JPS6365059B2 - - Google Patents
Info
- Publication number
- JPS6365059B2 JPS6365059B2 JP56123255A JP12325581A JPS6365059B2 JP S6365059 B2 JPS6365059 B2 JP S6365059B2 JP 56123255 A JP56123255 A JP 56123255A JP 12325581 A JP12325581 A JP 12325581A JP S6365059 B2 JPS6365059 B2 JP S6365059B2
- Authority
- JP
- Japan
- Prior art keywords
- htp
- trans
- cis
- hydroxide
- salt
- 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
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- -1 alkali metal salt Chemical class 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- JBJSVEVEEGOEBZ-SCZZXKLOSA-N coenzyme B Chemical compound OP(=O)(O)O[C@H](C)[C@@H](C(O)=O)NC(=O)CCCCCCS JBJSVEVEEGOEBZ-SCZZXKLOSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 238000006317 isomerization reaction Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004689 octahydrates Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- Catalysts (AREA)
- 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】
本発明はシスまたはシス、トランスの混合した
ヘキサヒドロテレフタル酸（以下HTPと略称す
る）のシス体をトランス体へ異性化するトランス
−HTPの製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing trans-HTP, which isomerizes the cis form of cis or mixed cis and trans hexahydroterephthalic acid (hereinafter abbreviated as HTP) to the trans form.
シス−HTPの異性化によるトランス−HTPの
製造法としては、(1)シス、トランス混合HTPを
当量の濃塩酸と密閉容器中で加熱する方法
（Helv.Chim.Acta.、21 141（1938））、(2)シス、
またはシス、トランス混合HTPを大気中で加熱
溶融する方法（特公昭39−27244）、(3)シス−
HTPを水溶液中で加熱する方法（特開昭49−
82648）更に(4)シス、トランス混合HTPのアルカ
リ金属塩またはアルカリ土類金属塩を水溶液中で
加熱する方法（特公昭50−10581）が知られてい
る。しかし、これらの方法はいずれも工業的見地
から次の様な欠点を有している。 As a method for producing trans-HTP by isomerizing cis-HTP, (1) a method of heating a mixture of cis and trans HTP with an equivalent amount of concentrated hydrochloric acid in a closed container (Helv.Chim.Acta., 21 141 (1938)) ), (2) cis,
Alternatively, a method of heating and melting cis and trans mixed HTP in the atmosphere (Japanese Patent Publication No. 39-27244), (3) cis-
Method of heating HTP in an aqueous solution
82648) Furthermore, a method (4) of heating an alkali metal salt or alkaline earth metal salt of cis and trans mixed HTP in an aqueous solution (Japanese Patent Publication No. 10581/1982) is known. However, all of these methods have the following drawbacks from an industrial standpoint.
即ち、(1)の酸異性化法は高温下に多量の強酸を
使用する為に装置面、操作面で大きな困難を有
す。(2)の溶融異性化法は溶融物が冷却過程でコン
クリート状に凝固するので後処理が非常に困難で
あると共に、昇華性を有するHTPを310℃という
高温で異性化するので大気中で大量処理すること
は事実上不可能である。(3)の熱水異性化法および
(4)のアルカリ塩熱水異性化法は共に250℃という
高温反応にも拘らずトランス体比率は高々70％前
後にすぎず、生産性が極めて低い。 That is, the acid isomerization method (1) uses a large amount of strong acid at high temperatures, and therefore has great difficulties in terms of equipment and operation. In the melt isomerization method (2), the molten material solidifies into a concrete-like form during the cooling process, making post-treatment extremely difficult.In addition, HTP, which has sublimation properties, isomerized at a high temperature of 310°C, so a large amount of it is exposed to the atmosphere. It is virtually impossible to process. (3) Hydrothermal isomerization method and
In the alkali salt hydrothermal isomerization method (4), the trans isomer ratio is only around 70% at most, despite the high temperature reaction of 250°C, and the productivity is extremely low.
本発明者らは、従来法のかかる欠点を克服すべ
く鋭意研究を重ねた結果、本発明に到達したもの
である。 The present inventors have arrived at the present invention as a result of extensive research to overcome these drawbacks of conventional methods.
