CN106565571A - Preparation method for 2,2'-di(4-methyl benzene sulfoamino)diphenyl disulphide - Google Patents
Preparation method for 2,2'-di(4-methyl benzene sulfoamino)diphenyl disulphide Download PDFInfo
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- CN106565571A CN106565571A CN201610977577.7A CN201610977577A CN106565571A CN 106565571 A CN106565571 A CN 106565571A CN 201610977577 A CN201610977577 A CN 201610977577A CN 106565571 A CN106565571 A CN 106565571A
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
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Abstract
The invention discloses a preparation method for 2,2'-di(4-methyl benzene sulfoamino)diphenyl disulphide as rubber peptizer. According to the method, 2,2'-diaminodiphenyl disulfide, N,N'-diisopropylcarbodiimide, N-methylmorpholine and tetrahydrofuran are placed in a round-bottom flask; stirring is started, and a tetrahydrofuran solution of p-toluene sulfonic acid is slowly dropped, wherein the reaction time is 20 h to 40 h; and after a reaction is finished, a product is obtained after a mixture is filtrated, washed and dried. The Mooney viscosity value of plasticated rubber of the peptizer is 62.7. The method has the technical beneficial effects that the reaction process is simple, the purity of the obtained product is high, and after-treatment is simple.
Description
Technical field
The present invention relates to the preparation method of a kind of two fragrant sulfoamino-group diphenyl disulfide compounds, particularly relates 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
Fatty 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, its range of application is less, and
And due to there is pigmentation, therefore 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.For many years China continues to use always the pentachlorothiophenol class product of Beyer Co., Ltd's exploitation, and effect is fine, but
Pentachlorothiophenol has larger toxicity.In recent years, one after another pentachlorothiophenol replaced using new kind in the world.Such as rubber in Beijing
Peptizer Z -230 of Kodak elastomeric material company limited, 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 company limited production in Hangzhou etc..Due to above rubber plastic solution
The preparation process of agent is more, and production cost is of a relatively high, therefore the synthesis for new chemical rubber peptizer and its application tool
There is very important meaning.
At present, in rubber industry commonly use peptizer be the sulfur of dibenzamidodiphenyl two, abbreviation DBD（Fan Guozhi, Zou
Soldier, Zhao Lei, Wuhan University of Technology's journal, 2010,32）, natural and elastomeric acid or viscosity can be reduced, improve uniform
Property, can be used for the rubber of the non-food applications such as tire, sebific duct, electric wire, cable.Domestic rubber industry required product is most of
Depend on import.
Up to the present, Taha, Muhammad and Fukata, Yukihiro et al. are studied respectively in pyridine solvent
Diphenyl diamine has been synthesized hexichol sulfonamide substitutions diphenyl-disulf iotade compound (Bioorg. with paratoluensulfonyl chloride
Chem., 2016, 68, 15-22;J. Am. Chem. Soc., 2015,137 (16), 5320-5323), course of reaction
Middle reaction condition is more harsh, it is desirable to anhydrous and oxygen-free, and has used pyridine, and to environment and health of human body serious shadow is brought
Ring.And for the modeling solution performance of hexichol sulfonamide substitutions diphenyl-disulf iotade compound yet there are no document report, we utilize two
Phenylenediamine has synthesized hexichol sulfonamide substitutions diphenyl-disulf iotade compound with p-methyl benzenesulfonic acid under catalyst action, it is to avoid
Pollution of the materials such as pyridine to environment, simplifies operating procedure, and further study its modeling solution performance.
The content of the invention
The purpose of the present invention is achieved by the following technical solution：
A kind of rubber peptizer 2,2'- bis-（4- methylbenzene sulfoamino-groups）The preparation method of diphenyl disulfide, step is as follows：Will
2,2'- diaminourea diphenyl disulfides, catalyst, tetrahydrofuran are placed in round-bottomed flask, and the tetrahydrofuran of p-methyl benzenesulfonic acid is molten
Liquid is slowly added dropwise in round-bottomed flask；After completion of the reaction, scrubbed, dry product.
Foregoing preparation method, it is preferred that described catalyst is N, N'- diisopropylcarbodiimides, N-
Methyl morpholine.
Foregoing preparation method, it is preferred that described 2,2 '-diaminourea diphenyl disulfide, N, N'- diisopropyls
Carbon imidodicarbonic diamide, N-methylmorpholine, the mol ratio of p-methyl benzenesulfonic acid are 1.0 ~ 1.4：0.1~0.5：0.3~0.8：2.0 ~ 2.6 are
Suitable scope（Preferably, described 2,2 '-diaminourea diphenyl disulfide, N, N'- diisopropylcarbodiimides, N-methylmorpholine,
The mol ratio of p-methyl benzenesulfonic acid is 1.2：0.3：0.6：2.2 are advisable scope）.
Preferably, the described response 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.
