JPH0149714B2 - - Google Patents
Info
- Publication number
- JPH0149714B2 JPH0149714B2 JP6240581A JP6240581A JPH0149714B2 JP H0149714 B2 JPH0149714 B2 JP H0149714B2 JP 6240581 A JP6240581 A JP 6240581A JP 6240581 A JP6240581 A JP 6240581A JP H0149714 B2 JPH0149714 B2 JP H0149714B2
- Authority
- JP
- Japan
- Prior art keywords
- pentaoxacyclododecane
- trioxane
- molecular weight
- present
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- UHWQXUPPGOXGPN-UHFFFAOYSA-N 1,3,5,7,10-pentaoxacyclododecane Chemical compound C1COCOCOCOCCO1 UHWQXUPPGOXGPN-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SFXNZFATUMWBHR-UHFFFAOYSA-N 2-morpholin-4-yl-2-pyridin-3-ylacetonitrile Chemical compound C=1C=CN=CC=1C(C#N)N1CCOCC1 SFXNZFATUMWBHR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は新規な環状ホルマールに関するもので
ある。さらに詳しくは、
構造式
〔１，３，５，７，10−ペンタオキサシクロド
デカン〕で表わされる環状ホルマールに関する。
一般に環状ホルマールで総称される化合物は多
く知られている。（例えば特公昭55−19941）しか
しながらこれら公知の環状ホルマールは、環構成
単位としての連続するオキシメチレン単位は１個
であることがほとんどであり、多くとも２個を越
えることはなかつた。本発明者らは鋭意検討の結
果、３個の連続するオキシメチレン単位を環構成
単位として有する環状ホルマールのひとつであ
る、１，３，５，７，10−ペンタオキサシクロド
デカンの存在を確認すると共に、これを合成、単
離することに成功した。
本発明による１，３，５，７，10−ペンタオキ
サシクロドデカンはそれ自身、良好な開環重合の
単量体となると共にポリエーテル、オキシメチレ
ン共重合体などの共単量体として有用である。
本発明の新規環状ホルマールは、エチレンオキ
シドとトリオキサンを、両者を共重合させうる能
力を有する触媒の存在下に反応させ、該反応を共
重合物の析出する前に停止させることによつて得
ることができる。
実施例
トリオキサン100重量部にエチレンオキシド５
重量部を溶解し、良く撹拌しながら70℃に保つ
た。これにトリオキサン１モルに対して７×10-5
モルに相当する三弗化硼素ジブチルエーテレート
をベンゼンで100倍に希釈したものを反応触媒と
して加え、良く撹拌した。３分後、触媒に対して
化学量論的に３倍量の水酸化カリウムを含むメタ
ノール溶液を加え、反応を停止した。得られた溶
液を常圧で150℃に加熱し、未反応のトリオキサ
ン及びメタノール、他の低沸点生成物を留去し
た。留去後の残液をさらに減圧下で分別蒸留し、
15mmHgにおいて約130℃で留出する１，３，５，
７，10−ペンタオキサシクロドデカンを純度約95
％で得た。このものは無色透明の液体でエチレン
オキシドからの収率は約17％であつた。
第１図にはこのもののH1核磁気共鳴スペクト
ルを示した。使用機器は日本電子社製JNMMH
−100型で基準物質はテトラメチルシランを用い
た。このスペクトルは、１，３，５，７，10−ペ
ンタオキサシクロドデカンであることを指示して
いる。
さらに分子量を確認するため、ベンゼンにこの
化合物を溶解したときのベンゼンの凝固点降下を
測定した。測定は通常のベツクマン法により行な
つた。結果は表−１に示した通りである。算出さ
れた分子量は174〜179であり、この化合物が１，
３，５，７，10−ペンタオキサシクロドデカン
（分子量178）であることを良く一致する。
The present invention relates to a novel cyclic formal. For more information, see Structural Formula It relates to a cyclic formal represented by [1,3,5,7,10-pentaoxacyclododecane]. Many compounds are generally known as cyclic formals. (For example, Japanese Patent Publication No. 55-19941) However, in most of these known cyclic formals, the number of consecutive oxymethylene units as a ring constituent unit is one, and the number never exceeds two at most. As a result of intensive studies, the present inventors confirmed the existence of 1,3,5,7,10-pentaoxacyclododecane, which is one of the cyclic formals having three consecutive oxymethylene units as ring constituent units. We also succeeded in synthesizing and isolating it. The 1,3,5,7,10-pentaoxacyclododecane according to the present invention itself is a good monomer for ring-opening polymerization and is useful as a comonomer for polyethers, oxymethylene copolymers, etc. be. The novel cyclic formal of the present invention can be obtained by reacting ethylene oxide and trioxane in the presence of a catalyst capable of copolymerizing both, and stopping the reaction before precipitation of the copolymer. can. Example: 5 parts by weight of ethylene oxide in 100 parts by weight of trioxane
