CN106565571B - One kind 2,2 '-two（4- methylbenzene sulfoamino-groups）The preparation method of diphenyl disulfide - Google Patents
One kind 2,2 '-two（4- methylbenzene sulfoamino-groups）The preparation method of diphenyl disulfide Download PDFInfo
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Abstract
The invention discloses a kind of rubber peptizer 2,2' bis-（4 methylbenzene sulfoamino-groups）2,2' diamino diphenyl disulfide, N, N' diisopropylcarbodiimides, N methyl morpholines, tetrahydrofuran are placed in round-bottomed flask by the preparation method of diphenyl disulfide, this kind of method.Start to stir, the tetrahydrofuran solution of p-methyl benzenesulfonic acid, 20~40h of reaction time is slowly added dropwise；After completion of the reaction, it filters, washing, dry product, the Mooney viscosity value of the broken-down rubber of this peptizer is 62.7.The method of the present invention has reaction process simple, and obtained product purity is high, post-processes simple technical advantage.
Description
Technical field
The present invention relates to the preparation methods of a kind of two fragrant sulfoamino-group diphenyl disulfide compounds, particularly relate to 2,2'- bis-
（4- methylbenzene sulfoamino-groups）The preparation method of diphenyl disulfide belongs to chemical assistant technical field.
Background technology
Rubber peptizer is commonly divided into physics rubber peptizer and chemical rubber peptizer.Physics rubber peptizer includes
Aliphatic acid and derivative of fatty acid, unsaturated fatty acid zinc salt, esters, wax class etc.；Chemical rubber peptizer includes pentachlorothiophenol
Class, diaryl disulfide class, organic sulfonic acid salt.But for physics rubber peptizer, application range is smaller, and
And due to there is pigmentation, therefore it should not be used in white sizing material etc..Therefore, work of the chemical rubber peptizer in rubber plastic solution preocess
With more and more important.
Chemical rubber peptizer is indispensable auxiliary chemicals in rubber processing, as long as adding 0.3 part or so in sizing material
Just there is modeling solution effect well.China continues to use the pentachlorothiophenol class product of Beyer Co., Ltd's exploitation always for many years, and effect is fine, but
Pentachlorothiophenol has larger toxicity.In recent years, pentachlorothiophenol is replaced using new kind one after another in the world.Such as rubber in Beijing
Peptizer Z -230 of Kodak rubber material Co., Ltd, the compound peptizer HTA of Shandong Yanggu Hua Tai chemical companies exploitation,
Novel environment friendly peptizer ZD -4 and ZD -8 of the Sino-German chemical industry Co., Ltd production in Hangzhou etc..Due to more than rubber plastic solution
The preparation process of agent is more, and production cost is relatively high, therefore the synthesis for new chemical rubber peptizer and its application tool
There is very important meaning.
At present, in rubber industry common peptizer be two sulphur of dibenzamidodiphenyl, abbreviation DBD（Fan Guozhi, Zou
Soldier, Zhao Lei, Wuhan University of Technology's journal, 2010,32）, natural and synthetic rubber acidity or viscosity can be reduced, is improved uniform
Property, the rubber available for non-food applications such as tire, sebific duct, electric wire, cables.Domestic rubber industry required product is most of
Dependent on import.
Up to the present, Taha, Muhammad and Fukata, Yukihiro et al. are studied in pyridine solvent respectively
Diphenyl diamine has synthesized hexichol sulfonamide substitutions diphenyl-disulf iotade compound (Bioorg. with the reaction of paratoluensulfonyl chloride
Chem., 2016, 68, 15-22;J. Am. Chem. Soc., 2015,137 (16), 5320-5323), reaction process
Middle reaction condition is more harsh, it is desirable that anhydrous and oxygen-free, and pyridine has been used, serious shadow is brought to environment and health of human body
It rings.And document report yet there are no for the modeling solution performance of hexichol sulfonamide substitutions diphenyl-disulf iotade compound, we utilize two
Phenylenediamine has synthesized hexichol sulfonamide substitutions diphenyl-disulf iotade compound with p-methyl benzenesulfonic acid under catalyst action, avoids
Pollution of the substances such as pyridine to environment, simplifies operating procedure, and further studies its modeling solution performance.