Of the invention the characteristics of is：
（1）The selection of proportioning raw materials
The present invention be with 2,2 '-diaminourea diphenyl disulfide for raw material, using its with p-methyl benzenesulfonic acid with carry out substitution reaction
Slough a molecular water productive target product.To improve reaction yield, proportioning raw materials are most important, Jing repetition tests, with 2,2 '-two
ADP disulfide, N, N'- diisopropylcarbodiimides, N-methylmorpholine, p-methyl benzenesulfonic acid mol ratio be 1.0 ~
1.4：0.1~0.5：0.3~0.8：2.0 ~ 2.6 are advisable, and catalysts are N, N'- diisopropylcarbodiimides/N- methyl
Quinoline.
（2）The selection of catalyst
2,2'- bis-（4- methylbenzene sulfoamino-groups）Diphenyl disulfide product is faint yellow solid, and its synthetic reaction is by fragrance
Amine is completed with the substitution reaction of pyridine -2- formic acid.Experiment proof adopts N, N'- diisopropylcarbodiimides, N-methylmorpholine
For catalyst, yield is up to 78%.
（3）The product for obtaining is a kind of 2,2'- bis-（4- methylbenzene sulfoamino-groups）Diphenyl disulfide, can reduce it is natural and
Elastomeric acid or viscosity, can improve rubber viscous, reduce temperature during mixing, improve mold flow properties, improve uniform
Property, can be used for the rubber of the non-food applications such as tire, sebific duct, electric wire, cable.Domestic rubber industry required product is most of
Depend on import.Therefore development and production new type rubber peptizer, with important using value.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1：
1.0mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.1mmolN, N'- diisopropylcarbodiimides, 0.2mmolN- methyl morpholines, Deca 2.0mmol are to methylbenzene sulphur
The tetrahydrofuran solution of acid, has at once yellow mercury oxide to generate, and reacts 20h, sucking filtration, dry, yield 61%.Fusing point：163-165℃.
Embodiment 2：
1.0mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.2mmolN, N'- diisopropylcarbodiimides, 0.3mmolN- methyl morpholines, Deca 2.0mmol are to methylbenzene sulphur
The tetrahydrofuran solution of acid, has at once yellow mercury oxide to generate, and reacts 20h, sucking filtration, dry, yield 64%.Fusing point：163-165℃.
Embodiment 3：
1.0mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.2mmolN, N'- diisopropylcarbodiimides, 0.4mmolN- methyl morpholines, Deca 2.1mmol are to methylbenzene sulphur
The tetrahydrofuran solution of acid, has at once yellow mercury oxide to generate, and reacts 25h, sucking filtration, dry, yield 65%.Fusing point：163-165℃.
Embodiment 4：
1.0mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.3mmolN, N'- diisopropylcarbodiimides, 0.5mmolN- methyl morpholines, Deca 2.2mmol are to methylbenzene sulphur
The tetrahydrofuran solution of acid, has at once yellow mercury oxide to generate, and reacts 30h, sucking filtration, dry, yield 69%.Fusing point：163-165℃.
Embodiment 5：
1.0mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.4mmolN, N'- diisopropylcarbodiimides, 0.3mmolN- methyl morpholines, Deca 2.2mmol are to methylbenzene sulphur
The tetrahydrofuran solution of acid, has at once yellow mercury oxide to generate, and reacts 25h, sucking filtration, dry, yield 71%.Fusing point：163-165℃.
Embodiment 6：
1.0mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.3mmolN, N'- diisopropylcarbodiimides, 0.8mmolN- methyl morpholines, Deca 2.0mmol are to methylbenzene sulphur
The tetrahydrofuran solution of acid, has at once yellow mercury oxide to generate, and reacts 25h, sucking filtration, dry, yield 75%.Fusing point：163-165℃.
Embodiment 7：
1.1mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.25mmolN, N'- diisopropylcarbodiimides, 0.5mmolN- methyl morpholines, Deca 2.2mmol are to methylbenzene
The tetrahydrofuran solution of sulfonic acid, has at once yellow mercury oxide to generate, and reacts 30h, sucking filtration, dry, yield 76%.Fusing point：163-165
℃。
Embodiment 8：
1.0mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.25mmolN, N'- diisopropylcarbodiimides, 0.7mmolN- methyl morpholines, Deca 2.2mmol are to methylbenzene
The tetrahydrofuran solution of sulfonic acid, has at once yellow mercury oxide to generate, and reacts 40h, sucking filtration, dry, yield 73%.Fusing point：163-165
℃。
Embodiment 9：
1.1mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.25mmolN, N'- diisopropylcarbodiimides, 0.4mmolN- methyl morpholines, Deca 2.2mmol are to methylbenzene
The tetrahydrofuran solution of sulfonic acid, has at once yellow mercury oxide to generate, and reacts 40h, sucking filtration, dry, yield 77%.Fusing point：163-165
℃。
Embodiment 10：
1.3mmol2,2 '-diaminourea diphenyl disulfide, 5mL tetrahydrofurans is added to be placed on magnetic stirring apparatuss and stir in reaction bulb
Mix, addition 0.25mmolN, N'- diisopropylcarbodiimides, 0.2mmolN- methyl morpholines, Deca 2.2mmol are to methylbenzene
The tetrahydrofuran solution of sulfonic acid, has at once yellow mercury oxide to generate, and reacts 30h, sucking filtration, dry, yield 66%.Fusing point：163-165
℃。
After above-described embodiment 1-10 reactions terminate, find with 2,2 '-diaminourea diphenyl disulfide, N, N'- diisopropyl carbon
Imidodicarbonic diamide, N-methylmorpholine, the mol ratio of p-methyl benzenesulfonic acid are 1.0 ~ 1.4：0.1~0.5：0.3~0.8：2.0 ~ 2.6 are
Preferably in scope, yield is higher, has reached target.
Gained 2,2'- bis-（4- methylbenzene sulfoamino-groups）The performance assessment criteria of diphenyl disulfide is as follows：
Outward 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 magnetic data of diphenyl disulfide：
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)：δ 141.52, 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 on nitrogen is molecule at 11.53ppm, 7.82-6.15 ppm
Benzene ring hydrogen in structure, methyl hydrogen is located at 2.34ppm, has 22 hydrogen, conforms exactly to product structure.In carbon spectrum on phenyl ring
Chemical shift between the 141.52-122.43ppm, methyl carbon is in 21.66ppm.
Analytical conclusions：As seen from the above analysis：After each step product Jing Modern spectroscopies are characterized, desired mesh is
Mark product.
Experimental example：
Rubber mixing technique
1st, banburying process（100 DEG C of initial temperature, rotating speed 60rpm）
（1）Plasticate：Take 500g natural gums to be plasticated, 30s adds rubber+peptizer, plasticate 40s, carry stone roller 30s, plasticate 40s, carries
Stone roller 30s, plasticate 40s, carries stone roller 30s, dumping（Common 240s）.
2nd, mill technique
4mm roll spacing bag roller 1min, add sulfur, accelerator to eat powder 1.5min, and after eating completely, three knives are respectively cut in left and right, make a call to six
Bottom sheet after four volumes is made a call in individual triangle bag, 4mm roll spacings.
Interpretation of result
1st, vulcanization characteristics：Add 2,2'- bis-（4- methylbenzene sulfoamino-groups）The peak torque of diphenyl disulfide, blank sizing material
MH, curingprocess rate and theoretical sulfurizing time quite, illustrate that this peptizer adds 0.3phr in sizing material and has little influence on glue
The crosslinking of material, has no adverse effects to the curingprocess rate of sizing material.
2nd, the Mooney viscosity of broken-down rubber：Add after this peptizer that Mooney viscosity is low than blank sizing material, illustrate this peptizer
There is good modeling solution effect.
Summary conclusion：The Mooney viscosity value that peptizer modeling solution effect mainly sees broken-down rubber is evaluated,
Experimental data subordinate list
1st, vulcameter
2nd, Mooney viscosity
Claims (5)
1. a kind of rubber peptizer 2,2'- bis-（4- methylbenzene sulfoamino-groups）The preparation method of diphenyl disulfide, is characterized in that,
Step is as follows：2,2'- diaminourea diphenyl disulfides, 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, scrubbed, dry product.
2. according to the preparation method described in claim 1, it is characterized in that, described catalyst is N, the acyl of N'- diisopropyls carbon two
Imines, N-methylmorpholine.
3. according to the preparation method described in claim 2, it is characterized in that, described 2,2 '-diaminourea diphenyl disulfide, N, N'-
Diisopropylcarbodiimide, N-methylmorpholine, the mol ratio of p-methyl benzenesulfonic acid are 1.0 ~ 1.4：0.1~0.5：0.3~0.8：
2.0 ~ 2.6 are advisable scope（Preferably, described 2,2 '-diaminourea diphenyl disulfide, N, N'- diisopropylcarbodiimides, N-
Methyl morpholine, the mol ratio of p-methyl benzenesulfonic acid are 1.2：0.3：0.6：2.2 are advisable scope）.
4. according to the preparation method described in claim 1, it is characterized in that, the described response time is 25-35h（It is preferred that 30h）.
5. according to the preparation method described in claim 1, it is characterized in that, the Mooney viscosity of gained rubber peptizer is 62.7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003114A (en) * | 2017-12-25 | 2018-05-08 | 聊城大学 | One kind 3,3 '-bis- phenyl -2H, the preparation method of 2 ' H-2,2 '-dibenzo [1,4] thiazine |
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Non-Patent Citations (3)
| Title |
|---|
| ORAPHIN CHANTARASRIWONG，等: "A practical and efficient method for the preparation of sulfonamides utilizing Cl3CCN/PPh3", 《TETRAHEDRON LETTERS》 * |
| STEPHEN CADDICK，等: "Direct Synthesis of Sulfonamides and Activated Sulfonate Esters from Sulfonic Acids", 《J. AM. CHEM. SOC.》 * |
| 郭济中: "橡胶塑解剂", 《江西化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003114A (en) * | 2017-12-25 | 2018-05-08 | 聊城大学 | One kind 3,3 '-bis- phenyl -2H, the preparation method of 2 ' H-2,2 '-dibenzo [1,4] thiazine |
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