JPS637571B2 - - Google Patents
Info
- Publication number
- JPS637571B2 JPS637571B2 JP18073881A JP18073881A JPS637571B2 JP S637571 B2 JPS637571 B2 JP S637571B2 JP 18073881 A JP18073881 A JP 18073881A JP 18073881 A JP18073881 A JP 18073881A JP S637571 B2 JPS637571 B2 JP S637571B2
- Authority
- JP
- Japan
- Prior art keywords
- thf
- polymerization
- carboxylic acid
- catalyst
- reaction
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000011964 heteropoly acid Substances 0.000 claims description 8
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- -1 polytetramethylene Polymers 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 11
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- OHAVYOCBYILSBZ-UHFFFAOYSA-M dihydroxyboron;hydroxy(dioxo)tungsten Chemical compound O[B]O.O[W](=O)=O OHAVYOCBYILSBZ-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Polyethers (AREA)
Description
本発明はポリテトラメチレングリコール（以
下、PTMGと略記する。）の製造方法の改良に関
する。詳しくは、出発原料であるテトラヒドロフ
ラン（以下、THFと略記する。）の重合に際し新
規な触媒を提供するにある。
PTMGはポリウレタンの原料等として工業的
に多方面の分野で利用されており、THFを適当
な触媒の存在下に重合して製造され、通常は数平
均分子量で1000〜3000程度のものがよく使用され
ている。
従来、THFの重合触媒としては、フルオロ硫
酸系、発煙硫酸系及び三弗化ホウ素系等と数多く
のものが知られているが、工業的に満足できるも
のは比較的少ない。例えば、フルオロ硫酸系触媒
は触媒自体の価格が高く、腐蝕性が大きいので取
扱いに難点がある。発煙硫酸系触媒は使用量が多
く、更に廃硫酸の処理をしなければならない難点
がある。又、三弗化ホウ素系触媒は重合速度の調
節が困難であるので、補助物質の追加の上で反応
条件の選択に難点がある。
本発明者は以上の欠点を克服するため、鋭意検
討を重ねた結果、ヘテロポリ酸とカルボン酸無水
物又はカルボン酸塩化物を組合せてなる触媒を用
いてTHFを重合させることにより、極めて容易
に分子量1000〜3000のPTMGを高い収率で製造
し得ることを見出し、本発明に到達した。
本発明の方法によれば、THFの重合を経る
PTMGの製造に際し、極めてわずかな触媒量と
極めて緩和な反応条件で、しかも装置への腐蝕性
がない等大きな工業的な利点を有する。又、主触
媒であるヘテロポリ酸は近年酸化反応触媒等で有
機合成の分野に利用されているが、THFの重合
触媒に使用された例は未だなく、しかも単独では
該重合触媒能がなく、カルボン酸無水物又はカル
ボン酸塩化物との組合せにより、はじめて触媒活
性が出て来ると言つた特異なものである。
本発明に使用されるヘテロポリ酸は特に限定さ
れるものではなく、最も一般的に用いられるもの
としてはケイタングステン酸、ケイモリブデン
酸、リンタングステン酸、リンモリブデン酸、ホ
ウタングステン酸、ホウモリブテン酸等が挙げら
れる。ヘテロポリ酸の使用量はTHFに対し1.0〜
10.0重量％、好ましくは1.0〜5.0重量％の範囲で
ある。なお、ヘテロポリ酸は本発明の条件下では
安定であり、加水分解系から生成物を分離した
後、後処理して循環使用することができる。
ヘテロポリ酸と併用するカルボン酸無水物又は
カルボン酸塩化物としては、例えば無水酢酸、無
水プロピオン酸、無水酪酸、塩化アセチル、塩化
プロピオニル、塩化ブチリル等が挙げられる。カ
ルボン酸無水物又はカルボン酸塩化物の使用量は
THFに対し10〜50重量％、好ましくは10〜20％
である。
触媒成分の添加方法としてはTHFにヘテロポ
リ酸を溶解若しくは懸濁させ、これにカルボン酸
無水物又はカルボン酸塩化物を滴下するのが普通
であるが、これに限定されることはない。
本発明に使用される反応温度は通常０〜60℃、
好ましくは０〜30℃の範囲である。反応時間は通
常１〜10Hr、好ましくは１〜4Hrの範囲である。
これ等の条件を厳しくすると反応液が着色し易
く、収率も低下するので好ましくない。又、重合
を行うに際しては反応器を予め窒素、アルゴン等
の不活性ガスで置換しておくことが望ましい。
本発明の方法にかゝるTHFの重合によつて得
られるPTMGの収率及び分子量は反応温度、反
応時間、触媒成分及びその使用量等によつて変化
し、各々の組合せを利用すれば、適宜任意の分子
量のものを製造することが期待できる。
重合反応終了後、反応液に水を加えて重合を停
止させ、加熱して未反応のTHFを溜去する。引
続き公知の方法で処理してPTMGを得ることが
できる。例えば、先ず得られた重合液にアルカリ
と共に、溶剤を加えて加熱し、加水分解する。次
いで、加水分解反応混合液を静置して、PTMG
を溶解した有機層と水層とに成層分離し、水洗、
分液を繰返して、該有機層を精製した後、溶剤を
溜去、乾燥すれば純粋なPTMGが回収される。
以下、実施例によつて、本発明を更に具体的に
説明する。
なお、PTMGの数平均分子量は蒸気圧滲透計
を用いて測定したものであり、水酸基価は
JIS1557−1970に従い、測定した。
実施例１〜３及び比較例
還流器、撹拌機及び温度計を付した四つ口フラ
ラスコに、THF100ｇを仕込み、これに表−１に
示すヘテロポリ酸を加え、撹拌しつつ外部冷却で
約０℃に保ちながら、表−１に示すカルボン酸無
水物又は塩化物を15分間かけて滴下し、引続き表
