガス雰囲気下
で行うことが好ましい。
本発明方法に示される反応の反応条件に関して
はまず、温度は０〜300℃が好ましく、圧力は反
応方式により異なり、通常は反応系の自圧で十分
であるが必要に応じて不活性ガス等で所望の圧力
に調節することが出来る。反応時間は用いる原
料、触媒の種類、溶媒の有無、設定された反応条
件によつて異なる。
ヘテロポリ酸類の使用量は前記の一般式〔〕
にて示されるアルキレングリコール類のモノアル
キルエーテルに対して0.01乃至50重量％であり、
好ましくは0.1乃至20重量％である。この使用量
が0.01重量％未満であると触媒として効果が少
く、本発明では50重量％を超えて用いる必要がな
い。しかしながら、固定床反応の如き場合には、
単位時間当り、ヘテロポリ酸類１重量部当り、原
料モノアルキルエーテルの通過量を0.01乃至10重
量部と調節して反応を進めることも出来る。
本発明方法に用いる反応にあつては、原料とし
て用いるアルキレングリコール類のモノアルキル
エーテルから主として
2R1−Ｏ−〔R2O−〕oＨ→R1−Ｏ−〔R2O−〕oR1＋
HO−〔R2−〕oＨ
「ここに、R1，R2及びｎは前述と同じであ
る。」なる反応式に従い、反応に供されるモノア
ルキルエーテルの１／２モル以下がジアルキルエ
ーテルとなり残りがアルキレングリコール類とな
る。一方、本発明の原料である一般式（）にて
示される化合物にあつては、酸性の化合物である
ヘテロポリ酸類の影響により主鎖が切断された
り、或はそれらが再結合したりしてオキシアルキ
レン基の繰返し単位数がｎと相違した２種以上の
アルキレングリコール類のモノアルキルエーテル
となる傾向が多少あり、従つて本発明に示される
のと同様の反応によつて繰返し単位数がｎと相違
したジアルキルエーテル及びグリコールが不可避
的に多少副成する。
更に、当然のことながら、一般式〔〕にて示
される化合物のオキシアルキレン基のくり返し単
位数ｎが２を大きく超えたアルキレングリコール
類のモノアルキルエーテルを原料として用いれ
ば、前述の如く、多岐にわたる反応が起り、従つ
て、多種類の生成物が生じ、これらの分離、精製
が煩雑となり好ましくなく、従つて本発明方法に
あつては、上記のｎが２以下のアルキレングリコ
ールモノアルキルエーテルを用いることが好まし
い。
以上述べた如き、反応を進めた後ヘテロポリ酸
類を分離するかあるいはしないで、公知の方法、
例えば蒸溜によつて、目的とする化合物あるいは
これらの混合物として分離すればよい。又、一部
の副生混合物、例えば蒸溜による分離が比較的に
煩雑なものは留出後、本発明方法の原料あるいは
他の目的の原料の一部あるいは、他の用途に用い
ることが出来る。更に、回収されるヘテロポリ酸
類は必要ならば処理をほどこした後、再使用する
ことが出来る。
以上述べた如く、本発明方法の特徴はアルキレ
ングリコールジアルキルエーテルを有利に提供す
るところにあるが、他に多量のかつ処理に手間の
かかる無機塩の副生がないことも特徴の１つとし
て挙げることが出来る。
次に実施例をあげ、本発明方法を更に詳しく説
明するが、本発明はこれらに限定されるものでは
ない。なお、以下の記述に於て、部と記述するも
のは限定のない限り、重量部である。
実施例 １
ステンレス製オートクレーブにエチレングリコ
ールモノメチルエーテル152.2部及び12−モリブ
ドリン酸２部を仕込み窒素シール後密封し、撹拌
下４時間170℃に加熱した。反応終了後、オート
クレーブを室温迄放冷し、開封し、内容物をとり
だしガスクロマトグラフイーにて分析したとこ
ろ、エチレングリコールモノメチルエーテルの反
応率は65.1％であり、生成物の組成（重量％）は
以下の通りであつた。
エチレングリコールジメチルエーテル 45.5％
ジエチレングリコールジメチルエーテル
11.7％
トリエチレングリコールジメチルエーテル
1.3％
メタノール 3.0％
１，４−ジオキサン 2.0％
エチレングリコール 21.0％
ジエチレングリコールモノメチルエーテル
11.0％
ジエチレングリコール 1.6％
その他 2.8％
上記の生成物を蒸溜によつて分離精製したとこ
ろ、合計99部となつた。
実施例 ２
実施例１と同様のオートクレーブにジエチレン
グリコールモノメチルエーテル120.1部及び12−
タングストリン酸２部を入れ、窒素シール後密封
し、撹拌下、４時間、170℃に加熱した。反応終
了後オートクレーブを室温迄放冷し、開封し、内
容物をとりだした後ガスクロマトグラフイーにて
分析したところ、ジエチレングリコールモノメチ
ルエーテルの反応率は50.9％であり、生成物の組
成（重量％）は以下の通りであつた。
ジエチレングリコールメチルエーテル 40.8％
トリエチレングリコールジメチルエーテル
10.4％
テトラエチレングリコールジメチルエーテル
3.4％
エチレングリコールジメチルエーテル 2.4％
１，４−ジオキサン 13.0％
エチレングリコール 5.2％
ジエチレングリコール 15.4％
エチレングリコールモノメチルエーテル
2.0％
トリエチレングリコールモノメチルエーテル
2.3％
その他 5.1％
実施例 ３−６
アルキレングリコール類のモノアルキルエーテ
ル及びヘテロポリ酸類をかえて実施例１に示す反
応をくり返し、結果を第１表に示した。
実施例 ７〜10
エチレングリコールモノメチルエーテル152.2
部及び各種のヘテロポリ酸類を用い、実施例１に
示す反応をくり返し、結果を第２表に示した。
The present invention relates to mono- and/or polyalkylene glycols (hereinafter abbreviated as alkylene glycols).
