JPH0148887B2 - - Google Patents
Info
- Publication number
- JPH0148887B2 JPH0148887B2 JP56174988A JP17498881A JPH0148887B2 JP H0148887 B2 JPH0148887 B2 JP H0148887B2 JP 56174988 A JP56174988 A JP 56174988A JP 17498881 A JP17498881 A JP 17498881A JP H0148887 B2 JPH0148887 B2 JP H0148887B2
- Authority
- JP
- Japan
- Prior art keywords
- olefin
- oligomerizing
- halogenated
- reaction
- aliphatic carboxylic
- 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
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- 239000004711 α-olefin Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 8
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical group CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 7
- 230000003606 oligomerizing effect Effects 0.000 claims description 7
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000006384 oligomerization reaction Methods 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- -1 chloropropionic acid Chemical compound 0.000 description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- QQHRHLXGCZWTDK-UHFFFAOYSA-L butylaluminum(2+);dibromide Chemical compound [Br-].[Br-].CCCC[Al+2] QQHRHLXGCZWTDK-UHFFFAOYSA-L 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- SGPRELKOQPLBKJ-UHFFFAOYSA-L dichloro(cyclohexyl)alumane Chemical compound [Cl-].[Cl-].[Al+2]C1CCCCC1 SGPRELKOQPLBKJ-UHFFFAOYSA-L 0.000 description 1
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- NARCMUVKZHPJHP-UHFFFAOYSA-L ethyl(diiodo)alumane Chemical compound [I-].[I-].CC[Al+2] NARCMUVKZHPJHP-UHFFFAOYSA-L 0.000 description 1
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はα―オレフインのオリゴマー化方法に
関するものである。
従来から、アルミニウムトリクロライドまたは
エチルアルミニウムジクロライドなどのハロゲン
化金属類を触媒としてα―オレフインを反応させ
オリゴマーを得る方法が知られている。しかる
に、これらハロゲン化金属類を触媒としてオリゴ
マー化を行なうと、かなりの高分子量の生成物、
例えば原料α―オレフインの五量体以上の生成物
が多量に副生する。
一方、α―オレフインのオリゴマー、すなわち
高級オレフインは、洗剤や可塑剤などの原料とし
て有用である。本発明者らは、α―オレフインの
オリゴマー化方法を研究した結果、ハロゲン化金
属類とプロトン酸であるハロゲン化脂肪族カルボ
ン酸との錯体を触媒としてα―オレフインを反応
させることにより、オリゴマーが収率よく生成す
ることを見出し、本発明を完成させたものであ
る。
すなわち、本発明は一般式AlX3（Ｘはハロゲン
原子）で示されるアルミニウムトリハライドおよ
び／または一般式AlRX2（Ｒはアルキル基、Ｘは
ハロゲン原子）で示される有機アルミニウムジハ
ライドと、ハロゲン化脂肪族カルボン酸とからな
る触媒の存在下に、無極性溶媒中でα―オレフイ
ンを反応させることを特徴とするα―オレフイン
のオリゴマー化方法を要旨とするものである。
本発明で使用する前記アルミニウムトリハライ
ドとしては、アルミニウムトリクロライド、アル
ミニウムトリブロマイドなどがある。また、前記
有機アルミニウムジハライドとしては、例えば、
メチルアルミニウムジクロライド、エチルアルミ
ニウムジクロライド、エチルアルミニウムジブロ
マイド、エチルアルミニウムジアイオダイド、プ
ロピルアルミニウムジクロライド、ブチルアルミ
ニウムジブロマイド、シクロヘキシルアルミニウ
ムジクロライドなどであつて、特に好ましくはエ
チルアルミニウムジクロライドである。なお、前
記アルミニウムトリハライドと前記有機アルミニ
ウムジハライドを適宜混合して使用することもで
きる。
次に本発明では、触媒として更にハロゲン化脂
肪族カルボン酸を添加する。このハロゲン化脂肪
族カルボン酸としては、たとえば、クロル酢酸、
ブロム酢酸などのハロゲン化酢酸、クロルプロピ
オン酸などのハロゲン化プロピオン酸などであ
り、特に好ましくはジクロル酢酸、トリクロル酢
酸などのポリハロゲン化脂肪族カルボン酸であ
る。
本発明の方法において、後者の触媒構成成分で
あるハロゲン化脂肪族カルボン酸は、アルミニウ
ムトリハライドおよび／または有機アルミニウム
ジハライドのアルミニウム原子１モルに対し、
0.05〜10モル好ましくは0.1モル〜２モル添加す
る。また、触媒の両成分を混合した後熟成操作を
