JPS62242657A - Production of 5-sulfoisophthalic acid ester derivative - Google Patents
Production of 5-sulfoisophthalic acid ester derivativeInfo
- Publication number
- JPS62242657A JPS62242657A JP8577886A JP8577886A JPS62242657A JP S62242657 A JPS62242657 A JP S62242657A JP 8577886 A JP8577886 A JP 8577886A JP 8577886 A JP8577886 A JP 8577886A JP S62242657 A JPS62242657 A JP S62242657A
- Authority
- JP
- Japan
- Prior art keywords
- sulfoisophthalic acid
- acid ester
- group
- ester derivative
- producing
- 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
- -1 5-sulfoisophthalic acid ester Chemical class 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 14
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- ZSOXGHJGIBWVFY-UHFFFAOYSA-N triphosphanium 2-sulfonatobenzene-1,3-dicarboxylate Chemical compound [PH4+].[PH4+].[PH4+].[O-]C(=O)c1cccc(C([O-])=O)c1S([O-])(=O)=O ZSOXGHJGIBWVFY-UHFFFAOYSA-N 0.000 claims 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical class OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007796 conventional method Methods 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 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 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- QCSIRLGSMWDFMF-UHFFFAOYSA-K 5-sulfonatobenzene-1,3-dicarboxylate tetrabutylphosphanium Chemical compound [O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC QCSIRLGSMWDFMF-UHFFFAOYSA-K 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005649 metathesis reaction Methods 0.000 description 4
- XUQXNWSQUUYHLJ-UHFFFAOYSA-N 4,6-dimethyl-5-sulfobenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(=C(C=C1C(=O)O)C(=O)O)C)S(=O)(=O)O XUQXNWSQUUYHLJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 3
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 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 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FQBFNWHUCKKJNN-UHFFFAOYSA-K CCCC[P+](C)(CCCC)CCCC.CCCC[P+](C)(CCCC)CCCC.CCCC[P+](C)(CCCC)CCCC.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O Chemical compound CCCC[P+](C)(CCCC)CCCC.CCCC[P+](C)(CCCC)CCCC.CCCC[P+](C)(CCCC)CCCC.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O FQBFNWHUCKKJNN-UHFFFAOYSA-K 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002202 Polyethylene glycol 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- UWTQSUHAFRGPMD-UHFFFAOYSA-L disodium 4,6-bis(2-hydroxyethyl)-5-sulfobenzene-1,3-dicarboxylate Chemical compound S(=O)(=O)(O)C=1C(=C(C=C(C(=O)[O-])C=1CCO)C(=O)[O-])CCO.[Na+].[Na+] UWTQSUHAFRGPMD-UHFFFAOYSA-L 0.000 description 1
- DJZZPSISXZXXNC-UHFFFAOYSA-L disodium 4,6-dimethyl-5-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].CC1=C(C(=C(C=C1C(=O)[O-])C(=O)[O-])C)S(=O)(=O)O.[Na+] DJZZPSISXZXXNC-UHFFFAOYSA-L 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
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid 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
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-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
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 description 1
- XKFPGUWSSPXXMF-UHFFFAOYSA-N tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC XKFPGUWSSPXXMF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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５−スルホイソフタル酸エステル誘導体の製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing 5-sulfoisophthalic acid ester derivatives.