Regarding the method for producing dialkyl ethers, more specifically, using only monoalkyl ethers of alkylene glycols as a raw material and using specific heteropolyacids and/or their acid salts (hereinafter abbreviated as heteropolyacids) as catalysts, the method for producing dialkyl ethers of alkylene glycols is described. The present invention relates to a method for producing dialkyl ether. The present inventors previously proposed a method for producing a different type of ether group-containing compound by reacting an ether group-containing compound and a hydroxyl group-containing compound using the same type of heteropolyacids as those used in the method of the present invention as a catalyst (patent application 57-193522) conducted a more detailed study, and found that even if only compounds containing both an ether group and a hydroxyl group in the same molecule, such as monoalkyl ethers of alkylene glycols, were used as raw materials, heteropolyacids could not be used as catalysts. If it exists,
It has been found that a so-called disproportionation reaction occurs between the molecules of the above compound, and dialkyl ethers of alkylene glycols are efficiently produced. That is, the present invention is based on the following general formula [] R 1 -O-[R 2 O-] o H ... [] where R 1 is an alkyl group having 1 to 4 carbon atoms,
Including those substituted with a heteroatom or a substituent containing a heteroatom. R 2 is an alkylene group having 2 to 4 carbon atoms, including those substituted with a hetero atom or a substituent containing a hetero atom. n is a positive number of 1 or 2 and indicates the number of repetition units. The following general formula [] R 1 -O- [R 2 O-] o R 1 ... [] is characterized by heating the monoalkyl ether of alkylene glycols represented by in the presence of a specific heteropolyacid. Here, for R 1 , R 2 and n, the general formula []
This is the same as shown in . This is a method for producing alkylene glycol dialkyl ether shown in As mentioned above, the raw materials used in the method of the present invention are only monoalkyl ethers of alkylene glycols represented by the general formula []. R1 as mentioned above
is an alkyl group having 1 to 4 carbon atoms, and includes those in which these alkyl groups are substituted with a hetero atom or a substituent containing a hetero atom. Specific examples of these include methyl group, ethyl group, iso-propyl group, n-propyl group, n-butyl group, sec-
Examples include haloalkyl groups such as butyl groups and tert-butyl groups in which the hydrogen atoms of these alkyl groups are substituted with Hangen atoms. Specific examples of R 2 include ethylene, propylene, and butylene groups, and also include those in which hydrogen atoms are substituted with halogen atoms, haloalkyl groups, and the like. In the method of the present invention, the ratio of the central atom to the coordinating atom of the heteropolyacids used as a catalyst is 1:6 to
1:12, and examples of central atoms constituting these heteropolyacids include boron, silicon, phosphorus, chromium, germanium, titanium, manganese, iron, cobalt, and arsenic. Coordinating atoms of the acid group covalently coordinating oxygen to these central atoms include molybdenum, tungsten, vanadium, niobium, etc., or mixtures thereof.