Invention content
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of rubber peptizer 2,2'- bis-（4- methylbenzene sulfoamino-groups）The preparation method of diphenyl disulfide, step is such as
Under：2,2'- diamino diphenyl disulfide, catalyst, tetrahydrofuran are placed in round-bottomed flask, by the tetrahydrochysene furan of p-methyl benzenesulfonic acid
Solution of muttering is slowly added dropwise in round-bottomed flask；After completion of the reaction, washed, dry product.
Foregoing preparation method, it is preferred that the catalyst is N, N'- diisopropylcarbodiimides, N-
Methyl morpholine.
Foregoing preparation method, it is preferred that described 2,2 '-diamino diphenyl disulfide, N, N'- diisopropyls
Carbon imidodicarbonic diamide, N-methylmorpholine, p-methyl benzenesulfonic acid molar ratio be 1.0 ~ 1.4：0.1~0.5：0.3~0.8：2.0 ~ 2.6 are
Suitable range（Preferably, described 2,2 '-diamino diphenyl disulfide, N, N'- diisopropylcarbodiimides, N-methylmorpholine,
The molar ratio of p-methyl benzenesulfonic acid is 1.2：0.3：0.6：2.2 are advisable range）.
Preferably, the reaction time is 25-35h（It is preferred that 30h）.
Preferably, the Mooney viscosity of gained rubber peptizer is 62.7.
Its molecular structure is：
This product can be weighed from nuclear magnetic resoance spectrum hydrogen spectrum, carbon spectrum, fusing point index.
The features of the present invention is：
（1）The selection of raw material proportioning
The present invention be with 2,2 '-diamino diphenyl disulfide be raw material, using its with p-methyl benzenesulfonic acid with being replaced
A molecular water productive target product is sloughed in reaction.To improve reaction yield, raw material proportioning is most important, through repetition test, with 2,
2 '-diamino diphenyl disulfide, N, N'- diisopropylcarbodiimides, N-methylmorpholine, p-methyl benzenesulfonic acid molar ratio be
1.0 ~1.4：0.1~0.5：0.3~0.8：2.0 ~ 2.6 are advisable, catalysts N, N'- diisopropylcarbodiimide/N- first
Base morpholine.
（2）The selection of catalyst
2,2'- bis-（4- methylbenzene sulfoamino-groups）Diphenyl disulfide product is faint yellow solid, and synthetic reaction passes through
The substitution reaction of aromatic amine and pyridine -2- formic acid is completed.Experiment is proved using N, N'- diisopropylcarbodiimides, N- methyl
Morpholine is catalyst, and yield is up to 78%.
（3）Obtained product is a kind of 2,2'- bis-（4- methylbenzene sulfoamino-groups）Diphenyl disulfide, can reduce it is natural and
The acidity or viscosity of synthetic rubber can improve rubber viscous, reduce temperature during mixing, improve mold flow properties, improve uniform
Property, the rubber available for non-food applications such as tire, sebific duct, electric wire, cables.Domestic rubber industry required product is most of
Dependent on import.Therefore development and production new type rubber peptizer has important application value.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1：
1.0mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.1mmolN, N'- diisopropylcarbodiimides, and 2.0mmol is added dropwise to methyl in 0.2mmolN- methyl morpholines
The tetrahydrofuran solution of benzene sulfonic acid has yellow mercury oxide generation at once, reacts 20h, filters, dry, yield 61%.Fusing point：163-
165℃。
Embodiment 2：
1.0mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.2mmolN, N'- diisopropylcarbodiimides, and 2.0mmol is added dropwise to methyl in 0.3mmolN- methyl morpholines
The tetrahydrofuran solution of benzene sulfonic acid has yellow mercury oxide generation at once, reacts 20h, filters, dry, yield 64%.Fusing point：163-
165℃。
Embodiment 3：
1.0mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.2mmolN, N'- diisopropylcarbodiimides, and 2.1mmol is added dropwise to methyl in 0.4mmolN- methyl morpholines
The tetrahydrofuran solution of benzene sulfonic acid has yellow mercury oxide generation at once, reacts 25h, filters, dry, yield 65%.Fusing point：163-
165℃。
Embodiment 4：
1.0mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.3mmolN, N'- diisopropylcarbodiimides, and 2.2mmol is added dropwise to methyl in 0.5mmolN- methyl morpholines
The tetrahydrofuran solution of benzene sulfonic acid has yellow mercury oxide generation at once, reacts 30h, filters, dry, yield 69%.Fusing point：163-
165℃。
Embodiment 5：
1.0mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.4mmolN, N'- diisopropylcarbodiimides, and 2.2mmol is added dropwise to methyl in 0.3mmolN- methyl morpholines
The tetrahydrofuran solution of benzene sulfonic acid has yellow mercury oxide generation at once, reacts 25h, filters, dry, yield 71%.Fusing point：163-
165℃。
Embodiment 6：
1.0mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.3mmolN, N'- diisopropylcarbodiimides, and 2.0mmol is added dropwise to methyl in 0.8mmolN- methyl morpholines
The tetrahydrofuran solution of benzene sulfonic acid has yellow mercury oxide generation at once, reacts 25h, filters, dry, yield 75%.Fusing point：163-
165℃。
Embodiment 7：
1.1mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.25mmolN, N'- diisopropylcarbodiimides, and 2.2mmol is added dropwise to first in 0.5mmolN- methyl morpholines
The tetrahydrofuran solution of base benzene sulfonic acid has yellow mercury oxide generation at once, reacts 30h, filters, dry, yield 76%.Fusing point：163-
165℃。
Embodiment 8：
1.0mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.25mmolN, N'- diisopropylcarbodiimides, and 2.2mmol is added dropwise to first in 0.7mmolN- methyl morpholines
The tetrahydrofuran solution of base benzene sulfonic acid has yellow mercury oxide generation at once, reacts 40h, filters, dry, yield 73%.Fusing point：163-
165℃。
Embodiment 9：
1.1mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.25mmolN, N'- diisopropylcarbodiimides, and 2.2mmol is added dropwise to first in 0.4mmolN- methyl morpholines
The tetrahydrofuran solution of base benzene sulfonic acid has yellow mercury oxide generation at once, reacts 40h, filters, dry, yield 77%.Fusing point：163-
165℃。
Embodiment 10：
1.3mmol2,2 '-diamino diphenyl disulfide are added in reaction bulb, 5mL tetrahydrofurans are placed on magnetic stirring apparatus
Upper stirring, adds in 0.25mmolN, N'- diisopropylcarbodiimides, and 2.2mmol is added dropwise to first in 0.2mmolN- methyl morpholines
The tetrahydrofuran solution of base benzene sulfonic acid has yellow mercury oxide generation at once, reacts 30h, filters, dry, yield 66%.Fusing point：163-
165℃。
Above-described embodiment 1-10 after reaction, is had found with 2,2 '-diamino diphenyl disulfide, N, N'- diisopropyl carbon
Imidodicarbonic diamide, N-methylmorpholine, p-methyl benzenesulfonic acid molar ratio be 1.0 ~ 1.4：0.1~0.5：0.3~0.8：2.0 ~ 2.6 are
In suitable range, yield is higher, has reached target.
Gained 2,2'- bis-（4- methylbenzene sulfoamino-groups）The performance assessment criteria of diphenyl disulfide is as follows：
Appearance：Faint yellow solid
Fusing point：163-165℃
The nuclear magnetic data of products obtained therefrom is as follows:2,2'- bis-（4- methylbenzene sulfoamino-groups）The nuclear-magnetism number of diphenyl disulfide
According to：
1H NMR (400 MHz, DMSO)：δ 11.53 (s, 2H), 7.82-7.75 (m,2H), 7.65(d,J 1 =
7.6 Hz, 2H),7.51(q, J=8.0 Hz, 2H), 7.32-7.15 (m, 10H), 2.34 (s, 6H).13C NMR (
100 MHz, CDCl3)：δ141.52, 137.25, 132.46, 131.57, 131.28, 129.54,129.36,
129.04,127.61, 127.35, 127.59, 122.43, 21.66.
From nuclear magnetic resonance data it can be seen that：The chemical shift of hydrogen is at 11.53ppm, 7.82-6.15 ppm on nitrogen
Benzene ring hydrogen in molecular structure, methyl hydrogen are located at 2.34ppm, share 22 hydrogen, conform exactly to product structure.Benzene in carbon spectrum
Chemical shift on ring is between 141.52-122.43ppm, and methyl carbon is in 21.66ppm.
Analytical conclusions：As seen from the above analysis：It is desired mesh after each step product is characterized through Modern spectroscopy
Mark product.
Experimental example：
Rubber mixing technique
1st, banburying process（100 DEG C of initial temperature, rotating speed 60rpm）
（1）It plasticates：500g natural gums is taken to plasticate, 30s adds raw rubber+peptizer, and plasticate 40s, carries stone roller 30s, plasticates
40s carries stone roller 30s, and plasticate 40s, carries stone roller 30s, dumping（Common 240s）.
2nd, mill technique
4mm roll spacing packet roller 1min, addition Sulfur, accelerating agent eat powder 1.5min, and after eating completely, three knives are respectively cut in left and right,
Six triangle bags are made a call to, bottom sheet after four volumes is made a call in 4mm roll spacings.
Interpretation of result
1st, vulcanization characteristics：Add in 2,2'- bis-（4- methylbenzene sulfoamino-groups）Diphenyl disulfide, the maximum of blank sizing material are turned round
Square MH, curingprocess rate and theoretical sulfurizing time are suitable, illustrate that this peptizer adds 0.3phr in sizing material and has little influence on
The crosslinking of sizing material has no adverse effects to the curingprocess rate of sizing material.
2nd, the Mooney viscosity of broken-down rubber：Mooney viscosity is lower than blank sizing material after adding in this peptizer, illustrates this peptizer
There is good modeling solution effect.
Summary conclusion：Evaluation peptizer modeling solution effect mainly sees the Mooney viscosity value of broken-down rubber,
Experimental data subordinate list
1st, vulcameter
2nd, Mooney viscosity
Claims (4)
1. a kind of rubber peptizer 2,2'- bis-（4- methylbenzene sulfoamino-groups）The preparation method of diphenyl disulfide, it is characterized in that,
Step is as follows：2,2'- diamino diphenyl disulfide, catalyst, tetrahydrofuran are placed in round-bottomed flask, by p-methyl benzenesulfonic acid
Tetrahydrofuran solution is slowly added dropwise in round-bottomed flask；After completion of the reaction, washed, dry product；The catalyst is
N, N'- diisopropylcarbodiimide, N-methylmorpholine.
2. preparation method described in accordance with the claim 1, it is characterized in that, described 2,2 '-diamino diphenyl disulfide, N, N'-
Diisopropylcarbodiimide, N-methylmorpholine, p-methyl benzenesulfonic acid molar ratio be 1.0 ~ 1.4：0.1~0.5：0.3~0.8：
2.0~2.6。
3. preparation method described in accordance with the claim 1, it is characterized in that, the reaction time is 25-35h.
4. preparation method described in accordance with the claim 1, it is characterized in that, the Mooney viscosity of gained rubber peptizer is 62.7.
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| A practical and efficient method for the preparation of sulfonamides utilizing Cl3CCN/PPh3;Oraphin Chantarasriwong，等;《Tetrahedron Letters》;20061231;第47卷;7489-7492 * |
| Direct Synthesis of Sulfonamides and Activated Sulfonate Esters from Sulfonic Acids;Stephen Caddick，等;《J. AM. CHEM. SOC.》;20040113;第126卷;1024-1025 * |
| 橡胶塑解剂;郭济中;《江西化工》;19951231(第3期);35-39 * |
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