−１に示す条件でTHFの重合反応を行つた。（窒
素雰囲気下）後、反応液に水100mlを加えて反応
を停止させ、未反応のTHFを減圧蒸溜々去した。
次いで、20％水酸化ナトリウム水溶液200ml及
びｎ−ブチルアルコール200mlを加え、還流下で
３時間加水分解した。
更に室温まで冷却し、静置して水層を分液し、
以下、水100mlを加えて撹拌し、静置して水層を
分液する精製操作を３回繰返した。後、有機層中
のｎ−ブチルアルコール及び残存する水を減圧蒸
溜々去してPTMGを得た。その収量及び分子量
は表−１に示す。
The present invention relates to an improvement in a method for producing polytetramethylene glycol (hereinafter abbreviated as PTMG). Specifically, the purpose is to provide a novel catalyst for the polymerization of tetrahydrofuran (hereinafter abbreviated as THF), which is a starting material. PTMG is used industrially in many fields as a raw material for polyurethane, etc., and is produced by polymerizing THF in the presence of an appropriate catalyst, and usually has a number average molecular weight of about 1000 to 3000. has been done. Conventionally, many THF polymerization catalysts have been known, such as fluorosulfuric acid, fuming sulfuric acid, and boron trifluoride, but relatively few of them are industrially satisfactory. For example, fluorosulfuric acid catalysts are difficult to handle because they are expensive and highly corrosive. A large amount of fuming sulfuric acid catalyst is used, and waste sulfuric acid must be disposed of. Furthermore, since it is difficult to control the polymerization rate of boron trifluoride catalysts, it is difficult to select reaction conditions in addition to adding auxiliary substances. In order to overcome the above-mentioned drawbacks, the present inventor has made extensive studies and found that by polymerizing THF using a catalyst consisting of a combination of a heteropolyacid and a carboxylic acid anhydride or a carboxylic acid chloride, the molecular weight can be extremely easily reduced. It was discovered that 1000 to 3000 PTMG can be produced in high yield, and the present invention was achieved. According to the method of the present invention, through the polymerization of THF
When producing PTMG, it requires a very small amount of catalyst and very mild reaction conditions, and has great industrial advantages such as not being corrosive to equipment. In addition, heteropolyacid, which is the main catalyst, has been used in the field of organic synthesis as an oxidation reaction catalyst in recent years, but it has not yet been used as a THF polymerization catalyst, and moreover, it does not have the polymerization catalytic ability alone, and carbon It is unique in that it exhibits catalytic activity only when combined with an acid anhydride or a carboxylic acid chloride. The heteropolyacids used in the present invention are not particularly limited, and the most commonly used ones include silicotungstic acid, silicomolybdic acid, phosphotungstic acid, phosphomolybdic acid, borotungstic acid, boromolybdic acid, etc. can be mentioned. The amount of heteropolyacid used is 1.0 to THF.