することが好ましく、熟成温度は50℃〜70℃、熟
成時間は１時間〜５時間が適当である。
本発明のオリゴマー化方法では無極性溶媒を使
用する。この無極性溶媒としては、ｎ―ヘキサ
ン、ｎ―ヘプタン等の飽和脂肪族炭化水素、シク
ロヘキサン等の脂環式炭化水素および四塩化炭素
等のハロゲン化炭化水素などがある。
反応温度は０℃〜80℃であり、より好ましくは
50℃〜80℃である。また反応圧力は特に高圧にす
る必要はなく、反応相を液相に保つために必要な
圧力であれば良い。
本発明の触媒系によりオリゴマー化し得るα―
オレフインの炭素数は限定しないが、例えば、ブ
テン―１、ヘキセン―１、オクテン―１などの炭
素数４以上のα―オレフインが好ましい。但し、
炭素数が15を越えると反応性が低くなるので好ま
しくない。
また反応後、触媒を失活し、蒸留など適宜の操
作によつて未反応のα―オレフインを分離するこ
とによりオリゴマーが得られる。得られるオリゴ
マーは主として二量体から四量体であるが、触媒
の種類、量比、モノマー濃度、触媒濃度、反応温
度を適宜に選択することにより、生成オリゴマー
の組成比を変えることができる。
次に実施例により本発明を詳述する。
実施例 １
ｎ―ヘキサン1000mlに、エチルアルミニウムジ
クロライド30ミリモル、トリクロル酢酸30ミリモ
ルおよびヘキセン―１を１モル加え、乾燥窒素気
流下において反応温度70℃で24時間反応させた。
反応終了後、高速液体クロマトグラフイーおよび
ガスクロマトグラフイーで反応生成物を分析し
た。その結果を表１に示す。
実施例 ２〜３
実施例２では、実施例１において、トリクロル
酢酸の代りにジクロル酢酸を用いたほかは同様に
反応させた。
また実施例３では同じく実施例１において、エ
チルアルミニウムジクロライドの代りにアルミニ
ウムトリクロライドを用いたほかは同様にして反
応させた。
実施例 ４
α―オレフインとして、ヘキセン―１の代りに
オクテン―１を反応させた以外は実施例１と同様
にして反応させた。
比較例 １〜２
比較例１では触媒として、エチルアルミニウム
ジクロライドのみを、また比較例２ではアルミニ
ウムトリクロライドのみを用いて実施例１と同様
にして反応させた。
比較例 ３
溶媒として、ｎ―ヘキサンの代りに１，２―ジ
クロルエタンを用いた以外は実施例１と同様にし
て反応させた。
比較例 ４
実施例１において、トリクロル酢酸の代りに酢
酸を使用したほかは、同様にして反応させたが、
ヘキセン―１は殆んど反応しなかつた。
結果はいずれも次表に示すが、本発明の方法に
よれば、二ないし四量体程度のオリゴマーが温和
な条件により高収率で合成されることがわかる。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for oligomerizing α-olefins. Conventionally, a method has been known in which an oligomer is obtained by reacting an α-olefin using a metal halide such as aluminum trichloride or ethylaluminum dichloride as a catalyst. However, when oligomerization is carried out using these metal halides as catalysts, products with considerably high molecular weight,
For example, a large amount of pentamer or higher products of the raw material α-olefin are produced as by-products. On the other hand, α-olefin oligomers, that is, higher olefins, are useful as raw materials for detergents, plasticizers, and the like. As a result of research into a method for oligomerizing α-olefin, the present inventors found that oligomers can be formed by reacting α-olefin with a complex of halogenated metals and a halogenated aliphatic carboxylic acid, which is a protonic acid. The present invention was completed by discovering that it can be produced in good yield. That is, the present invention relates to an aluminum trihalide represented by the general formula AlX 3 (X is a halogen atom) and/or an organoaluminum dihalide represented by the general formula AlRX 2 (R is an alkyl group, X is a halogen atom), and a halogenated The gist of this invention is a method for oligomerizing α-olefin, which is characterized by reacting α-olefin in a nonpolar solvent in the presence of a catalyst consisting of an aliphatic carboxylic acid. Examples of the aluminum trihalide used in the present invention include aluminum trichloride and aluminum tribromide. Further, as the organoaluminum dihalide, for example,