Part by weight was dissolved and kept at 70°C with thorough stirring. To this, 7×10 -5 per mole of trioxane
A mole of boron trifluoride dibutyl etherate diluted 100 times with benzene was added as a reaction catalyst and stirred well. After 3 minutes, a methanol solution containing potassium hydroxide in an amount stoichiometrically three times the amount of the catalyst was added to stop the reaction. The resulting solution was heated to 150° C. under normal pressure, and unreacted trioxane, methanol, and other low-boiling products were distilled off. The residual liquid after distillation is further fractionally distilled under reduced pressure,
1,3,5, which distills at about 130℃ at 15mmHg
7,10-pentaoxacyclododecane with a purity of approximately 95
Obtained in %. This product was a colorless and transparent liquid, and the yield from ethylene oxide was about 17%. Figure 1 shows the H 1 nuclear magnetic resonance spectrum of this product. The equipment used is JNMMH manufactured by JEOL Ltd.
For the −100 type, tetramethylsilane was used as the reference material. This spectrum indicates 1,3,5,7,10-pentaoxacyclododecane. Furthermore, to confirm the molecular weight, the freezing point depression of benzene was measured when this compound was dissolved in benzene. Measurements were carried out using the usual Beckman method. The results are shown in Table-1. The calculated molecular weight is 174-179, and this compound has a molecular weight of 1,
There is good agreement that it is 3,5,7,10-pentaoxacyclododecane (molecular weight 178).
【表】
として求めた。
[Table]
第１図は本発明１，３，５，７，10−ペンタオ
キサシクロドデカンのH1核磁気共鳴スペクトル
を示し、
同図中、ピークＡ，Ｂ，Ｃはそれぞれ下記式に
おけるHA，HB，HCで示された水素のスペクトル
を示す。
Figure 1 shows the H1 nuclear magnetic resonance spectrum of the 1,3,5,7,10-pentaoxacyclododecane of the present invention, in which peaks A, B, and C represent H A and H B in the following formula, respectively. , H C shows the spectrum of hydrogen.
Claims (1)
デカン〕で示される新規な環状ホルマール。[Claims] 1. Structural formula A novel cyclic formal represented by [1,3,5,7,10-pentaoxacyclododecane].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6240581A JPS57179181A (en) | 1981-04-27 | 1981-04-27 | Novel cyclic formal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6240581A JPS57179181A (en) | 1981-04-27 | 1981-04-27 | Novel cyclic formal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57179181A JPS57179181A (en) | 1982-11-04 |
| JPH0149714B2 true JPH0149714B2 (en) | 1989-10-25 |
Family
ID=13199192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6240581A Granted JPS57179181A (en) | 1981-04-27 | 1981-04-27 | Novel cyclic formal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57179181A (en) |
-
1981
- 1981-04-27 JP JP6240581A patent/JPS57179181A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57179181A (en) | 1982-11-04 |
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