As the acidic salt of the heteropolyacid, a metal salt obtained by substituting a part of the broton of the acid with a metal cation or a salt neutralized with an organic base such as ammonia or amine is used. Examples of metal cations include metal cations such as alkali metals, alkaline earth metals, copper, silver, cobalt, nickel, zinc, cadmium, aluminum, tin, and manganese. Among these salts, metal salts are the main Preferably used in the invention method. Among the heteropolyacids exemplified above, those preferably used in the method of the present invention have a ratio of the aforementioned central atom to coordinating atom of 1:12,
Specific examples include dodecamolybdophosphoric acid, dodecamolybdosilicic acid, dodecamolybdotitanic acid, dodecamolybdoarsenic acid, dodecamolybdogermanic acid, dodecatungstophosphoric acid, dodecatungstosilicic acid, dodecatungstoboric acid, and dodecatungstotitanium. acids, heteropolyacids such as dodecatungstoarsenic acid, dodecatungstoferric acid, dodecatungstocobaltate, dodecatungstomolybdophosphoric acid, dodecamolybdovanadophosphoric acid, dodecamolybdovanadosilicate and dodecatungstovanadosilicate , and disodium dodecamolybdosilicate,
Examples include acidic salts of heteropolyacids such as monocalcium dodecatungstosilicate, monocopper dodecamolybdophosphate, and dimanganese dodecamolybdophosphate. Furthermore, among these exemplified compounds, acidic monosodium salts of heteropolyacids in which the central atom is any one of boron, silicon, phosphorus, or germanium and the coordinating atom is any one of molybdenum or tungsten, or Particularly preferred are acidic monomanganese salts. Heteropolyacids are essential catalysts for the method of the present invention, and in addition to normal structural water, they contain a large amount of water of crystallization. Fluctuations in the amount of crystallization water generally often affect catalyst activity, but when used as a catalyst in the method of the present invention, not only does this fluctuation have little effect, but a wide range of other amounts of water can also be tolerated. . When carrying out the method of the present invention using the raw materials and catalyst as described above, first the water content of the catalyst to be used is adjusted by a known method. Various forms of use of these heteropolyacids can be considered, taking into consideration the reaction method, post-treatment of the reaction solution, recovery and reuse, etc.
For example, it can be used by adding it to raw materials as it is, or by supporting it on silica, alumina, activated carbon, etc. Next, the reaction of the method of the present invention is carried out in the presence of heteropolyacids. The reaction method can be continuous or batchwise, and can be carried out in either liquid phase or gas phase.Furthermore, considering that it can be used with heteropolyacids supported, fixed bed It will be advantageous if you do it in this way. In carrying out the method of the present invention, an inert solvent can be used if necessary for dissolving and mixing raw materials, removing reaction heat, etc. Examples of such inert solvents include dichloromethane, nitromethane, chlorobenzene,
Examples include benzene, ethyl acetate, and dioxane. In addition, when implementing the method of the present invention, safety,
Considering maintenance of catalyst activity and prevention of abnormal reactions,
It is preferable to carry out the reaction system under an inert gas atmosphere such as nitrogen or helium. Regarding the reaction conditions for the reaction shown in the method of the present invention, first, the temperature is preferably 0 to 300°C, and the pressure varies depending on the reaction method, and usually the own pressure of the reaction system is sufficient, but if necessary, inert gas etc. The pressure can be adjusted to the desired level. The reaction time varies depending on the raw materials used, the type of catalyst, the presence or absence of a solvent, and the set reaction conditions. The amount of heteropolyacids to be used is according to the above general formula []