Examples include methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum diiodide, propylaluminum dichloride, butylaluminum dibromide, and cyclohexylaluminum dichloride, with ethylaluminum dichloride being particularly preferred. Note that the aluminum trihalide and the organoaluminum dihalide may be used in an appropriate mixture. Next, in the present invention, a halogenated aliphatic carboxylic acid is further added as a catalyst. Examples of the halogenated aliphatic carboxylic acid include chloroacetic acid,
Examples include halogenated acetic acids such as bromoacetic acid, halogenated propionic acids such as chloropropionic acid, and particularly preferred are polyhalogenated aliphatic carboxylic acids such as dichloroacetic acid and trichloroacetic acid. In the method of the present invention, the halogenated aliphatic carboxylic acid, which is the latter catalyst component, is
It is added in an amount of 0.05 to 10 mol, preferably 0.1 mol to 2 mol. Further, it is preferable to carry out a ripening operation after mixing both components of the catalyst, and the ripening temperature is suitably 50°C to 70°C, and the ripening time is suitably 1 hour to 5 hours. The oligomerization method of the present invention uses non-polar solvents. Examples of the nonpolar solvent include saturated aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as carbon tetrachloride. The reaction temperature is 0°C to 80°C, more preferably
The temperature is between 50°C and 80°C. Further, the reaction pressure does not need to be particularly high, as long as it is a pressure necessary to maintain the reaction phase in a liquid phase. α- which can be oligomerized by the catalyst system of the present invention
Although the number of carbon atoms in the olefin is not limited, α-olefins having 4 or more carbon atoms, such as 1-butene, 1-hexene, and 1-octene, are preferred. however,
If the number of carbon atoms exceeds 15, the reactivity decreases, which is not preferable. Further, after the reaction, an oligomer can be obtained by deactivating the catalyst and separating unreacted α-olefin by an appropriate operation such as distillation. The oligomers obtained are mainly dimers to tetramers, but the composition ratio of the oligomers produced can be changed by appropriately selecting the type of catalyst, quantitative ratio, monomer concentration, catalyst concentration, and reaction temperature. Next, the present invention will be explained in detail with reference to Examples. Example 1 30 mmol of ethylaluminum dichloride, 30 mmol of trichloroacetic acid and 1 mole of hexene-1 were added to 1000 ml of n-hexane, and the mixture was reacted for 24 hours at a reaction temperature of 70° C. under a stream of dry nitrogen.
