JP2012087111A - Synthesis of dimethyl 2-sulfoterephthalate sodium, and addition to polycondensation system of dimethyl terephthalate and ethylene glycol - Google Patents

Synthesis of dimethyl 2-sulfoterephthalate sodium, and addition to polycondensation system of dimethyl terephthalate and ethylene glycol Download PDF

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JP2012087111A
JP2012087111A JP2010247881A JP2010247881A JP2012087111A JP 2012087111 A JP2012087111 A JP 2012087111A JP 2010247881 A JP2010247881 A JP 2010247881A JP 2010247881 A JP2010247881 A JP 2010247881A JP 2012087111 A JP2012087111 A JP 2012087111A
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sulfoterephthalate
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Shigeo Tanimoto
重夫 谷本
Katsumi Tanimoto
勝美 谷本
Tamako Tanimoto
たま子 谷本
Katsuya Tomizawa
勝也 富沢
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MONDA SHASHINGATA SEISAKUSHO KK
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Abstract

PROBLEM TO BE SOLVED: To examine physical properties of a straight line-shaped polyethylene terephthalate having a sulfone group, which is obtained by synthesizing dimethyl 2-sulfoterephthalate sodium with a purity of >98.0% and adding the same to a polycondensation system of dimethyl terephthalate and ethylene glycol.SOLUTION: A method for synthesizing dimethyl 2-sulfoterephthalate sodium with a purity of >98.0%, by sulfonating terephthalic acid with sulfur trioxide, then at first removing excessive sulfur trioxide, conducting esterification to produce dimethyl ester, and via treatment with a calcium hydroxide suspended aqueous solution and with a sodium carbonate saturated aqueous solution, is found. The straight line-shaped polyethylene terephthalate having a sulfone group is synthesized by adding dimethyl 2-sulfoterephthalate sodium to the polycondensation system of dimethyl terephthalate and ethylene glycol. The straight line-shaped polyethylene terephthalate having a sulfone group is compared with a non-straight line-shaped polyethylene terephthalate having a sulfone group and bent by 60° halfway, which is obtained by using commercially available dimethyl 5-sulfoisophthalate sodium and adding it to the same polycondensation system in place of dimethyl 2-sulfoterephthalate sodium.

Description

本研究は、テレフタル酸を３酸化イオウを用いてスルホン化することにより２−スルホテレフタル酸とし、過剰の３酸化イオウを独自の方法で除去してから２−スルホテレフタル酸をメタノ−ルでジメチルエステル化することにより２−スルホテレフタル酸ジメチルとし、さらに２−スルホテレフタル酸ジメチルを水酸化カルシウム懸濁水溶液処理および炭酸ナトリウム飽和水溶液処理を経由してナトリウム塩化することにより純度＞９８．０％あるいは＞９８．１％の２−スルホテレフタル酸ジメチルナトリウムを合成することに関する分野である。さらに、２−スルホテレフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に添加してスルホン基を有する直線状のポリエチレンテレフタレ−トを合成し、その物性について検討することに関する分野である。  In this study, 2-sulfoterephthalic acid was sulfonated with sulfur trioxide to form 2-sulfoterephthalic acid, excess sulfur trioxide was removed by a unique method, and 2-sulfoterephthalic acid was dimethylated with methanol. Esterification yields dimethyl 2-sulfoterephthalate, and dimethyl 2-sulfoterephthalate is sodium chloride via calcium hydroxide suspension aqueous solution treatment and sodium carbonate saturated aqueous solution treatment to obtain a purity of> 98.0% or It is in the field of synthesizing> 98.1% dimethyl sodium 2-sulfoterephthalate. Further, a field relating to the synthesis of linear polyethylene terephthalate having a sulfonic group by adding dimethyl sodium 2-sulfoterephthalate to a polycondensation system of dimethyl terephthalate and ethylene glycol, and studying the physical properties thereof. It is.

背景技術としては、塩化鉄（ＩＩ）を触媒として含むテレフタル酸あるいはそのアルキルエステル（Ｃ１−４のアルキル基）に、６０％発煙硫酸を１時間かけて加えてから１８０℃に１２時間加熱して２−スルホテレフタル酸あるいはそのアルキルエステル（Ｃ１−４のアルキル基）を得たという報告（特許文献１）があるだけで、他に類似した研究報告はない。 本研究に述べられているテレフタル酸のスルホン化の反応条件は特許文献１における反応条件と大きく異なっており、無触媒でもあるので比較することはできない。 また、本研究では２−スルホテレフタル酸をジメチルエステル化して得た２−スルホテレフタル酸ジメチルを水酸化カルシウム懸濁水溶液処理および炭酸ナトリウム飽和水溶液処理を経由して２−スルホテレフタル酸ジメチルナトリウム水溶液としこれを減圧濃縮している。この方法は本研究独自のものであり、これによりはじめて純度が＞９８．０％あるいは＞９８．１％の目的物の合成に成功しており貴重な成果である。一方にいて、２−スルホテレフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に加えてスルホン基を有する直線状のポリエチレンテレフタレ−トを合成する方法については、関連技術とも言えるであろう多数の特許文献がある。すなわち、５−スルホイソフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に加えて、スルホン基を有する非直線状のポリエチレンテレフタレ−トを合成している特許文献である。これらの殆んどは有効期限を過ぎたものであるが、本研究にとっては欠くことのできない参考文献となった。特許文献２、特許文献３、特許文献４を選択しこれらを参考にした。すなわち、これらの特許文献中に示されている５−スルホイソフタル酸ジメチルナトリウムの代わりに同じｍｏｌ数の２−スルホテレフタル酸ジメチルナトリウムを用いて同じ条件で重縮合反応を行って結果を比較したのである。As a background art, 60% fuming sulfuric acid was added to terephthalic acid or an alkyl ester thereof (C 1-4 alkyl group) containing iron (II) chloride as a catalyst over 1 hour, and then heated to 180 ° C. for 12 hours. There is only a report (Patent Document 1) that 2-sulfoterephthalic acid or its alkyl ester (C 1-4 alkyl group) was obtained, and there is no other similar report. The reaction conditions for sulfonation of terephthalic acid described in this study are significantly different from those in Patent Document 1 and are non-catalytic, so they cannot be compared. In this study, dimethyl 2-sulfoterephthalate obtained by dimethyl esterification of 2-sulfoterephthalic acid was converted into a dimethylsodium 2-sulfoterephthalate aqueous solution through treatment with a calcium hydroxide suspension and saturated aqueous sodium carbonate. This is concentrated under reduced pressure. This method is unique to this research, and for the first time, it has succeeded in synthesizing a target product having a purity of> 98.0% or> 98.1%, which is a valuable result. On the other hand, a method for synthesizing linear polyethylene terephthalate having a sulfone group by adding dimethyl sodium 2-sulfoterephthalate to a polycondensation system of dimethyl terephthalate and ethylene glycol can be said to be a related technique. There are many patent documents that would be. That is, this is a patent document in which dimethyl sodium 5-sulfoisophthalate is added to a polycondensation system of dimethyl terephthalate and ethylene glycol to synthesize a non-linear polyethylene terephthalate having a sulfone group. Most of these have expired but have become indispensable references for this study. Patent Document 2, Patent Document 3, and Patent Document 4 were selected and referred to. That is, since the polycondensation reaction was performed under the same conditions using the same mol number of dimethyl sodium 2-sulfoterephthalate instead of dimethyl sodium 5-sulfoisophthalate shown in these patent documents, the results were compared. is there.

Ｊａｐａｎ Ｋｏｋａｉ Ｔｏｋｋｙｏ Ｋｏｈｏ ＪＰ ０６３４０６１０；Ｃ．Ａ．，１２２，２６５０２８（１９９４）．Japan Kokai Tokyo Koho JP 06340610; C.I. A. 122, 265028 (1994). Ｔｅｉｊｉｎ，Ｊａｐａｎ Ｋｏｋａｉ ７５ ５３４９６；Ｃ．Ａ．，８３，１３３２２８（１９７５）．Teijin, Japan Kokai 75 53396; C.I. A. 83, 133228 (1975). Ｋｕｒａｒｅｙ，Ｊａｐａｎ ７４ ２３２６７；Ｃ．Ａ．，８２，５９７８８４（１９７５）．Kurarey, Japan 74 23267; C.I. A. , 82, 597884 (1975). Ｉｍｐｅｒｉａｌ Ｃｈｅｍ．Ｉｎｄ．，Ｌｔｄ．Ｂｅｌｇ．６４８５６５；Ｃ．Ａ．，６４，１１３７５（１９６６）．Imperial Chem. Ind. , Ltd., Ltd. Belg. 648565; A. 64, 11375 (1966).

発明が解決しようとする課題は次に示される。先ず、純度が＞９８．０％の２−スルホテレフタル酸ジメチルナトリウムを収率よく合成することである。また、その合成法が実験室的規模でも工業的規模でも遂行可能なものでなくてはならない。このことを成し遂げたうえで、次は、２−スルホテレフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に添加使用して撥水性の少ない染色性の改善されたスルホン基を有する直線状のポリエチレンテレフタレ−トを合成することである。現在までに同様な目的に５−スルホイソフタル酸ジメチルナトリウムが用いられているが、その場合はポリマ−分子が途中６０°折れ曲がる。スルホン基を有する直線状のポリエチレンテレフタレ−ト（Ｉ）と途中６０°折れ曲がるスルホン基を有する非直線状のポリエチレンテレフタレ−ト（ＩＩ）を比較して、前者の特徴を見出し、これを利用しようとするのが本研究が解決しようとする課題である。

Figure 2012087111
Figure 2012087111
 The problems to be solved by the invention are as follows. First, dimethyl sodium 2-sulfoterephthalate having a purity of> 98.0% is synthesized with good yield. Moreover, the synthesis method must be able to be carried out on a laboratory scale or an industrial scale. After achieving this, the next step is to use dimethyl sodium 2-sulfoterephthalate added to the polycondensation system of dimethyl terephthalate and ethylene glycol to have a sulfone group with less water repellency and improved dyeability. It is to synthesize linear polyethylene terephthalate. To date, dimethyl sodium 5-sulfoisophthalate has been used for similar purposes, but in this case the polymer molecule bends 60 ° in the middle. Comparison of linear polyethylene terephthalate (I) having a sulfone group and non-linear polyethylene terephthalate (II) having a sulfone group that bends 60 ° in the middle to find the characteristics of the former and use this This is the problem that this study tries to solve.
Figure 2012087111
Figure 2012087111

高純度の２−スルホテレフタル酸ジメチルナトリウムを合成することがすべてであると判断される。テレフタル酸のスルホン化、得られた２−スルホテレフタル酸のジメチルエステル化、得られた２−スルホテレフタル酸ジメチルのナトリウム塩化の各段階を繰り返し検討し、さらに２−スルホテレフタル酸ジメチルナトリウムの硫酸ナトリウム含有量を測定したうえで前に戻ってテレフタル酸のスルホン化から再びはじめたものである。従って特許請求の範囲の頭書に述べられているテレフタル酸と２．５ｍｏｌ当量の６０％発煙硫酸の混合物を２５０〜２５５℃に０．５〜１．０時間加熱して２−スルホテレフタル酸にするという記述は、長期間の試行錯誤の繰り返しの結果として得られたものである。イソフタル酸のスルホン化においては、イソフタル酸と２８％発煙硫酸を１９０℃に２時間加熱してから反応混合物を水に加え遠心分離している（特許文献５）。テレフタル酸のスルホン化においては、スルホン化後に水に加えてから同様にして遠心分離することは極めて困難で危険を伴う。このために、テレフタル酸のスルホン化後の反応混合物をそのままジメチルエステル化したのち、水酸化ナトリウム水溶液、塩化ナトリウム飽和水溶液あるいは炭酸ナトリウム飽和水溶液を用いて塩析したが好結果は得られなかった（実施例１）。次にテレフタル酸のスルホン化後の反応混合物中の３酸化イオウをメタノ−ルを用いてジメチル硫酸にし、減圧溜去してから、残留をジメチルエステル化したのち、同じように塩析したがひとつの例外を除いては好結果は得られなかった。その例外とは炭酸ナトリウム飽和水溶液を用いての塩析により得られた２−スルホテレフタル酸ジメチルナトリウムの純度が９６．２％であったことである。このことが理由でテレフタル酸のスルホン化後の反応混合物中の３酸化イオウをメタノ−ルを用いてジメチル硫酸にし減圧溜去する手段と、２−スルホテレフタル酸ジメチルのナトリウム塩化において水酸化カルシウム懸濁水溶液処理および炭酸ナトリウム飽和水溶液処理を経由して２−スルホテレフタル酸ジメチルナトリウム水溶液とする手段が連結させられたのである（実施例３）。また、実施例３で得られた２−スルホテレフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に加えることに関しては、課題として解決するための手段としてここに改めて記載するほどのことはない。

