JP6512970B2 - Purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester - Google Patents
Purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester Download PDFInfo
- Publication number
- JP6512970B2 JP6512970B2 JP2015135825A JP2015135825A JP6512970B2 JP 6512970 B2 JP6512970 B2 JP 6512970B2 JP 2015135825 A JP2015135825 A JP 2015135825A JP 2015135825 A JP2015135825 A JP 2015135825A JP 6512970 B2 JP6512970 B2 JP 6512970B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxy
- naphthoic acid
- glycidyl ether
- ether ester
- acid glycidyl
- 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.)
- Active
Links
- -1 6-hydroxy-2-naphthoic acid glycidyl ether ester Chemical class 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 24
- 238000000746 purification Methods 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000012535 impurity Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 150000004045 organic chlorine compounds Chemical class 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000007514 bases Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- TVOFMGLSTGREAI-OIXVIMQBSA-O C/C=C(\C(CCOCC(C1)C1[OH2+])C=C1)/C=C1C(OCC(CO)O)=O Chemical compound C/C=C(\C(CCOCC(C1)C1[OH2+])C=C1)/C=C1C(OCC(CO)O)=O TVOFMGLSTGREAI-OIXVIMQBSA-O 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- FWYSSOIRLVHQNC-UHFFFAOYSA-M benzyl(trimethyl)azanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)CC1=CC=CC=C1 FWYSSOIRLVHQNC-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの精製方法に関する。 The present invention relates to a method of purifying 6-hydroxy-2-naphthoic acid glycidyl ether ester.
ビスフェノールＡのジグリシジルエーテルに代表されるエポキシ化合物は、エポキシ樹脂の原料として用いられており、また、様々な樹脂の劣化防止や耐加水分解性向上のための添加剤としての用途が提案されている。 Epoxy compounds represented by diglycidyl ether of bisphenol A are used as raw materials for epoxy resins, and their use as additives for preventing deterioration of various resins and improving hydrolysis resistance has been proposed. There is.
例えば、特許文献１には、芳香族ポリエステル樹脂に特定のエポキシ化合物を配合することにより、熱劣化特性および耐加水分解性に優れた難燃性芳香族ポリエステル樹脂組成物が提案されている。 For example, Patent Document 1 proposes a flame-retardant aromatic polyester resin composition which is excellent in thermal deterioration characteristics and hydrolysis resistance by blending a specific epoxy compound with an aromatic polyester resin.
このようなエポキシ化合物の製造方法としては、触媒として四級アンモニウム塩および／または塩基性化合物の存在下、オキシナフトエ酸とエピハロヒドリンを反応せしめる方法が提案されている（特許文献２）。 As a method for producing such an epoxy compound, a method of reacting oxynaphthoic acid and epihalohydrin in the presence of a quaternary ammonium salt and / or a basic compound as a catalyst has been proposed (Patent Document 2).
しかしながら、このような方法で得られたエポキシ化合物は、有機塩素化合物や重合物等の不純物が残存した低純度のものであった。このエポキシ化合物は、エポキシ当量が１５０に近いほど高純度品であり、このような不純物が残存するエポキシ化合物のエポキシ当量は１６０〜１７０程度である。 However, the epoxy compound obtained by such a method has a low purity in which an impurity such as an organic chlorine compound or a polymer remains. The epoxy compound is a high purity product as the epoxy equivalent approaches 150, and the epoxy equivalent of the epoxy compound in which such an impurity remains is about 160 to 170.
不純物を含むエポキシ化合物を例えば電子部品材料として用いた場合、有機塩素化合物の塩素が電気絶縁性の低下やリード線の腐食等を起こすことが知られている。したがって、有機塩素化合物などの不純物の含有量の少ないエポキシ化合物が求められており、そのためには不純物を除去する精製操作を行う必要があった。 When an epoxy compound containing impurities is used as, for example, an electronic component material, it is known that chlorine of an organic chlorine compound causes a decrease in electrical insulation, corrosion of lead wires, and the like. Therefore, an epoxy compound having a low content of impurities such as organic chlorine compounds is required, and for that purpose, it is necessary to perform a purification operation to remove the impurities.