５−スルホイソフタル酸エステル誘導体は、ポリエチレ
ンテレフタレートに代表される網台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、５−スルホジメチルイソフタル酸ナトリ
ウムや５−スルホジ（２−ヒドロキシエチル）イソフタ
ル酸ナトリウムは、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、更にはコーティング剤や接着剤及び塗料
等へ用いられる給金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。ところ
が、上記のような５−スルホイソフタル酸エステルの金
属塩は、工業上域に有用ではあるが、使用する段階で、
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
合には、いくつかの不都合がある。例えば、５−スルホ
イソフタル酸エステルの金属塩がポリエチレンテレフタ
レートに対して溶解性が悪いため、共重合物の透明性が
低下し、これを繊維にした場合には染色後の仕上シの鮮
明さを悪くしたシ、また共重合時の金属塩の悪影響で共
重合物が着色したシすること等である。5-Sulfoisophthalic acid ester derivatives are copolymerized to impart useful properties to mesh-type polymers typified by polyethylene terephthalate, and are used in various fields. In particular, sodium 5-sulfodimethylisophthalate and sodium 5-sulfodi(2-hydroxyethyl)isophthalate are industrially used in large quantities as copolymerization monomers that make polyester fibers, which have a major problem with dyeability, cationic dyeable. used in Its application fields are extremely wide, including use for nylon for the same purpose, and furthermore, for the purpose of improving adhesion of molded polymers used in coating agents, adhesives, paints, etc. However, although the metal salts of 5-sulfoisophthalic acid esters as described above are useful in industrial fields, they
In particular, there are some disadvantages when copolymerizing to polyethylene terephthalate. For example, the metal salt of 5-sulfoisophthalic acid ester has poor solubility in polyethylene terephthalate, which reduces the transparency of the copolymer. In addition, the copolymer may be colored due to the adverse effects 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
されておシ、その一つとして、スルホン酸基の対イオン
を有機ホスホニウムにする方法がある（特公昭４７−２
２３３４号公報、ドイツ特許出願公開第２０４４９３１
号公報）０本発明は、対イオンにホスホニウムを有する
５−スルホイソ７タル酸エステル誘導体を製造する方法
に関するものである。Therefore, several methods have been proposed to alleviate these disadvantages, one of which is a method of using organic phosphonium as the counter ion of the sulfonic acid group (Japanese Patent Publication No. 47-2
Publication No. 2334, German Patent Application Publication No. 2044931
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a 5-sulfoisoheptatarate derivative having phosphonium as a counter ion.
〈従来の技術、その問題点〉
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いはアルカリ土類金
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５−スルホイ
ソフタル酸エステル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２０４
４９３１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５−スルホイソフタル酸ジメチルの製造に
際し、５−スルホジメチルイソフタル酸金属塩とホスホ
ニウム塩とを反応させて目的物を得ている。<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 5-sulfoisophthalic acid ester derivatives having phosphonium as a counterion (German Patent Application No. 204
4931, U.S. Patent No. 4006123)
. That is, in these conventional examples, when producing dimethyl 5-sulfoisophthalate having phosphonium as a counter ion, the desired product is obtained by reacting a metal salt of 5-sulfodimethylisophthalate with a phosphonium salt.
しかし、本発明者らが同様の目的物全書るべく上記の反
応を検討したところ、該反応によると、生成物中に未反
応の原料ホスホニウム塩が混入し易く、シたがって生成
物が加熱時に着色し易くなり、以後の精製も著るしく厄
介で、未反応の原料ホスホニウム塩の混入を減少させよ
うとすると、大過剰の５−スルホジメチルイソフタル酸
金属塩が必要になるという問題点があった。However, when the present inventors studied the above-mentioned reaction in order to write all the similar target products, it was found that according to the reaction, unreacted raw material phosphonium salt is likely to be mixed into the product, and therefore the product is It becomes easy to color, and subsequent purification is extremely troublesome, and there is a problem in that a large excess of 5-sulfodimethylisophthalate metal salt is required to reduce the contamination of unreacted raw material phosphonium salt. Ta.
〈発明が解決しようとする問題点、その解決手段〉
本発明は、叙上の如き従来の問題点を解決して、工業上
有利な方法で、収率良く、そして高品質の、対イオンに
ホスホニウムを有する５−スルホイソフタル酸エステル
誘導体を製造する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 counterions with good yield and high quality using an industrially advantageous method. A method for producing a phosphonium-containing 5-sulfoisophthalic acid ester derivative 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
、水を主体とする水系溶媒中で、カルボキシル基が遊離
状態の５−スルホイソフタル酸金属塩とホスホニウム塩
とを反応させ、しかる後にカルボキシル基をエステル化
する方法が正しく好適であることを見出し、本発明を完
成するに到ったのである。As a result of intensive research from the above viewpoint, the present inventors have found that a metal salt of 5-sulfoisophthalate in which the carboxyl group is in a free state is reacted with a phosphonium salt in an aqueous solvent mainly composed of water, and then They discovered that the method of esterifying carboxyl groups is correct and suitable, and completed the present invention.
すなわち本発明は、
対イオンにホスホニウムを有する５−スルホイソフタル
酸エステル誘導体を製造するに際し、下記式（Ｉ）で示
される５−スルホイソフタル酸塩と下記式（Ｉ）で示さ
れるホスホニウム塩とを、少なくとも５０重量係以上の
水を含有する水系溶媒中で反応させ、生成した５−スル
ホインフタル酸ホスホニウム塩を該溶媒中から分離した
後にそのカルボキシル基をエステル化することを特徴と
する５−スルホインフタル酸エステル誘導体の製造方法
に係る。That is, in the present invention, when producing a 5-sulfoisophthalic acid ester derivative having phosphonium as a counter ion, a 5-sulfoisophthalate salt represented by the following formula (I) and a phosphonium salt represented by the following formula (I) are combined. 5-, characterized in that the reaction is carried out in an aqueous solvent containing at least 50% by weight of water, and the produced 5-sulfoiphthalic acid phosphonium salt is separated from the solvent, and then its carboxyl group is esterified. The present invention relates to a method for producing a sulfoiphthalate derivative.
〔但し、Ｍｎ＠： ｎ価の金属イオン又はアンモニウム
イオン
ｎ ：１〜３の整数
Ｒ１−Ｒ４：少なくとも一つが炭素数１〜１８のアルキ
ル基又はベンジル基であ
る１価の有機基
Ｘｏ：アニオン 〕
本発明において、式（Ｉ）で示される５−スルホイソフ
タル酸塩は通常、インフタル酸を無水硫酸や発煙硫酸で
スルホン化し、次いで中和して得られるが、かかる５−
スルホイソフタル酸塩は、精製されたものであっても、
又はその製造途中で硫酸や硫酸ナトリウム等の不純物を
含んだものであってもよい。式（Ｉ）中のＭの具体例と
しては、Ｎａ ｓＫ％Ｌｉ ％ Ｃａ ％ Ｍｇ等が有
利に使用できるが、アンモニウムやテトラエチルアンモ
ニウム等でもよい。[However, Mn@: n-valent metal ion or ammonium ion n: integer of 1 to 3 R1-R4: monovalent organic group at least one of which is an alkyl group or benzyl group having 1 to 18 carbon atoms Xo: anion] In the present invention, the 5-sulfoisophthalate represented by formula (I) is usually obtained by sulfonating inphthalic acid with sulfuric anhydride or fuming sulfuric acid, and then neutralizing it.
Sulfoisophthalate, even if purified,
Alternatively, it may contain impurities such as sulfuric acid or sodium sulfate during its production. As a specific example of M in formula (I), Na sK % Li % Ca % Mg can be advantageously used, but ammonium, tetraethylammonium, etc. may also be used.
また本発明において、式（ＩＩ）で示されるホスホニウ
ム塩のうち、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、トリフチルベンジルホスホニ
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。一方、式（Ｉ）で示されるホス
ホニウム塩のうち、そのアニオン部の具体例としてはＣ
１゜Ｂｒ、Ｉ、ＣＨ３ＳＯ４、ＣＨ３ＳＯ４等が挙げら
れる。本発明で使用するホスホニウム塩は、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。Further, in the present invention, among the phosphonium salts represented by formula (II), specific examples of the phosphonium cation moiety include tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tributylmonomethylphosphonium, tributylmonoethylphosphonium, tributylmonoctyl Examples include aliphatic phosphoniums such as phosphonium, tributylmonotetradecylphosphonium, tributylmonoctadecylphosphonium, trioctylmonomethylphosphonium, and aromatic phosphoniums such as triphenylmethylphosphonium, triphenylethylphosphonium, triethylbenzylphosphonium, and triphthylbenzylphosphonium. Furthermore, it may be a phosphonium having a substituent such as an ether group, an ester group, or an amide group. On the other hand, among the phosphonium salts represented by formula (I), specific examples of the anion moiety include C
Examples include 1°Br, I, CH3SO4, CH3SO4, and the like. The phosphonium salts used in the present invention consist of a wide range of combinations of cation moieties and anion moieties as exemplified above.
本発明において水系溶媒は、水単独、或いは水と水に可
溶な有機溶媒との混合溶媒である。水単独が好ましいが
、水可溶な有機溶媒、例えばメタノール、エタノール、
インプロパツール、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％未満で含
有する水系溶媒でもよい。In the present invention, the aqueous solvent is water alone or a mixed solvent of water and a water-soluble organic solvent. Water alone is preferred, but water-soluble organic solvents such as methanol, ethanol,
An aqueous solvent containing less than 50% by weight of impropatol, dioxane, acetone, tetrahydrofuran, ethylene glycol, etc. may also be used.
本発明は、上記のような水系溶媒中で、式（Ｉ）で示さ
れる５−スルホインフタル酸塩と式（Ｉ）で示されるホ
スホニウム塩とを複分解反応させる。In the present invention, a 5-sulfoinphthalate salt represented by formula (I) and a phosphonium salt represented by formula (I) are subjected to a metathesis reaction in an aqueous solvent as described above.
濃度や温度等の反応条件の最適範囲は、ホスホニウム塩
によって大きく異なるが、反応モル比は以後の精製や経
済性等から理論比に近くすることが好ましい。複分解反
応の結果、生成する粗生成物は、５−スルホジメチルイ
ソフタル酸金属塩を原料に用いる従来法では本来その融
点が室温より高いものでも結晶化し難いために反応系で
油状に分離する傾向が強いのに比べ、５−スルホイソフ
タル酸金属塩を用いる本発明では反応系で結晶となって
析出するために分離操作が容易であり且つ品質面でも有
利である。Although the optimum range of reaction conditions such as concentration and temperature varies greatly depending on the phosphonium salt, the reaction molar ratio is preferably close to the theoretical ratio from the viewpoint of subsequent purification and economic efficiency. As a result of the metathesis reaction, in the conventional method using 5-sulfodimethylisophthalic acid metal salt as a raw material, the crude product tends to separate into an oily state in the reaction system because it is difficult to crystallize even if its melting point is higher than room temperature. In contrast, the present invention, which uses 5-sulfoisophthalic acid metal salt, is advantageous in terms of quality as well as easier separation operation because it crystallizes and precipitates in the reaction system.
複分解反応による生成物を、水系溶媒で形成される反応
系から分離した後、そのカルボキシル基をエステル化す
る。エステル化を生成水の除去が難しい系で行なう場合
には、エステル化の反応率を上げるため、前もって上記
生成物を乾燥しておくことが好ましい。エステル化につ
いては、メタノールの如き低沸点アルコールを用いる場
合の加圧法、エチレングリコールの如き高沸点アルコー
ルを用いる場合の常圧或いは減圧法、アルキレンオキサ
イドの付加による方法等、周知の方法が適用でき、この
際、必要に応じて触媒を使用することもできる。本発明
は、エステル化反応それ自体の方法や条件等を特に限定
するものではない。After the product of the metathesis reaction is separated from the reaction system formed by the aqueous solvent, its carboxyl group is esterified. When esterification is carried out in a system in which it is difficult to remove produced water, it is preferable to dry the product in advance in order to increase the esterification reaction rate. For esterification, well-known methods can be applied, such as a pressurization method when using a low-boiling alcohol such as methanol, a normal pressure or reduced pressure method when using a high-boiling alcohol such as ethylene glycol, and a method by addition of alkylene oxide. At this time, a catalyst may be used if necessary. The present invention does not particularly limit the method or conditions of the esterification reaction itself.
本発明で得られる５−スルホイソフタル酸エステル誘導
体は、エステル化剤として何を用いるかによシ、その構
造を広範に取り得るが、工業的にはメチルエステル誘導
体及び２−ヒドロキシエチルエステル誘導体が重要であ
る。The 5-sulfoisophthalic acid ester derivative obtained in the present invention can have a wide range of structures depending on what is used as the esterifying agent, but industrially, methyl ester derivatives and 2-hydroxyethyl ester derivatives are used. is important.
以下、本発明の実施例等を挙げて本発明の構成及び効果
をより具体的にするが、本発明はそれらの実施例に限定
されるものではない。EXAMPLES Hereinafter, the structure and effects of the present invention will be made more concrete by giving examples of the present invention, but the present invention is not limited to these examples.
〈実施例等〉
・実施例１
温度計及び攪拌機付きのフラスコに５−スルホイソフタ
ル酸モノナトリウム塩８０．４ｇ（０，３モル）及び水
３００ ｍｌを入れて溶解した。このフラスコに、別に
１８０ ｔｅｌの水へ溶解しておいたテトラブチルホス
ホニウムプロマイ）”１０１．７９（０゜３モル）を加
え、６０℃に加温して、１時間攪拌した。析出した固形
物を吸引ｒ過し、水６００ｍで洗浄した後に、１２０℃
にて４時間減圧下で乾燥し、５−スルホイソフタル酸テ
トラブチルホスホニウム塩（Ａ−１）１４８．２ｇを得
た（収率９８チ、対５−スルホイソフタル酸モノナトリ
ウム塩、以下同じ）。生成物（Ａ−１）の品質は以下の
通りであった。<Examples, etc.> - Example 1 80.4 g (0.3 mol) of 5-sulfoisophthalic acid monosodium salt and 300 ml of water were placed in a flask equipped with a thermometer and a stirrer and dissolved therein. To this flask was added 101.79 (0.3 mol) of tetrabutylphosphonium puramine, which had been separately dissolved in 180 tel of water, heated to 60°C and stirred for 1 hour. After suctioning the material and washing it with 600 m of water, it was heated to 120°C.
The mixture was dried under reduced pressure for 4 hours to obtain 148.2 g of 5-sulfoisophthalic acid tetrabutylphosphonium salt (A-1) (yield: 98 g, based on 5-sulfoisophthalic acid monosodium salt; the same applies hereinafter). The quality of the product (A-1) was as follows.
Ｂｒ＝ ０．０５ ％、酸価＝２２１．５（計算値２２
２゜２）、水分＝０．１５％
次いで、生成物（Ａ−１）１００ｆ及びメタノール１９
２ｇを攪拌機付きの加圧反応装置に入れ、常法によって
、１９０℃加圧下でメチルエステル化を行なった。反応
液よシ溶媒を除去し、ジメチルエステル化物（Ｂ−１）
５３０．３９を得た（エステル化率９４％）。Br = 0.05%, acid value = 221.5 (calculated value 22
2゜2), moisture = 0.15% Next, 100f of product (A-1) and methanol 19
2 g was placed in a pressurized reactor equipped with a stirrer, and methyl esterification was carried out at 190° C. under pressure according to a conventional method. Remove the solvent from the reaction solution and dimethyl ester compound (B-1)
530.39 was obtained (esterification rate 94%).
ジメチルエステル化物（Ｉ３−１）３ｆを試験管にとシ
、内部を窒素置換して、２５０℃の浴中に３０分間浸し
た後に取シ出し、冷却して着色の有無を観察したところ
、着色は認められなかった。Dimethyl ester compound (I3-1) 3f was placed in a test tube, the interior was replaced with nitrogen, and the tube was immersed in a bath at 250°C for 30 minutes, taken out, cooled, and observed for the presence or absence of coloration. was not recognized.
・実施例２
実施例１と同様にして得た生成物（Ａ−１）１００ｇ及
びエチレングリコール２００ ｆｉｔフラスコに入れ、
２００℃に加熱して常法によシ塔頂から少量の留出物を
除去しながら４時間攪拌した。- Example 2 100 g of the product (A-1) obtained in the same manner as in Example 1 and ethylene glycol were placed in a 200 fit flask,
The mixture was heated to 200° C. and stirred for 4 hours while removing a small amount of distillate from the top of the column in a conventional manner.
得うれたジヒドロキシエチルエステル化物（工 −ステ
ル化率９９チ）の４０チ工チレングリコール溶液１００
ｇをコンデンサー付きのフラスコに入れ、還流下に３時
間加熱して着色の有無を調べたところ、着色は殆んど認
められず、その色相はハーゼン＆４０であった。A solution of 40% dihydroxyethyl ester of the obtained dihydroxyethyl ester (sterification rate: 99%) in 100% polyethylene glycol.
g was placed in a flask equipped with a condenser and heated under reflux for 3 hours, and the presence or absence of coloration was examined. Almost no coloration was observed, and the hue was Hazen & 40.
・実施例３
テトラブチルホスホニウムブロマイド１０１．７ｇの代
わシにトリブチルメチルホスホニウムクロライド７５．
８ｇを使用し、その他は実施例１と同様にして、５−ス
ルホイソフタル酸トリブチルメチルホスホニウム塩（Ａ
−２）１３５．８ｆｔ−得た（収率９８チ）。生成物（
Ａ−２）の品質は以下の通りであった。- Example 3 In place of 101.7 g of tetrabutylphosphonium bromide, 75.0 g of tributylmethylphosphonium chloride was used.
8 g of 5-sulfoisophthalic acid tributylmethylphosphonium salt (A
-2) 135.8 ft- was obtained (yield: 98 ft). product (
The quality of A-2) was as follows.
Ｃ１＝０．０２Ｔｏ、酸価＝２４１．５（計算値２４２
゜４）、水分＝ ０．２３チ
次いで、実施例１と同様にして、ジメチルエステル化物
（Ｂ−２）を得、更にこれを実施例１と同様にして着色
テストをしたところ、着色は認められなかった。C1 = 0.02To, acid value = 241.5 (calculated value 242
゜4), Moisture = 0.23% Next, dimethyl ester compound (B-2) was obtained in the same manner as in Example 1, and a coloring test was performed on this in the same manner as in Example 1, and no coloring was observed. I couldn't.
ｅ実施例４〜６
第１表記載の各側について、同表記載の内容で、実施例
１又は実施例２と同様にして反応、エステル化及び着色
テストを行なった。結果を同表に示した。e Examples 4 to 6 For each side listed in Table 1, reaction, esterification, and coloring tests were conducted in the same manner as in Example 1 or Example 2, with the contents listed in Table 1. The results are shown in the same table.
第１表
注）Ｍ、Ｒ１〜Ｒ’、Ｘは前述の式（Ｉ）又は（Ｉ）の
それぞれに相当する０生成物は前述の（Ａ−１）や（Ａ
−２）の段階に相当するもので、エステル化物は前述の
（Ｂ−１）や（Ｂ−２）の段階に相当するもの。俤は全
て重量係。Table 1 Note) M, R1 to R', and X are 0 corresponding to the above formula (I) or (I) respectively.
This corresponds to the step -2), and the esterified product corresponds to the above-mentioned steps (B-1) and (B-2). All prices are based on weight.
酸価の下段は計算値。＊ＩＩ書ゾヒドロキレニ＋１し。The lower row of acid values is the calculated value. *Book II Zohydrokireni +1.
・比較例１
温度計及び攪拌機付きのフラスコ［５−スルホイソフタ
ル酸ジメチルモノナトリウム塩８８．８ｇ（０，３モル
）及びテトラブチルホスホニウムブロマイド１０１．７
ｇ（０，３モル）並びに水４５ ｏＭｌを入れて溶解し
、６０℃にて１時間攪拌した。分離した油層を分液ロー
トで取り出し、更に分液ロートで水ｘｓｏｄづつを用い
て２回洗浄した。次いで、５０ ｍ Ｋｇ以下の減圧下
に、１２０℃にて４時間乾燥し、生成エステル化物１２
７．７９を得た（収率ＳＯＳ、対５−スルホイソフタル
酸ジメチルモノナトリウム塩、以下同じ）。生成エステ
ル化物の品質は以下の通りであった。Comparative Example 1 Flask with thermometer and stirrer [88.8 g (0.3 mol) of 5-sulfoisophthalic acid dimethyl monosodium salt and 101.7 g of tetrabutylphosphonium bromide
g (0.3 mol) and 45 oMl of water were added thereto and dissolved, and the mixture was stirred at 60°C for 1 hour. The separated oil layer was taken out with a separatory funnel, and further washed twice with xsod of water in the separatory funnel. Next, it was dried at 120° C. for 4 hours under reduced pressure of 50 m kg or less to obtain the esterified product 12.