Figure 2012087111
The synthesis of high purity dimethyl sodium 2-sulfoterephthalate is judged to be all. Each step of sulfonation of terephthalic acid, dimethyl esterification of the obtained 2-sulfoterephthalic acid, and sodium chlorination of the obtained dimethyl 2-sulfoterephthalate was repeatedly examined, and sodium sulfate of dimethyl sodium 2-sulfoterephthalate After measuring the content, we went back and started again from the sulfonation of terephthalic acid. Accordingly, a mixture of terephthalic acid and 2.5 mol equivalent of 60% fuming sulfuric acid described in the heading of claims is heated to 250 to 255 ° C. for 0.5 to 1.0 hour to 2-sulfoterephthalic acid. The description is obtained as a result of repeated trial and error over a long period of time. In sulfonation of isophthalic acid, isophthalic acid and 28% fuming sulfuric acid are heated to 190 ° C. for 2 hours, and then the reaction mixture is added to water and centrifuged (Patent Document 5). In sulfonation of terephthalic acid, it is extremely difficult and dangerous to add it to water after sulfonation and then perform centrifugation in the same manner. For this reason, the reaction mixture after sulfonation of terephthalic acid was converted into dimethyl ester as it was, and then salted out using a sodium hydroxide aqueous solution, a sodium chloride saturated aqueous solution or a sodium carbonate saturated aqueous solution, but no good results were obtained ( Example 1). Next, sulfur trioxide in the reaction mixture after sulfonation of terephthalic acid was converted to dimethyl sulfate using methanol, distilled under reduced pressure, the residue was converted to dimethyl ester, and then salted out in the same manner. With the exception of, good results were not obtained. The exception is that the purity of dimethyl sodium 2-sulfoterephthalate obtained by salting out using a saturated aqueous solution of sodium carbonate was 96.2%. For this reason, sulfur trioxide in the reaction mixture after sulfonation of terephthalic acid is converted into dimethyl sulfate using methanol and distilled under reduced pressure, and calcium hydroxide suspension in sodium chloride of dimethyl 2-sulfoterephthalate. A means for forming an aqueous solution of dimethyl sodium 2-sulfoterephthalate through a turbid aqueous solution treatment and a saturated aqueous sodium carbonate treatment was linked (Example 3). Further, regarding the addition of dimethyl sodium 2-sulfoterephthalate obtained in Example 3 to the polycondensation system of dimethyl terephthalate and ethylene glycol, it is described here as a means to solve as a problem. There is nothing.
Figure 2012087111

Ｃｚｅｃｈ．１３３６３５；Ｃ．Ａ．，７３，１０９５０８（１９７０）Czech. 133635; C.I. A. 73, 109508 (1970)

市販の５−スルホイソフタル酸ジメチルナトリウム中の不純物としての硫酸ナトリウム含有量を測定して２．４％という値をえている。実際に工業的に用いられているものもこの前後であろう。すなわち、本研究で得られた２−スルホテレフタル酸ジメチルナトリウム中の不純物としての硫酸ナトリウム含有量が＜２．４％でなければ、本発明が期待する効果は得られないのである。換言すれば本研究で得られた２−スルホテレフタル酸ジメチルナトリウムの純度が＞９７．６％でなければ、テレフタル酸ジメチルとエチレングリコ−ルの重縮合系に添加使用してスルホン基を有する直線状のポリエチレンテレフタレ−トを合成しても無意味なのである。そのために、テレフタル酸から２−スルホテレフタル酸ジメチルナトリウムまでの各段階を繰り返し検討して、純度が＞９８．０％の２−スルホテレフタル酸ジメチルナトリウムを合成したのである。ここではじめて本発明の効果が見えてきたのである。すなわち、テレフタル酸ジメチルとエチレングリコ−ル重縮合系に５−スルホイソフタル酸ジメチルナトリウムを添加して途中６０°折れ曲がるスルホン基を有する非直線状のポリエチレンテレフタレ−トを合成した研究例があれば、代わりに２−スルホテレフタル酸ジメチルナトリウムを添加してスルホン基を有する直線状のポリエチレンテレフタレ−トを合成し、両結果を比較検討することが可能となったのである。  The content of sodium sulfate as an impurity in commercially available dimethyl sodium 5-sulfoisophthalate was measured and found to be 2.4%. The ones that are actually used industrially will be around this. That is, unless the content of sodium sulfate as an impurity in dimethyl sodium 2-sulfoterephthalate obtained in this study is <2.4%, the effect expected by the present invention cannot be obtained. In other words, if the purity of the dimethyl sodium 2-sulfoterephthalate obtained in this study is not> 97.6%, it is added to the polycondensation system of dimethyl terephthalate and ethylene glycol and is used as a straight line having a sulfone group. It is meaningless to synthesize a polyethylene terephthalate in the shape of a tube. To that end, the stages from terephthalic acid to dimethyl sodium 2-sulfoterephthalate were repeatedly studied to synthesize dimethyl sodium 2-sulfoterephthalate having a purity of> 98.0%. This is the first time that the effects of the present invention have been seen. That is, if there is a research example in which dimethyl terephthalate and ethylene glycol polycondensation system are added with dimethyl sodium 5-sulfoisophthalate to synthesize a non-linear polyethylene terephthalate having a sulfone group that is bent 60 ° in the middle. Instead, dimethyl sodium 2-sulfoterephthalate was added to synthesize a linear polyethylene terephthalate having a sulfone group, and both results could be compared.

先ず、２−スルホテレフタル酸ジメチルナトリウムの合成においては、得られたものの中の不純物としての硫酸ナトリウムの含有量を測定して純度の指標とした。これは繰り返された合成実験において、不純物としては硫酸ナトリウムが主たるものであり、他の不純物は殆んど含まれていないと判断されたからである。このことは実施例３において得られた２−スルホテレフタル酸ジメチルナトリウムの元素分析値を見れば明らかである。さらに、次の実験事実もこのことの傍証となりうるであろう。すなわち、実施例１において得られた２−スルホテレフタル酸ジメチルを含む反応混合物を塩化ナトリウム飽和水溶液で塩析した場合において、得られた２−スルホテレフタル酸ジメチルナトリウムの硫酸ナトリウム含有量は１０％、塩化ナトリウム含有量は０％であった。  First, in the synthesis of dimethyl sodium 2-sulfoterephthalate, the content of sodium sulfate as an impurity in the obtained product was measured and used as an indicator of purity. This is because, in repeated synthesis experiments, it was determined that sodium sulfate was the main impurity and that other impurities were hardly contained. This is apparent from the elemental analysis value of dimethyl sodium 2-sulfoterephthalate obtained in Example 3. In addition, the following experimental fact may be a proof of this. That is, when the reaction mixture containing dimethyl 2-sulfoterephthalate obtained in Example 1 was salted out with a saturated aqueous sodium chloride solution, the sodium sulfate content of the obtained dimethylsodium 2-sulfoterephthalate was 10%, The sodium chloride content was 0%.

テレフタル酸２０ｇ（０．１２ｍｏｌ）と６０％発煙硫酸４０ｇ（３酸化イオウとして０．３ｍｏｌ）を混合し、かき混ぜながら温度を徐々に上げて最終的には２５０〜２５５℃に０．５〜１．０時間加熱して反応させた。反応が終了したか否かについては還流している３酸化イオウの量より大凡に判断できる。３酸化イオウが円滑に還流するように還流冷却器の水の温度を適当に調節しなければならない。また、反応温度および時間はテレフタル酸等の仕込み量にもある程度影響を受けるので注意が肝要である。反応後、７０〜８０ｇ（２．２〜２．５ｍｏｌ）のメタノ−ルを加えて３．５時間還流煮沸した。得られた２−スルホテレフタル酸ジメチルを含む反応混合物を塩析した結果について述べる。反応混合物に５０％水酸化ナトリウム水溶液を加えると途中にかき混ぜ不能になる。少量のメタノ−ルを加えかき混ぜてから濾過して得られた２−スルホテレフタル酸ジメチルナトリウムの硫酸ナトリウム含有量は７〜８％であった。５０％水酸化ナトリウム水溶液の代わりに１０〜２０％水酸化ナトリウム水溶液を加えると少時間経過後に２−スルホテレフタル酸ジメチルナトリウムが析出した。このものの硫酸ナトリウム含有量は＞５０％であった。また、塩化ナトリウム飽和水溶液を用い、この中に反応混合物を加えると２−スルホテレフタル酸ジメチルナトリウムが析出した。このものの硫酸ナトリウム含有量は１０％、塩化ナトリウム含有量は０％であった。そして、炭酸ナトリウム飽和水溶液を用い、これを反応混合物に加えると２−スルホテレフタル酸ジメチルナトリウムが析出したが極めて低収率であった。  20 g (0.12 mol) of terephthalic acid and 40 g of 60% fuming sulfuric acid (0.3 mol as sulfur trioxide) are mixed, and the temperature is gradually raised while stirring to finally reach a temperature of 250 to 255 ° C. to 0.5 to 1. The reaction was performed by heating for 0 hour. Whether or not the reaction is completed can be roughly judged from the amount of sulfur trioxide being refluxed. The temperature of the water in the reflux condenser must be adjusted appropriately so that sulfur trioxide is smoothly refluxed. In addition, it is important to note that the reaction temperature and time are affected to some extent by the amount of terephthalic acid charged. After the reaction, 70 to 80 g (2.2 to 2.5 mol) of methanol was added and reflux-boiled for 3.5 hours. The results of salting out the obtained reaction mixture containing dimethyl 2-sulfoterephthalate will be described. When 50% aqueous sodium hydroxide solution is added to the reaction mixture, stirring becomes impossible during the process. The sodium sulfate content of dimethyl sodium 2-sulfoterephthalate obtained by adding a small amount of methanol and stirring and filtering was 7-8%. When 10-20% sodium hydroxide aqueous solution was added instead of 50% sodium hydroxide aqueous solution, dimethyl sodium 2-sulfoterephthalate was precipitated after a short time. The sodium sulfate content of this was> 50%. Moreover, when sodium chloride saturated aqueous solution was used and the reaction mixture was added thereto, dimethyl sodium 2-sulfoterephthalate was precipitated. This had a sodium sulfate content of 10% and a sodium chloride content of 0%. When a saturated aqueous sodium carbonate solution was used and added to the reaction mixture, dimethyl sodium 2-sulfoterephthalate was precipitated, but the yield was extremely low.

実施例Ｉと全く同様にしてテレフタル酸をスルホン化した。 反応後、１２ｇ以上のメタノ−ルを冷却下加えて過剰の３酸化イオウをジメチル硫酸にした。ジメチル硫酸を減圧溜去してから残留に６０〜７０ｇ（１．９〜２．２ｍｏｌ）のメタノ−ルを加えて３．５時間還流煮沸した。得られた２−スルホテレフタル酸ジメチルを含む反応混合物を塩析した結果について述べる。反応混合物に５０％水酸化ナトリウム水溶液を加えると途中にかき混ぜ不能になる。少量のメタノ−ルを加えてから濾過して得られた２−スルホテレフタル酸ジメチルナトリウムの硫酸ナトリウム含有量は８〜９％であった。 ５０％水酸化ナトリウム水溶液の代わりに塩化ナトリウム飽和水溶液を用い、この中に反応混合物を加えると２−スルホテレフタル酸ジメチルナトリウムが析出した。このものの硫酸ナトリウム含有量は＞１０％であった。 しかし、炭酸ナトリウム飽和水溶液を用い、 これを反応混合物に加えると比較的高収率で２−スルホテレフタル酸ジメチルナトリウムが得られた。このものの硫酸ナトリウム含有量は３．８％であった。  Terephthalic acid was sulfonated in exactly the same way as in Example I. After the reaction, 12 g or more of methanol was added under cooling to convert excess sulfur trioxide to dimethyl sulfate. Dimethyl sulfuric acid was distilled off under reduced pressure, and then 60 to 70 g (1.9 to 2.2 mol) of methanol was added to the residue, followed by boiling at reflux for 3.5 hours. The results of salting out the obtained reaction mixture containing dimethyl 2-sulfoterephthalate will be described. When 50% aqueous sodium hydroxide solution is added to the reaction mixture, stirring becomes impossible during the process. The sodium sulfate content of dimethyl sodium 2-sulfoterephthalate obtained by adding a small amount of methanol and filtering was 8-9%. A saturated aqueous sodium chloride solution was used in place of the 50% aqueous sodium hydroxide solution, and when the reaction mixture was added thereto, dimethyl sodium 2-sulfoterephthalate was precipitated. The sodium sulfate content of this was> 10%. However, when a saturated aqueous sodium carbonate solution was used and added to the reaction mixture, dimethyl sodium 2-sulfoterephthalate was obtained in a relatively high yield. The sodium sulfate content of this product was 3.8%.

実施例２の結果から、２−スルホテレフタル酸を合成した反応混合物中の過剰の３酸化イオウをジメチル硫酸にし、それを減圧溜去することを含む方法が好結果をもたらすと考えた。この方法と、水酸化カルシウム懸濁水溶液処理および炭酸ナトリウム飽和水溶液処理を経由して２−スルホテレフタル酸ジメチルを２−スルホテレフタル酸ジメチルナトリウム水溶液にする方法が連結させられたのである。これを以下に示す。実施例１と同様にしてテレフタル酸をスルホン化した。反応後、実施例２と同様にして過剰の３酸化イオウをジメチル硫酸にし、これを減圧溜去し、残留をメタノ−ルと還流煮沸して２−スルホテレフタル酸ジメチチルを含む反応混合物を得た。未反応のメタノ−ルの大部分を溜去してから、水酸化カルシウム懸濁水溶液を加えてｐＨ７とした。これを減圧下で７０℃に１時間加熱するとｐＨ６位になる。生成した硫酸カルシウムを濾別し、濾液に炭酸ナトリウム飽和水溶液を加えてｐＨ７〜７．５とした。さらに炭酸ナトリウム飽和水溶液を加えても新たに沈殿が生じないことを確かめてから活性炭処理後濾過した。濾液を減圧濃縮して析出した２−スルホテレフタル酸ジメチルナトリウムを濾過しとった。得られたものの硫酸ナトリウム含有量は１．８〜１．９％。また、このさいの濾液を蒸発乾固して得られたものの硫酸ナトリウム含有量は１．９〜２．０％であった。すなわち、２−スルホテレフタル酸ジメチルナトリウム水溶液の減圧濃縮にさいしては析出結晶を分別する必要はないのである。メタノ−ル−水（１：１容積比）で再結晶しうる。粗収率７６〜８４％。再結晶前の元素分析値（％）Ｃ３５．９，Ｈ３．０，Ｎ＜０．３。再結晶後の元素分析値（％）Ｃ４０．０，Ｈ３．１，Ｎ＜０．３；Ｃ１０Ｈ９ＮａＯ７Ｓに対する計算値（％）Ｃ４０．５，Ｈ３．１，Ｎ０。From the results of Example 2, it was considered that a method including converting excessive sulfur trioxide in the reaction mixture obtained by synthesizing 2-sulfoterephthalic acid into dimethyl sulfate and distilling it under reduced pressure would be successful. This method and the method of converting dimethyl 2-sulfoterephthalate into an aqueous solution of dimethylsodium 2-sulfoterephthalate via a calcium hydroxide suspension aqueous solution treatment and a sodium carbonate saturated aqueous solution treatment were linked. This is shown below. In the same manner as in Example 1, terephthalic acid was sulfonated. After the reaction, excess sulfur trioxide was converted to dimethyl sulfate in the same manner as in Example 2, and this was distilled under reduced pressure. The residue was boiled with methanol to obtain a reaction mixture containing dimethylic 2-sulfoterephthalate. . After most of the unreacted methanol was distilled off, the pH was adjusted to 7 by adding an aqueous calcium hydroxide suspension. When this is heated to 70 ° C. under reduced pressure for 1 hour, it reaches pH 6 position. The produced calcium sulfate was filtered off, and a saturated aqueous sodium carbonate solution was added to the filtrate to adjust the pH to 7 to 7.5. Further, it was confirmed that no new precipitate was formed even when a saturated aqueous solution of sodium carbonate was added, and then the resultant was treated with activated carbon and then filtered. The filtrate was concentrated under reduced pressure, and the precipitated dimethyl sodium 2-sulfoterephthalate was filtered off. The sodium sulfate content of what was obtained was 1.8-1.9%. Moreover, the sodium sulfate content of what was obtained by evaporating and drying the filtrate of this time was 1.9 to 2.0%. That is, it is not necessary to fractionate the precipitated crystals during the vacuum concentration of the aqueous dimethyl sodium 2-sulfoterephthalate solution. It can be recrystallized with methanol-water (1: 1 volume ratio). Crude yield 76-84%. Elemental analysis before recrystallization (%) C35.9, H3.0, N <0.3. Elemental analysis after recrystallization (%) C40.0, H3.1, N <0.3; C 10 H 9 NaO 7 Calculated for S (%) C40.5, H3.1, N0.

実施例１と全く同様にしてテレフタル酸をスルホン化した。反応後、過剰の３酸化イオウを硫酸にするために必要最小限の水を加えた。これには極めて熟練した技術が必要とされるから、必要以上の水を加えて余分のものをあとで蒸散除去してもよい。次に、７０〜８０ｇ（２．２〜２．５ｍｏｌ）のメタノ−ルを加えて３．５時間還流煮沸して２−スルホテレフタル酸ジメチルを含む反応混合物を得た。以下は実施例３と同様にして、活性炭処理後濾過して得た濾液を減圧濃縮して析出した２−スルホテレフタル酸ジメチルナトリウムを濾過しとった。
得られたものの硫酸ナトリウム含有量は２．７％。また、このさいの濾液を蒸発乾固して得られたものの硫酸ナトリウム含有量は４．０％であった。すなわち、テレフタル酸のスルホン化後の過剰の３酸化イオウを水を用いて硫酸にしから反応系にそのまま残すという方法は勧められない。In the same manner as in Example 1, terephthalic acid was sulfonated. After the reaction, the minimum amount of water necessary to convert the excess sulfur trioxide to sulfuric acid was added. Since this requires very skilled techniques, excess water may be added to remove excess afterwards. Next, 70 to 80 g (2.2 to 2.5 mol) of methanol was added and refluxed for 3.5 hours to obtain a reaction mixture containing dimethyl 2-sulfoterephthalate. In the same manner as in Example 3, the filtrate obtained after the treatment with activated carbon was concentrated under reduced pressure, and the precipitated dimethyl sodium 2-sulfoterephthalate was filtered off.
The sodium sulfate content of what was obtained was 2.7%. Moreover, the sodium sulfate content of what was obtained by evaporating to dryness the filtrate of this time was 4.0%. That is, it is not recommended to use a method in which excess sulfur trioxide after sulfonation of terephthalic acid is converted into sulfuric acid using water and then left in the reaction system.

実施例１と全く同様にしてテレフタル酸をスルホン化した。反応後、過剰の３酸化イオウを水を用いて硫酸にしてから、さらに水を追加して反応混合物がグラスフィルタ−で濾過し易いようにした。２−スルホテレフタル酸を濾過しとり、濾液から水を減圧溜去して得られた析出物を前のものに合した。この操作を繰り返して得られた２−スルホテレフタル酸を合わせ一緒にした。これに６０〜７０ｇ（１．９〜２．０ｍｏｌ）のメタノ−ルを加えて３．５時間還流煮沸して２−スルホテレフタル酸ジメチルを含む反応混合物をえた。以下は実施例３と同様にして、活性炭処理後濾過して得た濾液を減圧濃縮して析出した２−スルホテレフタル酸ジメチルナトリウムを濾過しとった。得られたものの硫酸ナトリウム含有量は１．８〜１．９％。また、このさいの濾液を蒸発乾固して得られたものの硫酸ナトリウム含有量は２．８％であった。すなわち、減圧濃縮の比較的初期に析出した２−スルホテレフタル酸ジメチルナトリウムは純度＞９８．１％であることから、特許請求の範囲の請求項３に示されている。  In the same manner as in Example 1, terephthalic acid was sulfonated. After the reaction, excess sulfur trioxide was converted to sulfuric acid using water, and water was further added to make the reaction mixture easy to filter through a glass filter. 2-sulfoterephthalic acid was filtered off, and water was removed from the filtrate by distillation under reduced pressure, and the precipitate obtained was combined with the previous one. 2-Sulfoterephthalic acid obtained by repeating this operation was combined and combined. 60-70 g (1.9-2.0 mol) of methanol was added thereto, and the mixture was boiled at reflux for 3.5 hours to obtain a reaction mixture containing dimethyl 2-sulfoterephthalate. In the same manner as in Example 3, the filtrate obtained after the treatment with activated carbon was concentrated under reduced pressure, and the precipitated dimethyl sodium 2-sulfoterephthalate was filtered off. The sodium sulfate content of what was obtained was 1.8-1.9%. Moreover, the sodium sulfate content of what was obtained by evaporating and drying this filtrate was 2.8%. That is, dimethyl sodium 2-sulfoterephthalate deposited at a relatively early stage of concentration under reduced pressure has a purity of> 98.1%, and therefore is shown in claim 3 of the claims.

テレフタル酸ジメチル９．７ｇ（０．０５０ｍｏｌ）、酢酸マンガン（ＩＩ）４水和物３．７ｍｇ（０．０１５ｍｍｏｌ）、実施例３で得られた２−スルホテレフタル酸ジメチルナトリウム０．３４ｇ（０．００１１５ｍｏｌ）、酸化アンチモン（ＩＩＩ）３．９ｍｇ（０．０１３４ｍｍｏｌ）、酢酸ナトリウム６．６ｍｇ（０．０８０４ｍｍｏｌ）およびエチレングリコ−ル６．４ｇ（０．１０３ｍｏｌ）を混合し、蒸溜フラスコに加え、これに窒素ガスを通じつつ常圧で１７０〜２３０℃に長時間加熱した。反応により生成したメタノ−ルが殆んど溜出し

Figure 2012087111
０．３５ｄｌ・ｇ−１（ο−クロロフェノ−ル、２５℃）であった。9.7 g (0.050 mol) of dimethyl terephthalate, 3.7 mg (0.015 mmol) of manganese (II) acetate tetrahydrate, and 0.34 g (0. (00115 mol), 3.9 mg (0.0134 mmol) of antimony (III) oxide, 6.6 mg (0.0804 mmol) of sodium acetate and 6.4 g (0.103 mol) of ethylene glycol were added to a distillation flask, The sample was heated to 170-230 ° C. for a long time at normal pressure while passing nitrogen gas through the tube. Most of the methanol produced by the reaction is distilled out
Figure 2012087111
0.35 dl · g −1 (ο-chlorophenol, 25 ° C.).

実施例１と同様にしてポリエステルを合成した。ただし、実施例６における２７５℃／１〜３ｍｍＨｇでの３時間加熱の代わりに２７５℃／５〜７ｍｍＨｇでの３時間加熱とした。得られた

Figure 2012087111
た。A polyester was synthesized in the same manner as in Example 1. However, instead of heating at 275 ° C./1-3 mmHg in Example 6 for 3 hours, heating at 275 ° C./5-5 mmHg was performed for 3 hours. Obtained
Figure 2012087111
It was.

テレフタル酸ジメチル９．７ｇ（０．０５０ｍｏｌ）、酢酸マンガン（ＩＩ）４水和物３．７ｍｇ（０．０１５ｍｍｏｌ）、市販の５−スルホイソフタル酸ジメチルナトリウム０．３４ｇ（０．００１１５ｍｏｌ）、酸化アンチモン（ＩＩＩ）３．９ｍｇ（０．０１３４ｍｍｏｌ）、酢酸ナトリウム６．６ｍｇ（０．０８０４ｍｍｏｌ）およびエチレングリコ−ル６．４ｇ（０．１０３ｍｏｌ）を混合し、蒸溜フラスコに加え、これに窒素ガスを通じつつ常圧で１７０〜２３０℃に長時間加熱した。反応により生成したメタノ−ルの殆んどが溜出してから

Figure 2012087111
ｄｌ・ｇ−１（ο−クロロフェノ−ル、２５℃）であった。9.7 g (0.050 mol) of dimethyl terephthalate, 3.7 mg (0.015 mmol) of manganese (II) acetate tetrahydrate, 0.34 g (0.00115 mol) of commercially available dimethyl sodium 5-sulfoisophthalate, antimony oxide (III) 3.9 mg (0.0134 mmol), sodium acetate 6.6 mg (0.0804 mmol) and ethylene glycol 6.4 g (0.103 mol) were mixed, added to the distillation flask, and nitrogen gas was passed through it. Heated at normal pressure to 170-230 ° C for a long time. After most of the methanol produced by the reaction has distilled out
Figure 2012087111
dl · g −1 (ο-chlorophenol, 25 ° C.).

テレフタル酸ジメチル１０．０ｇ（０．０５１５ｍｏｌ）、酢酸亜鉛４ｍｇ（０．０２２ｍｍｏｌ）、実施例３で得られた２−スルホテレフタル酸ジメチルナトリウム０．１５ｇ（０．０００５１ｍｏｌ）、およびエチレングリコ−ル８．０ｇ（０．１２９ｍｏｌ）を混合し、蒸溜フラスコに加え、これに窒素ガスを通じつつ常圧で１７０〜２３０℃に長時間加熱した。反応により生成したメタノ−ルの殆んどが溜出してから、蒸溜フラスコを冷却し、これに酸化アンチモン（ＩＩＩ）３ｍｇ（０．０１ｍｍｏｌ）、酸化チタン（ＩＶ）４５ｍｇ（０．５６３ｍｍｏｌ）およびリン酸トリメチル５ｍｇ（０．０３６ｍｍｏｌ）を加え、再び窒素ガス

Figure 2012087111
［η］＝０．３７ｄｌ・ｇ−１（ο−クロロフェノ−ル、２５℃）であった。10.0 g (0.0515 mol) of dimethyl terephthalate, 4 mg (0.022 mmol) of zinc acetate, 0.15 g (0.00051 mol) of dimethyl sodium 2-sulfoterephthalate obtained in Example 3, and ethylene glycol 8 0.0 g (0.129 mol) was mixed, added to the distillation flask, and heated to 170-230 ° C. at normal pressure for a long time while passing nitrogen gas through it. After most of the methanol produced by the reaction was distilled off, the distillation flask was cooled to 3 mg (0.01 mmol) of antimony (III) oxide, 45 mg (0.563 mmol) of titanium (IV) oxide and phosphorus. 5 mg (0.036 mmol) of trimethyl acid was added and again nitrogen gas
Figure 2012087111
[Η] = 0.37 dl · g −1 (ο-chlorophenol, 25 ° C.).

実施例９における２−スルホテレフタル酸ジメチルナトリウム０．１５ｇ（０．０００５１ｍｏｌ）の代わりに、市販の５−イソフタル酸ジメチルナトリウム０．１５ｇ（０．０００５１ｍｏｌ）を用い、他は実施例９と同様にしてポリエステルを得た。ただし、重縮合反応の最終段階における２８０℃／１〜２ｍｍＨｇでの２．５時間加熱の代わりに２８０℃／２〜４ｍｍＨｇでの２．５時間加熱とした。得ら

Figure 2012087111
った。Instead of 0.15 g (0.00051 mol) of dimethyl sodium 2-sulfoterephthalate in Example 9, 0.15 g (0.00051 mol) of commercially available dimethyl sodium 5-isophthalate was used. To obtain polyester. However, heating at 280 ° C./2 to 4 mmHg for 2.5 hours was used instead of heating at 280 ° C./1 to 2 mmHg for 2.5 hours in the final stage of the polycondensation reaction. Obtained
Figure 2012087111
It was.

テレフタル酸ジメチル１７．９ｇ（０．０９２２ｍｏｌ）、酢酸カルシウム１水和物１７．０３ｍｇ（０．０９６６ｍｍｏｌ）、酸化アンチモン（ＩＩＩ）８．３３ｍｇ（０．０２８５ｍｍｏｌ）、実施例３で得られた２−スルホテレフタル酸ジメチルナトリウム３．０３３ｇ（０．０１０２４ｍｏｌ）およびエチレングリコ−ル１４．３３ｇ（０．２３１ｍｏｌ）を混合し、蒸溜フラスコに加え、これに窒素ガスを通じつつ常圧で１７０〜２３０℃に長時間加熱した。反応により生成したメタノ−ルの半分以上が溜出してから、すなわち、幾分の生成メタノ−ルを残して蒸溜フラスコを冷却し、これにリン酸３０ｍｇ（０．３１ｍｍｏｌ）を加え、再び窒素ガスを通じつつ１００〜１５０℃／１００ｍｍＨｇに少時間加熱したのち、

Figure 2012087111
０．２１ｄｌ・ｇ−１（ο−クロロフェノ−ル，２５℃）であった。Dimethyl terephthalate 17.9 g (0.0922 mol), calcium acetate monohydrate 17.03 mg (0.0966 mmol), antimony (III) oxide 8.33 mg (0.0285 mmol), 2- 3.033 g (0.01024 mol) of dimethyl sodium sulfoterephthalate and 14.33 g (0.231 mol) of ethylene glycol were mixed and added to the distillation flask. Heated for hours. After more than half of the methanol produced by the reaction has been distilled off, that is, the distillation flask is cooled leaving some of the produced methanol, 30 mg (0.31 mmol) of phosphoric acid is added thereto, and nitrogen gas is added again. After heating to 100-150 ° C./100 mmHg for a short time,
Figure 2012087111
It was 0.21 dl · g −1 (ο-chlorophenol, 25 ° C.).

実施例１１における２−スルホテレフタル酸ジメチルナトリウム３．０３３ｇ（０．０１０２４ｍｏｌ）の代わりに、市販の５−スルホイソフタル酸ジメチルナトリウム３．０３３ｇ（０．０１０２４ｍｏｌ）を用い、他は実施例１１と同様にしてポリエステルを得た。ただし、重縮合反応の最終段階における２８１〜２８８℃／１〜２ｍｍＨｇでの２．５時間加熱の代わりに、２８１〜２８６℃／１〜２ｍｍＨｇでの

Figure 2012087111
フェノ−ル、２５℃）であった。Instead of 3.033 g (0.01024 mol) of dimethyl sodium 2-sulfoterephthalate in Example 11, 3.033 g (0.01024 mol) of commercially available dimethyl sodium 5-sulfoisophthalate was used, and the others were similar to Example 11. To obtain a polyester. However, instead of heating at 281 to 288 ° C./1 to 2 mmHg for 2.5 hours in the final stage of the polycondensation reaction, at 281 to 286 ° C./1 to 2 mmHg
Figure 2012087111
Phenol, 25 ° C.).

産業上の利用可能性となると、２−スルホテレフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に添加使用した場合に得られたポリマ−の利用可能性ということになる。実施例６と実施例８が比較可能な場合である。実施例６で

Figure 2012087111
２４０〜２４２℃である。前者が５２°低融点であった。実施例９と実施例１０が比較可能な場合
Figure 2012087111
あった。何れの場合においても２−スルホテレフタル酸ジメチルナトリウムを用いた前者が約５０°低融点となっている。すなわち、テレフタル酸ジメチルとエチレングリコ−ルの重縮合系に５−スルホイソフタル酸ジメチルナトリウムを添加するより２−スルホテレフタル酸ジメチルナトリウムを添加する方が、得られたスルホン基を有するポリエチレンテレフタレ−トが比較的低温度で熔融紡糸できて有利であることが示された。しかも、大きい抗張力を示すことが定性的ではあるが認められた。すなわち、より細い繊維になりうるのである。延伸についてははっきりしないが、その化学構造式からみてより延伸し易いことは明らかである。When it comes to industrial applicability, it means the applicability of the polymer obtained when dimethyl sodium 2-sulfoterephthalate is added to the polycondensation system of dimethyl terephthalate and ethylene glycol. This is a case where Example 6 and Example 8 can be compared. In Example 6
Figure 2012087111
240-242 ° C. The former had a 52 ° low melting point. When Example 9 and Example 10 are comparable
Figure 2012087111
there were. In any case, the former using dimethyl sodium 2-sulfoterephthalate has a low melting point of about 50 °. That is, the addition of dimethyl sodium 2-sulfoterephthalate to the polycondensation system of dimethyl terephthalate and ethylene glycol is more effective than the addition of dimethyl sodium 2-sulfoterephthalate to the obtained polyethylene terephthalate having a sulfone group. It has been shown to be advantageous that the melt can be melt spun at a relatively low temperature. Moreover, it was qualitatively shown to exhibit a high tensile strength. That is, it can be a finer fiber. Although it is not clear about stretching, it is clear that stretching is easier in view of its chemical structural formula.

それ以上に注目すべきことは、純度＞９８．０％の２−スルホテレフタル酸ジメチルナトリウムを実験室的規模においても工業的規模においても合成しうる方法が見出されたことである。ここで純度＞９８．０％のものが合成されてはじめてテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に添加使用して、５−スルホイソフタル酸ジメチルナトリウムを用いている場合と比較検討することが可能となったのである。  More importantly, a process has been found that can synthesize dimethyl sodium 2-sulfoterephthalate with a purity> 98.0% on both a laboratory scale and an industrial scale. It should be added to the polycondensation system of dimethyl terephthalate and ethylene glycol for the first time when a purity> 98.0% is synthesized, and compared with the case using dimethyl sodium 5-sulfoisophthalate. Is now possible.

実施例３で得られた２−スルホテレフタル酸ジメチルナトリウムのＩＲスペクトル（ＫＢｒ錠剤法）である。 市販の５−スルホイソフタル酸ジメチルナトリウムのＩＲスペクトル（ＫＢｒ錠剤法）である。

Figure 2012087111
Figure 2012087111
2 is an IR spectrum (KBr tablet method) of dimethyl sodium 2-sulfoterephthalate obtained in Example 3. FIG. It is IR spectrum (KBr tablet method) of commercially available dimethyl sodium 5-sulfoisophthalate.
Figure 2012087111
Figure 2012087111

Claims (4)

テレフタル酸と２．５ｍｏｌ当量の６０％発煙硫酸の混合物を２５０〜２５５℃に０．５〜１．０時間加熱して２−スルホテレフタル酸にした。反応混合物中の３酸化イオウをメタノ−ルを用いてジメチル硫酸にしてから減圧溜去した。残溜をメタノ−ルと還流煮沸して２−スルホテレフタル酸ジメチルとし、水酸化カルシウム懸濁水溶液処理および炭酸ナトリウム飽和水溶液処理を経由して２−スルホテレフタル酸ジメチルナトリウム水溶液とした。これを乾固に近い状態まで減圧濃縮して純度が＞９８．０％の２−スルホテレフタル酸ジメチルナトリウムを合成する方法。  A mixture of terephthalic acid and 2.5 mol equivalent of 60% fuming sulfuric acid was heated to 250 to 255 ° C. for 0.5 to 1.0 hour to give 2-sulfoterephthalic acid. The sulfur trioxide in the reaction mixture was converted to dimethyl sulfate using methanol and distilled off under reduced pressure. The residue was boiled under reflux with methanol to give dimethyl 2-sulfoterephthalate, and treated with a calcium hydroxide suspension aqueous solution and a saturated aqueous sodium carbonate solution to give a dimethylsodium 2-sulfoterephthalate aqueous solution. A method of synthesizing dimethyl sodium 2-sulfoterephthalate having a purity of> 98.0% by concentration under reduced pressure to a state close to dryness. 請求項１に示された方法で得られた純度が＞９８．０％の２−スルホテレフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に添加してスルホン基を有する直線状のポリエチレンテレフタレ−トを合成する方法。  A linear form having a sulfone group obtained by adding dimethyl sodium 2-sulfoterephthalate having a purity of> 98.0% obtained by the method shown in claim 1 to a polycondensation system of dimethyl terephthalate and ethylene glycol. Of synthesizing polyethylene terephthalate. テレフタル酸と２．５ｍｏｌ当量の６０％発煙硫酸の混合物を２５０〜２５５℃に０．５〜１．０時間加熱して２−スルホテレフタル酸にした。反応混合物中の３酸化イオウを水を用いて硫酸にしてから水を追加して、反応混合物を濾過し易いようにした。２−スルホテレフタル酸を濾過しとり、濾液から水を減圧溜去して得られた析出物を前のものに合した。この操作を繰り返して得た２−スルホテレフタル酸を一緒にした。 これをメタノ−ルと還流煮沸して２−スルホテレフタル酸ジメチルとし、水酸化カルシウム懸濁水溶液処理および炭酸ナトリウム飽和水溶液処理を経由して２−スルホテレフタル酸ジメチルナトリウム水溶液にした。若干の水を残して減圧濃縮してから濾過しとって純度が＞９８．１％の２−スルホテレフタル酸ジメチルナトリウムを合成する方法。  A mixture of terephthalic acid and 2.5 mol equivalent of 60% fuming sulfuric acid was heated to 250 to 255 ° C. for 0.5 to 1.0 hour to give 2-sulfoterephthalic acid. The sulfur trioxide in the reaction mixture was made sulfuric with water and then water was added to make the reaction mixture easier to filter. 2-sulfoterephthalic acid was filtered off, and water was removed from the filtrate by distillation under reduced pressure, and the precipitate obtained was combined with the previous one. 2-Sulfoterephthalic acid obtained by repeating this operation was combined. This was boiled under reflux with methanol to give dimethyl 2-sulfoterephthalate, which was treated with an aqueous solution of calcium hydroxide suspension and a saturated aqueous solution of sodium carbonate to give an aqueous solution of dimethyl sodium 2-sulfoterephthalate. A method of synthesizing dimethyl sodium 2-sulfoterephthalate having a purity of> 98.1% by concentrating under reduced pressure while leaving some water. 請求項３に示された方法で得られた純度が＞９８．１％の２−スルホテレフタル酸ジメチルナトリウムをテレフタル酸ジメチルとエチレングリコ−ルの重縮合系に添加してスルホン基を有する直線状のポリエチレンテレフタレ−トを合成する方法。  A linear shape having a sulfone group by adding dimethyl sodium 2-sulfoterephthalate having a purity of> 98.1% obtained by the method shown in claim 3 to a polycondensation system of dimethyl terephthalate and ethylene glycol. Of synthesizing polyethylene terephthalate.
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