CN106316907A - Compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene and synthetic method thereof - Google Patents
Compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene and synthetic method thereof Download PDFInfo
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- CN106316907A CN106316907A CN201610694171.8A CN201610694171A CN106316907A CN 106316907 A CN106316907 A CN 106316907A CN 201610694171 A CN201610694171 A CN 201610694171A CN 106316907 A CN106316907 A CN 106316907A
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- bis
- compound
- amino toluene
- methyl mercapto
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- PKTOHHARFZTJFR-UHFFFAOYSA-N CC(C(NC(N)=S)=C1SC)=CCC(SC)=C1N Chemical compound CC(C(NC(N)=S)=C1SC)=CCC(SC)=C1N PKTOHHARFZTJFR-UHFFFAOYSA-N 0.000 description 1
- GUUPOEYWBKRZNQ-UHFFFAOYSA-N Cc(c(NC(N)=S)c1SC)cc(SC)c1N Chemical compound Cc(c(NC(N)=S)c1SC)cc(SC)c1N GUUPOEYWBKRZNQ-UHFFFAOYSA-N 0.000 description 1
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N Cc(cc(c(N)c1SC)SC)c1N Chemical compound Cc(cc(c(N)c1SC)SC)c1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C335/20—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene, having a molecular formula of C10N3S3H15 and a following structural formula; a synthetic method of the compound includes: condensing dimethythiotoluene diamine and thiourea to obtain the 2-thiourea-3,5-bis(methylthio)-4-amino toluene. The compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene herein is used as a novel curing agent, the defect that a common amine curing agent is highly volatile and toxic is overcome, and the problem that an aromatic amine curing agent that is solid is unable to cure epoxy resin at room temperature is also solved.
Description
Technical field
The present invention relates to and the invention belongs to epoxide resin material technical field, particularly relates to compound 2-ghiourea group-3,5-bis-
(methyl mercapto)-4-amino toluene and synthetic method, application.
Background technology
In miscellaneous epoxy curing agent, aromatic amine curing agent the most all contains heat stability
Good phenyl ring, the thermostability of its solidfied material, resistance to chemical reagents, mechanical strength are relatively good.But unmodified aromatic amine curing agent
Major part is solid-state at normal temperatures, must heat it, and the activity of aromatic amine all ratios are relatively low, take with epoxy resin during use
It is generally required to high temperature adds heat fusing to it when joining use, the most unmodified aromatic amine toxicity is big.
The such a purpose of resin system of superior heat resistance is obtained having in order to realize intermediate temperature setting, can be to aromatic amine
It is modified, is so possible not only to modified aromatic amine that obtain liquefaction, that activity is high, and remains its heat stability, reduce
Toxicity, thus reach the effect of room temperature curing epoxy, and the heat resistance of material is good, good mechanical properties, solid
Have when changing epoxy resin process of manufacture save time, laborsaving, economize on resources, the series of advantages such as easy to use, be possible not only to
Reduce the cost of product, and can significantly simplify the course of processing.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides compound 2-sulfur
Urea groups-3,5-bis-(methyl mercapto)-4-amino toluene and synthetic method, application, this compound is the solidification of highly active aromatic amine
Agent, containing five active hydrogens, is applied to cured epoxy resin, the most just has the most compatible with epoxy resin
Property, it is also possible to improve the heat distortion temperature of solidfied material, and make it have good thermostability and mechanical property.
The present invention solves that the technical scheme that problem set forth above is used is:
Compound 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene, its molecular formula is C10N3S3H15, structural formula
As follows:
The synthetic method of above-claimed cpd 2-ghiourea group-3,5-two (methyl mercapto)-4-amino toluene is: dimethyl sulphur-based toluene
Diamidogen and thiourea, by condensation reaction, obtain 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene.
By such scheme, the structural formula of described dimethythiotoluene diamine is as described below:
By such scheme, described thiourea is 1:5～6 with the mol ratio of dimethythiotoluene diamine.
By such scheme, the temperature of described condensation reaction is 125～135 DEG C, and the response time is 6～8h.
By such scheme, the atmosphere of described condensation reaction is inert atmosphere.Inert atmosphere can be by being passed through argon, helium
Gas, nitrogen realize, and to get rid of the air in reaction unit, prevent reactant dimethythiotoluene diamine oxidized.
By such scheme, after described condensation reaction, also include the step of extracting and refining.Wherein, described extractant selected from stupid,
The organic solvent such as toluene, dimethylbenzene；The purpose of described exquisiteness is to remove reactant dimethyl sulphur-based toluene two unnecessary in reaction
Amine and other impurity, can use the means such as rotary evaporation.
Preferably, compound 2-ghiourea group-3 of the present invention, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
Specifically include following steps:
(1) under inert gas shielding, by dimethythiotoluene diamine and thiourea 1:5 in molar ratio～6 mixing, then rise
Temperature, to 125～135 DEG C, reacts 6～8h；
(2) after step (1) products therefrom cooling discharge, after extraction, refining, it is thus achieved that pure 2-ghiourea group-3,5-bis-
(methyl mercapto)-4-amino toluene.