エポキシ化合物の精製方法としては、通常、不純物である有機塩素化合物を塩基により加水分解した後、水洗等によって除去する方法が知られているが、この方法では目的物のエポキシ基が分解する等の問題点があった。 As a method of purifying an epoxy compound, a method of hydrolyzing an organic chlorine compound which is an impurity with a base and then removing it by washing with water or the like is generally known. There was a problem.
また、金属アミド化合物により有機塩素化合物を除去する方法（特許文献３）も提案されているが、除去操作に長時間要することに加え、中和や水洗等の工程が必要であるなどの問題点があった。 In addition, a method of removing organic chlorine compounds by metal amide compounds (Patent Document 3) has also been proposed, but in addition to the fact that the removal operation takes a long time, steps such as neutralization and water washing are required. was there.
本発明の目的は、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物から不純物を除去し、高純度の６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを高収率で得られる精製方法を提供することにある。 An object of the present invention is a purification method for removing impurities from a crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester to obtain high purity 6-hydroxy-2-naphthoic acid glycidyl ether ester in high yield To provide.
本発明者らは、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの精製方法について鋭意検討した結果、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物をメタノール等のアルコールに溶解させた後、晶析させることによって、有機塩素化合物や重合物等の不純物を容易に除去し、高純度の６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies on the purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester, the present inventors dissolved a crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester in an alcohol such as methanol After that, by crystallization, impurities such as organic chlorine compounds and polymers are easily removed, and it is found that high purity 6-hydroxy-2-naphthoic acid glycidyl ether ester is obtained, and the present invention is completed. It reached.
すなわち本発明は式（１）で表される６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを含む粗組成物をアルコールに溶解させる工程、および得られた溶液を晶析させる工程を含む、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの精製方法を提供する。
本発明によれば、有機塩素化合物や重合物等の不純物を含む６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物をメタノール等のアルコールに溶解させ、得られた溶液を晶析することにより効率よく不純物を除去し、高純度の６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを得ることができる。 According to the present invention, a crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester containing impurities such as organic chlorine compounds and polymers is dissolved in an alcohol such as methanol, and the resulting solution is crystallized. Impurities can be removed more efficiently, and high purity 6-hydroxy-2-naphthoic acid glycidyl ether ester can be obtained.
本発明において６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを含む粗組成物とは、目的物である式（１）で表される６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステル以外に、式（２）で表される有機塩素化合物や式（３）で表される重合物を含むものを意味する。
本発明において、原料である６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物（以下、粗組成物ともいう）は、上述の特許文献２に記載の触媒として四級アンモニウム塩および／または塩基性化合物の存在下、オキシナフトエ酸とエピハロヒドリンを反応せしめる方法によって得られるものを用いてもよく、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを含む市販の試薬等を用いてもよい。 In the present invention, a crude composition (hereinafter, also referred to as a crude composition) of 6-hydroxy-2-naphthoic acid glycidyl ether ester as a raw material is a quaternary ammonium salt and / or a catalyst as described in Patent Document 2 mentioned above. A product obtained by reacting oxynaphthoic acid and epihalohydrin in the presence of a basic compound may be used, or a commercially available reagent containing 6-hydroxy-2-naphthoic acid glycidyl ether ester may be used.
例えば６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物は、６−ヒドロキシ−２−ナフトエ酸とエピクロロヒドリンを四級アンモニウム塩および／または塩基性化合物の存在下で反応させることにより得ることができる。 For example, a crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester can be prepared by reacting 6-hydroxy-2-naphthoic acid with epichlorohydrin in the presence of a quaternary ammonium salt and / or a basic compound. You can get it.
エピクロロヒドリンは、６−ヒドロキシ−２−ナフトエ酸１モルに対し２倍モル以上、好ましくは４倍モル以上、より好ましくは７倍モル以上の量で用いることができる。未反応のエピクロロヒドリンは反応終了後に容易に回収され、再び反応に使用することができる。 Epichlorohydrin can be used in an amount of 2 moles or more, preferably 4 moles or more, more preferably 7 moles or more per mole of 6-hydroxy-2-naphthoic acid. Unreacted epichlorohydrin is easily recovered after completion of the reaction and can be used again for the reaction.