After the reaction was completed, the reaction product was analyzed by high performance liquid chromatography and gas chromatography. The results are shown in Table 1. Examples 2 to 3 In Example 2, the reaction was carried out in the same manner as in Example 1 except that dichloroacetic acid was used instead of trichloroacetic acid. In Example 3, the reaction was carried out in the same manner as in Example 1 except that aluminum trichloride was used instead of ethylaluminum dichloride. Example 4 A reaction was carried out in the same manner as in Example 1 except that octene-1 was used instead of hexene-1 as the α-olefin. Comparative Examples 1 and 2 In Comparative Example 1, only ethylaluminum dichloride was used as a catalyst, and in Comparative Example 2, only aluminum trichloride was used as a catalyst, and the reaction was carried out in the same manner as in Example 1. Comparative Example 3 A reaction was carried out in the same manner as in Example 1 except that 1,2-dichloroethane was used as the solvent instead of n-hexane. Comparative Example 4 The reaction was carried out in the same manner as in Example 1, except that acetic acid was used instead of trichloroacetic acid.
Hexene-1 hardly reacted. The results are shown in the following table, and it can be seen that according to the method of the present invention, oligomers in the order of dimers and tetramers can be synthesized in high yield under mild conditions. 【table】
Claims (1)
されるアルミニウムトリハライドおよび／または
一般式AlRX2（但し、Ｒはアルキル基、Ｘはハロ
ゲン原子）で示される有機アルミニウムジハライ
ドと、ハロゲン化脂肪族カルボン酸との錯体から
なる触媒の存在下に、無極性溶媒中でα―オレフ
インを反応させることを特徴とするα―オレフイ
ンのオリゴマー化方法。 ２ 前記有機アルミニウムジハライドがエチルア
ルミニウムジクロライドである特許請求の範囲第
１項記載のα―オレフインのオリゴマー化方法。 ３ 前記ハロゲン化脂肪族カルボン酸がハロゲン
化酢酸である特許請求の範囲第１項または第２項
記載のα―オレフインのオリゴマー化方法。 ４ 前記無極性溶媒が飽和脂肪族炭化水素である
特許請求の範囲第１項ないし第３項いずれかに記
載のα―オレフインのオリゴマー化方法。 ５ 前記α―オレフインの炭素数が４以上である
特許請求の範囲第１項ないし第４項いずれかに記
載のα―オレフインのオリゴマー化方法。[Claims] 1. Aluminum trihalide represented by the general formula AlX 3 (wherein, X is a halogen atom) and/or organoaluminum represented by the general formula AlRX 2 (wherein, R is an alkyl group and X is a halogen atom) A method for oligomerizing α-olefin, which comprises reacting α-olefin in a nonpolar solvent in the presence of a catalyst consisting of a complex of a dihalide and a halogenated aliphatic carboxylic acid. 2. The method for oligomerizing α-olefin according to claim 1, wherein the organoaluminum dihalide is ethylaluminum dichloride. 3. The α-olefin oligomerization method according to claim 1 or 2, wherein the halogenated aliphatic carboxylic acid is halogenated acetic acid. 4. The method for oligomerizing α-olefin according to any one of claims 1 to 3, wherein the nonpolar solvent is a saturated aliphatic hydrocarbon. 5. The method for oligomerizing α-olefin according to any one of claims 1 to 4, wherein the α-olefin has 4 or more carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56174988A JPS5877827A (en) | 1981-10-31 | 1981-10-31 | Oligomerization of alpha-olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56174988A JPS5877827A (en) | 1981-10-31 | 1981-10-31 | Oligomerization of alpha-olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5877827A JPS5877827A (en) | 1983-05-11 |
| JPH0148887B2 true JPH0148887B2 (en) | 1989-10-20 |
Family
ID=15988247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56174988A Granted JPS5877827A (en) | 1981-10-31 | 1981-10-31 | Oligomerization of alpha-olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5877827A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938247A (en) * | 1972-08-15 | 1974-04-09 |
-
1981
- 1981-10-31 JP JP56174988A patent/JPS5877827A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938247A (en) * | 1972-08-15 | 1974-04-09 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5877827A (en) | 1983-05-11 |
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