0.01 to 50% by weight based on the monoalkyl ether of alkylene glycols shown in
Preferably it is 0.1 to 20% by weight. If the amount used is less than 0.01% by weight, the effect as a catalyst will be low, and in the present invention, it is not necessary to use more than 50% by weight. However, in cases such as fixed bed reactions,
The reaction can also be carried out by adjusting the amount of raw material monoalkyl ether passing through 0.01 to 10 parts by weight per 1 part by weight of heteropolyacids per unit time. In the reaction used in the method of the present invention, 2R 1 -O-[R 2 O-] o H→R 1 -O-[R 2 O-] o R is mainly obtained from the monoalkyl ether of alkylene glycol used as a raw material. 1+
HO−[R 2 −] o H According to the reaction formula “Here, R 1 , R 2 and n are the same as above,” 1/2 mole or less of the monoalkyl ether used in the reaction is dialkyl ether. The remainder is alkylene glycols. On the other hand, in the case of the compound represented by the general formula (), which is a raw material of the present invention, the main chain is cleaved due to the influence of heteropolyacids, which are acidic compounds, or they are recombined, resulting in oxidation. There is a slight tendency to form monoalkyl ethers of two or more alkylene glycols in which the number of repeating units of the alkylene group is different from n, and therefore, by the same reaction as shown in the present invention, the number of repeating units is n. Different dialkyl ethers and glycols are inevitably formed to some extent. Furthermore, as a matter of course, if a monoalkyl ether of an alkylene glycol in which the number n of repeating units of the oxyalkylene group of the compound represented by the general formula [] greatly exceeds 2 is used as a raw material, a wide variety of products can be produced as described above. The reaction takes place, and therefore many types of products are produced, which makes the separation and purification of these products complicated and undesirable. Therefore, in the method of the present invention, the above-mentioned alkylene glycol monoalkyl ether in which n is 2 or less is used. It is preferable. As described above, after proceeding with the reaction, the heteropolyacids may or may not be separated, using known methods,
For example, the target compound or a mixture thereof may be separated by distillation. Further, some by-product mixtures, for example those whose separation by distillation is relatively complicated, can be used as a raw material for the method of the present invention, as a raw material for other purposes, or for other uses after distillation. Furthermore, the recovered heteropolyacids can be reused after being treated if necessary. As mentioned above, the feature of the method of the present invention is that alkylene glycol dialkyl ether is advantageously provided, but another feature is that there is no by-product of large amounts of inorganic salts that require time and effort to process. I can do it. Next, the method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In the following description, parts are by weight unless otherwise specified. Example 1 A stainless steel autoclave was charged with 152.2 parts of ethylene glycol monomethyl ether and 2 parts of 12-molybdophosphoric acid, sealed with nitrogen, and heated to 170° C. for 4 hours with stirring. After the reaction was completed, the autoclave was allowed to cool to room temperature, opened, and the contents were taken out and analyzed by gas chromatography. The reaction rate of ethylene glycol monomethyl ether was 65.1%, and the composition (wt%) of the product was It was as follows. Ethylene glycol dimethyl ether 45.5% Diethylene glycol dimethyl ether
11.7% triethylene glycol dimethyl ether
1.3% Methanol 3.0% 1,4-dioxane 2.0% Ethylene glycol 21.0% Diethylene glycol monomethyl ether
11.0% Diethylene glycol 1.6% Others 2.8% The above product was separated and purified by distillation, resulting in a total of 99 parts. Example 2 120.1 parts of diethylene glycol monomethyl ether and 12-