Main chemical reactions equation involved in the present invention is as follows:
The fundamental reaction mechanism of the present invention is: the present invention utilizes thiourea-polyamine condensation reaction, makes thiourea and dimethyl sulphur-based
Compound 2-ghiourea group-3,5-two (methyl mercapto)-4-amino toluene is prepared in toluenediamine reaction.This compound is a kind of high alive
The aromatic amine curing agent of property, containing five active hydrogens, is applied to cured epoxy resin, the most just with asphalt mixtures modified by epoxy resin
Fat has the more preferable compatibility, reduces energy consumption；It addition, it can also improve the heat distortion temperature of solidfied material, more solid than common amine
Agent performance is more preferable, is applied to cured epoxy resin and can obtain the solidfied material of better performances, and makes it have good heat-resisting
Property and mechanical property.
Compared with prior art, the invention has the beneficial effects as follows:
1, compound 2-ghiourea group-3,5-two (methyl mercapto)-4-amino toluene of the present invention is by thiourea-polyamine contracting
Close reaction obtained, at room temperature have the more preferable compatibility as firming agent with epoxy resin, can be with room under accelerator coordinates
Temperature cured epoxy resin；Furthermore it is also possible to improve the heat distortion temperature of solidfied material, can reach 130 DEG C or more than, and make it have
Good thermostability and mechanical property.
2, compound 2-ghiourea group-3,5-two (methyl mercapto)-4-amino toluene of the present invention is as novel liquid curing
Agent, had both overcome the shortcoming that the volatile toxicity of common amine curing agent is big, solved again aromatic amine curing agent solid-state and can not room
The problem of temperature cured epoxy resin.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of 2-ghiourea group-3,5-two (methyl mercapto)-4-amino toluene.
Fig. 2 is the technique preparation flow figure of 2-ghiourea group-3,5-two (methyl mercapto)-4-amino toluene.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with example, but the present invention is not only
It is limited only to the following examples.
Material used in the present invention, reagent etc. if no special instructions, the most commercially obtain.
Embodiment 1
Compound 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene, its molecular formula is C10N3S3H15, structural formula
As follows:
Above-claimed cpd synthetic method, step is as follows:
(1) weigh appropriate thiourea to put into thermometer, agitating device and vent gas treatment with dimethythiotoluene diamine
In the four-hole boiling flask of device, wherein thiourea: dimethythiotoluene diamine=1:5, it is passed through nitrogen, in 130 DEG C under stirring
Under react, reaction 6h after, cooling discharge；
(2) being extracted as extractant by step (1) products therefrom toluene, vibration, after stratification, in extraction
Layer liquid moves in container, and rotated evaporation removes in reaction after remaining reactant dimethythiotoluene diamine and other impurity,
Obtain yellow oily liquid, be 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene.
Embodiment 2
Compound 2-ghiourea group-3, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene, specifically comprise the following steps that
(1) weigh appropriate thiourea to put into thermometer, agitating device and vent gas treatment with dimethythiotoluene diamine
In the four-hole boiling flask of device, wherein thiourea: dimethythiotoluene diamine=1:5.5, it is passed through argon, in 135 under stirring
React at DEG C, after reaction 8h, cooling discharge；
(2) being extracted as extractant by step (1) products therefrom toluene, vibration, after stratification, in extraction
Layer liquid moves in container, after rotated evaporation, it is thus achieved that yellow oily liquid, is 2-ghiourea group-3,5-bis-(methyl mercapto)-4-ammonia
Base toluene.
Embodiment 3
Compound 2-ghiourea group-3, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene, specifically comprise the following steps that
(1) weigh appropriate thiourea to put into thermometer, agitating device and vent gas treatment with dimethythiotoluene diamine
In the four-hole boiling flask of device, wherein thiourea: dimethythiotoluene diamine=1:6, it is passed through nitrogen, in 130 DEG C under stirring
Under react, reaction 7h after, cooling discharge；
(2) step (1) products therefrom dimethylbenzene is extracted as extractant, vibration, after stratification, extraction
Upper liquid is moved in container, after rotated evaporation, it is thus achieved that yellow oily liquid, 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino
Toluene.
Table 1 2-ghiourea group-3,5-two (methyl mercapto)-4-amino toluene infrared signature peak
As shown in figure 1 and table 1, above-described embodiment is by the refined product obtained later, at 3354cm-1And 3455cm-1Place
The N-H stretching vibration characteristic absorption peak that peak is primary amine and secondary amine, 1602cm-1The absworption peak at place is the feature of the C=C key of phenyl ring
Absworption peak, 1132cm-1Absworption peak be the stretching vibration of C=S, thus prove: thiourea instead of dimethythiotoluene diamine
(DMTDA), there is condensation reaction in the hydrogen of a upper amino, products therefrom is 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino first
Benzene.
Application examples
Compound 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene is at the application process of epoxy-resin systems, and it walks
Rapid as follows:
(1) in parts by weight, E-51 epoxy resin 100 parts is weighed, firming agent 2-ghiourea group-3,5-bis-(methyl mercapto)-
4-amino toluene 20 parts, DMP-30 accelerator 2 parts is standby；
(2) by said ratio, by firming agent 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene and epoxy resin E-
51 mixing, add DMP-30, cold curing 8h；
(3) solidification afterwards: the product after cold curing, prior to 110 DEG C of solidification 2h, then at 130 DEG C of solidification 2h, obtains asphalt mixtures modified by epoxy resin
Fat solidfied material.This firming agent can quick epoxy resin, cured product has good mechanical property and heat resistance.
The above is only the preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
Saying, without departing from the concept of the premise of the invention, it is also possible to make some modifications and variations, these broadly fall into the present invention's
Protection domain.
Claims (10)
1. compound 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene, it is characterised in that its molecular formula is
C10N3S3H15, structural formula is as follows:
2. compound 2-ghiourea group-3, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene, it is characterised in that dimethyl sulphur-based
Toluenediamine and thiourea, by condensation reaction, obtain 2-ghiourea group-3,5-bis-(methyl mercapto)-4-amino toluene.
Compound 2-ghiourea group-3 the most according to claim 2, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
It is characterized in that, the structural formula of described dimethythiotoluene diamine is as described below:
Compound 2-ghiourea group-3 the most according to claim 2, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
It is characterized in that, described thiourea is 1:5～6 with the mol ratio of dimethythiotoluene diamine.
Compound 2-ghiourea group-3 the most according to claim 2, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
It is characterized in that, the temperature of described condensation reaction is 125～135 DEG C.
Compound 2-ghiourea group-3 the most according to claim 2, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
It is characterized in that, the time of described condensation reaction is 6～8h.
Compound 2-ghiourea group-3 the most according to claim 2, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
It is characterized in that, the atmosphere of described condensation reaction is inert atmosphere.
Compound 2-ghiourea group-3 the most according to claim 2, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
It is characterized in that, after described condensation reaction, also include the step of extracting and refining.
Compound 2-ghiourea group-3 the most according to claim 8, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene,
It is characterized in that, described extractant is selected from stupid, toluene, dimethylbenzene.
10. compound 2-ghiourea group-3, the synthetic method of 5-bis-(methyl mercapto)-4-amino toluene, it is characterised in that it specifically wraps
Include following steps:
(1) under inert gas shielding, by dimethythiotoluene diamine and thiourea 1:5 in molar ratio～6 mixing, then heat to
125～135 DEG C, react 6～8h；
(2) after step (1) products therefrom cooling discharge, after extraction, refining, it is thus achieved that pure 2-ghiourea group-3,5-bis-(first sulfur
Base)-4-amino toluene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610694171.8A CN106316907A (en) | 2016-08-19 | 2016-08-19 | Compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene and synthetic method thereof |
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| CN201610694171.8A CN106316907A (en) | 2016-08-19 | 2016-08-19 | Compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene and synthetic method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2426157A1 (en) * | 2010-09-02 | 2012-03-07 | Lonza Ltd. | Diamine compositions and use thereof |
| CN102604044A (en) * | 2012-02-28 | 2012-07-25 | 武汉工程大学 | Thiourea modified low temperature curing agent and preparation method thereof |
| CN103319853A (en) * | 2012-03-23 | 2013-09-25 | 台光电子材料股份有限公司 | Resin composition for insulation film, and insulation film and circuit board containing same |
| CN103333323A (en) * | 2013-06-13 | 2013-10-02 | 武汉市科达云石护理材料有限公司 | High-toughness high-activity epoxy resin curing agent and preparation method thereof |
| CN104844784A (en) * | 2015-04-13 | 2015-08-19 | 长江大学 | Epoxy resin flexible curing agent and synthetic method thereof |
-
2016
- 2016-08-19 CN CN201610694171.8A patent/CN106316907A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2426157A1 (en) * | 2010-09-02 | 2012-03-07 | Lonza Ltd. | Diamine compositions and use thereof |
| CN102604044A (en) * | 2012-02-28 | 2012-07-25 | 武汉工程大学 | Thiourea modified low temperature curing agent and preparation method thereof |
| CN103319853A (en) * | 2012-03-23 | 2013-09-25 | 台光电子材料股份有限公司 | Resin composition for insulation film, and insulation film and circuit board containing same |
| CN103333323A (en) * | 2013-06-13 | 2013-10-02 | 武汉市科达云石护理材料有限公司 | High-toughness high-activity epoxy resin curing agent and preparation method thereof |
| CN104844784A (en) * | 2015-04-13 | 2015-08-19 | 长江大学 | Epoxy resin flexible curing agent and synthetic method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 杨青海等: "硫脲改性胺环氧树脂固化剂的合成及性能研究", 《热固性树脂》 * |
| 王延飞 等: "二甲硫基甲苯二胺的合成与表征", 《应用化学》 * |
| 程秀莲 等: "硫脲改性物对环氧树脂固化促进作用的研究", 《粘结》 * |
| 程秀莲 等: "硫脲改性苯胺和己二胺环氧树脂固化剂的合成及性能研究", 《粘结》 * |
| 胡玉明 等编: "《固化剂》", 30 April 2004, 化学工业出版社材料科学与工程出版中心出版发行 * |
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