JPH02188592A - Production of 3,5-dicarboxybenzenesulfonic acid phosphonium salt - Google Patents
Production of 3,5-dicarboxybenzenesulfonic acid phosphonium saltInfo
- Publication number
- JPH02188592A JPH02188592A JP879789A JP879789A JPH02188592A JP H02188592 A JPH02188592 A JP H02188592A JP 879789 A JP879789 A JP 879789A JP 879789 A JP879789 A JP 879789A JP H02188592 A JPH02188592 A JP H02188592A
- Authority
- JP
- Japan
- Prior art keywords
- product
- dicarboxybenzenesulfonic acid
- phosphonium salt
- dicarboxybenzenesulfonic
- acid
- 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.)
- Granted
Links
- CGDQWDRVKLBTBN-UHFFFAOYSA-N [PH4+].S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].[PH4+].[PH4+] Chemical compound [PH4+].S(=O)(=O)([O-])C=1C=C(C=C(C(=O)[O-])C1)C(=O)[O-].[PH4+].[PH4+] CGDQWDRVKLBTBN-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 phosphonium compound Chemical class 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract 2
- 125000000962 organic group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005649 metathesis reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract description 29
- 239000006227 byproduct Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- 239000012736 aqueous medium Substances 0.000 abstract 1
- 150000004714 phosphonium salts Chemical class 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 3
- XGYQCXAJJSNIJB-UHFFFAOYSA-M 3,5-dicarboxybenzenesulfonate;tetrabutylphosphanium Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1.CCCC[P+](CCCC)(CCCC)CCCC XGYQCXAJJSNIJB-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MDJDSMCAEWPLOY-UHFFFAOYSA-M 3,5-dicarboxybenzenesulfonate;tetraphenylphosphanium Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MDJDSMCAEWPLOY-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KIKZFTWGZWHHNP-UHFFFAOYSA-N [PH4+].COC(C1=CC(C(=O)OC)=CC(=C1)S(=O)(=O)[O-])=O Chemical compound [PH4+].COC(C1=CC(C(=O)OC)=CC(=C1)S(=O)(=O)[O-])=O KIKZFTWGZWHHNP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- VHTDHSVPBYDDAM-UHFFFAOYSA-N benzyl(triethyl)phosphanium Chemical compound CC[P+](CC)(CC)CC1=CC=CC=C1 VHTDHSVPBYDDAM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- GELSOTNVVKOYAW-UHFFFAOYSA-N ethyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 GELSOTNVVKOYAW-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- MCGZLOLFUZDFNP-UHFFFAOYSA-N phosphane;5-sulfobenzene-1,3-dicarboxylic acid Chemical class P.OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 MCGZLOLFUZDFNP-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YZLGIRGCZODDCE-UHFFFAOYSA-M sodium;3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate Chemical compound [Na+].OCCOC(=O)C1=CC(C(=O)OCCO)=CC(S([O-])(=O)=O)=C1 YZLGIRGCZODDCE-UHFFFAOYSA-M 0.000 description 1
- LLHSEQCZSNZLRI-UHFFFAOYSA-M sodium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Na+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LLHSEQCZSNZLRI-UHFFFAOYSA-M 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は３．５−ジカルボキシベンゼンスルホン酸ホス
ホニウム塩の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing 3,5-dicarboxybenzenesulfonic acid phosphonium salt.
３．５−ジカルボキシベンゼンスルホンＭ誘導体は、ポ
リエチレンテレフタレートに代表される縮合型高分子へ
有用な特性を付与するために共重合され、種々の分野に
利用されている。特に、３．５−ジメトキシカルボニル
ベンゼンスルホン猷ナトリウムや３．５−ジ（２−ヒド
ロキシエトキシカルボニル）ベンゼンスルホン酸ナトリ
ウムは、染色性に大きな問題を有するポリエステル繊維
をカチオン可染にする共重合用単量体として、工業上多
量に使用されている。同様の目的でナイロンへも使用さ
れ、更にはコーチイブ剤や接着剤及び塗料等へ用いられ
る縮合型高分子へ接着性の向上等を目的として利用され
る等、その応用分野は極めて広い。3.5-Dicarboxybenzenesulfone M derivatives are copolymerized to impart useful properties to condensation polymers typified by polyethylene terephthalate, and are used in various fields. In particular, sodium 3.5-dimethoxycarbonylbenzenesulfonate and sodium 3.5-di(2-hydroxyethoxycarbonyl)benzenesulfonate are monomers for copolymerization that make polyester fibers, which have major problems in dyeability, cationic dyeable. It is used in large quantities industrially as a polymer. It is also used for nylon for the same purpose, and it is also used for the purpose of improving adhesion to condensation polymers used in coachib agents, adhesives, paints, etc., and its application fields are extremely wide.