即ち、本発明はシスまたはシス、トランスの混
合したHTPのアルカリ金属塩またはアルカリ土
類金属塩を水酸化アルカリ金属または水酸化アル
カリ土類金属の存在下固相で加熱してトランス−
HTPを製造する方法である。 That is, the present invention heats an alkali metal salt or alkaline earth metal salt of cis or a mixture of cis and trans HTP in a solid phase in the presence of an alkali metal hydroxide or an alkaline earth metal hydroxide to convert trans-
This is a method for producing HTP.
本発明方法において用いるHTPの塩および水
酸化物におけるアルカリ金属、アルカリ土類金属
としては、ナトリウム、カリウム、カルシウム、
バリウム等を挙げることができる。 The alkali metals and alkaline earth metals in the HTP salts and hydroxides used in the method of the present invention include sodium, potassium, calcium,
Examples include barium.
水酸化アルカリ金属または水酸化アルカリ土類
金属は、HTPの塩に対して多く用いる程異性化
反応は速く進むので、0.5倍当量位まで加えても
よいが、多い場合は後処理の点で不利であり、通
常は0.1倍当量程度が適当であり、それ以下でも
よいがあまり少ないと異性化率が低下する。 The more alkali metal hydroxide or alkaline earth metal hydroxide is used than the HTP salt, the faster the isomerization reaction progresses, so it may be added up to about 0.5 times the equivalent, but if it is in a large amount, it will be disadvantageous in terms of post-treatment. Usually, about 0.1 equivalent is appropriate, and it may be less than that, but if it is too small, the isomerization rate will decrease.
本発明を実施するには、予め製したHTPの塩
に水酸化物を加えて加熱してもよいが、遊離の
HTPに当量よりやや過剰（例えば1.1倍当量）の
水酸化物を加えて処理し、HTPの塩形成と水酸
化物の添加を同時に行なつてもよい。また、
HTPの合成法として通常行なわれているテレフ
タル酸のアルカリ金属塩またはアルカリ土類金属
塩の接触還元において、同様に水酸化物を過剰に
用いて塩を形成させたテレフタル酸塩と水酸化物
の混合物を接触還元に付し、反応物から触媒を除
き、溶媒を留去したものをそのまま用いることも
可能であり、原料源として経済的にも、また操作
面でも有利である。 To carry out the present invention, hydroxide may be added to pre-prepared HTP salt and heated;
HTP may be treated by adding a slightly excess amount of hydroxide (for example, 1.1 times the equivalent) to form a salt of HTP and add the hydroxide at the same time. Also,
In the catalytic reduction of alkali metal salts or alkaline earth metal salts of terephthalic acid, which is commonly performed as a synthesis method for HTP, terephthalate and hydroxide are similarly used in excess of hydroxide to form a salt. It is also possible to subject the mixture to catalytic reduction, remove the catalyst from the reactant, and distill off the solvent, and then use the mixture as it is, which is advantageous both economically and in terms of operation as a raw material source.
異性化に必要な温度、時間は塩の種類およびア
ルカリ量によつて異なるが、例えば、水酸化ナト
リウムをHTPの1.1倍当量用いて得たHTPのナ
トリウム塩と水酸化ナトリウムの混合物の場合、
130℃で加熱することにより異性化は進行し、170
℃、２時間の加熱によりトランス体比率は95％以
上に達する。350℃程度で反応を行なうことも可
能であるが、工業的に得策ではなく、170〜250℃
の範囲が好ましい。 The temperature and time required for isomerization vary depending on the type of salt and the amount of alkali, but for example, in the case of a mixture of sodium salt of HTP and sodium hydroxide obtained using 1.1 times the equivalent of HTP,
Isomerization progresses by heating at 130℃, and 170
After heating at ℃ for 2 hours, the trans isomer ratio reaches 95% or more. Although it is possible to carry out the reaction at around 350℃, it is not industrially advisable to carry out the reaction at a temperature of 170 to 250℃.
A range of is preferred.
固相異性化反応は開放系でも密閉系でも進行す
るが、後者の方がトランス体比率が若干向上し、
最適条件下ではトランス体比率は98％程度に達す
る。 The solid-phase isomerization reaction proceeds in both open and closed systems, but the latter has a slightly higher trans isomer ratio,
Under optimal conditions, the trans isomer ratio reaches approximately 98%.
