JPH08253462A - Production of n-vinyloxazolidones - Google Patents
Production of n-vinyloxazolidonesInfo
- Publication number
- JPH08253462A JPH08253462A JP7057876A JP5787695A JPH08253462A JP H08253462 A JPH08253462 A JP H08253462A JP 7057876 A JP7057876 A JP 7057876A JP 5787695 A JP5787695 A JP 5787695A JP H08253462 A JPH08253462 A JP H08253462A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- oxazolidones
- group
- oxazolidone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ｎ−（１−アルキルオ
キシアルキル）−２−オキサゾリドン類をＮ−ビニル−
２−オキサゾリドン類に転化する際に用いる、Ｎ−（１
−アルキルオキシアルキル）−２−オキサゾリドン類の
気相分子内脱アルコール反応用触媒、およびその触媒を
用いるＮ−ビニル−２−オキサゾリドン類の製造方法に
関する。The present invention relates to N- (1-alkyloxyalkyl) -2-oxazolidones and N-vinyl-
N- (1 used for conversion to 2-oxazolidones
TECHNICAL FIELD The present invention relates to a catalyst for gas phase intramolecular dealcoholization reaction of -alkyloxyalkyl) -2-oxazolidones and a method for producing N-vinyl-2-oxazolidones using the catalyst.
【０００２】Ｎ−ビニル−２−オキサゾリドン類は、単
独あるいは他のモノマーとの共重合によりポリマーとす
ることで、コンプレックス化剤、接着剤、繊維改質剤、
染色助剤、樹脂添加剤等の原料となるポリＮ−ビニル−
２−オキサゾリドン類およびその共重合体の原料モノマ
ーとして有用な化合物である。N-vinyl-2-oxazolidones are used alone or as a polymer by copolymerization with other monomers to form a complexing agent, an adhesive, a fiber modifier,
Poly N-vinyl-, which is a raw material for dyeing aids and resin additives
It is a compound useful as a raw material monomer for 2-oxazolidones and copolymers thereof.
【０００３】[0003]
【従来の技術】Ｎ−ビニル−２−オキサゾリドン類の製
造方法として、米国特許第６７６４４３号に、ルテニウ
ム触媒を用いる２−オキサゾリドンとカルボン酸ビニル
エステルとの液相エステル交換反応による方法が開示さ
れている。この方法は、触媒が高価であること、原料２
−オキサゾリドンと当量の副原料（カルボン酸ビニルエ
ステル）を要する上に、副原料由来のカルボン酸が多量
に副生する等の問題がある。2. Description of the Related Art As a method for producing N-vinyl-2-oxazolidones, US Pat. No. 676443 discloses a method by a liquid phase transesterification reaction between 2-oxazolidone and a vinyl carboxylate ester using a ruthenium catalyst. There is. In this method, the catalyst is expensive and the raw material 2
There is a problem that an equivalent amount of an auxiliary raw material (carboxylic acid vinyl ester) to oxazolidone is required and a large amount of carboxylic acid derived from the auxiliary raw material is by-produced.
【０００４】また、米国特許第３０３８２９号には、水
銀系触媒を用いる２−オキサゾリドンとアルキルビニル
エーテルとの液相エーテル交換反応による方法が開示さ
れている。この方法は、原料に高価なアルキルビニルエ
ーテルを用いること、アセタールの副生が多いこと、触
媒が毒物である等の問題がある。Further, US Pat. No. 3,032,829 discloses a method by liquid phase ether exchange reaction between 2-oxazolidone and alkyl vinyl ether using a mercury catalyst. This method has problems that an expensive alkyl vinyl ether is used as a raw material, that many acetals are by-produced, and that the catalyst is a poison.
【０００５】上記のような交換反応によらない方法とし
ては、Ｎ−（２−クロロエチル）−２−オキサゾリドン
をアルカリを用いて脱塩酸する方法（ドイツ特許第９７
２３０４号およびＪ．Ｏｒｇ．Ｃｈｅｍ．，ｖｏｌ．２
２，８４９−５１，１９５７）や、Ｎ−（２−アセトキ
シエチル）−２−オキサゾリドンを高温で脱酢酸する方
法（Ｊ．Ｏｒｇ．Ｃｈｅｍ．，ｖｏｌ．２６，３４６
５，１９６１）等があるが、前者は低収率でしかも塩酸
塩が多量に副生するという問題があり、後者は非常に高
温（５８０℃）で行うため、２−オキサゾリドン環が熱
分解し低収率となる等の問題がある。As a method that does not rely on the above-mentioned exchange reaction, a method of dehydrochlorinating N- (2-chloroethyl) -2-oxazolidone using an alkali (German Patent No. 97)
2304 and J. Org. Chem. , Vol. Two
2, 849-51, 1957) and a method of deacetic acid N- (2-acetoxyethyl) -2-oxazolidone at high temperature (J. Org. Chem., Vol. 26, 346).
No. 5,1961), the former has a problem that the yield is low and a large amount of hydrochloride is by-produced, and the latter is carried out at an extremely high temperature (580 ° C.), so that the 2-oxazolidone ring is thermally decomposed. There are problems such as low yield.
【０００６】また、特開昭５８−１５７７６６号公報で
は、ジエタノールアミンと炭酸ジエチルから合成した炭
酸Ｎ−２−オキサゾリジノイルエチルエチルを、ＮａＯ
Ｈ存在下に熱分解する方法が開示されている。この方法
は、原料の炭酸Ｎ−２−オキサゾリジノイルエチルエチ
ルを製造するために高価な炭酸ジエチルを多量に用いる
必要があり経済性が低い。Further, in JP-A-58-157766, N-2-oxazolidinoylethyl ethyl carbonate synthesized from diethanolamine and diethyl carbonate was added to NaO.
A method of thermally decomposing in the presence of H is disclosed. This method requires a large amount of expensive diethyl carbonate in order to produce the raw material N-2-oxazolidinoylethyl ethyl carbonate, and is economically disadvantageous.
【０００７】他方、米国特許第２９０５６９０号には、
２−オキサゾリドンとアセチレンとの付加反応による方
法が開示されているが、この方法は高圧でアセチレンを
取り扱うためアセチレンの分解爆発の危険性が伴う。On the other hand, in US Pat. No. 2,905,690,
Although a method by an addition reaction between 2-oxazolidone and acetylene is disclosed, this method involves the risk of decomposition and explosion of acetylene because acetylene is handled at high pressure.
【０００８】以上に述べた従来方法に比べ改善された方
法として、米国特許第４８３１１５３号では、Ｎ−（１
−ヒドロキシアルキル）−２−オキサゾリドンまたはＮ
−（１−ヒドロキシカルビルオキシアルキル）−２−オ
キサゾリドンを気相で熱分解する方法が提案されてい
る。この方法では、弱酸およびその金属塩類が触媒に用
いられており、Ｈ3ＢＯ4，Ｎａ2ＳＯ4，Ｋ2ＳＯ4，Ｃｕ
ＳＯ4等が好適とされている。しかしながら、この方法
を工業的に実施するには目的Ｎ−ビニル−２−オキサゾ
リドンの収率が十分でなく、また触媒寿命について全く
検討されておらず、実用的技術とは言い難い。As an improved method over the conventional method described above, US Pat. No. 4,831,153 discloses N- (1
-Hydroxyalkyl) -2-oxazolidone or N
A method of thermally decomposing-(1-hydroxycarbyloxyalkyl) -2-oxazolidone in a gas phase has been proposed. In this method, a weak acid and its metal salt are used as a catalyst, and H 3 BO 4 , Na 2 SO 4 , K 2 SO 4 , and Cu are used.
SO 4 and the like are preferred. However, the yield of the objective N-vinyl-2-oxazolidone is not sufficient to carry out this method industrially, and the catalyst life has not been studied at all, and it cannot be said to be a practical technique.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、Ｎ−
（１−アルキルオキシアルキル）−２−オキサゾリドン
類を反応原料とし、副原料や溶媒を一切用いずに、気相
において直接一段でＮ−ビニル−２−オキサゾリドン類
に高転化率で、極めて高選択的に転化できるＮ−（１−
アルキルオキシアルキル）−２−オキサゾリドン類の気
相分子内脱アルコール反応用触媒を提供することにあ
る。The object of the present invention is to provide N-
(1-Alkyloxyalkyl) -2-oxazolidones are used as a reaction raw material, without using any auxiliary raw materials or solvents, and in a gas phase, in a single stage, directly converted into N-vinyl-2-oxazolidones with a high conversion rate and extremely high selection. N- (1-
It is intended to provide a catalyst for vapor phase intramolecular dealcoholization reaction of alkyloxyalkyl) -2-oxazolidones.
【００１０】また本発明の他の目的は、Ｎ−（１−アル
キルオキシアルキル）−２−オキサゾリドン類を反応原
料とし、副原料や溶媒を一切用いずに、気相において直
接一段でＮ−ビニル−２−オキサゾリドン類に高転化率
で、極めて高選択的に転化するＮ−ビニル−２−オキサ
ゾリドン類の製造方法を提供することにある。Another object of the present invention is to use N- (1-alkyloxyalkyl) -2-oxazolidones as a reaction raw material, and to use N-vinyl directly in a gas phase in a single step without using any auxiliary raw material or solvent. It is an object of the present invention to provide a method for producing N-vinyl-2-oxazolidones which can be converted into 2-oxazolidones with a high conversion rate and which is extremely highly selectively converted.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、Ｎ−（１
−アルキルオキシアルキル）−２−オキサゾリドン類を
気相において直接一段で脱アルコール反応させ得る方法
およびそれに用いる触媒について鋭意検討する中で、リ
ンを含有して成る固体酸化物を触媒に用いると、Ｎ−
（１−アルキルオキシアルキル）−２−オキサゾリドン
類が、従来になく高転化率で高選択的に長期にわたり安
定的に、Ｎ−ビニル−２−オキサゾリドン類に転化でき
ることを見いだし、本発明を完成するに至った。The present inventors have developed N- (1
When a solid oxide containing phosphorus is used as a catalyst, the inventors of the present invention have studied intensively the method for directly carrying out a one-step dealcoholization reaction of -alkyloxyalkyl) -2-oxazolidones in a gas phase and a catalyst used therefor. −
The inventors have found that (1-alkyloxyalkyl) -2-oxazolidones can be converted to N-vinyl-2-oxazolidones with high conversion and high selectivity stably over a long period of time, and have completed the present invention. Came to.