Two parts of tungstophosphoric acid was added, the mixture was sealed with nitrogen, and the mixture was heated to 170° C. for 4 hours with stirring. After the reaction was completed, the autoclave was allowed to cool to room temperature, opened, and the contents were taken out and analyzed by gas chromatography. The reaction rate of diethylene glycol monomethyl ether was 50.9%, and the composition (wt%) of the product was It was as follows. Diethylene glycol methyl ether 40.8% Triethylene glycol dimethyl ether
10.4% Tetraethylene glycol dimethyl ether
3.4% Ethylene glycol dimethyl ether 2.4% 1,4-dioxane 13.0% Ethylene glycol 5.2% Diethylene glycol 15.4% Ethylene glycol monomethyl ether
2.0% triethylene glycol monomethyl ether
2.3% Others 5.1% Example 3-6 The reaction shown in Example 1 was repeated by changing the monoalkyl ether of alkylene glycol and the heteropolyacid, and the results are shown in Table 1. Examples 7-10 Ethylene glycol monomethyl ether 152.2
The reaction shown in Example 1 was repeated using different types of heteropolyacids and various heteropolyacids, and the results are shown in Table 2.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
り、ヘテロ原子又はヘテロ原子を含む置換基で置
換されたものを含む。R2は炭素数２〜４のアル
キレン基でありヘテロ原子又はヘテロ原子を含む
置換基で置換されたものを含む。ｎは１又は２で
ある。」 にて示されるアルキレングリコールモノアルキル
エーテルを、中心原子がホウ素、ケイ素、リン、
砒素、チタン又はゲルマニウムからなる群から選
ばれる原子であり、配位原子がモリブデン又はタ
ングステン原子であり、かつ中心原子と配位原子
の比が１：12であるヘテロポリ酸又はヘテロポリ
酸の酸性塩の存在下に加熱することを特徴とす
る、下記一般式（） R1−Ｏ−〔R2O−〕oR1 ……（） 「ここに、R1，R2及びｎは一般式［］に示
されるものと同じである。」 にて示されるアルキレングリコールジアルキルエ
ーテルの製造方法。 ２ ヘテロポリ酸又はヘテロポリ酸の酸性塩がド
デカタングストケイ酸モノナトリウム塩又はドデ
カタングストリン酸モノマンガン塩である特許請
求の範囲第１項記載の製造方法。[Claims] 1 The following general formula () R 1 -O- [R 2 O-] o H... () "Here, R 1 is an alkyl group having 1 to 4 carbon atoms, and is a hetero atom or a hetero atom. Including those substituted with a substituent containing an atom. R 2 is an alkylene group having 2 to 4 carbon atoms and includes those substituted with a hetero atom or a substituent containing a hetero atom. n is 1 or 2. The alkylene glycol monoalkyl ether shown in
A heteropolyacid or an acid salt of a heteropolyacid, which is an atom selected from the group consisting of arsenic, titanium, or germanium, and a coordinating atom is a molybdenum or tungsten atom, and the ratio of the central atom to the coordinating atom is 1:12. The following general formula () R 1 -O- [R 2 O-] o R 1 ... () "Here, R 1 , R 2 and n are the general formula [] The method for producing an alkylene glycol dialkyl ether shown in 2. The manufacturing method according to claim 1, wherein the heteropolyacid or the acid salt of the heteropolyacid is monosodium dodecataungstosilicate or monomanganese dodecataungstophosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58227016A JPS60120829A (en) | 1983-12-02 | 1983-12-02 | Production of alkylene glycol dialkyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58227016A JPS60120829A (en) | 1983-12-02 | 1983-12-02 | Production of alkylene glycol dialkyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60120829A JPS60120829A (en) | 1985-06-28 |
| JPH0137381B2 true JPH0137381B2 (en) | 1989-08-07 |
Family
ID=16854192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58227016A Granted JPS60120829A (en) | 1983-12-02 | 1983-12-02 | Production of alkylene glycol dialkyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60120829A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5837809B2 (en) * | 2010-12-27 | 2015-12-24 | 日本乳化剤株式会社 | Method for producing (poly) alkylene glycol diether |
| CN105772066B (en) * | 2014-12-22 | 2018-11-02 | 中国科学院大连化学物理研究所 | A kind of catalyst and preparation method thereof being used to prepare bi-end-blocking glycol ether |
| CN106554250B (en) * | 2015-09-30 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of method for preparing ethylene glycol by hydrolysis of ethylene glycol monomethyl ether |
| CN106554258B (en) * | 2015-09-30 | 2019-07-26 | 中国科学院大连化学物理研究所 | Method for directly preparing ethylene glycol dimethyl ether and co-producing ethylene glycol from ethylene glycol monomethyl ether |
-
1983
- 1983-12-02 JP JP58227016A patent/JPS60120829A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60120829A (en) | 1985-06-28 |
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