10.0% by weight, preferably in the range 1.0-5.0% by weight. Note that the heteropolyacid is stable under the conditions of the present invention, and after separating the product from the hydrolysis system, it can be post-treated and recycled for reuse. Examples of the carboxylic acid anhydride or carboxylic acid chloride used in combination with the heteropolyacid include acetic anhydride, propionic anhydride, butyric anhydride, acetyl chloride, propionyl chloride, butyryl chloride, and the like. The amount of carboxylic acid anhydride or carboxylic acid chloride used is
10-50% by weight relative to THF, preferably 10-20%
It is. The usual method for adding the catalyst component is to dissolve or suspend the heteropolyacid in THF and dropwise add the carboxylic acid anhydride or carboxylic acid chloride thereto, but the method is not limited thereto. The reaction temperature used in the present invention is usually 0 to 60°C,
Preferably it is in the range of 0 to 30°C. The reaction time is usually in the range of 1 to 10 hours, preferably 1 to 4 hours.
If these conditions are made too strict, the reaction solution tends to become colored and the yield decreases, which is not preferable. Furthermore, when carrying out polymerization, it is desirable to purge the reactor with an inert gas such as nitrogen or argon in advance. The yield and molecular weight of PTMG obtained by polymerization of THF according to the method of the present invention vary depending on the reaction temperature, reaction time, catalyst components and their usage amounts, etc., and if each combination is used, It can be expected that products with arbitrary molecular weights can be produced as appropriate. After the polymerization reaction is completed, water is added to the reaction solution to stop the polymerization, and unreacted THF is distilled off by heating. PTMG can then be obtained by further processing in known manner. For example, first, an alkali and a solvent are added to the obtained polymerization solution, and the mixture is heated and hydrolyzed. Next, the hydrolysis reaction mixture was allowed to stand, and the PTMG
Stratified into an organic layer and an aqueous layer, washed with water,
After purifying the organic layer by repeating separation, pure PTMG is recovered by distilling off the solvent and drying. Hereinafter, the present invention will be explained in more detail with reference to Examples. The number average molecular weight of PTMG was measured using a vapor pressure percolation meter, and the hydroxyl value was
Measured according to JIS1557-1970. Examples 1 to 3 and Comparative Examples 100g of THF was charged into a four-necked flask equipped with a refluxer, stirrer, and thermometer, and the heteropolyacid shown in Table 1 was added thereto, and the temperature was heated to about 0°C by external cooling while stirring. The carboxylic acid anhydride or chloride shown in Table 1 was added dropwise over 15 minutes while maintaining the temperature, and then a THF polymerization reaction was carried out under the conditions shown in Table 1. After that (under nitrogen atmosphere), 100 ml of water was added to the reaction solution to stop the reaction, and unreacted THF was distilled off under reduced pressure. Next, 200 ml of 20% aqueous sodium hydroxide solution and 200 ml of n-butyl alcohol were added, and the mixture was hydrolyzed under reflux for 3 hours. Further cool to room temperature, leave to stand, and separate the aqueous layer.