四級アンモニウム塩としては、例えばテトラメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド、ベンジルトリメチルアンモニウムクロリド、ベンジルトリメチルアンモニウムアセテート等のテトラアルキル型またはベンジルトリアルキル型のものが挙げられる。四級アンモニウム塩の使用量は、６−ヒドロキシ−２−ナフトエ酸１モルに対し好ましくは１〜７５モル％、より好ましくは３〜２０モル％である。 Examples of quaternary ammonium salts include those of tetraalkyl type or benzyl trialkyl type such as tetramethyl ammonium chloride, tetraethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyl trimethyl ammonium acetate and the like. The amount of quaternary ammonium salt to be used is preferably 1 to 75 mol%, more preferably 3 to 20 mol%, per 1 mol of 6-hydroxy-2-naphthoic acid.
塩基性化合物としては、ナトリウム、カリウム等アルカリ金属および／またはその水酸化物あるいは炭酸塩等の弱酸塩が挙げられる。塩基性化合物の使用量は、６−ヒドロキシ−２−ナフトエ酸１モルに対し１当量以上、好ましくは１．２〜３．５当量、より好ましくは１．５〜３当量、特に好ましくは１．８〜２．２当量である。 Examples of the basic compound include alkali metals such as sodium and potassium and / or weak acid salts such as hydroxides or carbonates thereof. The amount of the basic compound used is at least 1 equivalent, preferably 1.2 to 3.5 equivalents, more preferably 1.5 to 3 equivalents, particularly preferably 1. per equivalent of 1-hydroxy-2-naphthoic acid. 8 to 2.2 equivalents.
反応温度は、通常３０〜１５０℃、好ましくは５０〜１３０℃、特に好ましくは６０〜１２０℃である。 The reaction temperature is generally 30 to 150 ° C., preferably 50 to 130 ° C., particularly preferably 60 to 120 ° C.
また、得られた反応混合物から未反応のエピクロロヒドリンを分離したのち、反応生成物をさらに塩基性化合物と反応させることもできる。この場合、塩基性化合物の量は、６−ヒドロキシ−２−ナフトエ酸に対し好ましくは当量以下、より好ましくは０．６当量以下、特に好ましくは０．２〜０．５当量である。 In addition, after the unreacted epichlorohydrin is separated from the obtained reaction mixture, the reaction product can be further reacted with a basic compound. In this case, the amount of the basic compound is preferably at most equivalent, more preferably at most 0.6 equivalent, particularly preferably 0.2 to 0.5 equivalent to 6-hydroxy-2-naphthoic acid.
本発明では、例えば６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物は、以下の通り行うことにより得ることができる。エピクロロヒドリンに６−ヒドロキシ−２−ナフトエ酸を添加し、加熱下に四級アンモニウム塩水溶液を滴下したのち、水酸化アルカリ水溶液を滴下して反応させる。次いで未反応のエピクロロヒドリンを減圧蒸留により回収し、残留物に疎水性有機溶媒、例えばトルエンを加え、析出した塩化アルカリを濾去する。ろ液を水洗した後、トルエン相に水酸化アルカリ水溶液を加えさらに反応させる。反応混合物に水を加え、過剰の水酸化アルカリおよび析出した塩化アルカリを洗浄除去する。その後、疎水性有機溶媒相から溶液を留去することにより、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物を得ることができる。 In the present invention, for example, a crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester can be obtained by performing as follows. After adding 6-hydroxy -2- naphthoic acid to epichlorohydrin and dripping quaternary ammonium salt aqueous solution under heating, alkali hydroxide aqueous solution is dripped and it is made to react. Unreacted epichlorohydrin is then recovered by distillation under reduced pressure, a hydrophobic organic solvent such as toluene is added to the residue, and the precipitated alkali chloride is filtered off. After the filtrate is washed with water, an aqueous solution of alkali hydroxide is added to the toluene phase to further react. Water is added to the reaction mixture and excess alkali hydroxide and precipitated alkali chloride are washed away. Thereafter, the solution is distilled away from the hydrophobic organic solvent phase to obtain a crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester.
本発明の精製方法は、まず溶解工程において６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物をアルコールに溶解させる。 The purification method of the present invention first dissolves the crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester in alcohol in the dissolution step.