【００１２】すなわち、本発明の触媒は、Ｎ−（１−ア
ルキルオキシアルキル）−２−オキサゾリドン類をＮ−
ビニル−２−オキサゾリドン類に転化する際に用いる触
媒であって、該触媒が、リンを含有して成る固体酸化物
であることを特徴とする、Ｎ−（１−アルキルオキシア
ルキル）−２−オキサゾリドン類の気相分子内脱アルコ
ール反応用触媒である。That is, the catalyst of the present invention comprises N- (1-alkyloxyalkyl) -2-oxazolidones.
N- (1-alkyloxyalkyl) -2-, which is a catalyst used when converting to vinyl-2-oxazolidones, wherein the catalyst is a solid oxide containing phosphorus. It is a catalyst for gas phase intramolecular dealcoholization reaction of oxazolidones.
【００１３】前記触媒は、さらにアルカリ金属元素およ
びアルカリ土類金属元素からなる群より選ばれる一種以
上の元素を含有してなる固体酸化物であることが好まし
いものである。The catalyst is preferably a solid oxide further containing one or more elements selected from the group consisting of alkali metal elements and alkaline earth metal elements.
【００１４】前記触媒は、Ｔｉ，Ｚｒ，Ｎｂ，Ｂ，Ａｌ
およびＳｉからなる群より選ばれる１種以上の元素を含
有してなる固体酸化物であることがさらに好ましいもの
である。The catalyst is Ti, Zr, Nb, B, Al.
It is more preferable that the solid oxide contains one or more elements selected from the group consisting of and Si.
【００１５】さらには前記触媒が、下記一般式（１）Further, the catalyst is represented by the following general formula (1)
【００１６】[0016]
【化４】 [Chemical 4]
【００１７】（式中、Ｐはリン、Ｘはアルカリ金属元素
およびアルカリ土類金属元素からなる群より選ばれる一
種以上の元素、ＹはＴｉ，Ｚｒ，Ｎｂ，Ｂ，Ａｌおよび
Ｓｉからなる群より選ばれる１種以上の元素であり、Ｏ
は酸素である。また添字ａ，ｂ，ｃ，ｄは、それぞれの
元素の原子比を表し、ａ＝１のときｂ＝０〜５、ｃ＝１
〜５００の範囲をとり、ｄはａ、ｂ、ｃの値および各種
構成元素の結合状態により定まる数値である。）で表さ
れる固体酸化物であることが好ましいものである。(Wherein P is phosphorus, X is one or more elements selected from the group consisting of alkali metal elements and alkaline earth metal elements, and Y is from the group consisting of Ti, Zr, Nb, B, Al and Si. O, which is one or more elements selected
Is oxygen. The subscripts a, b, c, and d represent atomic ratios of the respective elements, and when a = 1, b = 0 to 5 and c = 1.
The range is from ~ 500, and d is a numerical value determined by the values of a, b, c and the bonding state of various constituent elements. It is preferable that it is a solid oxide represented by the following.
【００１８】なお本発明における固体酸化物には、その
組成中にプロトンを含有するものも含むものである また本発明の製造方法は、Ｎ−（１−アルキルオキシア
ルキル）−２−オキサゾリドン類をＮ−ビニル−２−オ
キサゾリドン類に転化する際に、前記気相分子内脱アル
コール反応用触媒を用いることを特徴とするものであ
る。The solid oxide in the present invention includes those containing a proton in its composition. Further, in the production method of the present invention, N- (1-alkyloxyalkyl) -2-oxazolidones are converted into N- (1-alkyloxyalkyl) -2-oxazolidones. It is characterized by using the above-mentioned gas phase intramolecular dealcoholization reaction catalyst when converting to vinyl-2-oxazolidones.
【００１９】特に前記Ｎ−（１−アルキルオキシアルキ
ル）−２−オキサゾリドン類が下記一般式（２）Particularly, the N- (1-alkyloxyalkyl) -2-oxazolidones are represented by the following general formula (2):
【００２０】[0020]
【化５】 Embedded image
【００２１】（式中、Ｒ1は独立して水素、メチル基お
よびエチル基からなる群より選ばれる１種であり、Ｒ2
はメチル基、エチル基、プロピル基およびブチル基から
なる群より選ばれる１種である。）で表される化合物で
あり、Ｎ−ビニル−２−オキサゾリドン類が下記一般式
（３）[0021] (In the formula, R 1 is independently hydrogen, a one selected from the group consisting of methyl and ethyl, R 2
Is one selected from the group consisting of a methyl group, an ethyl group, a propyl group and a butyl group. ), N-vinyl-2-oxazolidones are represented by the following general formula (3):
【００２２】[0022]
【化６】 [Chemical 6]
【００２３】（式中、Ｒ1は前記一般式（２）と同じで
ある。）で表される化合物である際に特に有用である。It is particularly useful when the compound is represented by the formula (wherein R 1 is the same as in the general formula (2)).
【００２４】[0024]
【作用】以下に本発明を詳しく説明する。The present invention will be described in detail below.
【００２５】本発明の触媒は、例えば下記一般式（４）The catalyst of the present invention has, for example, the following general formula (4):
【００２６】[0026]
【化７】 [Chemical 7]
【００２７】（式中、Ｒは独立して水素、またはアルキ
ル基であり、Ｒ’はアルキル基を表わす。）で表される
Ｎ−（１−アルキルオキシアルキル）−２−オキサゾリ
ドン類のＮ−ビニル−２−オキサゾリドン類への気相分
子内脱アルコール反応に有効に作用する。なかでも、前
記一般式（４）中のＲが、独立して水素、メチル基およ
びエチル基からなる群より選ばれる１種であり、Ｒ’が
メチル基、エチル基、プロピル基およびブチル基からな
る群より選ばれる１種である反応に、極めて有効に作用
する。(In the formula, R is independently hydrogen or an alkyl group, and R'represents an alkyl group.) N- (1-alkyloxyalkyl) -2-oxazolidone N- It effectively acts on the vapor phase intramolecular dealcoholization reaction of vinyl-2-oxazolidones. Among them, R in the general formula (4) is one type independently selected from the group consisting of hydrogen, a methyl group and an ethyl group, and R ′ is a methyl group, an ethyl group, a propyl group and a butyl group. It acts extremely effectively on a reaction which is one kind selected from the group consisting of
【００２８】本発明の触媒の触媒活性は、長時間連続で
反応しても殆ど低下しない。また仮に、コーキング等で
劣化しても、空気を通しコークを燃焼すれば活性は回復
するものである。The catalytic activity of the catalyst of the present invention hardly decreases even if the reaction is continued for a long time. Even if the coke is deteriorated by coking or the like, the activity is restored by burning the coke by passing air.
【００２９】本発明の触媒は、リンを含有して成る固体
酸化物である。好ましくは、さらにアルカリ金属元素お
よびアルカリ土類金属元素からなる群より選ばれる１種
以上の元素を含有してなる固体酸化物である。また、リ
ンの他にＴｉ，Ｚｒ，Ｎｂ，Ｂ，ＡｌおよびＳｉよりな
る群から選ばれる１種以上の元素を含有してなる固体酸
化物であることが好ましい。それら構成元素の原子比に
ついては特に限定されないが、特に下記一般式（１）The catalyst of the present invention is a solid oxide containing phosphorus. Preferably, it is a solid oxide further containing one or more elements selected from the group consisting of alkali metal elements and alkaline earth metal elements. Further, it is preferably a solid oxide containing, in addition to phosphorus, one or more elements selected from the group consisting of Ti, Zr, Nb, B, Al and Si. The atomic ratio of the constituent elements is not particularly limited, but particularly the following general formula (1)
【００３０】[0030]
【化８】 Embedded image
【００３１】（式中、Ｐはリン、Ｘはアルカリ金属元素
およびアルカリ土類金属元素からなる群より選ばれる一
種以上の元素、ＹはＴｉ，Ｚｒ，Ｎｂ，Ｂ，Ａｌおよび
Ｓｉからなる群より選ばれる１種以上の元素であり、Ｏ
は酸素である。また添字ａ，ｂ，ｃ，ｄは、それぞれの
元素の原子比を表し、ａ＝１のときｂ＝０〜５、ｃ＝１
〜５００の範囲をとり、ｄはａ、ｂ、ｃの値および各種
構成元素の結合状態により定まる数値である。）で表さ
れる固体酸化物が好ましく、更に好ましくは、リンと、
アルカリ金属元素および／またはアルカリ土類金属元素
と、Ｔｉ，Ｚｒ，Ｎｂ，Ｂ，ＡｌおよびＳｉからなる群
より選ばれる１種以上の元素とを複合して成る固体酸化
物である。(Wherein P is phosphorus, X is one or more elements selected from the group consisting of alkali metal elements and alkaline earth metal elements, and Y is from the group consisting of Ti, Zr, Nb, B, Al and Si. O, which is one or more elements selected
Is oxygen. The subscripts a, b, c, and d represent atomic ratios of the respective elements, and when a = 1, b = 0 to 5 and c = 1.
The range is from ~ 500, and d is a numerical value determined by the values of a, b, c and the bonding state of various constituent elements. ) Is preferably a solid oxide represented by the above, more preferably phosphorus,
It is a solid oxide formed by combining an alkali metal element and / or an alkaline earth metal element and one or more elements selected from the group consisting of Ti, Zr, Nb, B, Al and Si.