Thereafter, the purification operation of adding 100 ml of water, stirring, and standing still to separate the aqueous layer was repeated three times. Thereafter, n-butyl alcohol and remaining water in the organic layer were distilled off under reduced pressure to obtain PTMG. The yield and molecular weight are shown in Table-1.
【表】
＊ 比較例では反応液から減圧蒸溜々去したとこ
ろ、重合物は殆んど残らず、ヘテロポリ
酸単独ではTHFの重合触媒能がないことが明ら
かである。
[Table] * In the comparative example, when the reaction solution was distilled off under reduced pressure, almost no polymer remained, and the heteropolymer was removed by distillation under reduced pressure.
It is clear that acid alone does not have the ability to catalyze the polymerization of THF.
Claims (1)
ン酸塩化物から選ばれた１種とを組合わせてなる
触媒の存在下で、テトラヒドロフランを重合させ
ることを特徴とするポリテトラメチレングリコー
ルの製造方法。1. A method for producing polytetramethylene glycol, which comprises polymerizing tetrahydrofuran in the presence of a catalyst comprising a combination of a heteropolyacid and one selected from carboxylic acid anhydrides and carboxylic acid chlorides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18073881A JPS5883028A (en) | 1981-11-10 | 1981-11-10 | Preparation of polytetramethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18073881A JPS5883028A (en) | 1981-11-10 | 1981-11-10 | Preparation of polytetramethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5883028A JPS5883028A (en) | 1983-05-18 |
| JPS637571B2 true JPS637571B2 (en) | 1988-02-17 |
Family
ID=16088442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18073881A Granted JPS5883028A (en) | 1981-11-10 | 1981-11-10 | Preparation of polytetramethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5883028A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59159824A (en) * | 1983-03-02 | 1984-09-10 | Asahi Glass Co Ltd | Production of polyether compound |
| CA1216597A (en) * | 1983-05-23 | 1987-01-13 | Atsushi Aoshima | Process for producing polyetherglycol |
| DE3563447D1 (en) * | 1984-03-28 | 1988-07-28 | Asahi Chemical Ind | Process for producing polyether polyol, the produced polyether polyol and polyurethane |
| JPS61123629A (en) * | 1984-11-20 | 1986-06-11 | Asahi Chem Ind Co Ltd | Removal of heteropolyacid from polyalkylene ether |
| DE4108044A1 (en) * | 1991-03-13 | 1992-09-17 | Basf Ag | METHOD FOR PRODUCING POLYOXYALKYLENE GLYCOLES |
| DE4108046A1 (en) * | 1991-03-13 | 1992-09-17 | Basf Ag | METHOD FOR PRODUCING POLYOXYALKYLENE GLYCOL MONOESTERS FROM MONOCARBONIC ACIDS |
| US5302255A (en) * | 1992-03-06 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Reducing molecular weight distribution of polyether glycols by short-path distillation |
| DE4435934A1 (en) * | 1994-10-07 | 1996-04-11 | Basf Ag | Process for removing heteropoly compounds from polyethers, polyesters and polyetheresters |
| US5648557A (en) * | 1994-10-27 | 1997-07-15 | Mobil Oil Corporation | Polyether lubricants and method for their production |
| DE19527532A1 (en) * | 1995-07-27 | 1997-01-30 | Basf Ag | Process for the preparation of polyoxytetramethylene glycol |
| US5756604A (en) * | 1995-08-31 | 1998-05-26 | Hodogaya Chemical Co., Ltd. | Process for producing polyether, and process for recycling and reusing herteropolyacid |
| US6087307A (en) * | 1998-11-17 | 2000-07-11 | Mobil Oil Corporation | Polyether fluids miscible with non-polar hydrocarbon lubricants |
-
1981
- 1981-11-10 JP JP18073881A patent/JPS5883028A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5883028A (en) | 1983-05-18 |
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