7.79 was obtained (yield SOS, vs. 5-sulfoisophthalic acid dimethyl monosodium salt, the same hereinafter). The quality of the produced esterified product was as follows.
Ｂｒ＝ ０．９７ Ｔｏ、ケン化価＝２０２．７（計算
値２１０．５）、水分＝ ０．１２チ
生成エステル化物を実施例１と同様にして着色テストを
したところ、明確に黄色に着色した。Br = 0.97 To, saponification value = 202.7 (calculated value 210.5), moisture = 0.12 When the produced esterified product was subjected to a coloring test in the same manner as in Example 1, it was clearly colored yellow. did.
・比較例２
５−スルホイソフタル酸ジメチルモノナトリウム塩８８
．８ｇを１３：（，２１ｉＦ（０，４５モル）に変え、
また水１５０ｇ／を６００１１ｄに変えて、その他は比
較例１と同様にして生成エステル化物を得た（収率８８
チ）。生成エステル化物の品質は次の通シであった０
Ｂｒ＝０．２０％、ケン化価＝２０８．７（計算値２１
０．５）、水分＝ ０．１２係
生成エステル化物を実施例１と同様だして着色テストを
したところ、明確に黄色に着色した。- Comparative Example 2 5-sulfoisophthalic acid dimethyl monosodium salt 88
．． Change 8g to 13:(,21iF (0.45 mol),
In addition, an ester product was obtained in the same manner as in Comparative Example 1 except that 150 g of water was replaced with 60011 d (yield: 88
blood). The quality of the produced esterified product was as follows: 0 Br = 0.20%, saponification value = 208.7 (calculated value 21
0.5), moisture content = 0.12. When the produced esterified product was subjected to a coloring test in the same manner as in Example 1, it was clearly colored yellow.
・比較例３
テトラブチルホスホニウムブロマイド１０１．７ｇをト
リオクチルメチルホスホニウムクロライド１２６．２９
（０，３モル）に変え、その他は比較例１と同様にして
生成エステル化物を得た（収率９０％）。生成エステル
化物の品質は次の通シであった０
Ｃ１＝ ０．３１係、ケン化価＝１７０．２（計算値１
７７．８）、水分＝ ０．１０係
生成エステル化物を実施例１と同様にして着色テストを
したところ、明確に黄色に着色した。- Comparative Example 3 101.7g of tetrabutylphosphonium bromide was mixed with 126.29g of trioctylmethylphosphonium chloride
(0.3 mol), and in the same manner as in Comparative Example 1 except that an ester product was obtained (yield: 90%). The quality of the produced esterified product was as follows: 0 C1 = 0.31 coefficient, saponification value = 170.2 (calculated value 1
77.8), water content = 0.10 When the produced esterified product was subjected to a coloring test in the same manner as in Example 1, it was clearly colored yellow.
〈発明の効果〉
各比較例に対する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、工業上有利な方法で、収率
良く、そして高品質の、対イオンにホスホニラムラ有す
る５−スルホインフタル酸エステル誘導体を製造するこ
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 with respect to each Comparative Example, the present invention described above has the following advantages: There is an effect that a 5-sulfoiphthalic acid ester derivative can be produced.
Claims (1)
タル酸エステル誘導体を製造するに際し、下記式（ I
）で示される５−スルホイソフタル酸塩と下記式（II）
で示されるホスホニウム塩とを、少なくとも５０重量％
以上の水を含有する水系溶媒中で反応させ、生成した５
−スルホイソフタル酸ホスホニウム塩を該溶媒中から分
離した後にそのカルボキシル基をエステル化することを
特徴とする５−スルホイソフタル酸エステル誘導体の製
造方法。 （ I ）▲数式、化学式、表等があります▼ （II）▲数式、化学式、表等があります▼ 〔但し、Ｍ＾ｎ＾■：ｎ価の金属イオン又はアンモニウ
ムイオン ｎ：１〜３の整数 Ｒ＾１〜Ｒ＾４：少なくとも一つが炭素数１〜１８のア
ルキル基又はベンジル基 である１価の有機基 Ｘ＾■：アニオン〕 ２ 式（II）のＲ＾１〜Ｒ＾４のうちで、一つが炭素数
１〜１８のアルキル基又はベンジル基であり、残りの三
つが同一であって炭素数２〜１８の脂肪族炭化水素基、
アラルキル基又は芳香族炭化水素基である特許請求の範
囲第１項記載の５−スルホイソフタル酸エステル誘導体
の製造方法。 ３ カルボキシル基をメチルエステル化する特許請求の
範囲第１項又は第２項記載の５−スルホイソフタル酸エ
ステル誘導体の製造方法。 ４ カルボキシル基をヒドロキシエチルエステル化する
特許請求の範囲第１項又は第２項記載の５−スルホイソ
フタル酸エステル誘導体の製造方法。[Claims] 1. When producing a 5-sulfoisophthalic acid ester derivative having phosphonium as a counterion, the following formula (I
) and the following formula (II)
at least 50% by weight of a phosphonium salt represented by
5 produced by reacting in an aqueous solvent containing the above water.
- A method for producing a 5-sulfoisophthalic acid ester derivative, which comprises separating the sulfoisophthalic acid phosphonium salt from the solvent and then esterifying its carboxyl group. (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, M^n^■: n-valent metal ion or ammonium ion n: an integer from 1 to 3 R^1 to R^4: Monovalent organic group in which at least one is an alkyl group or benzyl group having 1 to 18 carbon atoms X^■: Anion] 2 Among R^1 to R^4 of formula (II) and one is an alkyl group or benzyl group having 1 to 18 carbon atoms, and the remaining three are the same aliphatic hydrocarbon group having 2 to 18 carbon atoms,
The method for producing a 5-sulfoisophthalic acid ester derivative according to claim 1, which is an aralkyl group or an aromatic hydrocarbon group. 3. A method for producing a 5-sulfoisophthalic acid ester derivative according to claim 1 or 2, which comprises converting a carboxyl group into a methyl ester. 4. A method for producing a 5-sulfoisophthalic acid ester derivative according to claim 1 or 2, which comprises converting a carboxyl group into a hydroxyethyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8577886A JPS62242657A (en) | 1986-04-14 | 1986-04-14 | Production of 5-sulfoisophthalic acid ester derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8577886A JPS62242657A (en) | 1986-04-14 | 1986-04-14 | Production of 5-sulfoisophthalic acid ester derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62242657A true JPS62242657A (en) | 1987-10-23 |
| JPH055827B2 JPH055827B2 (en) | 1993-01-25 |
Family
ID=13868338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8577886A Granted JPS62242657A (en) | 1986-04-14 | 1986-04-14 | Production of 5-sulfoisophthalic acid ester derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62242657A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02188593A (en) * | 1989-01-17 | 1990-07-24 | Takemoto Oil & Fat Co Ltd | Production of 3,5-dicarboxybenzenesulfonic acid phosphonium salt |
| CN113980258A (en) * | 2021-11-10 | 2022-01-28 | 重庆文理学院 | Antibacterial flame-retardant toughened multifunctional ionomer auxiliary agent and preparation method and application thereof |
-
1986
- 1986-04-14 JP JP8577886A patent/JPS62242657A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02188593A (en) * | 1989-01-17 | 1990-07-24 | Takemoto Oil & Fat Co Ltd | Production of 3,5-dicarboxybenzenesulfonic acid phosphonium salt |
| CN113980258A (en) * | 2021-11-10 | 2022-01-28 | 重庆文理学院 | Antibacterial flame-retardant toughened multifunctional ionomer auxiliary agent and preparation method and application thereof |
| CN113980258B (en) * | 2021-11-10 | 2023-01-17 | 重庆文理学院 | Antibacterial flame-retardant toughened multifunctional ionomer auxiliary agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH055827B2 (en) | 1993-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |