JPH03206087A - Production of oxetanes - Google Patents
Production of oxetanesInfo
- Publication number
- JPH03206087A JPH03206087A JP1340850A JP34085089A JPH03206087A JP H03206087 A JPH03206087 A JP H03206087A JP 1340850 A JP1340850 A JP 1340850A JP 34085089 A JP34085089 A JP 34085089A JP H03206087 A JPH03206087 A JP H03206087A
- Authority
- JP
- Japan
- Prior art keywords
- propanediol
- catalyst
- reaction
- oxetanes
- crystalline aluminosilicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002921 oxetanes Chemical class 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 16
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 abstract description 29
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 14
- 239000010457 zeolite Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- XHYFCIYCSYEDCP-UHFFFAOYSA-N 2,2-dimethyloxetane Chemical compound CC1(C)CCO1 XHYFCIYCSYEDCP-UHFFFAOYSA-N 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- -1 dioxane Chemical compound 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 150000000185 1,3-diols Chemical class 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 150000000093 1,3-dioxanes Chemical class 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QPYKYDBKQYZEKG-UHFFFAOYSA-N 2,2-dimethylpropane-1,1-diol Chemical compound CC(C)(C)C(O)O QPYKYDBKQYZEKG-UHFFFAOYSA-N 0.000 description 1
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 1
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- GZSSFSARCMSPPW-UHFFFAOYSA-N butane-2,2-diol Chemical compound CCC(C)(O)O GZSSFSARCMSPPW-UHFFFAOYSA-N 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はオキセタン類の製造方法の改良に関するもので
ある。さらに詳しくいえば、本発明は、反応液からの分
離、回収が容易な結晶性アルミノシリケート触媒を用い
、入手の容易な１．３−プロパンジオール類を環化させ
て、オキセタン類を収率よく工業的有利に製造する方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION FIELD OF INDUSTRIAL APPLICATION The present invention relates to an improvement in a method for producing oxetanes. More specifically, the present invention uses a crystalline aluminosilicate catalyst that is easily separated and recovered from the reaction solution to cyclize easily available 1,3-propanediols to produce oxetanes in high yields. This invention relates to an industrially advantageous manufacturing method.
従来の技術
従来、オキセタン類は、種々の有機薬品の合戒原料や水
溶性ポリマー原料などとして重要な化合物であり、その
製造方法としては、例えば（１）３−ハロゲノブ口バノ
ール類を水酸化カリウムで処理する方法、（２）３−ハ
ロゲノプロバノールの酢酸エステル類をアルカリで処理
する方法、（３）１．３−ジオールのカーポネートを加
熱分解する方法、（４）１．３−ジオキサン類を酸触媒
で分解する方法、（５）１．３−プロパンジオール類の
硫酸溶液を濃水酸化ナトリウム水溶液中に滴下する方法
〔「ネイチ＋ 一（Ｎａｔｕｒｅ）Ｊ第１８７巻、第４
７３号、第５９２ページ（１９６０午））、（６）ジオ
ール類をジアリールジアルコキシスル７ランと反応させ
る方法〔「ジャーナル・オブ・アメリカン・ケミカル・
ソサエテイ（Ｊ．Ａｍｅｒ．Ｃｈｅｍ．Ｓｏｃ．）Ｊ第
９６巻、第４６０４ページ（１９７４年）〕、（７）ジ
オール類をアルミナを用いて脱水する方法〔「ビュレテ
ィン・オブ・ケミカル・ソサエテ４”ジャパン（Ｂｕｌ
ｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ）Ｊ第５３巻、第３
０３１ページ（１９８０午））、（８）ジオール類をヘ
テロポリ酸を触媒に用いて環化する方法（特開昭６１−
１２６０８０号公報）などが知られている。Conventional technology Oxetanes have traditionally been important compounds as raw materials for various organic drugs and raw materials for water-soluble polymers, and their production methods include, for example, (1) mixing 3-halogenated vanols with potassium hydroxide; (2) A method of treating acetic esters of 3-halogenoprobanol with an alkali, (3) A method of thermally decomposing a carbonate of 1,3-diol, (4) A method of treating 1,3-dioxanes with an alkali. A method of decomposition with an acid catalyst, (5) A method of dropping a sulfuric acid solution of 1,3-propanediol into a concentrated aqueous sodium hydroxide solution [Nature J Vol. 187, No. 4]
73, p. 592 (1960 pm)), (6) Method of reacting diols with diaryldialkoxysul 7ranes [Journal of American Chemical
Society (J.Amer.Chem.Soc.) J Vol. 96, No. 4604 (1974)], (7) Method of dehydrating diols using alumina [``Buretin of Chemical Society 4'' Japan (Bul
l. Chem. Soc. Japan) J Vol. 53, No. 3
031 page (1980 noon)), (8) Method for cyclizing diols using a heteropolyacid as a catalyst (Japanese Unexamined Patent Publication No. 1983-1999)
126080) and the like are known.
しかしながら、前記（１）ないし（４）の製造方法にお
いては、原料として３−ハロゲノブロバノール、その酢
酸エステル、ｌ，３−ジオールのカーポネート、ｌ，３
−ジオキサン類などの１．３−プロパンジオールから誘
導されたものを用いるため、工程が煩雑である上、高濃
度のアルカリを用いたりするなど、実用的でないという
欠点があるし、（５）及び（６）の１，３−プロパンジ
オール類から直接オキセタン類を製造する方法は、高濃
度のアルカリ、硫酸を用いたり、特殊な反応試剤を用い
るため、前記と同様実用的でないという欠点を有してい
る。However, in the production methods (1) to (4) above, the raw materials are 3-halogenolobanol, its acetate, l,3-diol carbonate, l,3-diol carbonate,
- Because it uses a substance derived from 1,3-propanediol such as dioxane, it has the drawbacks that it is not practical as the process is complicated and a high concentration of alkali is used. The method (6) of directly producing oxetanes from 1,3-propanediol has the same drawbacks as above: it is not practical because it uses highly concentrated alkali or sulfuric acid, or special reaction reagents. ing.
一方、（７）のジオール類をアルミナを用いて脱水する
方法においては、触媒が固体であるため、反応液からの
触媒の分離回収が容易であるものの、該アルミナは極め
て触媒活性が低く、選択性に著しく劣るという欠点があ
る。さらに、（８）のジオール類をヘテロポリ酸を触媒
に用いて環化する方法は、該ヘテロポリ酸が反応液に溶
解するため、反応液からの触媒の分離、回収が困難であ
り、かつオキセタン類の選択率も十分でないなどの欠点
を有している。On the other hand, in the method (7) of dehydrating diols using alumina, since the catalyst is solid, it is easy to separate and recover the catalyst from the reaction solution, but the alumina has extremely low catalytic activity and is not suitable for use. It has the disadvantage of being significantly inferior in gender. Furthermore, in the method (8) of cyclizing diols using a heteropolyacid as a catalyst, since the heteropolyacid is dissolved in the reaction solution, it is difficult to separate and recover the catalyst from the reaction solution, and oxetane It has disadvantages such as insufficient selectivity.
発明が解決しようとする課題
本発明は、このような従来のオキセクン類の製造方法が
有する欠点を克服し、反応液からの分離、回収が容易な
、固体触媒を用い、入手の容易なｌ，３−プロパンジオ
ール類を環化させて、直接オキセタン類を収率よく工業
的有利に製造するための方法を提供することを目的とし
てなされたものである。Problems to be Solved by the Invention The present invention overcomes the drawbacks of such conventional methods for producing oxecunes, uses a solid catalyst that is easy to separate and recover from the reaction solution, and uses readily available l, The object of this invention is to provide a method for directly producing oxetanes in high yield and industrially advantageously by cyclizing 3-propanediols.
課題を解決するための手段
本発明者らは、前記目的を達戊するために鋭意研究を重
ねた結果、１，３−ブロバンジオール類を、結晶性アル
ミノシリケート触媒を用いて環化させることにより、そ
の目的を達成しうろことを見い出し、この知見に基づい
て本発明を完戒するに至つＩこ。Means for Solving the Problems As a result of extensive research to achieve the above object, the present inventors discovered that by cyclizing 1,3-brobanediols using a crystalline aluminosilicate catalyst, , I have discovered how to accomplish this purpose, and based on this knowledge, I have completed the present invention.
すなわち、本発明は、１．３−プロパンジオール類を環
化させて、オキセタン類を製造するに当り、触媒として
結晶性アルミノシリケートを用いることを特徴とするオ
キセタン類の製造方法を提供するものである。That is, the present invention provides a method for producing oxetanes, which is characterized in that a crystalline aluminosilicate is used as a catalyst in producing oxetanes by cyclizing 1,3-propanediol. be.
以下、本発明を詳細に説明する。The present invention will be explained in detail below.
本発明方法において、原料として用いられる１，３−ブ
ロバンジオール類としては、例えば１．３−プロパンジ
オール及び２，２−ジメチルプロパンジオール、２−メ
チルプロパンジオール、２−エチルブロバンジオール、
１−メチルプロパンジオール、１，２−ジメチルブロバ
ンジオールなどのアルキル置換１．３−ジオール類やこ
れらの置換基がハロゲンを含む１，３−ブロバンジオー
ル類など、さらにはこれらジオールの酢酸、プロビオン
酸などのエステル類を挙げることができる。In the method of the present invention, examples of 1,3-propanediol used as a raw material include 1,3-propanediol, 2,2-dimethylpropanediol, 2-methylpropanediol, 2-ethylbropanediol,
Alkyl-substituted 1,3-diols such as 1-methylpropanediol and 1,2-dimethylbrobanediol, and 1,3-brobanediols whose substituents contain halogen, as well as acetic acid and probionic acid of these diols. Examples include esters such as.
本発明方法で用いられる結晶性アルミノシリケートとし
ては、例えばゼオライトｘ，ｙ，モルデナイ１−、ヘー
タ、Ｌ，ＺＳＩＪ−５、ＺＳＭ− １０， ＺＳＭ−
１１，ＺＳＭ−１２、ＺＳＭ−２０などを挙げることが
できるが、これらの中で特にゼオライトＹ１モルデナイ
ト及びベータが好適である。これらの結晶性アルミノシ
リケートは、公知の方法により部分的に脱アルミニウム
処理したものも用いることができる。これら結晶性アル
ミノシリケートは、通常プロトン又はＮａ， Ｋ１Ｒｂ
， Ｃｓ％Ｃｕ， Ａｇなどの１族、ｌＪｇ， Ｃａ，
Ｓｒ， Ｚｎなとの２族金属、ＡＱ．Ｃａ．Ｙ−， Ｌ
ａ， Ｃｅなどの３族、Ｇｅ， Ｉｎ， ＴｉＳＺｒな
どの４族、Ｖ， Ｓｂ， Ｂｉなどの５族、ＣｒＳＭｏ
、．Ｗなどの６族、Ｍｎ， Ｒｅなとの７族、Ｆｅ，
Ｃｏ、Ｎｉ， Ｒｕ１Ｒｈ， Ｐｄ， Ｐｔ， ｂなど
の８族金属或分のいずれか１つ以上を含有した状態で用
いられるが、特に、アルカリ金属カチオン、アルカリ土
類カチオンから選ばれたカチオンを有するものが好まし
い。前記結晶性アルミノシリケートは１種用いてもよい
し、２種以上を組み合わせて用いてもよい。Examples of the crystalline aluminosilicate used in the method of the present invention include zeolite x,y, mordenai 1-, heta, L, ZSIJ-5, ZSM-10, ZSM-
Among them, zeolite Y1 mordenite and beta are particularly preferred. These crystalline aluminosilicates may also be partially dealuminated by a known method. These crystalline aluminosilicates are usually proton or Na, K1Rb
, Cs%Cu, Group 1 such as Ag, lJg, Ca,
Group 2 metals such as Sr and Zn, AQ. Ca. Y-, L
Group 3 such as a, Ce, Group 4 such as Ge, In, TiSZr, Group 5 such as V, Sb, Bi, CrSMo
,． Group 6 such as W, Group 7 such as Mn, Re, Fe,
It is used in a state containing one or more of Group 8 metals such as Co, Ni, Ru1Rh, Pd, Pt, b, etc., and in particular, it has a cation selected from alkali metal cations and alkaline earth cations. Preferably. One type of the crystalline aluminosilicate may be used, or two or more types may be used in combination.
本発明方法は液相で実施してもよいし、気相で実施して
もよく、また、固体触媒の使用形式としては、固定床方
式や流動床方式など、通常固体触媒の使用に際して用い
られている方式を採用することができる。該結晶性アル
ミノシリケートを固定床方式などで用いる場合、通常結
晶性アルミノシリケートは、シリカ、アルミナ、ジルコ
ニア、マグネシア、チタニア、粘土などの無機バインダ
ーを添加して用いられる。The method of the present invention may be carried out in a liquid phase or a gas phase, and the method of using a solid catalyst may be a fixed bed method or a fluidized bed method, which is usually used when using a solid catalyst. It is possible to adopt the following method. When the crystalline aluminosilicate is used in a fixed bed method or the like, the crystalline aluminosilicate is usually used with the addition of an inorganic binder such as silica, alumina, zirconia, magnesia, titania, or clay.
本発明における環化反応条件については、反応温度は、
通常５０〜３５０°Ｃ１好ましくはｌＯＯ〜３００゜Ｃ
の範囲で選ばれる。また、バッチ方式で実施する場合に
は、反応時間は触媒量や反応温度によって異なるが、通
常０．１〜２０時間程度で十分であり、触媒の使用量は
通常ジオール類に対して０．Ｏｌ〜５重量倍、好ましく
は０．０５〜１重量倍の範囲で選ばれる。一方、流通方
式で実施する場合には、重量時間空間速度（ ＷＨＳＶ
）として、通常０．０５〜２０Ｈｒ−’、好ましくは０
．１−１０８ｒ−’が用いられる。Regarding the cyclization reaction conditions in the present invention, the reaction temperature is:
Normally 50-350°C1 Preferably lOO-300°C
selected within the range. In addition, when carrying out in a batch method, the reaction time varies depending on the amount of catalyst and reaction temperature, but usually about 0.1 to 20 hours is sufficient, and the amount of catalyst used is usually 0.1 to 20 hours relative to the diols. The amount is selected within the range of 0.05 to 1 times by weight, preferably 0.05 to 1 times by weight. On the other hand, when implementing the distribution method, the weight hourly space velocity (WHSV
), usually 0.05 to 20 Hr-', preferably 0
．． 1-108r-' is used.
このようにして、■，３−プロパンジオール類から、収
率よく対応するオキセタン類が得られる。In this way, the corresponding oxetanes can be obtained from the 1,3-propanediols in good yields.
発明の効果
本発明方法によると、１．３−プロパンジオール類から
、直接オキセタン類を収率よく製造することができ、か
つ触媒として反応原料や反応生戒物に不溶な固体触媒を
用いるため、反応液からの触媒の分離、回収が極めて容
易であり、また、酸やアルカリなどの処理も必要がない
。このように、本発明方法は優れた特徴を有し、工業的
価値が大きい。Effects of the Invention According to the method of the present invention, oxetanes can be produced directly from 1,3-propanediol in good yield, and a solid catalyst that is insoluble in the reaction raw materials and reactants is used as a catalyst. It is extremely easy to separate and recover the catalyst from the reaction solution, and there is no need for treatment with acids or alkalis. As described above, the method of the present invention has excellent characteristics and is of great industrial value.
実施例
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.
実施例ｌ
２．２−ジメチル−１，３−プロパンジオール１０９及
び触媒としてのプロトン交換のＹ型ゼオライト２ｇを、
スタラー及び流出冷却管付き５０ｃｃ三つ口フラスコに
入れ、オイルバスにて所定温度に設定し反応を行った。Example l 2.2-dimethyl-1,3-propanediol 109 and 2 g of proton-exchanged Y-type zeolite as a catalyst,
The mixture was placed in a 50 cc three-necked flask equipped with a stirrer and an outflow condenser, and the reaction was carried out by setting a predetermined temperature in an oil bath.
２時間反応させたところ、約４ｇの流出液が得られた。After reacting for 2 hours, about 4 g of effluent was obtained.
この流出液をオイル相と水相とに分離し、オイル相をガ
スクロマトグラフにより分析した。また、流出残液は冷
却後、クロロホルムを加え溶解させてろ過し、ろ液を同
様にガスクロマトグラフにより分析した。This effluent was separated into an oil phase and an aqueous phase, and the oil phase was analyzed by gas chromatography. After cooling, the residual liquid was dissolved in chloroform and filtered, and the filtrate was similarly analyzed by gas chromatography.
反応温度１７０〜１７５°Ｃで実施した結果、２，２−
ジメチルオキセタンの収率は１２ｍｏ１％であった。As a result of carrying out the reaction at a temperature of 170 to 175°C, 2,2-
The yield of dimethyloxetane was 12 mo1%.
実施例２
実施例１において、触媒としてプロトン交換Ｙ型ゼオラ
イトの代りに、市販のＹ型ゼオライトを塩化カリウム水
溶液を用いてカリウム交換したものを用いた以外は、実
施例１と同様にして実施した。２．２−ジメチルオキセ
タンの収率は１５ｍｏ１％であった。Example 2 The procedure was carried out in the same manner as in Example 1, except that instead of the proton-exchanged Y-type zeolite as the catalyst, a commercially available Y-type zeolite that had been potassium-exchanged using an aqueous potassium chloride solution was used. . The yield of 2.2-dimethyloxetane was 15 mo1%.
実施例３
触媒として、市販のモルデナイト型ゼオライト（ンリカ
／アルミナ比２０）を公知方法により塩化アンモニウム
水溶液を用いアンモニウムカチオン交換し、次いで１２
０ ’Ｏで乾燥したのち、４５０゜Ｃで加熱処理して
プロトン交換モルデナイトとしたものを用い、実施例ｌ
同様条件で反応させた。２，２ージメチルオキセタンの
収率はｌｏｍｏｌ％であった。Example 3 As a catalyst, commercially available mordenite-type zeolite (phosphoric acid/alumina ratio 20) was subjected to ammonium cation exchange using an aqueous ammonium chloride solution by a known method, and then 12
Example l
The reaction was carried out under the same conditions. The yield of 2,2-dimethyloxetane was lomol%.
実施例４
触媒として、米国特許第３，３０８，０６９号明細書に
従って、テトラエチルアンモニウムヒドロキシドをテン
プレートに用い、１５０゜Ｃ，６日間水熱合或したベー
タ型ゼオライトを１規定硝酸により室温で約６時間処理
して、プロトン型（シリカ／アルミナ比９０）としたも
のを用い、反応温度１６０’ｃ！，反応時間３時間の条
件で、実施例１と同様にして反応を行った。２．２−ジ
メチルオキセタンの収率はｌｌｍｏｌ％であった。Example 4 Beta-type zeolite, which was hydrothermally synthesized at 150° C. for 6 days using tetraethylammonium hydroxide as a template according to U.S. Pat. A proton type (silica/alumina ratio of 90) was used after 6 hours of treatment, and the reaction temperature was 160'c! The reaction was carried out in the same manner as in Example 1 under the following conditions: , reaction time 3 hours. The yield of 2.2-dimethyloxetane was 11mol%.
実施例５
実施例１において、２．２−ジメチル−１．３−プロパ
ンジオールの代りに１．３−プロパンジオールを用い、
かつ反応温度を１６０°Ｃ１反応時間を２時間とした以
外は、実施例ｌと同様にして反応を行ったところ、オキ
セタンの収率は３ｍｏ１％であった。Example 5 In Example 1, 1,3-propanediol was used instead of 2,2-dimethyl-1,3-propanediol,
The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 160° C. and the reaction time was 2 hours, and the yield of oxetane was 3 mo1%.
実施例６
内径１０ｍｍの石英製反応管に、８〜２０メッシュの粒
度のプロトン型モルデナイト（シリカ／アルミナ比９６
）及びプロトン型ＺＳＭ−５ゼオライト（アルミナバイ
ンダー３Ｑｗｔ％を含む） ２．５ｇづつを混合し充て
んした。Example 6 A proton-type mordenite (silica/alumina ratio 96) with a particle size of 8 to 20 mesh was placed in a quartz reaction tube with an inner diameter of 10 mm.
) and proton type ZSM-5 zeolite (containing 3Qwt% alumina binder) were mixed and filled.
この反応管を電気炉により３００’Ｃに加熱し、窒素を
流しながら十分な乾燥を行ったのち、反応温度２００゜
Ｃに設定し、これに、２．２−ジメチル−１，３ープロ
パンジオールの１５ｗｔ％クロロホルム溶液を２．５ｃ
ｃ／Ｈｒの流量で供給し、反応させた。・反応流出物は
氷冷しトラップした。通液開始後５時間目？流出液を分
析したところ、２．２−ジメチル−１，３ープロパンジ
オールの転化率は６５％で、２．２−ジメチルオキセタ
ンの選択率は３３ｍｏ１％であった。This reaction tube was heated to 300°C in an electric furnace, thoroughly dried while flowing nitrogen, and then the reaction temperature was set at 200°C, and 2,2-dimethyl-1,3-propanediol 2.5c of a 15wt% chloroform solution of
It was supplied at a flow rate of c/Hr and reacted.・The reaction effluent was ice-cooled and trapped. 5th hour after starting fluid passage? Analysis of the effluent revealed that the conversion rate of 2,2-dimethyl-1,3-propanediol was 65% and the selectivity of 2,2-dimethyloxetane was 33 mo1%.
実施例７
触媒として、Ｎａ−Ｙゼオライト（ＵＣｃ社製）戊形品
５ｇを充てんして用い、２，２−ジメチル−１，３一プ
ロパンジオールの５０ｖｔ％水溶液を２．５ｃｃ／Ｈｒ
で供給し、反応温度２２０℃にて実施例６と同様に反応
を行ったところ、２，２−ジメチルーｌ，３−プロパン
ジオールの転化率は１５％で、２．２−ジメチルオキセ
タンの選択率は３５ｍｏ１％であった。Example 7 As a catalyst, 5 g of Na-Y zeolite (manufactured by UCc) was filled and used, and a 50 vt% aqueous solution of 2,2-dimethyl-1,3-propanediol was added at 2.5 cc/Hr.
When the reaction was carried out in the same manner as in Example 6 at a reaction temperature of 220°C, the conversion rate of 2,2-dimethyl-l,3-propanediol was 15%, and the selectivity of 2,2-dimethyloxetane was was 35mo1%.
実施例８
市販のＹ型ゼオライトを常法により塩化リチウム水溶液
を用いカチオン交換して、Ｌｉ交換Ｙ型ゼオライトパウ
ダーを調製したのち、シリカゾル（Ｓ１０■として３０
ｗｔ％）をバインダーに用い、押出し戊形して約１．５
ｍｍｐ Ｘ ４ ｍｍのペレットとし、次いでｌｌｏ’
ｃ！で乾燥後、５５０°Ｃで仮焼したものを触媒として
用い、反応温度２５０゜Ｏ， ＷＨＳＶ ０．２Ｈｒ−
’の条件にて実施例７と同様に反応させた。通液開始後
１０〜１５時間目の流出反応液を分析したところ、２．
２−ジメチル−１．３−プロパンジオールの転化率はｌ
６％で、２．２−ジメチルオキセタンの選択率は４Ｑｍ
ｏｌ％であった。Example 8 A commercially available Y-type zeolite was cation-exchanged using a lithium chloride aqueous solution in a conventional manner to prepare a Li-exchanged Y-type zeolite powder.
wt%) as a binder and extruded into a shape of approximately 1.5
mmp x 4 mm pellets, then llo'
c! After drying at 550°C, the catalyst was calcined at 550°C, and the reaction temperature was 250°O, WHSV 0.2Hr-
The reaction was carried out in the same manner as in Example 7 under the conditions of '. Analysis of the effluent reaction solution 10 to 15 hours after the start of liquid passage revealed that 2.
The conversion rate of 2-dimethyl-1,3-propanediol is l
6%, the selectivity for 2,2-dimethyloxetane is 4Qm
It was ol%.
実施例９
触媒として市販のＹ型ゼオライトを常法により塩化セシ
ウム水溶液を用いてＣｓ交換Ｙゼオライトとしたものを
用い、反応温度２２０’ＯＳＷＨＳＶ Ｏ．４Ｈｒ”’
の条件で実施例７と同様にして反応を行ったとこロ、２
．２−ジメチル−１，３−プロパンジオールの転化率は
ｌ５％で、２，２−ジメチルオキセタンの選択率は３０
ｍｏ１％であった。Example 9 Commercially available Y-type zeolite was converted into Cs-exchanged Y-zeolite using a cesium chloride aqueous solution in a conventional manner as a catalyst, and the reaction temperature was 220'OSWHSV O. 4Hr"'
The reaction was carried out in the same manner as in Example 7 under the conditions of 2.
．． The conversion rate of 2-dimethyl-1,3-propanediol was 15%, and the selectivity of 2,2-dimethyloxetane was 30%.
The mo was 1%.
Claims (1)
タン類を製造するに当り、触媒として結晶性アルミノシ
リケートを用いることを特徴とするオキセタン類の製造
方法。1. A method for producing oxetanes, which comprises using a crystalline aluminosilicate as a catalyst in producing oxetanes by cyclizing 1,3-propanediol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1340850A JPH03206087A (en) | 1989-12-30 | 1989-12-30 | Production of oxetanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1340850A JPH03206087A (en) | 1989-12-30 | 1989-12-30 | Production of oxetanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03206087A true JPH03206087A (en) | 1991-09-09 |
Family
ID=18340883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1340850A Pending JPH03206087A (en) | 1989-12-30 | 1989-12-30 | Production of oxetanes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03206087A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5418296A (en) * | 1993-11-23 | 1995-05-23 | Shell Oil Company | Capping of anionic polymers with oxetanes |
| JP2007217382A (en) * | 2006-02-20 | 2007-08-30 | Ube Ind Ltd | Method for producing oxetane compound |
| JP2008150300A (en) * | 2006-12-15 | 2008-07-03 | Ube Ind Ltd | Method for producing oxetane compound |
| JP2008149230A (en) * | 2006-12-15 | 2008-07-03 | Ube Ind Ltd | Solid catalyst for manufacturing oxetane compound, and its manufacturing method |
| EP3409663A1 (en) * | 2017-06-01 | 2018-12-05 | Vioryl Chemical and Agricultural Industry, Research S.A. | Conversion of sclareol to manoyl oxide under mordenite catalysis |
-
1989
- 1989-12-30 JP JP1340850A patent/JPH03206087A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5418296A (en) * | 1993-11-23 | 1995-05-23 | Shell Oil Company | Capping of anionic polymers with oxetanes |
| JP2007217382A (en) * | 2006-02-20 | 2007-08-30 | Ube Ind Ltd | Method for producing oxetane compound |
| JP2008150300A (en) * | 2006-12-15 | 2008-07-03 | Ube Ind Ltd | Method for producing oxetane compound |
| JP2008149230A (en) * | 2006-12-15 | 2008-07-03 | Ube Ind Ltd | Solid catalyst for manufacturing oxetane compound, and its manufacturing method |
| EP3409663A1 (en) * | 2017-06-01 | 2018-12-05 | Vioryl Chemical and Agricultural Industry, Research S.A. | Conversion of sclareol to manoyl oxide under mordenite catalysis |
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