反応生成物はHTPの塩の状態なので水に容易
に溶解し、この水溶液を単に鉱酸で酸性とするこ
とにより高純度のトランス−HTPが結晶として
得られる。 Since the reaction product is in the form of a salt of HTP, it is easily dissolved in water, and by simply acidifying this aqueous solution with a mineral acid, highly pure trans-HTP can be obtained as crystals.
本発明方法は、従来知られている異性化法に比
し、低温、短時間の加熱によりシス−HTPの高
収率でトランス−HTPに異性化でき、異性化後
の反応生成物の処理も容易である。 Compared to conventional isomerization methods, the method of the present invention can isomerize cis-HTP to trans-HTP with a high yield by heating at a low temperature and in a short time, and the treatment of the reaction product after isomerization is also easy. It's easy.
次に本発明を実施例によつて説明する。 Next, the present invention will be explained with reference to examples.
実施例 １
シス−ヘキサヒドロテレフタル酸3.44ｇ、水酸
化ナトリウム1.76ｇおよび水50mlを混合し、減圧
下に濃縮乾固した後封管中200℃で１時間加熱し
た。冷後反応物を水に溶解、濃塩酸で酸性とし析
出したトランス−ヘキサヒドロテレフタル酸3.27
ｇを濾取した。（収率95％）
この物をガスクロマトグラフイー分析したとこ
ろトランス体の比率は99.5％以上であつた。Example 1 3.44 g of cis-hexahydroterephthalic acid, 1.76 g of sodium hydroxide and 50 ml of water were mixed, concentrated to dryness under reduced pressure, and then heated at 200° C. for 1 hour in a sealed tube. After cooling, the reaction product was dissolved in water and acidified with concentrated hydrochloric acid to precipitate trans-hexahydroterephthalic acid 3.27
g was collected by filtration. (Yield 95%) Gas chromatography analysis of this product revealed that the ratio of trans isomer was 99.5% or more.
実施例 ２
シス−ヘキサヒドロテレフタル酸3.44ｇ、水酸
化カリウム2.46ｇおよび水50mlを混合し、減圧下
に濃縮乾固した後大気中200℃で１時間加熱した。
冷後反応物を水に溶解、濃塩酸で酸性とし析出し
たトランス−ヘキサヒドロテレフタル酸3.20ｇを
濾取した。（収率93％）
この物をガスクロマトグラフイー分析したとこ
ろトランス体の比率は99.5％以上であつた。Example 2 3.44 g of cis-hexahydroterephthalic acid, 2.46 g of potassium hydroxide, and 50 ml of water were mixed, concentrated to dryness under reduced pressure, and then heated in the air at 200° C. for 1 hour.
After cooling, the reaction product was dissolved in water and acidified with concentrated hydrochloric acid, and 3.20 g of precipitated trans-hexahydroterephthalic acid was collected by filtration. (Yield 93%) Gas chromatography analysis of this product revealed that the ratio of trans isomer was 99.5% or more.
実施例 ３
シス−ヘキサヒドロテレフタル酸3.44ｇ、水酸
化バリウム（８水塩）9.48ｇおよび水50mlを混合
し、減圧下に濃縮乾固した後封管中250℃で６時
間加熱した。反応物中のトランス体の比率は85％
であつた。Example 3 3.44 g of cis-hexahydroterephthalic acid, 9.48 g of barium hydroxide (octahydrate), and 50 ml of water were mixed, concentrated to dryness under reduced pressure, and then heated at 250° C. for 6 hours in a sealed tube. The ratio of trans isomer in the reactant is 85%
It was hot.
実施例 ４
テレフタル酸3.32ｇ、展開ラネーニツケル１
ｇ、水酸化ナトリウム1.92ｇ、水40mlの混合物を
100mlオートクレーブに入れ、初期圧100Kg／cm2、
温度160℃で２時間加熱撹拌した後ニツケルを濾
別、濾液を減圧下に濃縮乾固した。Example 4 Terephthalic acid 3.32g, expanded Raney nickel 1
g, a mixture of 1.92 g of sodium hydroxide and 40 ml of water.
Place in a 100ml autoclave, initial pressure 100Kg/cm 2 ,
After heating and stirring at a temperature of 160°C for 2 hours, the nickel was filtered off, and the filtrate was concentrated to dryness under reduced pressure.
残渣を封管中170℃で２時間加熱し、冷後反応
物を水に溶解、濃塩酸で酸性とし析出したトラン
ス−ヘキサヒドロテレフタル酸3.24ｇを濾取し
た。（収率94％）
この物をガスクロマトグラフイー分析したとこ
ろトランス体の比率は99.5％以上であつた。 The residue was heated in a sealed tube at 170° C. for 2 hours, and after cooling, the reaction product was dissolved in water and acidified with concentrated hydrochloric acid, and 3.24 g of precipitated trans-hexahydroterephthalic acid was collected by filtration. (Yield 94%) Gas chromatography analysis of this product revealed that the ratio of trans isomer was 99.5% or more.
Claims (1)
テレフタル酸のアルカリ金属塩またはアルカリ土
類金属塩を水酸化アルカリ金属または水酸化アル
カリ土類金属の存在下固相で加熱することを特徴
とするトランス−ヘキサヒドロテレフタル酸の製
造法。1 Trans-hexahydro which is characterized by heating an alkali metal salt or alkaline earth metal salt of cis or cis or trans mixed hexahydroterephthalic acid in a solid phase in the presence of an alkali metal hydroxide or an alkaline earth metal hydroxide. Method for producing terephthalic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56123255A JPS5824540A (en) | 1981-08-06 | 1981-08-06 | Preparation of trans-hexyhydroterephthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56123255A JPS5824540A (en) | 1981-08-06 | 1981-08-06 | Preparation of trans-hexyhydroterephthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5824540A JPS5824540A (en) | 1983-02-14 |
| JPS6365059B2 true JPS6365059B2 (en) | 1988-12-14 |
Family
ID=14856039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56123255A Granted JPS5824540A (en) | 1981-08-06 | 1981-08-06 | Preparation of trans-hexyhydroterephthalic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5824540A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0757792A (en) * | 1993-08-17 | 1995-03-03 | Nec Corp | Pressure-connection type connector |
| WO2003035597A1 (en) | 2001-10-26 | 2003-05-01 | Mitsubishi Chemical Corporation | Method for producing trans-1,4-cyclohexane dicarboxylic acid |
| JP4513256B2 (en) * | 2001-12-04 | 2010-07-28 | 三菱化学株式会社 | Process for producing trans-1,4-cyclohexanedicarboxylic acid |
| JP5003231B2 (en) * | 2007-03-23 | 2012-08-15 | Ｄｉｃ株式会社 | Process for producing trans, trans-4,4'-bicyclohexyldicarboxylic acid |
| JP5315496B2 (en) * | 2008-01-18 | 2013-10-16 | 和光純薬工業株式会社 | Novel (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride and use thereof |
| CN103539660A (en) * | 2013-09-25 | 2014-01-29 | 江苏康恒化工有限公司 | Method of preparing trans-1,4-cyclohexane dicarboxylic acid from hybrid 1,4-cyclohexane dicarboxylic acid |
| KR102336273B1 (en) | 2018-06-15 | 2021-12-06 | 한화솔루션 주식회사 | Isomerization method of cyclohexane dicarboxylic acid |
| KR102446307B1 (en) | 2018-12-27 | 2022-09-21 | 한화솔루션 주식회사 | Method for preparation 1, 4-cyclohexanedimethanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS435953Y1 (en) * | 1964-06-01 | 1968-03-15 | ||
| JPS5610233A (en) * | 1979-07-07 | 1981-02-02 | Horiba Ltd | Continuous photometric analyzer |
-
1981
- 1981-08-06 JP JP56123255A patent/JPS5824540A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS435953Y1 (en) * | 1964-06-01 | 1968-03-15 | ||
| JPS5610233A (en) * | 1979-07-07 | 1981-02-02 | Horiba Ltd | Continuous photometric analyzer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5824540A (en) | 1983-02-14 |
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