ところが、工業上域に有用ではあるが、上記の３．５−
ジカルボキシベンゼンスルホン酸誘導体の′金属塩には
、これを共重合しようとすると、得られる共重合体の溶
融粘度が高くなってしまうためにその重合度を上げ難く
、また特にポリエチレンテレフタレートへ共重合するよ
うな場合においては、例えば該金属塩のポリエチレンテ
レフタレート重合系に対する溶解度が低いためにその共
重合反応性が悪く、得られる共重合物を繊維にした場合
には染色後の仕上りの鮮明さを悪くしたり、或は共重合
時の該金属塩の悪影響で得られる共重合物が着色したり
する等、不都合がある。However, although it is useful in the industrial area, the above 3.5-
If you try to copolymerize a metal salt of a dicarboxybenzenesulfonic acid derivative, the resulting copolymer will have a high melt viscosity, making it difficult to increase the degree of polymerization. In such cases, for example, the copolymerization reactivity is poor due to the low solubility of the metal salt in the polyethylene terephthalate polymerization system, and when the resulting copolymer is made into fibers, the sharpness of the finish after dyeing may be affected. There are inconveniences such as the copolymerized product being colored due to the adverse effect of the metal salt during copolymerization.
そこで、これらの不都合を軽減する方法がいくつか提案
されており、その一つとして、スルホン酸基の対イオン
をホスホニウムにする方法がある（特公昭４７−２２３
３４号公報、ドイツ特許出願公開第２０４４９３１号公
報）。Therefore, several methods have been proposed to alleviate these disadvantages, and one of them is a method of using phosphonium as the counter ion of the sulfonic acid group (Japanese Patent Publication No. 47-223
34, German Patent Application No. 2044931).
本発明は、スルホン酸基の対イオンがホスホニウムであ
る、３．５−ジカルボキシベンゼンスルホン酸ホスホニ
ウム塩の製造方法に関するものである。The present invention relates to a method for producing a 3,5-dicarboxybenzenesulfonic acid phosphonium salt, in which the counter ion of the sulfonic acid group is phosphonium.
〈従来の技術、その課題〉
対イオンに有機のオニウムイオンを有する有機スルホン
酸を、有機スルホン酸のアルカリ或はアルカリ土類金属
塩と、ハロゲンの如き別の対イオンを有する有機オニウ
ム塩とから、複分解により合成することはよく知られて
いる。対イオンにホスホニウムを有する３、５−ジカル
ボキシベンゼンスルホン酸誘導体の合成についても従来
、同様の反応が適用されている（ドイツ特許出願公開第
２０４４９３１号公報、米国特許第４００６１２３号明
細書）、すなわち、これらの従来例では、対イオンにホ
スホニウムを有する３、５−ジメトキシカルボニルベン
ゼンスルホン酸の製造に際して、３．５−ジメトキシカ
ルボニルベンゼンスルホン酸金属塩とホスホニウム塩と
を反応させて目的物を得ているのである。<Prior art and its problems> An organic sulfonic acid having an organic onium ion as a counter ion is prepared from an alkali or alkaline earth metal salt of the organic sulfonic acid and an organic onium salt having another counter ion such as a halogen. , is well known to be synthesized by metathesis. A similar reaction has conventionally been applied to the synthesis of 3,5-dicarboxybenzenesulfonic acid derivatives having phosphonium as a counterion (German Patent Application No. 2044931, US Pat. No. 4006123), i.e. In these conventional examples, when producing 3,5-dimethoxycarbonylbenzenesulfonic acid having phosphonium as a counterion, the desired product is obtained by reacting a 3,5-dimethoxycarbonylbenzenesulfonic acid metal salt with a phosphonium salt. There is.
ところが、上記の反応を実際に検討すると、生成物中に
未反応の原料ホスホニウム塩が混入し易く、したがって
生成物が加熱時に着色し易くなり、以後の精製も著しく
厄介という課題がある。However, when the above reaction is actually studied, there is a problem that unreacted raw material phosphonium salt tends to be mixed into the product, and therefore the product tends to be colored when heated, and subsequent purification is extremely complicated.
