JP3124250B2 - Boron trifluoride complex compound for trioxane polymerization - Google Patents
Boron trifluoride complex compound for trioxane polymerizationInfo
- Publication number
- JP3124250B2 JP3124250B2 JP09195217A JP19521797A JP3124250B2 JP 3124250 B2 JP3124250 B2 JP 3124250B2 JP 09195217 A JP09195217 A JP 09195217A JP 19521797 A JP19521797 A JP 19521797A JP 3124250 B2 JP3124250 B2 JP 3124250B2
- Authority
- JP
- Japan
- Prior art keywords
- boron trifluoride
- complex compound
- polymerization
- trioxane
- solution
- 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 - Lifetime
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
- Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、三フッ化ホウ素錯
化合物に関するものであり、更に詳しくは、トリオキサ
ンの単独重合またはトリオキサンと環状エーテルとの共
重合において特に優れた運転安定性を有する三フッ化ホ
ウ素錯化合物触媒に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a boron trifluoride complex compound and, more particularly, to a trifluoride trifluoride compound having particularly excellent operational stability in homopolymerization of trioxane or copolymerization of trioxane and cyclic ether. The present invention relates to a boron compound complex catalyst.
【０００２】[0002]
【従来の技術】三フッ化ホウ素は、アルキル化反応、縮
合反応、転位反応、環化反応などに加え、各種の重合反
応などの触媒として古くから広く利用されている。三フ
ッ化ホウ素は、常温・常圧下では無色の不燃性気体であ
り、そのままガスの状態で利用されたり、又、酸素等を
含む有機化合物との錯化合物として利用されている。三
フッ化ホウ素と錯化合物を形成する酸素等を含む有機化
合物としては、アルコール、エーテル、酸、エステルな
どの有機化合物が挙げられ、具体的にはメチルアルコー
ル、エチルアルコール、フェノール、酢酸、ジエチルエ
ーテル、ジｎ−プロピルエーテル、ジｎ−ブチルエーテ
ルなどが挙げられる。2. Description of the Related Art Boron trifluoride has been widely used as a catalyst for various polymerization reactions in addition to alkylation reactions, condensation reactions, rearrangement reactions, cyclization reactions, and the like. Boron trifluoride is a colorless nonflammable gas at normal temperature and normal pressure, and is used as it is or as a complex compound with an organic compound containing oxygen or the like. Examples of the organic compound containing oxygen or the like that forms a complex compound with boron trifluoride include organic compounds such as alcohols, ethers, acids, and esters, and specifically, methyl alcohol, ethyl alcohol, phenol, acetic acid, and diethyl ether. , Di-n-propyl ether, di-n-butyl ether and the like.
【０００３】また、これらの物性についての学術的観点
からの研究も古くから行われている。即ち、例えば、三
フッ化ホウ素と錯化合物を形成しうる有機化合物との比
率を三フッ化ホウ素に対して有機化合物を過剰とした溶
液についての赤外線吸収に関する研究（Ｚｈ．Ｆｉｚ．
Ｋｈｉｍ．（１９６７），４１（１１），２７７２−
６）や、三フッ化ホウ素錯化合物についてのケミカルシ
フトに関する研究（Ｚｈ．Ｆｉｚ．Ｋｈｉｍ．：１９７
４，４８（４），８１０−１２）がなされている。な
お、これら文献には、触媒として使用することに関する
記載はなく、またその効果に関しても記載されていな
い。[0003] In addition, research on these properties from an academic viewpoint has been carried out for a long time. That is, for example, a study on infrared absorption of a solution in which the ratio of boron trifluoride to an organic compound capable of forming a complex compound is excessive with respect to boron trifluoride (Zh. Fiz.
Khim. (1967), 41 (11), 2772-
6) and studies on chemical shifts of boron trifluoride complex compounds (Zh. Fiz. Khim .: 197)
4, 48 (4), 810-12). In these documents, there is no description regarding the use as a catalyst, and no description is given of its effect.