【００３２】触媒調製法としては、特に限定されるもの
ではなく、従来公知のあらゆる方法が適用できる。触媒
の必須成分であるリンは、その原料として五塩化リン、
リン酸、リン酸塩類、リン酸エステル類、およびその他
の有機リン化合物等が用いられる。The catalyst preparation method is not particularly limited, and any conventionally known method can be applied. Phosphorus, which is an essential component of the catalyst, has phosphorus pentachloride as its raw material,
Phosphoric acid, phosphates, phosphates, and other organic phosphorus compounds are used.
【００３３】また、アルカリ金属元素および／またはア
ルカリ土類金属元素は、その原料として、酸化物、水酸
化物、ハロゲン化物、塩類（炭酸塩、硝酸塩、カルボン
酸塩、リン酸塩、硫酸塩等）および金属などが用いられ
る。The alkali metal element and / or alkaline earth metal element is used as a raw material for oxides, hydroxides, halides, salts (carbonates, nitrates, carboxylates, phosphates, sulfates, etc.). ) And metals are used.
【００３４】その他の成分（好ましくはＴｉ，Ｚｒ，Ｎ
ｂ，Ｂ，ＡｌおよびＳｉからなる群より選ばれる１種以
上の元素）は、その原料として酸化物、水酸化物、ハロ
ゲン化物、塩類および金属等が用いられる。Other components (preferably Ti, Zr, N
For one or more elements selected from the group consisting of b, B, Al and Si), oxides, hydroxides, halides, salts and metals are used as the raw materials.
【００３５】本発明の触媒の調製法例を挙げれば、
（１）リン酸塩類単独、またはそれとアルカリ金属元素
および／またはアルカリ土類金属元素源を、その他の成
分元素源と共に適当な成型助剤（水、アルコール等）を
加え成型後、乾燥、焼成を経て触媒とする方法、（２）
リン酸あるいはリン酸塩類の水溶液を、その他の成分元
素の酸化物に含浸または混合し成型後、乾燥、焼成を経
て触媒とする方法、（３）リン酸あるいはリン酸塩類の
水溶液を、その他の成分元素の酸化物の成型体（球状、
円柱状、リング状等）に含浸し、乾燥、焼成を経て触媒
とする方法、（４）リン源単独または、それとアルカリ
金属元素および／またはアルカリ土類金属元素源を、そ
の他の成分元素源と共に水中に溶解もしくは懸濁させ、
かくはん下加熱濃縮し、乾燥後成型し、焼成を経て触媒
とする方法等がある。Examples of the method for preparing the catalyst of the present invention include:
(1) Phosphates alone, or together with an alkali metal element and / or alkaline earth metal element source, a suitable molding aid (water, alcohol, etc.) together with other component element sources, and after molding, drying and firing. After that, the method (2)
A method of impregnating or mixing an aqueous solution of phosphoric acid or a phosphate with an oxide of another component element, molding, and then drying and firing to obtain a catalyst, (3) an aqueous solution of phosphoric acid or a phosphate. Molded body of oxide of component element (spherical,
(Cylindrical shape, ring shape, etc.), followed by drying and firing to make a catalyst, (4) Phosphorus source alone or with it and an alkali metal element and / or alkaline earth metal element source together with other component element sources Dissolved or suspended in water,
There is a method of concentrating by heating under stirring, drying, molding, and firing to obtain a catalyst.
【００３６】本発明の触媒の焼成温度は、用いる触媒原
料の種類にもよるが、３００〜１０００℃の広い範囲を
とれ、好ましくは４００〜８００℃の範囲である。Although the calcination temperature of the catalyst of the present invention depends on the kind of the catalyst raw material used, it can be set in a wide range of 300 to 1000 ° C, and preferably in the range of 400 to 800 ° C.
【００３７】また本発明の製造方法は、Ｎ−（１−アル
キルオキシアルキル）−２−オキサゾリドン類をＮ−ビ
ニル−２−オキサゾリドン類に転化する際に、前記気相
分子内脱アルコール反応用触媒を前述のごとく用いるも
のである。Further, the production method of the present invention is a catalyst for the gas phase intramolecular dealcoholization reaction when converting N- (1-alkyloxyalkyl) -2-oxazolidones to N-vinyl-2-oxazolidones. Is used as described above.
【００３８】本発明の製造方法が用いられる反応は、例
えば前記一般式（４）で示されるが、なかでも、前記一
般式（４）中のＲが、独立して水素、メチル基およびエ
チル基からなる群より選ばれる１種であり、Ｒ’がメチ
ル基、エチル基、プロピル基およびブチル基からなる群
より選ばれる１種である場合の反応に、極めて有用であ
る。The reaction in which the production method of the present invention is used is represented by, for example, the above-mentioned general formula (4). Among them, R in the general formula (4) is independently hydrogen, methyl group and ethyl group. It is extremely useful for the reaction when R ′ is one selected from the group consisting of a methyl group, an ethyl group, a propyl group and a butyl group.
【００３９】本発明の実施にあたり反応器は、固定床流
通型および流動床型のいずれでも使用できる。In carrying out the present invention, the reactor may be either a fixed bed flow type or a fluidized bed type.
【００４０】反応は、原料のＮ−（１−アルキルオキシ
アルキル）−２−オキサゾリドン類が、気相状態を維持
し得る反応温度および反応圧力下で行う。反応圧力は通
常、常圧または減圧であるが、加圧も可能である。反応
温度は、他の反応条件によっても異なるが、２００〜４
００℃、好ましくは２５０〜３５０℃の範囲が適当であ
る。反応温度が２００℃より低いと原料Ｎ−（１−アル
キルオキシアルキル）−２−オキサゾリドン類の転化率
が大幅に低下し、４００℃より高いと目的Ｎ−ビニル−
２−オキサゾリドン類の選択率が著しく低下する。The reaction is carried out at a reaction temperature and a reaction pressure at which the raw material N- (1-alkyloxyalkyl) -2-oxazolidones can maintain a gas phase state. The reaction pressure is usually atmospheric pressure or reduced pressure, but increased pressure is also possible. The reaction temperature varies depending on other reaction conditions, but is 200 to 4
A range of 00 ° C, preferably 250-350 ° C is suitable. If the reaction temperature is lower than 200 ° C, the conversion rate of the raw material N- (1-alkyloxyalkyl) -2-oxazolidones is significantly lowered, and if it is higher than 400 ° C, the target N-vinyl-
The selectivity of 2-oxazolidones is significantly reduced.
【００４１】原料のＮ−（１−アルキルオキシアルキ
ル）−２−オキサゾリドン類は、窒素、ヘリウム、アル
ゴン、炭化水素等の、目的反応に不活性な物質による希
釈および／または減圧により、Ｎ−（１−アルキルオキ
シアルキル）−２−オキサゾリドン類の分圧を５〜６０
０ｍｍＨｇとして触媒層に供給する。原料Ｎ−（１−ア
ルキルオキシアルキル）−２−オキサゾリドン類の空間
速度（ＧＨＳＶ）は、他の反応条件によっても異なり、
通常１〜１０００ｈ-1、好ましくは１０〜５００ｈ-1の
範囲である。The starting material N- (1-alkyloxyalkyl) -2-oxazolidones is diluted with a substance inert to the intended reaction, such as nitrogen, helium, argon or hydrocarbon, and / or reduced pressure to give N- ( The partial pressure of 1-alkyloxyalkyl) -2-oxazolidones is 5 to 60
It is supplied to the catalyst layer as 0 mmHg. The space velocity (GHSV) of the raw material N- (1-alkyloxyalkyl) -2-oxazolidones varies depending on other reaction conditions,
It is usually in the range of 1 to 1000 h -1 , preferably 10 to 500 h -1 .
【００４２】[0042]
【実施例】以下、実施例により、本発明を具体的に説明
するが、本発明はこれらにより何等限定されるものでは
ない。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
【００４３】なお、実施例中の転化率、選択率、および
単流収率は、次の定義に従う。The conversion, selectivity, and single-flow yield in the examples are defined as follows.
【００４４】・転化率（モル％）＝（消費したＮ−（１
−アルキルオキシアルキル）−２−オキサゾリドンのモ
ル数／供給したＮ−（１−アルキルオキシアルキル）−
２−オキサゾリドンのモル数）×１００ ・選択率（モル％）＝（生成したＮ−ビニル−２−オキ
サゾリドンのモル数／消費したＮ−（１−アルキルオキ
シアルキル）−２−オキサゾリドンのモル数）×１００ ・単流収率（モル％）＝（生成したＮ−ビニル−２−オ
キサゾリドンのモル数／供給したＮ−（１−アルキルオ
キシアルキル）−２−オキサゾリドンのモル数）×１０
０ 実施例１ （触媒調製）８５％リン酸水溶液０．１２ｇを水８０ｇ
に加えた溶液に球状シリカゲル（５−１０メッシュ）３
０．０ｇを５時間浸した後、加熱かくはんしながら水を
蒸発し、内容物を乾固させた。次いで、空気中１２０℃
で２０時間乾燥し、空気中５００℃で２時間焼成して、
酸素を除く原子比でＰ1Ｓｉ500なる組成の触媒を調製し
た。Conversion (mol%) = (consumed N- (1
-Alkyloxyalkyl) -2-oxazolidone moles / N- (1-alkyloxyalkyl) -supplied
2-mol of 2-oxazolidone) × 100 Selectivity (mol%) = (mol of generated N-vinyl-2-oxazolidone / mol of consumed N- (1-alkyloxyalkyl) -2-oxazolidone) × 100 ・ Single-flow yield (mol%) = (moles of N-vinyl-2-oxazolidone produced / moles of N- (1-alkyloxyalkyl) -2-oxazolidone supplied) × 10
0 Example 1 (Catalyst preparation) 0.12 g of 85% phosphoric acid aqueous solution and 80 g of water
Spherical silica gel (5-10 mesh) 3 in the solution added to
After soaking 0.0 g for 5 hours, the water was evaporated while heating and stirring to dry the contents. Then, in air 120 ° C
At 20 ° C for 20 hours, then bake in air at 500 ° C for 2 hours,
A catalyst having a composition of P 1 Si 500 in terms of atomic ratio excluding oxygen was prepared.
【００４５】（反応）この触媒５ｍｌを、内径１０ｍｍ
のステンレス製反応管に充填した後、２７０℃の溶融塩
浴に浸漬し、該反応管内にＮ−（１−メトキシエチル）
−２−オキサゾリドンを、その分圧が７６ｍｍＨｇとな
るまで窒素で希釈した原料ガスを、Ｎ−（１−メトキシ
エチル）−２−オキサゾリドンの空間速度２００ｈ-1
で供給し、常圧で反応を行った。供給開始１時間後の反
応管出口ガスをメタノールに捕集し、ガスクロマトグラ
フにより分析した結果、Ｎ−（１−メトキシエチル）−
２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキサ
ゾリドンの選択率および単流収率は、それぞれ９９．５
モル％，９６．８モル％，９６．３モル％であった。(Reaction) 5 ml of this catalyst was added to an inner diameter of 10 mm.
The reaction tube made of stainless steel is filled with N- (1-methoxyethyl) and then immersed in a molten salt bath at 270 ° C.
A raw material gas obtained by diluting 2-oxazolidone with nitrogen until the partial pressure thereof reached 76 mmHg was used, and the space velocity of N- (1-methoxyethyl) -2-oxazolidone was 200 h -1.
And the reaction was carried out at normal pressure. After 1 hour from the start of supply, the reaction tube outlet gas was collected in methanol and analyzed by gas chromatography. As a result, N- (1-methoxyethyl)-
The conversion of 2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone, and the single-flow yield were 99.5, respectively.
It was mol%, 96.8 mol%, and 96.3 mol%.
【００４６】比較例１ （触媒調製）球状シリカゲル（５−１０メッシュ）３
０．０ｇを、空気中１２０℃で２０時間乾燥後、空気中
５００℃で２時間焼成して、触媒とした。Comparative Example 1 (Catalyst preparation) Spherical silica gel (5-10 mesh) 3
After drying 0.0 g in air at 120 ° C. for 20 hours, it was calcined in air at 500 ° C. for 2 hours to obtain a catalyst.
【００４７】（反応）この触媒を用いて、実施例１と同
様にして反応を行った。供給開始１時間後の、Ｎ−（１
−メトキシエチル）−２−オキサゾリドンの転化率、Ｎ
−ビニル−２−オキサゾリドンの選択率および単流収率
は、それぞれ６９．０モル％，９７．９モル％，６７．
６モル％であった。(Reaction) Using this catalyst, a reaction was carried out in the same manner as in Example 1. One hour after the start of supply, N- (1
-Methoxyethyl) -2-oxazolidone conversion, N
-Vinyl-2-oxazolidone selectivity and single stream yield are 69.0 mol%, 97.9 mol% and 67.
It was 6 mol%.
【００４８】実施例２ （触媒調製）リン酸水素二アンモニウム１３．２ｇを水
５０ｇに溶かした溶液を、硝酸アルミニウム（９水和
物）３７．５ｇを水１００ｇに溶かした溶液にかくはん
しながら加えた後、加熱かくはんしながら水を蒸発し、
内容物を乾固させた。次いで、空気中１２０℃で２０時
間乾燥し、９−１６メッシュに破砕後、空気中７００℃
で２時間焼成して、酸素を除く原子比でＰ1Ａｌ1なる組
成の触媒を調製した。Example 2 (Catalyst preparation) A solution of 13.2 g of diammonium hydrogen phosphate dissolved in 50 g of water was added to a solution of 37.5 g of aluminum nitrate (9 hydrate) dissolved in 100 g of water with stirring. After that, evaporate the water while heating and stirring,
The contents were allowed to dry. Then, it is dried in air at 120 ° C for 20 hours, crushed to 9-16 mesh, and then in air at 700 ° C.
The mixture was calcined for 2 hours to prepare a catalyst having a composition of P 1 Al 1 in terms of atomic ratio excluding oxygen.
【００４９】（反応）この触媒を用いて、実施例１と同
じ反応を行った。供給開始１時間後のＮ−（１−メトキ
シエチル）−２−オキサゾリドンの転化率、Ｎ−ビニル
−２−オキサゾリドンの選択率および単流収率は、それ
ぞれ９８．９モル％，９７．０モル％，９５．９モル％
であった。(Reaction) The same reaction as in Example 1 was carried out using this catalyst. The conversion rate of N- (1-methoxyethyl) -2-oxazolidone, the selectivity rate of N-vinyl-2-oxazolidone, and the single-flow yield 1 hour after the start of feeding are 98.9 mol% and 97.0 mol, respectively. %, 95.9 mol%
Met.
【００５０】実施例３ （触媒調製）８５％リン酸水溶液２３．１ｇを水１００
ｇに加えた溶液に、酸化ジルコニウム２４．６ｇを加え
た後、加熱かくはんしながら水を蒸発し、内容物を乾固
させた。次いで、空気中１２０℃で２０時間乾燥し、９
−１６メッシュに破砕後、空気中７００℃で２時間焼成
して、酸素を除く原子比でＰ1Ｚｒ1なる組成の触媒を調
製した。Example 3 (Catalyst preparation) 23.1 g of an 85% aqueous phosphoric acid solution was added to 100 parts of water.
After adding 24.6 g of zirconium oxide to the solution added to g, the water was evaporated while heating and stirring to dry the contents. Then, dry in air at 120 ° C. for 20 hours, and
After crushing to -16 mesh, it was calcined in air at 700 ° C. for 2 hours to prepare a catalyst having a composition of P 1 Zr 1 in terms of atomic ratio excluding oxygen.
【００５１】（反応）この触媒を用いて、反応原料をＮ
−（１−プロピルオキシエチル）−２−オキサゾリドン
に変更した他は、実施例１と同様にして反応を行った。
供給開始１時間後のＮ−（１−プロピルオキシエチル）
−２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキ
サゾリドンの選択率および単流収率は、それぞれ９５．
２モル％，９０．６モル％，８６．３モル％であった。(Reaction) Using this catalyst, the reaction raw material was
The reaction was carried out in the same manner as in Example 1 except that it was changed to-(1-propyloxyethyl) -2-oxazolidone.
N- (1-propyloxyethyl) 1 hour after the start of feeding
The conversion of 2--2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone and the single-flow yield were 95.
It was 2 mol%, 90.6 mol%, and 86.3 mol%.
【００５２】実施例４ （触媒調製）８５％リン酸水溶液３４．６ｇを水２００
ｇに加えた溶液に、ホウ酸１８．５ｇを加え３時間かく
はんした後、加熱かくはんしながら水を蒸発し、内容物
を乾固させた。次いで、空気中１２０℃で２０時間乾燥
し、９−１６メッシュに破砕後、空気中５００℃で２時
間焼成して、酸素を除く原子比でＰ1Ｂ1なる組成の触媒
を調製した。Example 4 (Catalyst preparation) 34.6 g of an 85% phosphoric acid aqueous solution was added to 200 parts of water.
To the solution added to g, 18.5 g of boric acid was added, and the mixture was stirred for 3 hours, then water was evaporated while stirring with heating to dry the contents. Then, it was dried in air at 120 ° C. for 20 hours, crushed to 9-16 mesh, and calcined in air at 500 ° C. for 2 hours to prepare a catalyst having a composition of P 1 B 1 in an atomic ratio excluding oxygen.
【００５３】（反応）この触媒を用いて、実施例３と同
じ反応を行った。供給開始１時間後のＮ−（１−プロピ
ルオキシエチル）−２−オキサゾリドンの転化率、Ｎ−
ビニル−２−オキサゾリドンの選択率および単流収率
は、それぞれ９８．８モル％，９０．５モル％，８９．
４モル％であった。(Reaction) The same reaction as in Example 3 was carried out using this catalyst. Conversion of N- (1-propyloxyethyl) -2-oxazolidone 1 hour after the start of feeding, N-
The selectivity and the single-flow yield of vinyl-2-oxazolidone are 98.8 mol%, 90.5 mol% and 89.
It was 4 mol%.
【００５４】実施例５ （触媒調製）酸化ケイ素３０ｇに、８５％リン酸水溶液
１．１５ｇを水５０ｇに加えた溶液を加えて乳鉢中で十
分に混練した。次いで、空気中１２０℃で２０時間乾燥
し、９−１６メッシュに破砕後、空気中７００℃で３時
間焼成して、酸素を除く原子比でＰ1Ｓｉ50なる組成の
触媒を調製した。Example 5 (Catalyst preparation) To 30 g of silicon oxide, a solution prepared by adding 1.15 g of an 85% phosphoric acid aqueous solution to 50 g of water was added and sufficiently kneaded in a mortar. Then, it was dried in air at 120 ° C. for 20 hours, crushed to 9-16 mesh, and calcined in air at 700 ° C. for 3 hours to prepare a catalyst having a composition of P 1 Si 50 at an atomic ratio excluding oxygen.
【００５５】（反応）この触媒を用いて、反応原料をＮ
−（１−メトキシエチル）−５−メチル−２−オキサゾ
リドンに変更した他は実施例１と同様にして反応を行っ
た。供給開始１時間後のＮ−（１−メトキシエチル）−
５−メチル−２−オキサゾリドンの転化率、Ｎ−ビニル
−５−メチル−２−オキサゾリドンの選択率および単流
収率は、それぞれ９９．８モル％，９７．０モル％，９
６．８モル％であった。(Reaction) Using this catalyst, the reaction raw material was
The reaction was carried out in the same manner as in Example 1 except that it was changed to-(1-methoxyethyl) -5-methyl-2-oxazolidone. 1 hour after the start of feeding, N- (1-methoxyethyl)-
The conversion of 5-methyl-2-oxazolidone, the selectivity of N-vinyl-5-methyl-2-oxazolidone, and the single-flow yield were 99.8 mol%, 97.0 mol%, and 9%, respectively.
It was 6.8 mol%.
【００５６】実施例６ （触媒調製）リン酸水素二アンモニウム１３．２ｇを水
５０ｇに溶かした溶液を、水酸化リチウム（１水和物）
４．２ｇを水５０ｇに溶かした溶液に加え、そこに酸化
ケイ素３０．０ｇを加えて、加熱かくはんしながら水を
蒸発し、内容物を乾固させた。次いで、空気中１２０℃
で２０時間乾燥し、９−１６メッシュに破砕後、空気中
６００℃で２時間焼成して、酸素を除く原子比でＰ1Ｌ
ｉ1Ｓｉ5なる組成の触媒を調製した。Example 6 (Catalyst preparation) A solution prepared by dissolving 13.2 g of diammonium hydrogen phosphate in 50 g of water was added to lithium hydroxide (monohydrate).
4.2 g was added to a solution obtained by dissolving 50 g in water, 30.0 g of silicon oxide was added thereto, and water was evaporated while heating and stirring to dry the contents. Then, in air 120 ° C
At 20 ° C. for 20 hours, crushed to 9-16 mesh, and fired in air at 600 ° C. for 2 hours to obtain an atomic ratio of P 1 L excluding oxygen.
A catalyst having a composition of i 1 Si 5 was prepared.
【００５７】（反応）この触媒を用いて、実施例１と同
じ反応を行った。供給開始１時間後のＮ−（１−メトキ
シエチル）−２−オキサゾリドンの転化率、Ｎ−ビニル
−２−オキサゾリドンの選択率および単流収率は、それ
ぞれ９９．０モル％，９８．０モル％，９７．０モル％
であった。(Reaction) The same reaction as in Example 1 was performed using this catalyst. The conversion rate of N- (1-methoxyethyl) -2-oxazolidone, the selectivity rate of N-vinyl-2-oxazolidone, and the single-flow yield one hour after the start of feeding are 99.0 mol% and 98.0 mol, respectively. %, 97.0 mol%
Met.
【００５８】実施例７ （触媒調製）実施例６において、水酸化リチウムを水酸
化ナトリウム４．０ｇに変えた他は同様にして、酸素を
除く原子比でＰ1Ｎａ1Ｓｉ5なる組成の触媒を調製し
た。Example 7 (Preparation of catalyst) A catalyst having a composition of P 1 Na 1 Si 5 in terms of atomic ratio excluding oxygen was prepared in the same manner as in Example 6 except that lithium hydroxide was changed to 4.0 g of sodium hydroxide. Was prepared.
【００５９】（反応）この触媒を用いて、実施例１と同
じ反応を行った。供給開始１時間後のＮ−（１−メトキ
シエチル）−２−オキサゾリドンの転化率、Ｎ−ビニル
−２−オキサゾリドンの選択率および単流収率は、それ
ぞれ９８．５モル％，９７．８モル％，９６．３モル％
であった。(Reaction) The same reaction as in Example 1 was performed using this catalyst. The conversion rate of N- (1-methoxyethyl) -2-oxazolidone, the selectivity rate of N-vinyl-2-oxazolidone, and the single-flow yield one hour after the start of feeding are 98.5 mol% and 97.8 mol, respectively. %, 96.3 mol%
Met.
【００６０】実施例８ （触媒調製）実施例６において、水酸化リチウムを水酸
化カリウム５．６ｇに変えた他は同様にして、酸素を除
く原子比でＰ1Ｋ1Ｓｉ5なる組成の触媒を調製した。Example 8 (Catalyst preparation) A catalyst having a composition of P 1 K 1 Si 5 in terms of atomic ratio excluding oxygen was prepared in the same manner as in Example 6 except that lithium hydroxide was changed to 5.6 g of potassium hydroxide. Was prepared.
【００６１】（反応）この触媒を用いて、実施例１と同
じ反応を行った。供給開始１時間後のＮ−（１−メトキ
シエチル）−２−オキサゾリドンの転化率、Ｎ−ビニル
−２−オキサゾリドンの選択率および単流収率は、それ
ぞれ９８．０モル％，９８．９モル％，９６．９モル％
であった。(Reaction) The same reaction as in Example 1 was carried out using this catalyst. The conversion rate of N- (1-methoxyethyl) -2-oxazolidone, the selectivity rate of N-vinyl-2-oxazolidone, and the single-flow yield 1 hour after the start of feeding are 98.0 mol% and 98.9 mol, respectively. %, 96.9 mol%
Met.
【００６２】実施例９ （触媒調製）リン酸水素二アンモニウム１３．２ｇを水
５０ｇに溶かした溶液を、水酸化リチウム（１水和物）
３．４ｇおよび水酸化セシウム３．０ｇを水５０ｇに溶
かした液に加え、そこに酸化ケイ素３０．０ｇを加え
て、加熱かくはんしながら水を蒸発し、内容物を乾固さ
せた。次いで、空気中１２０℃で２０時間乾燥し、９−
１６メッシュに破砕後、空気中６００℃で２時間焼成し
て、酸素を除く原子比でＰ1Ｌｉ0.8Ｃｓ0.2Ｓｉ5なる組
成の触媒を調製した。Example 9 (Catalyst preparation) 13.2 g of diammonium hydrogen phosphate was dissolved in 50 g of water to prepare lithium hydroxide (monohydrate).
3.4 g and 3.0 g of cesium hydroxide were added to a solution obtained by dissolving 50 g of water, 30.0 g of silicon oxide was added thereto, and water was evaporated while heating with stirring to dry the contents. Then, it is dried in air at 120 ° C. for 20 hours, and 9-
After crushing to 16 mesh, it was calcined in air at 600 ° C. for 2 hours to prepare a catalyst having a composition of P 1 Li 0.8 Cs 0.2 Si 5 in terms of atomic ratio excluding oxygen.
【００６３】（反応）この触媒を用いて、実施例３と同
じ反応を行った。供給開始１時間後のＮ−（１−プロピ
ルオキシエチル）−２−オキサゾリドンの転化率、Ｎ−
ビニル−２−オキサゾリドンの選択率および単流収率
は、それぞれ９９．６モル％，９９．２モル％，９８．
８モル％であった。(Reaction) The same reaction as in Example 3 was performed using this catalyst. Conversion of N- (1-propyloxyethyl) -2-oxazolidone 1 hour after the start of feeding, N-
The selectivity and single-flow yield of vinyl-2-oxazolidone are 99.6 mol%, 99.2 mol% and 98.
It was 8 mol%.
【００６４】実施例１０ （触媒調製）リン酸水素二アンモニウム２．６４ｇを水
３０ｇに溶かした溶液を、水酸化リチウム（１水和物）
０．８４ｇを水３０ｇに溶かした液に加え、そこに五酸
化ニオブ２６．６ｇを加えて、加熱かくはんしながら水
を蒸発し、内容物を乾固させた。次いで、空気中１２０
℃で２０時間乾燥し、９−１６メッシュに破砕後、空気
中５００℃で２時間焼成して、酸素を除く原子比でＰ1
Ｌｉ1Ｎｂ10なる組成の触媒を調製した。Example 10 (Catalyst preparation) A solution prepared by dissolving 2.64 g of diammonium hydrogen phosphate in 30 g of water was treated with lithium hydroxide (monohydrate).
0.84 g was added to a solution prepared by dissolving 30 g of water, 26.6 g of niobium pentoxide was added thereto, and the water was evaporated while heating and stirring to dry the contents. Then 120 in air
After drying at ℃ for 20 hours, crushing to 9-16 mesh, calcination in air at 500 ℃ for 2 hours, P 1 in atomic ratio excluding oxygen.
A catalyst having a composition of Li 1 Nb 10 was prepared.
【００６５】（反応）この触媒を用いて、実施例５と同
じ反応を行った。供給開始１時間後のＮ−（１−メトキ
シエチル）−５−メチル−２−オキサゾリドンの転化
率、Ｎ−ビニル−５−メチル−２−オキサゾリドンの選
択率および単流収率は、それぞれ９７．６モル％，９
８．７モル％，９６．３モル％であった。(Reaction) The same reaction as in Example 5 was carried out using this catalyst. The conversion rate of N- (1-methoxyethyl) -5-methyl-2-oxazolidone, the selectivity rate of N-vinyl-5-methyl-2-oxazolidone, and the single-flow yield one hour after the start of feeding were 97. 6 mol%, 9
It was 8.7 mol% and 96.3 mol%.
【００６６】実施例１１ （触媒調製）リン酸水素二アンモニウム６．６ｇを水５
０ｇに溶かした溶液を、水酸化リチウム（１水和物）
２．１ｇを水５０ｇに溶かした液に加え、そこにケイ酸
ジルコニウム４６．２ｇを加えて、加熱かくはんしなが
ら水を蒸発し、内容物を乾固させた。次いで、空気中１
２０℃で２０時間乾燥し、９−１６メッシュに破砕後、
空気中５００℃で２時間焼成して、酸素を除く原子比で
Ｐ1Ｌｉ1Ｚｒ5Ｓｉ5なる組成の触媒を調製した。Example 11 (Catalyst preparation) 6.6 g of diammonium hydrogen phosphate was added to 5 parts of water.
Lithium hydroxide (monohydrate) was added to 0 g of the solution.
2.1 g was added to a solution obtained by dissolving 50 g in water, 46.2 g of zirconium silicate was added thereto, and the water was evaporated while heating and stirring to dry the contents. Then 1 in the air
After drying at 20 ° C for 20 hours and crushing to 9-16 mesh,
It was calcined in air at 500 ° C. for 2 hours to prepare a catalyst having a composition of P 1 Li 1 Zr 5 Si 5 in terms of atomic ratio excluding oxygen.