そこで本出願人は、上記従来法の課題を解決するために
、３．５−ジカルボキシベンゼンスルホン猷塩例えばそ
のアルカリ金属塩とホスホニウム塩とを、水系溶媒中で
複分解し、得られる中間生成物としての３．５−ジカル
ボキシベンゼンスルホン酸ホスホニウム塩のカルボキシ
ル基をエステル化して、３，５−ジメトキシカルボニル
ベンゼンスルホン酸ホスホニウム塩を得るという改良法
を提案しているＣ４１開昭６２−２４２６５７号公報）
。Therefore, in order to solve the problems of the above-mentioned conventional method, the present applicant has decomposed the 3,5-dicarboxybenzenesulfone salt, for example, its alkali metal salt and phosphonium salt, in an aqueous solvent to produce an intermediate product. C41 Publication No. 1987-242657 proposes an improved method of obtaining a 3,5-dimethoxycarbonylbenzenesulfonic acid phosphonium salt by esterifying the carboxyl group of a 3,5-dicarboxybenzenesulfonic acid phosphonium salt. )
.
しかし、上記改良法において、３．５−ジカルボキシベ
ンゼンスルホン酸アルカリ金属塩は、３．５−ジカルボ
キシベンゼンスルホン酸と当モルの水酸化アルカリ等を
用いて中和することにより得られるのであるが、もとも
と３．５−ジカルボキシベンゼンスルホン酸にはスルホ
ン酸基とカルボン酸基の二種の酸基が存在するため、上
記中和の際の中和度の若干の変動によって、カルボン酸
基が一部中和された３、５−ジカルボキシベンゼンスル
ホン酸ジアルカリ金属塩が生成混入してしまい、これを
混入した３、５−ジカルボキシベンゼンスルホン酸アル
カリ金属塩を用いて上記複分解を行うと、得られる中間
生成物中には、スルホン酸基のみがホスホニウム塩で交
換された所期の３．５−ジカルボキシベンゼンスルホン
酸ホスホニウム塩の他に、カルボン酸基がホスホニウム
塩で交換された副生物が生成混入してしまうという課題
がある。該副生物は、通常の方法によっては除去するこ
とが困難であるため、工業上は該副生物の混入したもの
を利用することとなり、結局は、得られる生成物を共重
合用単量体としてポリエステルの製造へ供した場合に、
該副生物に起因してその共重合反応性が低下したり、ま
た共重合物であるポリエステルの色相や物性等が悪くな
ってしまうのである。However, in the above improved method, the alkali metal salt of 3,5-dicarboxybenzenesulfonic acid is obtained by neutralizing it with an equimolar amount of alkali hydroxide or the like to 3,5-dicarboxybenzenesulfonic acid. However, since 3,5-dicarboxybenzenesulfonic acid originally has two types of acid groups, a sulfonic acid group and a carboxylic acid group, due to slight fluctuations in the degree of neutralization during the above neutralization, the carboxylic acid group A partially neutralized dialkali metal salt of 3,5-dicarboxybenzenesulfonic acid is produced and mixed in, and when the above metathesis is carried out using the alkali metal salt of 3,5-dicarboxybenzenesulfonic acid mixed with this, In addition to the desired phosphonium salt of 3,5-dicarboxybenzenesulfonic acid in which only the sulfonic acid group was exchanged with the phosphonium salt, the resulting intermediate product contained a secondary 3,5-dicarboxybenzenesulfonic acid phosphonium salt in which only the sulfonic acid group was exchanged with the phosphonium salt. There is a problem of contamination by living organisms. Since this by-product is difficult to remove by normal methods, products contaminated with this by-product are used industrially, and the resulting product is ultimately used as a comonomer for copolymerization. When used in the production of polyester,
Due to the by-products, the copolymerization reactivity decreases, and the hue, physical properties, etc. of the copolyester polyester deteriorate.
〈発明が解決しようとする課題、その解決手段〉本発明
は、叙上の如き従来の課題を解決する、工業上有利な且
つ収率の良いそして品質の高い３．５−ジカルボキシベ
ンゼンスルホン酸ホスホニウム塩の製造方法を提供する
ものである。<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention solves the conventional problems as described above, and provides industrially advantageous, high-yield, and high-quality 3,5-dicarboxybenzenesulfonic acid. A method for producing a phosphonium salt is provided.
しかして本発明者らは、上記の観点で鋭意研究した結果
、所定の水系溶媒中で、３．５−ジカルボキ、シベンゼ
ンスルホン酸とホスホニウム化合物とを複分解反応させ
、酸性条件下に生成物を分離すると、ジホスホニウム塩
等の副生物を含有しない高品質の３，５−ジカルボキシ
ベンゼンスルホン酸ホスホニウム塩を工業上安定して得
ることができることを見出し、本発明を完成するに至っ
たのである。As a result of intensive research from the above viewpoint, the present inventors conducted a metathesis reaction between 3,5-dicarboxylic acid, cybenzenesulfonic acid and a phosphonium compound in a predetermined aqueous solvent, and released the product under acidic conditions. The inventors discovered that by separating the phosphonium salt of 3,5-dicarboxybenzenesulfonic acid, which does not contain by-products such as diphosphonium salts, a high-quality phosphonium salt of 3,5-dicarboxybenzenesulfonic acid can be obtained in an industrially stable manner, leading to the completion of the present invention. .
すなわち本発明は、
下記一般式（Ｉ）で示される３、５−ジカルボキシベン
ゼンスルホン酸ホスホニウム塩の製造において、水を５
０重量％以上含有する水系溶媒中で、３，５−ジカルボ
キシベンゼンスルホン酸と下記一般式（ＩＩ ）で示さ
れるホスホニウム化合物とを複分解反応させ、次いで酸
性条件下にその反応液から生成物である３、５−ジカル
ボキシベンゼンスルホン酸ホスホニウム塩を分離するこ
とを骨子とする３、５−ジカルボキシベンゼンスルホン
酸ホスホニウム塩の製造方法に係る。That is, the present invention provides a method for producing a 3,5-dicarboxybenzenesulfonic acid phosphonium salt represented by the following general formula (I), in which water is
In an aqueous solvent containing 0% by weight or more, 3,5-dicarboxybenzenesulfonic acid and a phosphonium compound represented by the following general formula (II) are subjected to a metathesis reaction, and then the product is extracted from the reaction solution under acidic conditions. The present invention relates to a method for producing a 3,5-dicarboxybenzenesulfonic acid phosphonium salt, the main point of which is to separate a certain 3,5-dicarboxybenzenesulfonic acid phosphonium salt.
一般式（Ｉ）
一般式（ＩＩ ）
Ｒ１−ｐＯ−Ｒ３・ ｘｅ
［１１７１〜Ｒ４、少なくとも一つが炭素数１〜１８の
アルキル基、フェニル基又はベンジ
ル基である一価の有機基
Ｘ：Ｃ１又はＢｒ ］
本発明において、３．５−ジカルボキシベンゼンスルホ
ン酸は、イソフタル酸を無水硫酸或は発煙硫酸でスルホ
ン化して得られるものや、３．５−ジメトキシカルボニ
ルベンゼンスルホン酸又はその中和塩をアルカリで加水
分解し、これに無機酸を加えて遊離の醜としたもの等を
使用することができる。３．５−ジカルボキシベンゼン
スルホン酸は精製されたものであっても又は硫酸や硫酸
ナトリウム等の無機酸や無機塩を含むものであってもよ
い。General formula (I) General formula (II) R1-pO-R3. Br ] In the present invention, 3,5-dicarboxybenzenesulfonic acid is one obtained by sulfonating isophthalic acid with sulfuric anhydride or fuming sulfuric acid, or 3,5-dimethoxycarbonylbenzenesulfonic acid or its neutralized salt. A product obtained by hydrolyzing with an alkali and adding an inorganic acid to the free form can be used. 3.5-dicarboxybenzenesulfonic acid may be purified or may contain an inorganic acid or an inorganic salt such as sulfuric acid or sodium sulfate.
また本発明において、式（ＩＩ ）で示されるホスホニ
ウム化合物のうち、そのホスホニウムカチオン部の具体
例としては、テトラエチルホスホニウム、テトラプロピ
ルホスホニウム、テトラブチルホスホニウム、トリブチ
ルモノメチルホスホニウム、トリブチルモノエチルホス
ホニウム、トリブチルモノオクチルホスホニウム、トリ
ブチルモノテトラデシルホスホニウム、トリブチルモノ
オクタデシルホスホニウム、トリオクチルモノメチルホ
スホニウム等の脂肪族ホスホニウム、トリフェニルメチ
ルホスホニウム、トリフェニルエチルホスホニウム、ト
リエチルベンジルホスホニウム、トリブチルベンジルホ
スホニウム、テトラフェニルホスホニウム等の芳香族ホ
スホニウムが挙げられるが、更にエーテル基、エステル
基、アミド基等を有する置換基を持つホスホニウムでも
よい。In the present invention, among the phosphonium compounds represented by formula (II), specific examples of the phosphonium cation moiety include tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tributylmonomethylphosphonium, tributylmonoethylphosphonium, tributylmonoctyl Aliphatic phosphoniums such as phosphonium, tributylmonotetradecylphosphonium, tributylmonoctadecylphosphonium, and trioctylmonomethylphosphonium; aromatic phosphoniums such as triphenylmethylphosphonium, triphenylethylphosphonium, triethylbenzylphosphonium, tributylbenzylphosphonium, and tetraphenylphosphonium; However, it may also be a phosphonium having a substituent such as an ether group, an ester group, or an amide group.
なかでも工業上の入手の容易さや製造の容易さ等から、
式（ＩＩ ）のＲ１〜Ｒ３が同一であって且つ炭素数１
〜８のアルキル基又はフェニル基であり、モしてＲ４が
炭素数１〜１８のアルキル基又はフェニル基であるもの
が好ましい。Among them, it is easy to obtain industrially and easy to manufacture, etc.
R1 to R3 of formula (II) are the same and have 1 carbon number
-8 alkyl group or phenyl group, and those in which R4 is an alkyl group having 1 to 18 carbon atoms or phenyl group are particularly preferred.
一方、式（ＩＩ ）で示されるホスホニウム化合物のう
ち、そのアニオン部の具体例としては、ＣｌＧ又はＢｒ
Ｏがある。なかでもより高品質の生成物を得るためにＣ
ｌＣ）が好ましい。On the other hand, among the phosphonium compounds represented by formula (II), specific examples of the anion moiety include ClG or Br.
There is an O. Among them, C to obtain higher quality products.
IC) is preferred.
本発明で使用するホスホニウム化合物は以上例示したよ
うなカチオン部とアニオン部との広範な組合わせからな
るものである。The phosphonium compounds used in the present invention are composed of a wide range of combinations of cation moieties and anion moieties as exemplified above.
更に本発明において、反応溶媒は、水を５０重量％以上
含有する水系溶媒であって、水単独、或は水と水に可溶
な有機溶媒との混合溶媒である。Further, in the present invention, the reaction solvent is an aqueous solvent containing 50% by weight or more of water, and is water alone or a mixed solvent of water and a water-soluble organic solvent.
水単独が好ましいが、水に可溶な有機溶媒１例えばメタ
ノール、エタノール、イソプロパツール、ジオキサン、
アセトン、テトラヒドロフラン、エチレングリコール等
を５０重量％以下で含有する水系溶媒でもよい。Water alone is preferred, but water-soluble organic solvents such as methanol, ethanol, isopropanol, dioxane,
An aqueous solvent containing 50% by weight or less of acetone, tetrahydrofuran, ethylene glycol, etc. may also be used.
本発明では、上記のような水系溶媒中で、３゜５−ジカ
ルボキシベンゼンスルホン酸と式（ＩＩ ）で示される
ホスホニウム化合物とを、複分解反応させる０反応系は
触性条件下にあり、このために過剰のホスホニウム化合
物が存在しても、カルボン酸基が塩交換された化合物や
ジホスホニウム化合物は副生しない、複分解反応後に、
酸性反応液から生成物を分離するには種々の方法が可能
である０通常、生成物は酸性反応液中に析出するため、
該生成物を加圧或は減圧下の濾過によって酸性反応液か
ら分離し、更に水洗して高品質の３．５−ジカルボキシ
ベンゼンスルホン酸ホスホニウム塩を得ることができ６
．生成物が温度との関係で液状となる場合には、常法の
液−液分離操作で該生成物の液層を酸性反応液から分離
し、更に分離後の生成物の液層を水洗して高品質の３．
５−ジカルボキシベンゼンスルホン酸ホスホニウム塩を
得ることができる。上記の分離に先立ち又は分離の際に
、アルカリ金属の水酸化物や炭酸塩、或はアンモニウム
塩等の塩基性物質を用いて反応系のＰＨを４以上にする
と、生成物中にジホスホニウム化合物或は３．５−ジカ
ルボキシベンゼンスルホン酸のアルカリ金属塩やアンモ
ニウム塩等の副生物が含まれてくるため好ましくない。In the present invention, the reaction system in which 3゜5-dicarboxybenzenesulfonic acid and the phosphonium compound represented by formula (II) undergo a metathesis reaction in an aqueous solvent as described above is under tactile conditions. Therefore, even if there is an excess of phosphonium compounds, compounds with salt-exchanged carboxylic acid groups and diphosphonium compounds are not produced as by-products after the metathesis reaction.
Various methods are possible to separate the product from the acidic reaction solution.Normally, the product is precipitated in the acidic reaction solution.
The product can be separated from the acidic reaction solution by filtration under pressure or reduced pressure, and further washed with water to obtain a high quality 3,5-dicarboxybenzenesulfonic acid phosphonium salt6.
．． When the product becomes liquid due to temperature, the liquid layer of the product is separated from the acidic reaction liquid by a conventional liquid-liquid separation operation, and the liquid layer of the product after separation is further washed with water. 3. High quality.
A 5-dicarboxybenzenesulfonic acid phosphonium salt can be obtained. If the pH of the reaction system is raised to 4 or higher using a basic substance such as an alkali metal hydroxide, carbonate, or ammonium salt prior to or during the above separation, diphosphonium compounds may be present in the product. Alternatively, it is not preferable because by-products such as alkali metal salts and ammonium salts of 3,5-dicarboxybenzenesulfonic acid are included.
以下、本発明の構成及び効果をより具体的にするため実
施例等を挙げるが、本発明が該実施例に限定されるとい
うものではない。Examples are given below to make the structure and effects of the present invention more concrete, but the present invention is not limited to these Examples.
〈実施例等〉
・試験区分ｌ
フラスコ中に３，５−ジカルボキシベンゼンスルホン酸
２４６ｇ （Ｉモル）及び水５００ｍ１を入れて溶解し
た。このフラスコに、別に水２゛００ｍ１に溶解してお
いた第１表に示す量のテトラブチルホスホニウムクロラ
イドを加え、７０”Ｏに加温して１時間攪拌した。攪拌
中、逐次、白色固状物が析出した。このときの反応液の
ＰＨは１以下であった。反応液から白色固状物を吸引濾
過し、濾別した白色固状物を水５０１で洗浄した後、１
００℃で３時間真空乾燥した。得られた生成物（３゜５
−ジカルボキシベンゼンスルホン酸テトラブチルホスホ
ニウム）について理論収量に対する収率及び分析値を第
１表に示した。<Examples, etc.> - Test Category 1 246 g (1 mol) of 3,5-dicarboxybenzenesulfonic acid and 500 ml of water were placed in a flask and dissolved. Tetrabutylphosphonium chloride in the amount shown in Table 1, which had been separately dissolved in 2,00 ml of water, was added to this flask, heated to 70"O, and stirred for 1 hour. During stirring, white solids gradually formed. A substance was precipitated.The pH of the reaction solution at this time was 1 or less.The white solid was suction-filtered from the reaction solution, and the filtered white solid was washed with water 501.
It was vacuum dried at 00°C for 3 hours. The obtained product (3゜5
-Tetrabutylphosphonium dicarboxybenzenesulfonate) The yield and analytical values relative to the theoretical yield are shown in Table 1.
第１表
注） 准１： ３，５−シカｈポキシペシゼシスル
ネン酸／テトラブチル本ス本ニウムクロライド（モル比
）、零２： ＫＯＩ１ｍｇ／ｇ、以下同じ。Table 1 Note) Substance 1: 3,5-poxypecizesis lunenic acid/tetrabutyl dispensinium chloride (molar ratio), Zero 2: KOI 1 mg/g, the same applies hereinafter.
・試験区分２
試験区分１中のテトラブチルホスホニウムクロライドに
代えて第２表に示す量のテトラフェニルクロライドを用
いた以外は全て試験区分１と同様の操作を行い（反応液
のＰＨは１以下）、生成物（３，５−ジカルボキシベン
ゼンスルホン酸テトラフェニルホスホニウム）を得た。・Test Section 2 All operations were performed in the same manner as in Test Section 1, except that tetraphenyl chloride in the amount shown in Table 2 was used in place of the tetrabutylphosphonium chloride in Test Section 1 (PH of the reaction solution was 1 or less). , the product (tetraphenylphosphonium 3,5-dicarboxybenzenesulfonate) was obtained.
結果を第２表に示した。The results are shown in Table 2.
第２表
固状物を炉別し、４．８％の硫酸と２．７％の水を含有
する粗製３．５−ジカルボキシベンゼンスルホン酸を得
た。The solid material in Table 2 was furnace-separated to obtain crude 3,5-dicarboxybenzenesulfonic acid containing 4.8% sulfuric acid and 2.7% water.
試験区分１中の３．５−ジカルボキシベンゼンスルホン
酸２４６ｇに代えて上記の粗製３，５−ジカルボキシベ
ンゼンスルホン酸２６７ｇを用いた以外は全て試験区分
ｌと同様の操作を行い（反応液のＰＨは１以下）、生成
物（３，５−ジカルボキシベンゼンスルホン酸テトラブ
チルホスホニウム）を得た。結果を第３表に示した。All operations were performed in the same manner as in Test Section 1, except that 267 g of the above crude 3,5-dicarboxybenzenesulfonic acid was used in place of 246 g of 3,5-dicarboxybenzenesulfonic acid in Test Section 1. PH was 1 or less), and a product (tetrabutylphosphonium 3,5-dicarboxybenzenesulfonate) was obtained. The results are shown in Table 3.
第３表
・試験区分３
イソフタル酸と等モルの５０３を含有する２０％発煙硫
酸とを反応させて得たスルホン化マスを。Table 3/Test Category 3 A sulfonated mass obtained by reacting isophthalic acid with 20% oleum containing equimolar 503.
該スルホン化マスの１／３最の水中へ投入溶解し、次い
で冷却放置して、固状物を析出させた。該・試験区分４
実施例３中の３．５−ジカルボキシベンゼンスルホン酸
２４６ｇに代えて３．５−ジカルボキシベンゼンスルホ
ン酸ナトリウム２６８ｇ （Ｉモル３．５−ジカルボキ
シベンゼンスルホン酸と水酸化ナトリウムを等モル中和
したもの）を用いた以外は全て実施例３と同様の操作を
行い（但し、反応液のＰＨは４）、生成物（比較例１．
３．５−ジカルボキシベンゼンスルホン酸テトラブチル
ホスホニウム）を得た。生成物の収率＝９３％、Ａ、Ｖ
、−２１７、５、Ｐ＝６．２％、水分＝０．２９％であ
り、Ａ、Ｖ、及びＰ％に理論値との差が大きかった。One-third of the sulfonated mass was dissolved in water and then left to cool to precipitate a solid substance. Test Category 4 In place of 246 g of 3.5-dicarboxybenzenesulfonic acid in Example 3, 268 g of sodium 3.5-dicarboxybenzenesulfonate (1 mol 3.5-dicarboxybenzenesulfonic acid and sodium hydroxide) The same operations as in Example 3 were carried out except that the product (comparative example 1) was used (however, the pH of the reaction solution was 4).
Tetrabutylphosphonium 3.5-dicarboxybenzenesulfonate) was obtained. Product yield = 93%, A, V
, -217,5, P = 6.2%, water content = 0.29%, and there were large differences in A, V, and P% from the theoretical values.
品質確認のため、以下の方法により１重合試験を行った
ところ、実施例３で得た生成物の場合には）１．！、＝
２３であったのに対し、比較例１で得た生成物の場合
にはに、１．＝ １７０であり、重合速度に悪影響のあ
ることが認められた。For quality confirmation, a single polymerization test was conducted using the following method, and in the case of the product obtained in Example 3) 1. ! ,=
23, whereas in the case of the product obtained in Comparative Example 1, it was 1. = 170, and it was recognized that there was an adverse effect on the polymerization rate.
・・重合試験
ジメチルテレフタレート４８５ｇ、１．４−ブタンジオ
ール５００ｇ、生成物（３，５−ジカルボキシベンゼン
スルホン酸テトラブチルホスホニウム）６３ｇ及びテト
ラブチルチタネートＩｇを反応容器に仕込み、窒素気流
下に１８０℃で２時間、エステル交換を行った０次いで
、減圧下に２６０℃まで昇温し、同温度にて０．５〜１
ｍｄＨの減圧下に２時間重縮合反応を行った。そして
得られた重合体のに、■、値をメルトインデクサ−によ
り測定した。...Polymerization test 485 g of dimethyl terephthalate, 500 g of 1,4-butanediol, 63 g of the product (tetrabutylphosphonium 3,5-dicarboxybenzenesulfonate) and Ig of tetrabutyl titanate were charged into a reaction vessel, and heated at 180°C under a nitrogen stream. Transesterification was carried out for 2 hours at 0, then the temperature was raised to 260℃ under reduced pressure, and at the same temperature
Polycondensation reaction was carried out for 2 hours under reduced pressure of mdH. Then, the value of (1) of the obtained polymer was measured using a melt indexer.
〈発明の効果〉
各実施例の結果からも明らかなように、以上説明した本
発明には、実際の使用に際して悪影響を及ぼすことのな
い高品質の３，５−ジカルボキシベンゼンスルホン酩ホ
スホニウム塩を工業上収率良く製造することができると
いう効果がある。<Effects of the Invention> As is clear from the results of each example, the present invention described above contains a high quality 3,5-dicarboxybenzenesulfone phosphonium salt that does not have any adverse effects in actual use. It has the effect of being able to be produced industrially with good yield.
特許出願人 竹本油脂株式会社 代理人 弁理士 入 山 宏 正Patent applicant: Takemoto Yushi Co., Ltd. Agent: Hiroshi Yama, Patent Attorney
Claims (1)
シベンゼンスルホン酸ホスホニウム塩の製造において、
水を５０重量％以上含有する水系溶媒中で、３，５−ジ
カルボキシベンゼンスルホン酸と下記一般式（II）で示
されるホスホニウム化合物とを複分解反応させ、次いで
酸性条件下にその反応液から生成物である３，５−ジカ
ルボキシベンゼンスルホン酸ホスホニウム塩を分離する
ことを特徴とする３，５−ジカルボキシベンゼンスルホ
ン酸ホスホニウム塩の製造方法。 一般式（ I ） ▲数式、化学式、表等があります▼ 一般式（II） ▲数式、化学式、表等があります▼ ［Ｒ＾１〜Ｒ＾４：少なくとも一つが炭素数１〜１８の
アルキル基、フェニル基又はベンジ ル基である一価の有機基 Ｘ：Ｃｌ又はＢｒ］ ２、反応液から生成物を分離した後、更に水洗する請求
項１記載の３，５−ジカルボキシベンゼンスルホン酸ホ
スホニウム塩の製造方法。 ３、分離する際の反応液のＰＨが３．５以下である請求
項１又は２記載の３，５−ジカルボキシベンゼンスルホ
ン酸ホスホニウム塩の製造方法。 ４、式（II）で示されるホスホニウム化合物のＸがＣｌ
である請求項１、２又は３記載の３，５−ジカルボキシ
ベンゼンスルホン酸ホスホニウム塩の製造方法。 ５、式（II）で示されるホスホニウム化合物のＲ＾１〜
Ｒ＾３が同一であって且つ炭素数１〜８のアルキル基又
はフェニル基であり、Ｒ＾４が炭素数１〜１８のアルキ
ル基又はフェニル基である請求項１、２、３又は４記載
の３，５−ジカルボキシベンゼンスルホン酸ホスホニウ
ム塩の製造方法。[Claims] 1. In the production of 3,5-dicarboxybenzenesulfonic acid phosphonium salt represented by the following general formula (I),
In an aqueous solvent containing 50% by weight or more of water, 3,5-dicarboxybenzenesulfonic acid and a phosphonium compound represented by the following general formula (II) are subjected to a metathesis reaction, and then produced from the reaction solution under acidic conditions. 1. A method for producing 3,5-dicarboxybenzenesulfonic acid phosphonium salt, which comprises separating 3,5-dicarboxybenzenesulfonic acid phosphonium salt, which is a product. General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R^1 to R^4: At least one alkyl group with 1 to 18 carbon atoms , phenyl group or benzyl group, monovalent organic group manufacturing method. 3. The method for producing 3,5-dicarboxybenzenesulfonic acid phosphonium salt according to claim 1 or 2, wherein the pH of the reaction solution during separation is 3.5 or less. 4. X of the phosphonium compound represented by formula (II) is Cl
The method for producing a 3,5-dicarboxybenzenesulfonic acid phosphonium salt according to claim 1, 2 or 3. 5. R^1~ of the phosphonium compound represented by formula (II)
Claim 1, 2, 3 or 4, wherein R^3 are the same and are an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R^4 is an alkyl group having 1 to 18 carbon atoms or a phenyl group. A method for producing 3,5-dicarboxybenzenesulfonic acid phosphonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP879789A JPH0819143B2 (en) | 1989-01-17 | 1989-01-17 | Method for producing 3,5-dicarboxybenzenesulfonic acid phosphonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP879789A JPH0819143B2 (en) | 1989-01-17 | 1989-01-17 | Method for producing 3,5-dicarboxybenzenesulfonic acid phosphonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02188592A true JPH02188592A (en) | 1990-07-24 |
| JPH0819143B2 JPH0819143B2 (en) | 1996-02-28 |
Family
ID=11702858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP879789A Expired - Fee Related JPH0819143B2 (en) | 1989-01-17 | 1989-01-17 | Method for producing 3,5-dicarboxybenzenesulfonic acid phosphonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0819143B2 (en) |
-
1989
- 1989-01-17 JP JP879789A patent/JPH0819143B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0819143B2 (en) | 1996-02-28 |
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