【０００４】これらの有機化合物と三フッ化ホウ素との
錯化合物の中でも、特に三フッ化ホウ素とエーテル化合
物との錯化合物が好適であることが知られている。さら
にこの三フッ化ホウ素錯化合物を各種反応に使用するに
際しては、三フッ化ホウ素錯化合物を三フッ化ホウ素と
不活性な有機溶媒により希釈して用いられる場合が多
く、不活性な有機溶媒としては、ペンタン、ヘキサン、
ヘプタン、シクロヘキサン等の脂肪族炭化水素やベンゼ
ン、トルエン等の芳香族炭化水素などを用いることが公
知である。[0004] Among these complex compounds of an organic compound and boron trifluoride, it is known that a complex compound of boron trifluoride and an ether compound is particularly suitable. Furthermore, when using this boron trifluoride complex compound in various reactions, the boron trifluoride complex compound is often used after being diluted with boron trifluoride and an inert organic solvent. Is pentane, hexane,
It is known to use aliphatic hydrocarbons such as heptane and cyclohexane and aromatic hydrocarbons such as benzene and toluene.
【０００５】特にトリオキサンの単独重合及びトリオキ
サンと環状エーテルとの共重合反応においては、三フッ
化ホウ素錯化合物溶液が重合触媒として用いられ、この
三フッ化ホウ素と錯化合物を形成しうる有機化合物とし
て、ジエチルエーテル、ｎ−ブチルエーテルなどエーテ
ル類が通常用いられている。更にこれらの錯化合物はヘ
キサン、ヘプタン、シクロヘキサン、ベンゼン、トルエ
ン等の三フッ化ホウ素と不活性な有機溶媒により希釈し
て用いられている。例えば、米国特許第２、９８９、５
１０号明細書および米国特許第２，９８９，５０６号明
細書等には三フッ化ホウ素ジｎ−ブチルエーテルをトリ
オキサンの重合触媒として用いる方法、米国特許第３、
０２７、３５２号明細書には三フッ化ホウ素ジエチルエ
ーテルをトリオキサンとエチレンオキサイドとの重合触
媒として用いる方法が記載されている。さらに、最近の
米国特許第５、１４４、００５号明細書にはトリオキサ
ンとジオキソランとの共重合において三フッ化ホウ素と
ジｎ−ブチルエーテルが等モルである三フッ化ホウ素ジ
ｎ−ブチルエーテル錯化合物をシクロヘキサンで希釈し
重合触媒として用いることが記載されている。[0005] In the homopolymerization of trioxane and the copolymerization reaction of trioxane with a cyclic ether, a boron trifluoride complex compound solution is used as a polymerization catalyst, and as an organic compound capable of forming a complex compound with boron trifluoride. Ethers such as, diethyl ether and n-butyl ether are usually used. Further, these complex compounds are used after being diluted with boron trifluoride such as hexane, heptane, cyclohexane, benzene and toluene and an inert organic solvent. For example, U.S. Pat.
No. 10 and U.S. Pat. No. 2,989,506 disclose a method using boron trifluoride di-n-butyl ether as a polymerization catalyst for trioxane; U.S. Pat.
Nos. 027 and 352 describe a method using boron trifluoride diethyl ether as a polymerization catalyst for trioxane and ethylene oxide. Further, a recent U.S. Pat. No. 5,144,005 discloses a boron trifluoride di-n-butyl ether complex compound in which trioxane and dioxolane are equimolar in boron trifluoride and di-n-butyl ether. It is described that it is diluted with cyclohexane and used as a polymerization catalyst.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、従来の
三フッ化ホウ素と錯化合物を形成しうる有機化合物と三
フッ化ホウ素よりなる三フッ化ホウ素錯化合物、特にエ
ーテル類との錯化合物を三フッ化ホウ素と不活性な有機
溶媒に希釈混合してトリオキサンの重合触媒として使用
するに際しては、重合挙動が乱れ運転が不安定となり、
同時に重合収率が変動する等の問題点があった。従来、
これらの諸問題に対する有効な知見はなく、安定な重合
運転を継続することは困難であった。However, a conventional boron trifluoride complex compound composed of boron trifluoride and an organic compound capable of forming a complex compound with boron trifluoride, particularly a complex compound of ethers, is used as a trifluoride compound. When used as a polymerization catalyst for trioxane after being diluted and mixed with boron oxide and an inert organic solvent, the polymerization behavior is disturbed and the operation becomes unstable,
At the same time, there was a problem that the polymerization yield fluctuated. Conventionally,
There was no effective knowledge on these problems, and it was difficult to continue stable polymerization operation.