【００６７】（反応）この触媒を用いて、反応原料をＮ
−（１−プロピルオキシエチル）−５−メチル−２−オ
キサゾリドンに変更した他は実施例１と同様にして反応
を行った。供給開始１時間後のＮ−（１−プロピルオキ
シエチル）−５−メチル−２−オキサゾリドンの転化
率、Ｎ−ビニル−５−メチル−２−オキサゾリドンの選
択率および単流収率は、それぞれ９７．３モル％，９
９．３モル％，９６．６モル％であった。(Reaction) Using this catalyst, the reaction raw material was
The reaction was carried out in the same manner as in Example 1 except that it was changed to-(1-propyloxyethyl) -5-methyl-2-oxazolidone. The conversion rate of N- (1-propyloxyethyl) -5-methyl-2-oxazolidone, the selectivity of N-vinyl-5-methyl-2-oxazolidone and the single-flow yield one hour after the start of feeding were 97% each. .3 mol%, 9
It was 9.3 mol% and 96.6 mol%.
【００６８】実施例１２ （触媒調製）リン酸二水素ナトリウム（２水和物）１
５．６ｇを水５０ｇに溶かした溶液に二酸化チタン４
０．０ｇを加えて、加熱かくはんしながら水を蒸発し、
内容物を乾固させた。次いで、空気中１２０℃で２０時
間乾燥し、９−１６メッシュに破砕後、空気中５００℃
で２時間焼成して、酸素を除く原子比でＰ1Ｎａ1Ｔｉ5
なる組成の触媒を調製した。Example 12 (Catalyst preparation) Sodium dihydrogen phosphate (dihydrate) 1
Titanium dioxide 4 was added to a solution of 5.6 g dissolved in 50 g of water.
Add 0.0 g and evaporate the water with heating and stirring,
The contents were allowed to dry. Then, dry in air at 120 ° C for 20 hours, crush to 9-16 mesh, and then in air at 500 ° C.
Baking for 2 hours at an atomic ratio of P 1 Na 1 Ti 5 excluding oxygen.
A catalyst having the following composition was prepared.
【００６９】（反応）この触媒を用いて、反応原料をＮ
−（１−メトキシエチル）−５−エチル−２−オキサゾ
リドンに変更した他は実施例１と同様にして反応を行っ
た。供給開始１時間後のＮ−（１−メトキシエチル）−
５−エチル−２−オキサゾリドンの転化率、Ｎ−ビニル
−５−エチル−２−オキサゾリドンの選択率および単流
収率は、それぞれ９７．１モル％，９８．７モル％，９
５．８モル％であった。(Reaction) Using this catalyst, the reaction raw material was
The reaction was carried out in the same manner as in Example 1 except that it was changed to-(1-methoxyethyl) -5-ethyl-2-oxazolidone. 1 hour after the start of feeding, N- (1-methoxyethyl)-
The conversion of 5-ethyl-2-oxazolidone, the selectivity of N-vinyl-5-ethyl-2-oxazolidone and the single-flow yield are 97.1 mol%, 98.7 mol% and 9%, respectively.
It was 5.8 mol%.
【００７０】実施例１３ （触媒調製）リン酸水素マグネシウム（３水和物）１
７．４ｇと酸化ケイ素３０．０ｇを、水５０ｇを加え
て、乳鉢中で混練した。次いで、空気中１２０℃で２０
時間乾燥し、９−１６メッシュに破砕後、空気中５００
℃で２時間焼成して、酸素を除く原子比でＰ1Ｍｇ1Ｓｉ
5なる組成の触媒を調製した。Example 13 (Catalyst preparation) Magnesium hydrogen phosphate (trihydrate) 1
50 g of water was added to 7.4 g and 30.0 g of silicon oxide, and they were kneaded in a mortar. Then 20 at 120 ℃ in air
After drying for 5 hours and crushing to 9-16 mesh, 500 in air
After firing for 2 hours at ℃, the atomic ratio excluding oxygen is P 1 Mg 1 Si
A catalyst having a composition of 5 was prepared.
【００７１】（反応）この触媒を用いて、反応温度を２
５０℃、原料分圧を３８ｍｍＨｇ、原料空間速度を１０
０ｈｒ-1に変更した他は実施例１と同様にして反応を行
った。供給開始１時間後のＮ−（１−メトキシエチル）
−２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキ
サゾリドンの選択率および単流収率は、それぞれ９３．
１モル％，９８．２モル％，９１．４モル％であった。(Reaction) Using this catalyst, the reaction temperature was set to 2
50 ° C, raw material partial pressure 38 mmHg, raw material space velocity 10
The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 0 hr -1 . N- (1-methoxyethyl) 1 hour after the start of feeding
The conversion of 2--2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone and the single-flow yield are 93.
They were 1 mol%, 98.2 mol% and 91.4 mol%.
【００７２】実施例１４ （触媒調製）実施例１３において、リン酸水素マグネシ
ウムをリン酸水素カルシウム（２水和物）１７．２ｇに
変えた他は同様にして、酸素を除く原子比でＰ1Ｃａ1Ｓ
ｉ5なる組成の触媒を調製した。Example 14 (Catalyst preparation) In the same manner as in Example 13 except that magnesium hydrogen phosphate was changed to 17.2 g of calcium hydrogen phosphate (dihydrate), P 1 was used in the atomic ratio except oxygen. Ca 1 S
A catalyst having a composition of i 5 was prepared.
【００７３】（反応）この触媒を用いて、反応温度を２
５０℃、原料分圧を３８ｍｍＨｇ、原料空間速度を１０
０ｈｒ-1に変更した他は実施例１と同様にして反応を行
った。供給開始１時間後のＮ−（１−メトキシエチル）
−２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキ
サゾリドンの選択率および単流収率は、それぞれ９２．
９モル％，９８．６モル％，９１．６モル％であった。(Reaction) Using this catalyst, the reaction temperature was raised to 2
50 ° C, raw material partial pressure 38 mmHg, raw material space velocity 10
The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 0 hr -1 . N- (1-methoxyethyl) 1 hour after the start of feeding
The conversion of 2--2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone and the single-flow yield were 92.
They were 9 mol%, 98.6 mol% and 91.6 mol%.
【００７４】実施例１５ （触媒調製）実施例１３において、リン酸水素マグネシ
ウムをリン酸水素バリウム２３．３ｇに変えた他は同様
にして、酸素を除く原子比でＰ1Ｂａ1Ｓｉ5なる組成の
触媒を調製した。Example 15 (Catalyst preparation) A composition of P 1 Ba 1 Si 5 was obtained in the same manner as in Example 13 except that the magnesium hydrogen phosphate was changed to 23.3 g of barium hydrogen phosphate. Was prepared.
【００７５】（反応）この触媒を用いて、反応温度を２
００℃、原料分圧を３８ｍｍＨｇ、原料空間速度を１０
０ｈｒ-1に変更した他は実施例１と同様にして反応を行
った。供給開始１時間後のＮ−（１−メトキシエチル）
−２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキ
サゾリドンの選択率および単流収率は、それぞれ９６．
７モル％，９６．６モル％，９３．４モル％であった。(Reaction) Using this catalyst, the reaction temperature was set to 2
00 ° C, raw material partial pressure 38 mmHg, raw material space velocity 10
The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 0 hr -1 . N- (1-methoxyethyl) 1 hour after the start of feeding
The conversion of 2--2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone and the single-flow yield are 96.
It was 7 mol%, 96.6 mol%, and 93.4 mol%.
【００７６】実施例１６ （触媒調製）リン酸水素二アンモニウム１３．２ｇを水
４０ｇに溶かした溶液に、水酸化リチウム（１水和物）
５．２ｇを水５０ｇに溶かした液に加えた後、酸化ケイ
素３０．０ｇを加えて、加熱かくはんしながら水を蒸発
し、内容物を乾固させた。次いで、空気中１２０℃で２
０時間乾燥し、９−１６メッシュに破砕後、空気中７０
０℃で２時間焼成して、酸素を除く原子比でＰ1Ｌｉ
1.25Ｓｉ5なる組成の触媒を調製した。Example 16 (Catalyst preparation) 13.2 g of diammonium hydrogen phosphate was dissolved in 40 g of water, and lithium hydroxide (monohydrate) was added to the solution.
After adding 5.2 g to a solution prepared by dissolving 50 g in water, 30.0 g of silicon oxide was added, and water was evaporated while heating and stirring to dry the contents. Then 2 at 120 ° C in air
Dry for 0 hours, crush to 9-16 mesh, then in air 70
After firing at 0 ° C. for 2 hours, the atomic ratio excluding oxygen is P 1 Li
A catalyst having a composition of 1.25 Si 5 was prepared.
【００７７】（反応）この触媒を用いて、実施例１と同
じ反応を行った。供給開始１時間後のＮ−（１−メトキ
シエチル）−２−オキサゾリドンの転化率、Ｎ−ビニル
−２−オキサゾリドンの選択率および単流収率は、それ
ぞれ９９．５モル％，９９．５モル％，９９．０モル％
であった。(Reaction) The same reaction as in Example 1 was carried out using this catalyst. The conversion rate of N- (1-methoxyethyl) -2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone, and the single-flow yield 1 hour after the start of feeding are 99.5 mol% and 99.5 mol, respectively. %, 99.0 mol%
Met.
【００７８】実施例１７ 実施例１６において、反応原料をＮ−（１−メトキシエ
チル）−２−オキサゾリドンの代わりに、Ｎ−（１−メ
トキシエチル）−５−メチル−２−オキサゾリドンに変
更した他は、同様の反応条件で、５０時間連続して反応
を行った。反応開始１時間後のＮ−（１−メトキシエチ
ル）−５−メチル−２−オキサゾリドンの転化率、Ｎ−
ビニル−５−メチル−２−オキサゾリドンの選択率およ
び単流収率は、それぞれ９９．６モル％，９８．８モル
％，９８．４モル％であり、５０時間後では、それぞれ
９８．９モル％，９９．１モル％，９８．０モル％であ
った。Example 17 In Example 16, the reaction raw material was changed to N- (1-methoxyethyl) -5-methyl-2-oxazolidone instead of N- (1-methoxyethyl) -2-oxazolidone. Under the same reaction conditions, the reaction was continuously performed for 50 hours. Conversion rate of N- (1-methoxyethyl) -5-methyl-2-oxazolidone 1 hour after the start of reaction, N-
The selectivity and single-flow yield of vinyl-5-methyl-2-oxazolidone are 99.6 mol%, 98.8 mol% and 98.4 mol%, respectively, and after 50 hours, 98.9 mol% and 98.9 mol%, respectively. %, 99.1 mol% and 98.0 mol%.
【００７９】実施例１８ （触媒調製）リン酸水素二アンモニウム１３．２ｇを水
４０ｇに溶かした溶液に、水酸化リチウム（１水和物）
８．４ｇを水１００ｇに溶かした液に加えた後、酸化ケ
イ素３０．０ｇを加えて、加熱かくはんしながら水を蒸
発し、内容物を乾固させた。次いで、空気中１２０℃で
２０時間乾燥し、９−１６メッシュに破砕後、空気中７
００℃で２時間焼成して、酸素を除く原子比でＰ1Ｌｉ2
Ｓｉ5なる組成の触媒を調製した。Example 18 (Catalyst preparation) 13.2 g of diammonium hydrogen phosphate was dissolved in 40 g of water, and lithium hydroxide (monohydrate) was added to the solution.
After 8.4 g was added to a solution prepared by dissolving 100 g in water, 30.0 g of silicon oxide was added, and the water was evaporated while heating and stirring to dry the contents. Next, it is dried in air at 120 ° C. for 20 hours, crushed to 9-16 mesh, and then in air 7
Baking at 00 ° C. for 2 hours gives P 1 Li 2 in terms of atomic ratio excluding oxygen.
A catalyst having a composition of Si 5 was prepared.
【００８０】（反応）この触媒を用いて、反応温度を３
００℃に変更した他は実施例１と同様にして反応を行っ
た。供給開始１時間後のＮ−（１−メトキシエチル）−
２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキサ
ゾリドンの選択率および単流収率は、それぞれ９９．１
モル％，９７．８モル％，９６．９モル％であった。(Reaction) Using this catalyst, a reaction temperature of 3
The reaction was performed in the same manner as in Example 1 except that the temperature was changed to 00 ° C. 1 hour after the start of feeding, N- (1-methoxyethyl)-
The conversion of 2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone and the single-flow yield are 99.1 respectively.
It was mol%, 97.8 mol%, and 96.9 mol%.
【００８１】実施例１９ （触媒調製）８５％リン酸水溶液５７．６ｇを水２００
ｇに溶かした液を、水酸化リチウム（１水和物）２１．
０ｇおよび水酸化アルミニウム７．８ｇを水２００ｇに
溶かした液に加えた後、酸化ケイ素１２．０ｇを加え
て、加熱かくはんしながら水を蒸発し、内容物を乾固さ
せた。次いで、空気中１２０℃で２０時間乾燥し、９−
１６メッシュに破砕後、空気中５００℃で２時間焼成し
て、酸素を除く原子比でＰ1Ｌｉ1Ａｌ0.2Ｓｉ0.4なる組
成の触媒を調製した。Example 19 (Catalyst preparation) 57.6 g of an 85% phosphoric acid aqueous solution was added to 200 parts of water.
g of a solution of lithium hydroxide (monohydrate) 21.
After adding 0 g and 7.8 g of aluminum hydroxide to a solution prepared by dissolving 200 g of water, 12.0 g of silicon oxide was added, and water was evaporated while heating and stirring to dry the contents. Then, it is dried in air at 120 ° C. for 20 hours, and 9-
After crushing to 16 mesh, it was calcined in air at 500 ° C. for 2 hours to prepare a catalyst having a composition of P 1 Li 1 Al 0.2 Si 0.4 in terms of atomic ratio excluding oxygen.
【００８２】（反応）この触媒を用いて、反応温度を２
５０℃に変更した他は実施例１と同様にして反応を行っ
た。供給開始１時間後のＮ−（１−メトキシエチル）−
２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキサ
ゾリドンの選択率および単流収率は、それぞれ９５．９
モル％，９８．６モル％，９４．６モル％であった。(Reaction) Using this catalyst, the reaction temperature was set to 2
The reaction was carried out in the same manner as in Example 1 except that the temperature was changed to 50 ° C. 1 hour after the start of feeding, N- (1-methoxyethyl)-
The conversion rate of 2-oxazolidone, the selectivity rate of N-vinyl-2-oxazolidone, and the single-flow yield were 95.9 each.
It was mol%, 98.6 mol%, and 94.6 mol%.
【００８３】実施例２０ （触媒調製）８５％リン酸水溶液５７．６ｇを水２００
ｇに溶かした液を、水酸化リチウム（１水和物）２１．
０ｇおよび水酸化マグネシウム１４．５ｇを水２００ｇ
に懸濁させた液に加えた後、加熱かくはんしながら水を
蒸発し、内容物を乾固させた。次いで、空気中１２０℃
で２０時間乾燥し、９−１６メッシュに破砕後、空気中
５００℃で２時間焼成して、酸素を除く原子比でＰ1Ｌ
ｉ1Ｍｇ0.5なる組成の触媒を調製した。Example 20 (Catalyst preparation) 57.6 g of an 85% phosphoric acid aqueous solution was added to 200 parts of water.
g of a solution of lithium hydroxide (monohydrate) 21.
0 g and 14.5 g of magnesium hydroxide, 200 g of water
After being added to the solution suspended in, the water was evaporated while heating and stirring to dry the contents. Then, in air 120 ° C
At 20 ° C. for 20 hours, crushed to 9-16 mesh, and calcined in air at 500 ° C. for 2 hours to obtain an atomic ratio of P 1 L excluding oxygen.
A catalyst having a composition of i 1 Mg 0.5 was prepared.
【００８４】（反応）この触媒を用いて、反応温度を２
５０℃に変更した他は実施例１と同様にして反応を行っ
た。供給開始１時間後のＮ−（１−メトキシエチル）−
２−オキサゾリドンの転化率、Ｎ−ビニル−２−オキサ
ゾリドンの選択率および単流収率は、それぞれ９０．１
モル％，９７．９モル％，８８．２モル％であった。(Reaction) Using this catalyst, the reaction temperature was set to 2
The reaction was carried out in the same manner as in Example 1 except that the temperature was changed to 50 ° C. 1 hour after the start of feeding, N- (1-methoxyethyl)-
The conversion of 2-oxazolidone, the selectivity of N-vinyl-2-oxazolidone and the single-flow yield were respectively 90.1
It was mol%, 97.9 mol%, and 88.2 mol%.
【００８５】実施例２１ （反応）実施例１６で調製された触媒５ｍｌをステンレ
ス製反応管に充填した後、２７０℃の溶融塩浴に浸し
た。次いで、該反応管内を真空ポンプで減圧し、Ｎ−
（１−メトキシエチル）−２−オキサゾリドンを出口圧
３８ｍｍＨｇ、空間速度１００ｈｒ-1の条件で供給し
た。反応を５０時間連続して行った後、原料供給を停止
し、窒素を導入して解圧し、次いで２４時間空気を流通
し触媒に析出した炭素状物質を燃焼することにより触媒
を再生した。その後、再び前述の反応条件に戻し、５０
時間連続反応を行った。供給開始１時間、２０時間、５
０時間後および再生後１時間、２０時間、５０時間後の
Ｎ−（１−メトキシエチル）−２−オキサゾリドンの転
化率、Ｎ−ビニル−２−オキサゾリドンの選択率および
単流収率を表１に示した。Example 21 (Reaction) 5 ml of the catalyst prepared in Example 16 was charged into a stainless reaction tube and then immersed in a molten salt bath at 270 ° C. Then, the inside of the reaction tube is decompressed by a vacuum pump, and N-
(1-Methoxyethyl) -2-oxazolidone was supplied under the conditions of an outlet pressure of 38 mmHg and a space velocity of 100 hr −1 . After the reaction was continuously performed for 50 hours, the supply of raw materials was stopped, nitrogen was introduced to decompress, and then air was passed for 24 hours to burn the carbonaceous material deposited on the catalyst to regenerate the catalyst. After that, the reaction conditions are returned to the above-mentioned condition again, and 50
A continuous reaction was conducted for a time. Supply start 1 hour, 20 hours, 5
Table 1 shows conversion rates of N- (1-methoxyethyl) -2-oxazolidone, selectivity of N-vinyl-2-oxazolidone, and single-flow yield after 0 hours and 1 hour, 20 hours, and 50 hours after regeneration. It was shown to.
【００８６】[0086]
【表１】 [Table 1]
【００８７】[0087]
【発明の効果】本発明の触媒を用いれば、溶媒や副原料
を一切用いること無く、Ｎ−（１−アルキルオキシアル
キル）−２−オキサゾリドン類から直接一段反応で連続
的にＮ−ビニル−２−オキサゾリドン類を高転化率で高
選択的に、長期にわたり安定的に製造でき、副原料由来
の廃棄物の発生もなく、簡便かつ安全なＮ−ビニル−２
−オキサゾリドン類の製造が可能となる。EFFECTS OF THE INVENTION With the catalyst of the present invention, N- (2-alkyloxyalkyl) -2-oxazolidones can be directly and continuously used in a one-step reaction without using any solvent or auxiliary material. -Stable and safe production of oxazolidones with a high conversion rate over a long period of time, without the generation of waste materials derived from auxiliary materials, and simple and safe N-vinyl-2
-Enables the production of oxazolidones.
【００８８】また本発明の触媒は、その触媒活性が長時
間連続で反応しても殆ど低下せず、仮にコーキング等で
活性が劣化しても、空気を通しコークを燃焼すれば活性
は回復する特徴を有し、触媒寿命が長く工業上極めて有
利な触媒である。Further, the catalyst of the present invention has a catalytic activity which does not substantially decrease even if it reacts continuously for a long time, and even if the activity is deteriorated by coking or the like, the activity is restored by burning the coke through air. It is a catalyst that has characteristics and has a long catalyst life and is extremely advantageous industrially.
【００８９】本発明の製造方法を用いれば、溶媒や副原
料を一切用いること無く、Ｎ−（１−アルキルオキシア
ルキル）−２−オキサゾリドン類から直接一段反応で連
続的にＮ−ビニル−２−オキサゾリドン類を高転化率で
高選択的に、長期にわたり安定的に製造でき、副原料由
来の廃棄物の発生もなく、簡便かつ安全なＮ−ビニル−
２−オキサゾリドン類の製造が可能となる。According to the production method of the present invention, N- (1-alkyloxyalkyl) -2-oxazolidones are directly used in a one-step reaction in a continuous one-step reaction without using any solvent or auxiliary material. Oxazolidones can be produced with high conversion at high selectivity and stably for a long period of time, and there is no generation of waste materials derived from auxiliary materials. Simple and safe N-vinyl-
It becomes possible to produce 2-oxazolidones.
Claims (6)
２−オキサゾリドン類をＮ−ビニル−２−オキサゾリド
ン類に転化する際に用いる触媒であって、該触媒が、リ
ンを含有して成る固体酸化物であることを特徴とする、
Ｎ−（１−アルキルオキシアルキル）−２−オキサゾリ
ドン類の気相分子内脱アルコール反応用触媒。1. N- (1-alkyloxyalkyl)-
A catalyst used when converting 2-oxazolidones to N-vinyl-2-oxazolidones, wherein the catalyst is a solid oxide containing phosphorus,
A catalyst for gas phase intramolecular dealcoholization reaction of N- (1-alkyloxyalkyl) -2-oxazolidones.
よびアルカリ土類金属元素からなる群より選ばれる１種
以上の元素を含有してなる固体酸化物であることを特徴
とする請求項１に記載の触媒。2. The solid oxide according to claim 1, wherein the catalyst further contains one or more elements selected from the group consisting of alkali metal elements and alkaline earth metal elements. Catalyst.
ｌおよびＳｉからなる群より選ばれる１種以上の元素を
含有してなる固体酸化物であることを特徴とする請求項
１または２記載の触媒。3. The catalyst is Ti, Zr, Nb, B, A
The catalyst according to claim 1 or 2, which is a solid oxide containing one or more elements selected from the group consisting of 1 and Si.
リ土類金属元素からなる群より選ばれる一種以上の元
素、ＹはＴｉ，Ｚｒ，Ｎｂ，Ｂ，ＡｌおよびＳｉからな
る群より選ばれる１種以上の元素であり、Ｏは酸素であ
る。また添字ａ，ｂ，ｃ，ｄは、それぞれの元素の原子
比を表し、ａ＝１のときｂ＝０〜５、ｃ＝１〜５００の
範囲をとり、ｄはａ、ｂ、ｃの値および各種構成元素の
結合状態により定まる数値である。）で表される固体酸
化物である請求項１に記載の触媒。4. The catalyst has the following general formula (1): (In the formula, P is phosphorus, X is one or more elements selected from the group consisting of alkali metal elements and alkaline earth metal elements, and Y is selected from the group consisting of Ti, Zr, Nb, B, Al and Si. It is an element of at least one species, O is oxygen, and the subscripts a, b, c, and d represent the atomic ratio of each element, and when a = 1, b = 0 to 5 and c = 1 to 500. 2. The catalyst according to claim 1, wherein the solid oxide has a range, and d is a numerical value determined by the values of a, b, and c and the bonding state of various constituent elements.
２−オキサゾリドン類をＮ−ビニル−２−オキサゾリド
ン類に転化する際に、請求項１から４のいずれかに記載
の触媒を用いることを特徴とするＮ−ビニル−２−オキ
サゾリドン類の製造方法。5. N- (1-alkyloxyalkyl)-
A method for producing N-vinyl-2-oxazolidones, which comprises using the catalyst according to any one of claims 1 to 4 when converting 2-oxazolidones to N-vinyl-2-oxazolidones.
２−オキサゾリドン類が下記一般式（２） 【化２】 （式中、Ｒ1は独立して水素、メチル基およびエチル基
からなる群より選ばれる１種であり、Ｒ2はメチル基、
エチル基、プロピル基およびブチル基からなる群より選
ばれる１種である。）で表される化合物であり、Ｎ−ビ
ニル−２−オキサゾリドン類が下記一般式（３） 【化３】 （式中、Ｒ1は前記一般式（２）と同じである。）で表
される化合物である請求項５に記載の製造方法。6. N- (1-alkyloxyalkyl)-
2-oxazolidones are represented by the following general formula (2): (In the formula, R 1 is independently one selected from the group consisting of hydrogen, a methyl group and an ethyl group, R 2 is a methyl group,
It is one selected from the group consisting of ethyl group, propyl group and butyl group. ), Wherein N-vinyl-2-oxazolidones are represented by the following general formula (3): The production method according to claim 5, wherein the compound is represented by the formula (wherein R 1 is the same as in the general formula (2)).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05787695A JP3736871B2 (en) | 1995-03-17 | 1995-03-17 | Catalyst for gas-phase intramolecular dealcoholization reaction of N- (1-alkyloxyalkyl) -2-oxazolidone and method for producing N-vinyl-2-oxazolidone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05787695A JP3736871B2 (en) | 1995-03-17 | 1995-03-17 | Catalyst for gas-phase intramolecular dealcoholization reaction of N- (1-alkyloxyalkyl) -2-oxazolidone and method for producing N-vinyl-2-oxazolidone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08253462A true JPH08253462A (en) | 1996-10-01 |
| JP3736871B2 JP3736871B2 (en) | 2006-01-18 |
Family
ID=13068194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05787695A Expired - Fee Related JP3736871B2 (en) | 1995-03-17 | 1995-03-17 | Catalyst for gas-phase intramolecular dealcoholization reaction of N- (1-alkyloxyalkyl) -2-oxazolidone and method for producing N-vinyl-2-oxazolidone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3736871B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113549026A (en) * | 2021-08-30 | 2021-10-26 | 重庆市化工研究院有限公司 | Synthesis process of N-vinyl oxazolidinone compound |
-
1995
- 1995-03-17 JP JP05787695A patent/JP3736871B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113549026A (en) * | 2021-08-30 | 2021-10-26 | 重庆市化工研究院有限公司 | Synthesis process of N-vinyl oxazolidinone compound |
| CN113549026B (en) * | 2021-08-30 | 2023-09-08 | 重庆市化工研究院有限公司 | Synthesis process of N-vinyl oxazolidone compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3736871B2 (en) | 2006-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100513401C (en) | Method for preparing epoxy chloropropane by using glycerol method | |
| JP3571795B2 (en) | Catalyst for gas-phase intramolecular dealcoholation reaction of N- (1-alkyloxyalkyl) carbamates and method for producing N-vinyl carbamates | |
| TWI333873B (en) | Phosphorus/vanadium catalyst preparation | |
| US4382876A (en) | Method for producing catalysts for gas phase oxidation of saturated and/or unsaturated C4 -hydrocarbons to maleic anhydride | |
| KR100388696B1 (en) | Catalyst for production of tertiary n-alkenyl carboxylic acid amide, and process for production of tertiary n-alkenyl carboxylic acid amide using said catalyst | |
| US7141682B2 (en) | Liquid phase synthesis of methylene lactones using oxnitride catalyst | |
| US7151185B2 (en) | Gas phase synthesis of methylene lactones using oxynitride catalyst | |
| WO2004091778A1 (en) | Catalyst for dimethyl carbonate synthesis | |
| JPH08253462A (en) | Production of n-vinyloxazolidones | |
| US7348442B2 (en) | Gas phase synthesis of methylene lactones using catalysts derived from hydrotalcite precursors | |
| JPH09249644A (en) | Production of cyclic n-vinylcarboxylic acid amide | |
| EP0701986B1 (en) | Process for production of unsaturated ether and catalyst used for production of unsaturated ether | |
| JP2660169B2 (en) | Catalyst for producing tertiary N-alkenylcarboxylic amides and method for producing tertiary N-alkenylcarboxylic amides | |
| JP2740479B2 (en) | Process for producing unsaturated ethers and catalyst for producing unsaturated ethers | |
| JPH09291069A (en) | Production of n-vinyl compound | |
| JPH0530822B2 (en) | ||
| JPH0959186A (en) | Production of (perfluoroalkyl)ethene and catalyst therefor | |
| JPH08215564A (en) | Production of n-vinylsuccinic acid imide | |
| CN111974442B (en) | Catalyst for producing acrylic acid and methyl acrylate, and preparation method and application thereof | |
| JPS584704B2 (en) | Method for producing methyl methacrylate | |
| JPH03167155A (en) | Production of unsaturated carboxylic ester | |
| JPH1180096A (en) | Production of dimethyl carbonate | |
| JP2000167400A (en) | Preparation of carbonylation catalyst and acid ester | |
| JPH10324664A (en) | Production of unsaturated carboxylic acid ester | |
| JP2009126846A (en) | METHOD FOR PRODUCING alpha-UNSATURATED CYCLIC ETHER HAVING FIVE-MEMBERED RING STRUCTURE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20051011 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20051025 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081104 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091104 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091104 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101104 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |