JPH02258744A - Purification of p-oxybenzoic acid phenyl ester - Google Patents
Purification of p-oxybenzoic acid phenyl esterInfo
- Publication number
- JPH02258744A JPH02258744A JP7673289A JP7673289A JPH02258744A JP H02258744 A JPH02258744 A JP H02258744A JP 7673289 A JP7673289 A JP 7673289A JP 7673289 A JP7673289 A JP 7673289A JP H02258744 A JPH02258744 A JP H02258744A
- Authority
- JP
- Japan
- Prior art keywords
- oxybenzoic acid
- phenyl ester
- water
- acid phenyl
- organic solvent
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 31
- -1 phenyl ester Chemical class 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 17
- 239000004480 active ingredient Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000012264 purified product Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は芳香族ポリエステルの原料として有用なＰ−オ
キシ安息香酸フェニルエステルの精製方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for purifying P-oxybenzoic acid phenyl ester useful as a raw material for aromatic polyester.
（従来の技術）
Ｐ−オキシ安息香酸残基を構成成分に含む芳香族高分子
重合体は、−ｆｆｉに優れた機械的物性および熱的特性
等を有しており、特に溶融異方性を示す所謂液晶ポリマ
ーについては、近年積極的な用途面の開発が進められて
いる。(Prior art) Aromatic polymers containing P-oxybenzoic acid residues as constituent components have excellent mechanical properties and thermal properties, especially in melt anisotropy. Regarding the so-called liquid crystal polymer shown above, active development of applications has been progressing in recent years.
このような芳香族高分子重合体を合成する際には、Ｐ−
オキシ安息香酸をアセチル化してＰ−アセトキシ安息香
酸とするか、または酸ハロゲン化物として使用する方法
が多用されている。また、Ｐ−オキシ安息香酸をそのま
ま使用する場合には、芳香族アルコール成分をアシル化
物として反応せしめるか、または反応系内に低級脂肪酸
の酸無水物を共存させる方法が一般的である。When synthesizing such an aromatic polymer, P-
A method in which oxybenzoic acid is acetylated to produce P-acetoxybenzoic acid or used as an acid halide is often used. When P-oxybenzoic acid is used as it is, it is common to react it with an aromatic alcohol component as an acylated product, or to coexist an acid anhydride of a lower fatty acid in the reaction system.
しかしながら、これらの方法は反応時に低級脂肪酸やハ
ロゲン化水素酸が発生することから、装！材料としては
耐食性の優れたものを選定する必要があり、制約を受け
る。However, these methods generate lower fatty acids and hydrohalic acids during the reaction; It is necessary to select materials with excellent corrosion resistance, which is a constraint.
もっとも、特公昭５９−３０７２７号にＰ−オキシ安息
香酸をフェニルエステルとして使用する方法が記載され
ており、この場合には発生するフェノールの腐食性が比
較的少ないために、ポリエステル等の重合装置に通常使
用されている材料を使用できるという利点がある。However, Japanese Patent Publication No. 59-30727 describes a method of using P-oxybenzoic acid as a phenyl ester, and in this case, the generated phenol is relatively less corrosive, so it cannot be used in polymerization equipment for polyester, etc. It has the advantage that commonly used materials can be used.
〈発明が解決しようとする問題点）
Ｐ−オキシ安息香酸フェニルエステルの製造法としては
、特公昭５３−５２８４号、および特公昭６１−５９６
１９号に有機スルホン酸類を触媒としてＰ−オキシ安息
香酸とフェノールとをエステル化反応せしめる方法が記
載されており、いずれの文献も大過剰のフェノールおよ
び共沸溶媒を用いることによって高収率でＰ−オキシ安
息香酸フェニルエステルを得ている。そして、これら文
献に記載されている粗生成物の精製方法は、（１）大量
の水中へのエステルの投入、（２）石油ベンジンによる
再結晶などである。ところが、（１）の方法は濾過等の
操作が極めて困難であり、（２）の方法は不純物の除去
効果が不十分であるという点で精製技術としては不完全
なものと言わざるを得ない。(Problems to be Solved by the Invention) Methods for producing p-oxybenzoic acid phenyl ester are disclosed in Japanese Patent Publication No. 53-5284 and Japanese Patent Publication No. 61-596.
No. 19 describes a method of esterifying P-oxybenzoic acid and phenol using organic sulfonic acids as a catalyst, and both documents describe a method for esterifying P-oxybenzoic acid and phenol using a large excess of phenol and an azeotropic solvent. - Oxybenzoic acid phenyl ester is obtained. The methods for purifying the crude product described in these documents include (1) introducing the ester into a large amount of water, (2) recrystallization using petroleum benzene, and the like. However, method (1) has extremely difficult operations such as filtration, and method (2) has an insufficient effect on removing impurities, so it must be said that it is an incomplete purification technology. .
そこで、上述の問題点を解決するために、本発明は簡便
な操作で効率よくＰ−オキシ安息香酸フェニルエステル
を精製する方法を提供することをその目的とする。Therefore, in order to solve the above-mentioned problems, an object of the present invention is to provide a method for efficiently purifying P-oxybenzoic acid phenyl ester using simple operations.
（問題点を解決するための手段〉
本発明者は水溶性の有機溶媒の使用と、その溶液から有
効成分であるエステルを適切に析出し、分離するための
条件を選択することによって精製効果が高まることを見
出して本発明に到った。(Means for solving the problem) The present inventor has achieved a purification effect by using a water-soluble organic solvent and selecting conditions for appropriately precipitating and separating the ester, which is an active ingredient, from the solution. The present invention was developed based on the discovery that this can be improved.
即ち、本発明は、Ｐ−オキシ安息香酸フェニルエステル
粗生成物を水溶性の有機溶媒に溶解せしめた後、温水と
混合してその有効成分を析出せしめ、分離せしめること
からなるＰ−オキシ安息香酸フェニルエステルの精製方
法である。That is, the present invention provides P-oxybenzoic acid phenyl ester crude product, which is obtained by dissolving a P-oxybenzoic acid phenyl ester crude product in a water-soluble organic solvent, and then mixing it with hot water to precipitate and separate the active ingredient. This is a method for purifying phenyl ester.
本発明で使用できる水溶性の有機溶媒としては、メタノ
ール、エタノール、プロパツール等の低級脂肪族アルコ
ール類、アセトン、メチルエチルケ１−ン等の脂肪族ケ
トン類、および非プロトン性極性溶媒などがあげられる
。この中で乾燥時の溶媒の除去の容易さからメタノール
、アセトン等が好ましいが、Ｐ−オキシ安息香酸フェニ
ルエステルの回収時の温水使用量を勘案するとメタノー
ルが最も好ましい。ここで１．有機溶媒の使用量は、粗
生成物を実質的に溶解し得る量であれば特に限定されな
い。例えばメタノールを用いた場合では、その沸点以下
の温度で、理論ゲーク量に対して約２〜５重量倍使用す
ることが好適となる。Examples of water-soluble organic solvents that can be used in the present invention include lower aliphatic alcohols such as methanol, ethanol, and propatool; aliphatic ketones such as acetone and methyl ethyl ketone; and aprotic polar solvents. . Among these, methanol, acetone, etc. are preferred from the viewpoint of ease of removing the solvent during drying, but methanol is most preferred in consideration of the amount of hot water used during recovery of P-oxybenzoic acid phenyl ester. Here 1. The amount of organic solvent used is not particularly limited as long as it can substantially dissolve the crude product. For example, when methanol is used, it is preferable to use it at a temperature below its boiling point and in an amount of about 2 to 5 times the theoretical amount by weight.
また本発明において使用する温水の量は、既に使用され
た有機溶媒の種類によって異なるが、メタノールを用い
た場合には約２〜１０重量倍が好ましい。温水の１が少
ないときは精製効果は高くなるが、回収率が低下し、多
過ぎる時は精製物中の未反応の遊離カルボキシル末端基
が増加する。さらに有効成分を析出・分離する際の温度
としては３０〜８０℃の範囲を設定することが好ましい
。適用温度が高過ぎる場合には有機溶媒の蒸発が促進さ
れて操作が困難となり、また温度が低過ぎる場合にはフ
ェノールが精製物中に残留するのみならず、未反応の遊
離カルボキシル末端基が増加する傾向がある。従って、
精製には適切な温度条件が保たれねばならない。Further, the amount of hot water used in the present invention varies depending on the type of organic solvent already used, but when methanol is used, it is preferably about 2 to 10 times the amount by weight. When the amount of 1 in hot water is small, the purification effect becomes high, but the recovery rate decreases, and when it is too large, the number of unreacted free carboxyl terminal groups in the purified product increases. Further, the temperature at which the active ingredients are precipitated and separated is preferably set in the range of 30 to 80°C. If the applied temperature is too high, the evaporation of the organic solvent will be accelerated, making the operation difficult; if the temperature is too low, not only will phenol remain in the purified product, but also unreacted free carboxyl end groups will increase. There is a tendency to Therefore,
Appropriate temperature conditions must be maintained for purification.
なお、本発明の応用として温水中にアルカリを少量存在
させる方法も有効である。その場合（まアルカリの精製
物中への残留を抑えるための再洗浄が不可欠である。Note that as an application of the present invention, a method in which a small amount of alkali is present in hot water is also effective. In that case, re-washing is essential to prevent alkali from remaining in the purified product.
（発明の効果）
Ｐ−オキシ安息香酸フェニルエステルは芳香族高分子重
合体の原料として有用であるにもかかわらず、合成およ
び精製上の問題点のために効率的な生産がおこなわれて
いなかった。(Effect of the invention) Although P-oxybenzoic acid phenyl ester is useful as a raw material for aromatic polymers, it has not been efficiently produced due to problems in synthesis and purification. .
本発明は従来提案されてきた合成方法に対して最も効果
的な精製方法を見出したもので、その工業的意義が大き
い。The present invention has discovered the most effective purification method compared to the conventionally proposed synthesis methods, and has great industrial significance.
（実施例） 以下実施例により本発明を具体的に説明する。(Example) The present invention will be specifically explained below using Examples.
実施例において示すＰ−オキシ安息香酸フェニルエステ
ル精製物の遊離カルボキシル末端基の定量、およびエス
テル化触媒に由来する硫黄元素の残存量は、アルコール
性苛性カリによる滴定法、および重量元素分析計により
それぞれ測定した。The quantitative determination of the free carboxyl terminal group of the P-oxybenzoic acid phenyl ester purified product and the residual amount of sulfur derived from the esterification catalyst shown in the examples were determined by a titration method using alcoholic potassium hydroxide and a gravimetric elemental analyzer, respectively. did.
また重合原料としての精製物の評価は特公昭５９−３０
７２７号の記載に準じてハイドロキノン、炭酸ジフェニ
ルと共に重合して、その重合化反応の難易により判定し
た。In addition, the evaluation of purified products as polymerization raw materials was
Polymerization was carried out together with hydroquinone and diphenyl carbonate according to the description in No. 727, and judgment was made based on the difficulty of the polymerization reaction.
実施例１
攪拌機、温度計および水分離器を供えた環流冷却管を有
する内容積１ρのフラスコに、Ｐ−オキシ安息香酸１３
８ｇ （１，０モル）、フェノール１４１ｇ（１，５モ
ル）、ｐ−トルエンスルホン酸１水和物０．１５２ｇ
（０，０００８モル）、エチルベンゼン５０ｍ１を仕込
み、窒素ガス雰囲気下で徐々に昇温しな。内温か１６０
℃となった時点で水を含む溶媒の環流が始まった。水分
離器より水を系外に抜き出すと共に分離後の溶媒を再循
環しながら６時間反応を継続した。最終内温は１８２℃
に達し、発生した水の重量から計算した反応率は９６モ
ル％であった。得られた反応液を低真空下で加熱濃縮し
、フェノールを含む粗反応物２３５ｇを得た。この粗反
応物にメタノール５３５ｇを加え６０℃で加温溶解した
のち、５０℃の温水１．６００ｍ！中に投入した。析出
した結晶を４０℃以上の温度を保ちながら炉別し、更に
５０℃温水１００ ｍｌで洗浄をおこなったのち、熱風
乾燥して、白色のＰ−オキシ安息香酸フェニルエステル
１７２ｇを得た。このフェニルエステルの分析をおこな
ったところ、遊離カルボキシル末端基が７５ミル当量／
ｇ 、硫黄分含有量が６．０重量ｐｐｍであり、ハイド
ロノン、炭酸ジフェニルと重縮合させて高分子重合体を
得ることができた。Example 1 P-oxybenzoic acid 13
8g (1.0 mol), phenol 141g (1.5 mol), p-toluenesulfonic acid monohydrate 0.152g
(0,0008 mol) and 50 ml of ethylbenzene were charged, and the temperature was gradually raised under a nitrogen gas atmosphere. Internal temperature 160
When the temperature reached ℃, reflux of the solvent containing water started. The reaction was continued for 6 hours while removing water from the system from the water separator and recycling the separated solvent. Final internal temperature is 182℃
The reaction rate calculated from the weight of water generated was 96 mol%. The resulting reaction solution was heated and concentrated under low vacuum to obtain 235 g of a crude reaction product containing phenol. After adding 535 g of methanol to this crude reaction product and dissolving it by heating at 60°C, 1.600 m of 50°C hot water was added! I put it inside. The precipitated crystals were separated in a furnace while maintaining a temperature of 40° C. or higher, washed with 100 ml of 50° C. hot water, and then dried with hot air to obtain 172 g of white P-oxybenzoic acid phenyl ester. Analysis of this phenyl ester revealed that the free carboxyl end group was 75 mil equivalents/
g, the sulfur content was 6.0 ppm by weight, and a high molecular weight polymer could be obtained by polycondensation with hydronone and diphenyl carbonate.
比較例１
実施例１と同様の操作で反応率９５モル％の反応液を得
た。これを減圧濃縮して２３９ｇとした粗生成物にキシ
レン６５０ ｍｌを加えて、８０℃で加温溶解したのち
室温まで冷却した。析出しな結晶を濾過、乾燥すること
によって茶白色のＰ−オキシ安息香酸フェニルエステル
１８６ｇを得た。このフェニルエステル中の遊離カルボ
キシル末端基は２５３ミル当■／ｇ、硫黄分は８２．９
重量ｐｐｍと高く、重縮合反応の進行が著しく困難であ
った。Comparative Example 1 A reaction solution with a reaction rate of 95 mol% was obtained in the same manner as in Example 1. This was concentrated under reduced pressure to give a crude product of 239 g. To the crude product, 650 ml of xylene was added and dissolved by heating at 80° C., followed by cooling to room temperature. The precipitated crystals were filtered and dried to obtain 186 g of brown-white phenyl P-oxybenzoate. The free carboxyl terminal group in this phenyl ester is 253 mil/g, and the sulfur content is 82.9.
The content was as high as ppm by weight, making it extremely difficult for the polycondensation reaction to proceed.
実施例２
フェノール１８８ｇ （２，０モル＞、ｐ−）ルエンス
ルホン酸０．３８０ｇとした以外は実施例１と同様の操
作をおこない、反応率８３モル％の反応液を得た。Example 2 188 g of phenol (2.0 mol>, p-)The same operation as in Example 1 was carried out except that 0.380 g of luenesulfonic acid was used to obtain a reaction solution with a reaction rate of 83 mol%.
減圧濃縮後の粗生成物にメタノール５３５ｇを加えて６
０℃で加温溶解したのち、液中に５０℃の温水１．６０
０ｍ１を徐々に投入した。析出した結晶を４０〜５０℃
に保ちながら才濾過し、乾燥後重量で１７５ｇのＰ−オ
キシ安息香酸フェニルエステルを得た。このフェニルエ
ステルはわずかに褐色に着色していたが、遊離カルボキ
シル末端基が９０ミリ当量／ｇ、硫黄分含有量が１７．
４重ｉｐｐｍであり、重合反応に使用可能であった。Add 535 g of methanol to the crude product after concentration under reduced pressure and add 6
After heating and dissolving at 0℃, add 50℃ warm water 1.60 to the solution.
0ml was gradually added. The precipitated crystals were heated to 40-50°C.
After drying, 175 g of P-oxybenzoic acid phenyl ester was obtained. This phenyl ester was slightly brown in color, but had a free carboxyl end group of 90 meq/g and a sulfur content of 17.
It was 4-fold IPPM and could be used for polymerization reactions.
比較例２
実施例１と同様の操作で反応率９５モル％の反応液を得
た。減圧濃縮後の粗生成物にメタノール５３５ｇを加え
て溶解し、この溶液を２０℃の水１．６００ｍ！中に投
入した。得られたスラリーを１０°Ｃまで冷却したのち
濾過、乾燥して白色のＰ−オキシ安息香酸フェニルエス
テル１９０ｇを採取した。このフェニルエステルの分析
をおこなったところ、硫黄分含有量は１５．３ｐｐｍと
低かったが、遊離カルボキシル末端基が１９５ミリ当量
／ｇと高く、重合反応性に乏しかった。Comparative Example 2 A reaction solution with a reaction rate of 95 mol% was obtained in the same manner as in Example 1. 535g of methanol was added to the crude product after concentration under reduced pressure to dissolve it, and this solution was poured into 1.600ml of water at 20°C. I put it inside. The resulting slurry was cooled to 10°C, filtered, and dried to collect 190 g of white P-oxybenzoic acid phenyl ester. When this phenyl ester was analyzed, the sulfur content was as low as 15.3 ppm, but the free carboxyl terminal group was as high as 195 meq/g, indicating poor polymerization reactivity.
比較例３
実施例１と同様の操作で反応率９８モル％の反応液を得
た。これを低真空で２４０ｇに濃縮したのち６０℃の温
水１，６００ｍ１中に投入したところ、粘調な塊状固形
物が析出して）濾過分離が著しく困難となった。また、
通常の熱乾乾燥では残存フェノールが十分に除去できず
、乾燥後の着色も極めて大きかった。この生成物を重合
に使用したところ、極めて反応が遅く、実質的に重合物
は得られなかった。Comparative Example 3 A reaction solution with a reaction rate of 98 mol% was obtained in the same manner as in Example 1. When this was concentrated in a low vacuum to 240 g and then poured into 1,600 ml of 60° C. hot water, a viscous lumpy solid was precipitated, making separation by filtration extremely difficult. Also,
The residual phenol could not be sufficiently removed by normal heat drying, and the coloring after drying was also extremely large. When this product was used for polymerization, the reaction was extremely slow and virtually no polymer was obtained.
Claims (1)
して得られたＰ−オキシ安息香酸フェニルエステル粗成
物を水溶性の有機溶媒に溶解せしめ、しかる後温水と混
合して有効成分を析出せしめ、分離することからなるＰ
−オキシ安息香酸フェニルエステルの精製方法。 ２、水溶性の有機溶媒が低沸点のアルコール又はケトン
である請求項１に記載のＰ−オキシ安息香酸フェニルエ
ステルの精製方法。 ３、有効成分の析出及び分離を３０〜８０℃の温度で行
うことからなる請求項１に記載のＰ−オキシ安息香酸フ
ェニルエステルの精製方法。[Claims] 1. P-oxybenzoic acid phenyl ester crude product obtained by esterifying P-oxybenzoic acid and phenol is dissolved in a water-soluble organic solvent, and then mixed with warm water. P consists of precipitating and separating the active ingredients using
- A method for purifying oxybenzoic acid phenyl ester. 2. The method for purifying P-oxybenzoic acid phenyl ester according to claim 1, wherein the water-soluble organic solvent is a low boiling point alcohol or ketone. 3. The method for purifying P-oxybenzoic acid phenyl ester according to claim 1, which comprises performing precipitation and separation of the active ingredient at a temperature of 30 to 80°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7673289A JPH02258744A (en) | 1989-03-30 | 1989-03-30 | Purification of p-oxybenzoic acid phenyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7673289A JPH02258744A (en) | 1989-03-30 | 1989-03-30 | Purification of p-oxybenzoic acid phenyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02258744A true JPH02258744A (en) | 1990-10-19 |
Family
ID=13613753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7673289A Pending JPH02258744A (en) | 1989-03-30 | 1989-03-30 | Purification of p-oxybenzoic acid phenyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02258744A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016222551A (en) * | 2015-05-27 | 2016-12-28 | 上野製薬株式会社 | Purification method of 4-hydroxy benzoic acid long chain ester |
-
1989
- 1989-03-30 JP JP7673289A patent/JPH02258744A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016222551A (en) * | 2015-05-27 | 2016-12-28 | 上野製薬株式会社 | Purification method of 4-hydroxy benzoic acid long chain ester |
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