【０００７】[0007]
【課題を解決するための手段】本発明者らは前記問題点
を解決すべく鋭意研究を重ねた結果、三フッ化ホウ素と
該三フッ化ホウ素と錯化合物を形成しうる有機化合物と
の比率（モル比）をある特定の比率とすることにより、
重合運転の安定性が著しく向上することを見い出し、本
発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and have found that the ratio of boron trifluoride to an organic compound capable of forming a complex compound with the boron trifluoride is determined. (Molar ratio) is a specific ratio,
It has been found that the stability of the polymerization operation is remarkably improved, and the present invention has been completed.
【０００８】即ち、本発明は、（ａ）三フッ化ホウ素と
有機化合物との三フッ化ホウ素錯化合物、および（ｂ）
三フッ化ホウ素と錯化合物を形成し得るが錯化合物を形
成していない遊離の有機化合物からなる三フッ化ホウ素
錯化合物含有溶液であって、溶液中の全当該有機化合物
の１モルに対して該三フッ化ホウ素が０．９８モル以下
であることを特徴とするトリオキサン重合および共重合
用の三フッ化ホウ素錯化合物溶液に関するものである。
また、該三フッ化ホウ素錯化合物含有溶液を触媒として
用いるトリオキサンの重合および共重合方法に関する。That is, the present invention relates to (a) a boron trifluoride complex compound of boron trifluoride and an organic compound, and (b)
A solution containing a boron trifluoride complex compound comprising a free organic compound that can form a complex compound with boron trifluoride but does not form a complex compound, based on 1 mol of all the organic compounds in the solution. The present invention relates to a boron trifluoride complex compound solution for trioxane polymerization and copolymerization, wherein the boron trifluoride is 0.98 mol or less.
The present invention also relates to a method for polymerizing and copolymerizing trioxane using the boron trifluoride complex compound-containing solution as a catalyst.
【０００９】以下、本発明について詳細に説明する。本
発明の三フッ化ホウ素錯化合物含有溶液は、三フッ化ホ
ウ素と錯化合物を形成している有機化合物の量と錯化合
物を形成しておらず遊離の形で存在する該有機化合物の
合計量１モルに対して三フッ化ホウ素が０．９８モル以
下であり、好ましくは０．９８〜０．０１モル、更に好
ましくは０．９０〜０．１０モルの範囲である。三フッ
化ホウ素が０．９８モル以上の場合は、トリオキサンの
重合および共重合においてタール状析出物の発生が起こ
り重合の運転安定性が劣る。その下限は特にないが、あ
まりに小さいと多量の有機化合物を必要とし、経済的、
装置的観点からメリットが発現しにくい。Hereinafter, the present invention will be described in detail. The boron trifluoride complex compound-containing solution of the present invention comprises the total amount of the organic compound which forms a complex compound with boron trifluoride and the total amount of the organic compound which does not form a complex compound and exists in a free form. The amount of boron trifluoride is 0.98 mol or less, preferably 0.98 to 0.01 mol, more preferably 0.90 to 0.10 mol per mol. If the boron trifluoride content is 0.98 mol or more, tar-like precipitates are generated in the polymerization and copolymerization of trioxane, and the operation stability of the polymerization is poor. There is no particular lower limit, but if it is too small, it requires a large amount of organic compounds, and it is economical,
It is difficult to exhibit advantages from the viewpoint of equipment.
【００１０】本発明における三フッ化ホウ素と錯化合物
を形成しうる有機化合物としては、アルコール類、エー
テル類、有機酸類、エステル類等が挙げられる。具体的
には、メチルアルコール、エチルアルコール、プロピル
アルコール、酢酸、ジエチルエーテル、ジｎ−ブチルエ
ーテル等が三フッ化ホウ素と錯化合物を形成しうる有機
化合物として用いられる。本発明において特に好ましい
有機化合物として、各アルキル基の炭素数が１〜６のア
ルキルエーテル化合物であり、ジメチルエーテル、ジｎ
−プロピルエーテル、ジｎ−ブチルエーテル、ペンチル
エーテル等が挙げられる。これらのエーテル化合物は１
種でも良く、また２種以上の混合物でも良い。The organic compound capable of forming a complex compound with boron trifluoride in the present invention includes alcohols, ethers, organic acids, esters and the like. Specifically, methyl alcohol, ethyl alcohol, propyl alcohol, acetic acid, diethyl ether, di-n-butyl ether and the like are used as organic compounds capable of forming a complex compound with boron trifluoride. Particularly preferred organic compounds in the present invention are alkyl ether compounds having 1 to 6 carbon atoms in each alkyl group, such as dimethyl ether,
-Propyl ether, di-n-butyl ether, pentyl ether and the like. These ether compounds are 1
It may be a seed or a mixture of two or more.
【００１１】本発明の三フッ化ホウ素錯化合物の溶液
は、三フッ化ホウ素に不活性な有機溶媒で希釈されて使
用される。三フッ化ホウ素に不活性な有機溶媒として
は、ペンタン、ヘキサン、ヘプタン、オクタン、シクロ
ヘキサン等の脂肪族炭化水素、ベンゼン、トルエン等の
芳香族炭化水素などが用いられる。好ましい有機溶媒と
しては、シクロヘキサン、ベンゼン、トルエンが挙げら
れる。これらの有機溶媒は、そのまま前処理なしで用い
ても良いが、蒸留による水分除去やゼオライト等による
吸着脱水等の操作により水分を除去しても良く特に限定
されない。この三フッ化ホウ素と不活性な有機溶媒で希
釈する際の三フッ化ホウ素錯化合物の濃度は、通常０．
０１〜３０重量％であるが特に限定されない。The solution of the boron trifluoride complex compound of the present invention is used after being diluted with an organic solvent inert to boron trifluoride. Examples of the organic solvent inert to boron trifluoride include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane, and aromatic hydrocarbons such as benzene and toluene. Preferred organic solvents include cyclohexane, benzene, and toluene. These organic solvents may be used without any pretreatment as they are, but the water may be removed by an operation such as removal of water by distillation or adsorption and dehydration with zeolite or the like, and there is no particular limitation. The concentration of the boron trifluoride complex compound when diluted with this boron trifluoride and an inert organic solvent is usually 0.1.
The content is from 01 to 30% by weight, but is not particularly limited.
【００１２】本発明の三フッ化ホウ素錯化合物溶液の製
造方法は、特に限定されないが、例えば、エーテル、ア
ルコール等の三フッ化ホウ素と錯化合物を形成しうる有
機化合物中に三フッ化ホウ素ガスを所定量吹込む事によ
り得られる。又、三フッ化ホウ素と錯化合物を形成しう
る有機化合物と該三フッ化ホウ素が等モルである三フッ
化ホウ素錯化合物をさらに該有機化合物で希釈すること
等により製造することができる。以上の様にして得られ
た本発明の三フッ化ホウ素錯化合物の溶液は、そのまま
希釈せずトリオキサンの重合触媒として使用されるが、
三フッ化ホウ素に不活性な有機溶媒で希釈して用いるこ
とがより好ましい。The method for producing the boron trifluoride complex compound solution of the present invention is not particularly limited. For example, boron trifluoride gas is contained in an organic compound such as ether or alcohol which can form a complex compound with boron trifluoride. Is blown by a predetermined amount. Further, it can be produced by further diluting an organic compound capable of forming a complex compound with boron trifluoride and a boron trifluoride complex compound in which the boron trifluoride is equimolar, with the organic compound. The solution of the boron trifluoride complex compound of the present invention obtained as described above is used as a polymerization catalyst for trioxane without dilution.
It is more preferable to use the organic solvent diluted with an organic solvent inert to boron trifluoride.
【００１３】以下に更にトリオキサンの重合について述
べる。トリオキサンの重合としては、トリオキサンの単
独重合又はトリオキサンと環状エーテルとの共重合が挙
げられる。例えば、トリオキサンとコモノマーとの共重
合はセルフクリーニング型の反応機を用いる塊状重合法
等により重合を行う。コモノマーとしては、エチレンオ
キサイド、プロピレンオキサイド、１，３−ジオキソラ
ン、１，４−ブタンジオールホルマール等の環状エーテ
ルが挙げられ、トリオキサンに対して０．０１〜２０ｍ
ｏｌ％添加して共重合を行う。更に分子量調節剤として
メチラール等がトリオキサンとコモノマーとの混合物に
添加される。重合温度は５０℃〜１４０℃であり、又、
反応時間は０．５〜６０分間である。この重合反応にお
いて、三フッ化ホウ素と錯化合物を形成しうる有機化合
物１モルに対して、該三フッ化ホウ素は０．９８モル以
下である、三フッ化ホウ素錯化合物と錯化合物を形成し
ていない遊離の有機化合物と三フッ化ホウ素錯化合物よ
りなる三フッ化ホウ素錯化合物の溶液が、三フッ化ホウ
素に不活性な有機溶媒で希釈され重合触媒として用いら
れる。通常、重合触媒濃度は三フッ化ホウ素として全モ
ノマー１モルに対して１×１０-6〜１×１０-3ｍｏｌで
あるが特に限定されない。The polymerization of trioxane will be further described below. Examples of the polymerization of trioxane include homopolymerization of trioxane or copolymerization of trioxane and a cyclic ether. For example, copolymerization of trioxane and a comonomer is performed by a bulk polymerization method using a self-cleaning type reactor or the like. Examples of the comonomer include cyclic ethers such as ethylene oxide, propylene oxide, 1,3-dioxolan, and 1,4-butanediol formal, and 0.01 to 20 m with respect to trioxane.
ol% of the copolymer. Further, methylal or the like is added to the mixture of trioxane and comonomer as a molecular weight regulator. The polymerization temperature is 50C to 140C, and
The reaction time is 0.5 to 60 minutes. In this polymerization reaction, the boron trifluoride forms a complex compound with the boron trifluoride complex compound in an amount of 0.98 mol or less based on 1 mol of the organic compound capable of forming a complex compound with boron trifluoride. A solution of a boron trifluoride complex compound consisting of a free organic compound and a boron trifluoride complex compound is diluted with an organic solvent inert to boron trifluoride and used as a polymerization catalyst. Usually, the concentration of the polymerization catalyst is 1 × 10 −6 to 1 × 10 −3 mol per mol of all monomers as boron trifluoride, but is not particularly limited.
【００１４】[0014]
【実施例】以下、実施例により本発明を更に説明する
が、本発明は、これらの実施例により何ら限定されるも
のではない。次に、重合安定性の評価について説明す
る。 重合安定性：以下の重合方法によりトリオキサンと１、
３ージオキソランの共重合を連続的に行い、重合挙動
（運転の乱れ）を評価した。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Next, evaluation of polymerization stability will be described. Polymerization stability: trioxane and 1,
The copolymerization of 3-dioxolane was continuously performed, and the polymerization behavior (operation disorder) was evaluated.
【００１５】＜重合方法＞外部に熱媒を通すことが出来
るジャケットを備え、内部に同方向に回転する１対のシ
ャフトを有し、これらのシャフトには互いにかみ合う凸
レンズ型のパドルが組み込まれ、この長端部分がケーシ
ング内面及び他方のシャフトに組み込まれたパドルと僅
かなクリアランスを保ちながら回転する２軸のセルフク
リーニングタイプの反応機（Ｌ／Ｄ＝８）のジャケット
を８０℃に保ち、トリオキサンを２ｋｇ／ｈｒ、１、３
ージオキソランを８０ｇｒ／ｈｒ、メチラールを１．２
ｇｒ／ｈｒを連続的に供給した。同時に三フッ化ホウ素
と有機化合物のモル比がある比率の三フッ化ホウ素錯化
合物の溶液をシクロヘキサンで１重量％に希釈し、三フ
ッ化ホウ素の濃度がトリオキサン１モルに対して１．２
×１０-5モルとなる様に添加して重合を行った。<Polymerization method> A jacket through which a heat medium can pass is provided outside, and a pair of shafts rotating in the same direction is provided inside. These shafts incorporate a convex lens type paddle which meshes with each other, The jacket of a two-shaft self-cleaning type reactor (L / D = 8) that rotates while maintaining a small clearance with the paddle incorporated in the inner surface of the casing and the other shaft is maintained at 80 ° C. 2 kg / hr, 1, 3
-Dioxolane 80 gr / hr, methylal 1.2
gr / hr was continuously supplied. At the same time, a solution of a boron trifluoride complex compound having a molar ratio of boron trifluoride and an organic compound is diluted to 1% by weight with cyclohexane, and the concentration of boron trifluoride is adjusted to 1.2 mol per 1 mol of trioxane.
The polymerization was carried out by adding so as to be × 10 -5 mol.
【００１６】（実施例１〜６）三フッ化ホウ素錯化合物
の調整は、表１記載のジエチルエーテル、ジｎ−ブチル
エーテルそれぞれのエーテル化合物１モルに、三フッ化
ホウ素ガスを表１記載の所定のモル吹込み調製した。
又、三フッ化ホウ素錯化合物の希釈に用いた表１記載の
不活性な有機溶媒は、試薬特級を用いゼオライトにて１
０ｐｐｍ以下に脱水した後に調合した。この調合液を重
合触媒とし、上記重合方法により重合を行った。重合時
における重合安定性についての結果を表１に示す。表１
より、三フッ化ホウ素と錯化合物を形成する有機化合物
１モルに対する該三フッ化ホウ素が０．９８モル以下で
ある、錯化合物を形成していないフリーの有機化合物と
三フッ化ホウ素錯化合物よりなる三フッ化ホウ素錯化合
物の溶液を重合触媒として用いた場合は重合安定性に優
れることがわかる。(Examples 1 to 6) The boron trifluoride complex compound was prepared by adding boron trifluoride gas to one mole of each of the ether compounds of diethyl ether and di-n-butyl ether shown in Table 1 to a predetermined amount shown in Table 1. Was prepared.
The inert organic solvent shown in Table 1 used for diluting the boron trifluoride complex compound was prepared using zeolite using a special grade reagent.
It was prepared after dehydration to 0 ppm or less. Using this prepared liquid as a polymerization catalyst, polymerization was carried out by the above polymerization method. Table 1 shows the results of the polymerization stability during the polymerization. Table 1
From a free organic compound not forming a complex compound and a boron trifluoride complex compound in which the boron trifluoride is 0.98 mol or less relative to 1 mole of the organic compound forming a complex compound with boron trifluoride. It can be seen that when a solution of the boron trifluoride complex compound was used as a polymerization catalyst, the polymerization stability was excellent.
【００１７】（比較例１〜２）三フッ化ホウ素錯化合物
は、実施例と同様の方法で調整し、さらに重合を行い重
合安定性を評価した。結果を表１に示す。表１より、三
フッ化ホウ素錯化合物または三フッ化ホウ素と錯化合物
を形成する有機化合物１モルに対して該三フッ化ホウ素
が０．９８モルを超えている、錯化合物を形成していな
いフリーの有機化合物と三フッ化ホウ素錯化合物よりな
る三フッ化ホウ素錯化合物の溶液を重合触媒として用い
た場合は、重合安定性に劣ることがわかる。(Comparative Examples 1 and 2) The boron trifluoride complex compound was prepared in the same manner as in the examples, and was further polymerized to evaluate polymerization stability. Table 1 shows the results. As shown in Table 1, the boron trifluoride complex compound or the organic compound forming a complex compound with boron trifluoride is present in an amount exceeding 0.98 mol with respect to 1 mol of the organic compound, and does not form a complex compound. It can be seen that when a solution of a boron trifluoride complex compound comprising a free organic compound and a boron trifluoride complex compound is used as a polymerization catalyst, polymerization stability is poor.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】本発明における三フッ化ホウ素錯化合物
の溶液を触媒として用いる事により、トリオキサンの重
合または共重合のおける重合安定性は、三フッ化ホウ素
と錯化合物を形成する有機化合物１モルに対する該三フ
ッ化ホウ素が０．９８モル以下である、錯化合物を形成
していないフリーの有機化合物と三フッ化ホウ素錯化合
物よりなる初めて発現できるものである。本発明によ
り、重合挙動の乱れや、運転の不安定性がなくなり、同
時に重合収率が変動することもなく安定な重合運転を継
続することが可能となる。By using the solution of the boron trifluoride complex compound in the present invention as a catalyst, the polymerization stability in the polymerization or copolymerization of trioxane can be assured by one mole of an organic compound forming a complex compound with boron trifluoride. , Which can be expressed for the first time by a free organic compound not forming a complex compound and a boron trifluoride complex compound in which the boron trifluoride is 0.98 mol or less. ADVANTAGE OF THE INVENTION According to this invention, disorder of polymerization behavior and instability of operation are eliminated, and at the same time, stable polymerization operation can be continued without fluctuation in polymerization yield.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 31/16 C08G 2/00 - 2/34 ──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int. Cl. 7 , DB name) B01J 31/16 C08G 2/00-2/34
Claims (6)
三フッ化ホウ素錯化合物、及び（ｂ）三フッ化ホウ素と
錯化合物を形成し得るが錯化合物を形成していない遊離
の有機化合物からなる三フッ化ホウ素錯化合物含有溶液
であって、溶液中の全当該有機化合物の１モルに対して
該三フッ化ホウ素が０．９８モル以下であることを特徴
とするトリオキサン重合および共重合用の三フッ化ホウ
素錯化合物溶液。1. A (a) boron trifluoride complex compound of boron trifluoride and an organic compound, and (b) a free organic compound capable of forming a complex compound with boron trifluoride but not forming a complex compound. A solution containing a boron trifluoride complex compound comprising a compound, wherein the boron trifluoride is 0.98 mol or less based on 1 mol of all the organic compounds in the solution. Boron trifluoride complex compound solution for polymerization.
て三フッ化ホウ素が０．９８〜０．０１モルである請求
項１記載のトリオキサン重合および共重合用の三フッ化
ホウ素錯化合物溶液。2. The boron trifluoride complex compound for trioxane polymerization and copolymerization according to claim 1, wherein the amount of boron trifluoride is 0.98 to 0.01 mol based on 1 mol of all the organic compounds in the solution. solution.
が１〜６のアルキルエーテル化合物である請求項１また
は２記載のトリオキサン重合および共重合用の三フッ化
ホウ素錯化合物溶液。3. The boron trifluoride complex compound solution for trioxane polymerization and copolymerization according to claim 1, wherein the organic compound is an alkyl ether compound having 1 to 6 carbon atoms in each alkyl group.
て三フッ化ホウ素が０．９０〜０．１０モルである請求
項１、２または３記載のトリオキサン重合および共重合
用の三フッ化ホウ素錯化合物溶液。4. The trifluoride for trioxane polymerization and copolymerization according to claim 1, wherein the amount of boron trifluoride is 0.90 to 0.10 mol per 1 mol of all the organic compounds in the solution. Boron halide complex compound solution.
ホウ素に不活性な有機溶媒により希釈された溶液である
ことを特徴とする請求項１、２、３または４記載のトリ
オキサン重合および共重合用の三フッ化ホウ素錯化合物
溶液。5. The trioxane polymerization and polymerization method according to claim 1, wherein the boron trifluoride complex compound solution is a solution diluted with an organic solvent inert to boron trifluoride. Boron trifluoride complex compound solution for polymerization.
フッ化ホウ素錯化合物溶液を用いて、トリオキサン又は
トリオキサンと環状エーテルとを重合または共重合する
ことを特徴とするトリオキサンの重合方法。6. A polymerization of trioxane, comprising polymerizing or copolymerizing trioxane or trioxane with a cyclic ether using the boron trifluoride complex compound solution according to claim 1, 2, 3, 4, or 5. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09195217A JP3124250B2 (en) | 1996-07-11 | 1997-07-07 | Boron trifluoride complex compound for trioxane polymerization |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18185496 | 1996-07-11 | ||
| JP8-181854 | 1996-07-11 | ||
| JP09195217A JP3124250B2 (en) | 1996-07-11 | 1997-07-07 | Boron trifluoride complex compound for trioxane polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1081722A JPH1081722A (en) | 1998-03-31 |
| JP3124250B2 true JP3124250B2 (en) | 2001-01-15 |
Family
ID=26500858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09195217A Expired - Lifetime JP3124250B2 (en) | 1996-07-11 | 1997-07-07 | Boron trifluoride complex compound for trioxane polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3124250B2 (en) |
-
1997
- 1997-07-07 JP JP09195217A patent/JP3124250B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1081722A (en) | 1998-03-31 |
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