溶融工程において使用されるアルコールは、メタノール、エタノール、１−プロパノールおよび２−プロパノールからなる群から選択される１種以上であるのが好ましく、これらの中でも入手容易性および収率に優れる点でメタノールが好ましい。 The alcohol used in the melting step is preferably at least one selected from the group consisting of methanol, ethanol, 1-propanol and 2-propanol, and among these, methanol is preferred in terms of excellent availability and yield. Is preferred.
アルコールの使用量は溶媒の種類によっても異なるが、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物に対して１〜１０倍重量部であるのが好ましく、３〜５倍重量部であるのがより好ましい。粗組成物に対するアルコールの量が１０倍重量部を上回る場合、得られる６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの収率が低下する傾向があり、１倍重量部を下回る場合、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物が溶解し難くなる傾向がある。 The amount of alcohol used varies depending on the type of solvent, but it is preferably 1 to 10 parts by weight, preferably 3 to 5 parts by weight, based on the crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester. It is more preferable that there be. If the amount of alcohol relative to the crude composition exceeds 10 parts by weight, the yield of the resulting 6-hydroxy-2-naphthoic acid glycidyl ether ester tends to decrease, and if less than 1 part by weight, 6-hydroxy There is a tendency that the crude composition of 2-naphthoic acid glycidyl ether ester becomes difficult to dissolve.
粗組成物をアルコールに溶解させる温度は、用いるアルコールの種類により異なるため特に限定されないが、好ましくは４０℃〜８０℃、より好ましくは５０℃〜７０℃、さらに好ましくは５５℃〜６５℃である。 The temperature at which the crude composition is dissolved in alcohol is not particularly limited because it varies depending on the type of alcohol used, but is preferably 40 ° C to 80 ° C, more preferably 50 ° C to 70 ° C, and still more preferably 55 ° C to 65 ° C. .
６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物が溶解した溶液は、次いで結晶析出工程に供される。 The solution in which the crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester is dissolved is then subjected to the crystal precipitation step.
晶析工程は、５〜３０℃、好ましくは５〜２５℃、より好ましくは５〜１０℃の温度下で攪拌しながら行われる。 The crystallization step is carried out with stirring at a temperature of 5 to 30 ° C, preferably 5 to 25 ° C, more preferably 5 to 10 ° C.
晶析温度が５℃を下回る場合、有機塩素化合物や重合物などの不純物が結晶中に取り込まれてしまい、高純度の結晶を得ることが困難になる。晶析温度が３０℃を上回る場合、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物の収量が減少する傾向がある。 When the crystallization temperature is less than 5 ° C., impurities such as organic chlorine compounds and polymers are incorporated into the crystals, making it difficult to obtain crystals of high purity. When the crystallization temperature is higher than 30 ° C., the yield of the crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester tends to decrease.
晶析工程によって析出した結晶は濾過等の常套手段により固液分離し、目的物である６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを回収する。固液分離に際し、適宜アルコールを注いで結晶を洗浄するのが好ましい。固液分離の際に用いるアルコールとしては、メタノール、エタノール、１−プロパノールおよび２−プロパノールからなる群から選択される１種以上が好ましく使用される。 The crystals precipitated in the crystallization step are subjected to solid-liquid separation by conventional means such as filtration to recover the target substance 6-hydroxy-2-naphthoic acid glycidyl ether ester. At the time of solid-liquid separation, it is preferable to wash the crystals by pouring an appropriate alcohol. As alcohol used in solid-liquid separation, one or more selected from the group consisting of methanol, ethanol, 1-propanol and 2-propanol is preferably used.
固液分離によって回収された結晶は、減圧下、５０℃以下の温度下で結晶状態のまま乾燥するか、あるいは５０℃以上に加熱して結晶を溶融させた後、溶媒を留去することによって、高純度の６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを得ることができる。 The crystals recovered by solid-liquid separation are dried in the crystalline state under reduced pressure at a temperature of 50 ° C. or lower, or are heated to 50 ° C. or more to melt the crystals, and then the solvent is distilled off. Thus, high purity 6-hydroxy-2-naphthoic acid glycidyl ether ester can be obtained.
このようにして得られた６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルは、エポキシ当量が１５０〜１５９、好ましくは１５０〜１５５であり、不純物が除去された高純度のものである。エポキシ当量が１５０〜１５９である本発明の６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルは、様々な樹脂の劣化防止や耐加水分解性向上のための添加剤として使用される。 The 6-hydroxy-2-naphthoic acid glycidyl ether ester thus obtained has an epoxy equivalent of 150 to 159, preferably 150 to 155, and is of high purity from which impurities are removed. The 6-hydroxy-2-naphthoic acid glycidyl ether ester of the present invention having an epoxy equivalent of 150 to 159 is used as an additive for preventing deterioration of various resins and improving hydrolysis resistance.
以下、実施例により本発明を詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
［エポキシ当量の測定］
ＪＩＳ Ｋ７２３６に準拠して、エポキシ当量を測定した。
[Measurement of epoxy equivalent]
The epoxy equivalent was measured in accordance with JIS K7236.
［含塩素量分析］
下記条件にて測定した
機器： 三菱化学アナリテック ＴＯＸ−２１００Ｈ
温度： ９００℃
使用ガス: 酸素、アルゴン
電解液: 一般用電解液及び高濃度電解液使用
Chlorine content analysis
Equipment measured under the following conditions: Mitsubishi Chemical Analytech TOX-2100H
Temperature: 900 ° C
Gases used: Oxygen, Argon Electrolyte: Use of General-use Electrolyte and High Concentration Electrolyte
参考例１
１Ｌの４口コルベンに６−ヒドロキシ−２−ナフトエ酸９５．０ｇとエピクロロヒドリン４６７ｇ加え、窒素気流下８０℃に昇温した。次いで、テトラメチルアンモニウムクロリドの５０％水溶液を８０℃で２時間かけて滴下し、同温度で１時間撹拌した。さらに、４８％水酸化ナトリウム水溶液８７．１ｇを８０℃で３時間かけて滴下し、同温度で３０分撹拌した後、エピクロロヒドリンを減圧蒸留により除去した。残渣にトルエン５６０ｇを加えて１０分撹拌した後、析出物を濾過した。ろ液を水２５０ｇで洗浄した後、４８％ＮａＯＨ水溶液１９ｇを加えて、１時間還流した。さらに水２５０ｇで洗浄した後、５％リン水溶液２５０ｇで洗浄し、再び水２５０ｇで洗浄した。トルエンを減圧蒸留によって除去し、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物１０５ｇを得た。得られた６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物のエポキシ当量は１６８および含塩素量は１．６８％であった。
Reference Example 1
95.0 g of 6-hydroxy-2-naphthoic acid and 467 g of epichlorohydrin were added to 1 L of 4-neck Kolben, and the temperature was raised to 80 ° C. under a nitrogen stream. Then, a 50% aqueous solution of tetramethylammonium chloride was added dropwise at 80 ° C. over 2 hours, and stirred at the same temperature for 1 hour. Furthermore, 87.1 g of 48% aqueous sodium hydroxide solution was added dropwise over 3 hours at 80 ° C., and after stirring for 30 minutes at the same temperature, epichlorohydrin was removed by distillation under reduced pressure. After adding 560 g of toluene to the residue and stirring for 10 minutes, the precipitate was filtered. The filtrate was washed with 250 g of water, 19 g of 48% aqueous NaOH solution was added, and the mixture was refluxed for 1 hour. After further washing with 250 g of water, it was washed with 250 g of 5% aqueous phosphorus solution and again with 250 g of water. The toluene was removed by distillation under reduced pressure to obtain 105 g of a crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester. The epoxy equivalent of the crude composition of the resulting 6-hydroxy-2-naphthoic acid glycidyl ether ester was 168 and the chlorine content was 1.68%.
実施例１
２００ｍＬの４口コルベンに、参考例１で得られた６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物２０．０ｇおよびメタノール８０．０ｇを加えた後、窒素気流下６０℃に昇温し、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物が溶解するまで加熱撹拌を行った。その後、７℃まで徐冷することにより晶析し、濾過により固形物を得た。得られた固形物を減圧乾燥することにより６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの結晶を得た。得られた結晶のエポキシ当量は１５３および含塩素量は０．０９％であった。また、収率〔＝取得した結晶量（ｇ）／粗組成物（ｇ）×１００〕は６０．５％であった。
Example 1
After 20.0 g of the crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester obtained in Reference Example 1 and 80.0 g of methanol were added to 200 mL of 4-neck Kolben, the temperature was raised to 60 ° C. under a nitrogen stream. The mixture was heated and stirred until the crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester was dissolved. Thereafter, crystallization was performed by gradual cooling to 7 ° C., and a solid was obtained by filtration. The resulting solid was dried under reduced pressure to obtain crystals of 6-hydroxy-2-naphthoic acid glycidyl ether ester. The epoxy equivalent of the obtained crystals was 153 and the chlorine content was 0.09%. Further, the yield [= the obtained amount of crystals (g) / the crude composition (g) × 100] was 60.5%.
比較例１
２００ｍＬの４口コルベンに、参考例１で得られた６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステル粗組成物２０．０ｇおよびトルエン８０．０ｇを加えた後、窒素気流下５０℃に昇温し、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステル粗組成物が溶解するまで加熱撹拌を行った。その後、７℃まで徐冷したが、結晶は析出しなかった。
Comparative Example 1
After adding 20.0 g of the crude 6-hydroxy-2-naphthoic acid glycidyl ether ester composition obtained in Reference Example 1 and 80.0 g of toluene to 200 mL of 4-neck Kolben, the temperature was raised to 50 ° C. under a nitrogen stream. The mixture was heated and stirred until the crude 6-hydroxy-2-naphthoic acid glycidyl ether ester composition was dissolved. After that, although gradually cooled to 7 ° C., crystals did not precipitate.
比較例２
２００ｍＬの４口コルベンに、参考例１で得られた６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステル粗組成物２０．０ｇおよびアセトン４０．０ｇを加えた後、窒素気流下５０℃に昇温し、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステル粗組成物が溶解するまで加熱撹拌を行った。その後、７℃まで徐冷したが、結晶は析出しなかった。
Comparative example 2
After adding 20.0 g of 6-hydroxy-2-naphthoic acid glycidyl ether ester crude composition obtained in Reference Example 1 and 40.0 g of acetone to 200 mL of 4-neck Kolben, the temperature was raised to 50 ° C. under a nitrogen stream. The mixture was heated and stirred until the crude 6-hydroxy-2-naphthoic acid glycidyl ether ester composition was dissolved. After that, although gradually cooled to 7 ° C., crystals did not precipitate.
このように、本発明によれば、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの粗組成物から有機塩素化合物などの不純物が除去され、高純度の６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルが高収率で得られることが理解される。
本発明の好ましい態様は以下を包含する。
〔１〕式（１）で表される６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを含む粗組成物をアルコールに溶解させる工程、および得られた溶液を晶析する工程を含む、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルの精製方法。
〔３〕アルコールがメタノールである、〔１〕または〔２〕に記載の精製方法。
〔４〕アルコールの使用量が、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを含む粗組成物に対して１〜１０倍重量部である、〔１〕〜〔３〕のいずれかに記載の精製方法。
〔５〕アルコールの使用量が、６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルを含む粗組成物に対して３〜５倍重量部である、〔１〕〜〔４〕のいずれかに記載の精製方法。
〔６〕〔１〕〜〔５〕のいずれかに記載の精製方法で得られた６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステルであって、エポキシ当量が１５０〜１５９である６−ヒドロキシ−２−ナフトエ酸グリシジルエーテルエステル。
Thus, according to the present invention, impurities such as organic chlorine compounds are removed from the crude composition of 6-hydroxy-2-naphthoic acid glycidyl ether ester, and high purity 6-hydroxy-2-naphthoic acid glycidyl ether ester is obtained. Is understood to be obtained in high yield.
Preferred embodiments of the present invention include the following.
[1] A process of dissolving a crude composition containing 6-hydroxy-2-naphthoic acid glycidyl ether ester represented by the formula (1) in alcohol, and a process of crystallizing the obtained solution, 6-hydroxy Purification method of 2-naphthoic acid glycidyl ether ester.
[3] The purification method according to [1] or [2], wherein the alcohol is methanol.
[4] The method according to any one of [1] to [3], wherein the amount of alcohol used is 1 to 10 parts by weight with respect to the crude composition containing 6-hydroxy-2-naphthoic acid glycidyl ether ester Purification method.
[5] The method according to any one of [1] to [4], wherein the amount of the alcohol used is 3 to 5 parts by weight with respect to the crude composition containing 6-hydroxy-2-naphthoic acid glycidyl ether ester Purification method.
It is 6-hydroxy -2- naphthoic acid glycidyl ether ester obtained by the purification method in any one of [6] [1]-[5], Comprising: 6-hydroxy-2 whose epoxy equivalent is 150-159. -Naphthoic acid glycidyl ether ester.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015135825A JP6512970B2 (en) | 2015-07-07 | 2015-07-07 | Purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015135825A JP6512970B2 (en) | 2015-07-07 | 2015-07-07 | Purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017019883A JP2017019883A (en) | 2017-01-26 |
| JP6512970B2 true JP6512970B2 (en) | 2019-05-15 |
Family
ID=57889134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015135825A Active JP6512970B2 (en) | 2015-07-07 | 2015-07-07 | Purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6512970B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3578650A4 (en) | 2017-02-06 | 2021-03-24 | National Cancer Center Japan | Novel t-cell receptor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6245582A (en) * | 1985-08-22 | 1987-02-27 | Teijin Ltd | Oxynaphthoic acid glycidyl ether ester and production thereof |
| JPH0368568A (en) * | 1989-08-09 | 1991-03-25 | Nissan Chem Ind Ltd | Production of low chlorine-containing epoxy compound |
| JP3062822B2 (en) * | 1990-01-29 | 2000-07-12 | 大日本インキ化学工業株式会社 | Epoxy resin composition |
| JP2000119369A (en) * | 1998-10-09 | 2000-04-25 | Nippon Steel Chem Co Ltd | Solid epoxy resin, epoxy resin composition and its cured product |
| JP2011207932A (en) * | 2010-03-29 | 2011-10-20 | Mitsubishi Chemicals Corp | Epoxy resin and epoxy resin composition |
-
2015
- 2015-07-07 JP JP2015135825A patent/JP6512970B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017019883A (en) | 2017-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6426226B2 (en) | Crystal form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene | |
| JP6064724B2 (en) | Purified metal complex having oxalic acid as a ligand, and method for producing non-aqueous solvent purified solution of the metal complex | |
| JP6269508B2 (en) | Process for producing purified amine compound | |
| KR102219152B1 (en) | Crystal polymorph of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene and method for producing same | |
| JP6512970B2 (en) | Purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester | |
| CN101113153A (en) | Process for the preparation of boronic acids and derivatives thereof | |
| US9428521B2 (en) | Process for the production of a carbodiimide | |
| JP2002275132A (en) | Method for producing high purity quaternary ammonium inorganic acid salt | |
| JP5994352B2 (en) | Method for producing 2,2-bis (4-hydroxyphenyl) hexafluoropropane-quaternary phosphonium salt | |
| JP4592158B2 (en) | Method for producing carboxylic acid aryl ester | |
| JP2006117637A (en) | Method for producing cyclotriphosphazene derivative and cyclotriphosphazene derivative mixture | |
| JPH07330787A (en) | Synthesis of tetrasubstituted phosphonium organic acid salt | |
| JP4383180B2 (en) | Method for producing crystalline epoxy compound | |
| JP2006131612A (en) | Method for producing sulfonium compound | |
| JP4635156B2 (en) | Method for producing cyclotriphosphazene derivative | |
| JP4795968B2 (en) | Process for producing N, N-carbonyldiazoles | |
| EP2877477B1 (en) | Process for the preparation of phosphonium sulfonates | |
| JP2001261684A (en) | Tetrakis (acyloxy) borate (1-) and method for synthesizing substituted onium tetrakis(acyloxy) borate (1-) | |
| JP5754842B2 (en) | Method for producing p-iodophenol | |
| JP2006117639A (en) | Method for producing cyclotriphosphazene derivative and cyclotriphosphazene derivative mixture | |
| JP2006206732A (en) | 4,4'-biphenyldiyldimethylene-phenol resin and method for producting the same | |
| JP5525216B2 (en) | Method for producing trimellitic anhydride diester | |
| JP6042153B2 (en) | Olanzapine production method | |
| JP2001011021A (en) | Sterically hindered hydroxyphenylcarboxylic acid ester compound, its production and removal of organic tin compound | |
| JPH07149873A (en) | Production of low-molecular brominated epoxy polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20170817 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180424 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20181219 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190108 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190306 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190326 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190409 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6512970 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |