CN106146802B - Application of two (the methyl mercapto) -4- amino toluene of compound 2- ghiourea group -3,5- in epoxy-resin systems - Google Patents
Application of two (the methyl mercapto) -4- amino toluene of compound 2- ghiourea group -3,5- in epoxy-resin systems Download PDFInfo
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- CN106146802B CN106146802B CN201610695747.2A CN201610695747A CN106146802B CN 106146802 B CN106146802 B CN 106146802B CN 201610695747 A CN201610695747 A CN 201610695747A CN 106146802 B CN106146802 B CN 106146802B
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- curing agent
- epoxy resin
- methyl mercapto
- epoxy
- ghiourea group
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of compound 2- ghiourea groups -3, (the methyl mercapto) -4- amino toluene of 5- bis- as Novel curing agent epoxy-resin systems application method, include the following steps: appropriate 2- ghiourea group -3, (the methyl mercapto) -4- amino toluene of 5- bis- is added in epoxy-resin systems as curing agent and is uniformly mixed, and through molding, solidification, after solidify after, obtain epoxy resin cured product.The aromatic amine curing agent had not only overcome the big disadvantage of the volatile toxicity of common amine curing agent, but also solved the problems, such as common aromatic amine curing agent solid-state and be unable to room temperature curing epoxy；And, this kind of Novel curing agent can make solidfied material have excellent heat resistance and high intensity, can be applied to epoxy resin bonding, encapsulating, the techniques such as winding, molding, the injection of galss fiber reinforced resin based composites, application value and economic value are prominent.
Description
Technical field
The present invention relates to two (methyl mercapto) -4- amino toluene answering in epoxy-resin systems of compound 2- ghiourea group -3,5-
With.
Background technique
Currently, in epoxy curing agent, aromatic amine curing agent all good containing thermal stability benzene in the molecular structure
Ring, heat resistance, resistance to chemical reagents, the mechanical strength of solidfied material are all relatively good.But existing aromatic amine curing agent is in cured epoxy tree
Required reaction temperature is excessively high when rouge；Also, unmodified aromatic amine curing agent is largely at normal temperature solid-state, when use
It must be heated, and the activity of aromatic amine is all relatively low, generally requires high temperature when arranging in pairs or groups and use with epoxy resin and adds to it
Heat fusing, in addition unmodified aromatic amine toxicity is big.
Summary of the invention
The technical problem to be solved by the present invention is to provide new compound in view of the deficiency of the prior art
(the methyl mercapto) -4- amino toluene of 2- ghiourea group -3,5- bis-, in the application of epoxy-resin systems, had both overcome common as curing agent
The big disadvantage of the volatile toxicity of amine curing agent, and solve aromatic amine curing agent solid-state and be unable to room temperature curing epoxy
Problem compares other aromatic amine curing agents, can achieve the purpose that in mild room temperature curing epoxy.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
New compound 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene, its molecular formula are C10N3S3H15, knot
Structure formula is as follows:
Above-mentioned new compound 2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene is as Novel curing agent in epoxy
The application of resin system.In application, according to actual needs, by suitable curing agent 2- ghiourea group -3,5- bis- (methyl mercapto) -4- ammonia
Base toluene be added in epoxy-resin systems be uniformly mixed, and through molding, solidification, after solidify, obtain epoxy resin cured product,
Application of above-mentioned two (the methyl mercapto) -4- amino toluene of Novel curing agent 2- ghiourea group -3,5- in epoxy-resin systems
Method, comprising the following steps:
(1) according to 2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene dosage be epoxy resin quality 20~
40%, after epoxy resin is heated to 60~80 DEG C in advance, 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene is added, stirs
It mixes and is uniformly mixed and forms, gained mixture after molding is heated to 90~100 DEG C of 4~6h of solidification；
(2) solidify afterwards: by step (1) products therefrom in 120~130 DEG C of 2~4h of solidification, obtaining epoxy resin cured product.
Above-mentioned Novel curing agent 2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene is in the another of epoxy-resin systems
Kind application method, comprising the following steps:
It 1) is the 20~40% of epoxy resin quality according to 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene dosage,
Accelerator dosage is the 1~3% of epoxy resin quality, stock；2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene is added
Enter into epoxy resin, promotor and/or filler is then added, is uniformly mixed and forms, by gained mixing after molding
Object solidifies 6~8h at room temperature；
2) solidify afterwards: step 1) products therefrom being warming up to 100~110 DEG C of 2~4h of solidification, then then at 120~130 DEG C
Solidify 2~4h, obtains epoxy resin cured product.
Above-mentioned two (methyl mercapto) -4- amino toluene of Novel curing agent 2- ghiourea group -3,5- is the first of epoxy-resin systems
Kind application method, comprising the following steps:
It 1) is the 20~40% of epoxy resin quality according to 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene dosage,
The dosage of filler is the 2~10% of epoxy resin quality, stock；2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene is added
Enter into epoxy resin, filler is then added, be uniformly mixed and form, gained mixture after molding is heated to 90~
100 DEG C of 4~6h of solidification；
2) solidify afterwards: step 1) products therefrom being warming up to 100~110 DEG C of 2~4h of solidification, then then at 120~130 DEG C
Solidify 2~4h, obtains epoxy resin cured product.
According to the above scheme, described to be shaped to appointing in the methods of compression molding, moulding by casting, hand pasting forming, Wrapping formed
It anticipates one kind.
According to the above scheme, the epoxy resin is E-54, E-51, E-44, E-42, CYD127, the asphalt mixtures modified by epoxy resin such as CYD128
The mixture of one or more of rouge in any proportion.
According to the above scheme, the promotor is boron trifluoride~mono aminoethane complex compound, triethylamine, triethylamine alcohol, DMP-
The mixture of one or more of 30 equal promotors in any proportion.
According to the above scheme, the filler is that lightweight calcium silicates, fumed silica, talcum powder etc. are one such or several
The mixture of kind in any proportion.The dosage of filler is usually the 2~10% of epoxy resin quality.
Novel curing agent 2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene is applied to epoxy resin body in the present invention
When in system, curing mechanism is as shown in Figure 1.
Compared with prior art, this invention beneficial effect is:
1, the present invention provides a kind of novel epoxy curing agent -2- ghiourea group -3,5- two (methyl mercapto) -4- ammonia
Base toluene had not only overcome the big disadvantage of the volatile toxicity of common amine curing agent, but also solved aromatic amine curing agent solid-state and not
Can room temperature curing epoxy the problem of, compare other aromatic amine curing agents, can reach in mild room temperature curing epoxy
Purpose.
2,2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene is a kind of aromatic amine curing agent of high activity, this substance
It containing there are five active hydrogens, is compared with traditional aromatic amine curing agent, which is liquid, and small toxicity is applied to solid
Change epoxy resin, solidfied material can be made to have with excellent heat resistance and high intensity.
Above-mentioned Novel curing agent provided by the present invention can be applied to epoxy resin bonding, encapsulating, glass fibre
The techniques such as winding, molding, the injection of reinforced resin based composites, application value and economic value are prominent.
Detailed description of the invention
Fig. 1 is 2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene using the curing mechanism with epoxy-resin systems.
Specific embodiment
For a better understanding of the present invention, below with reference to the example content that the present invention is furture elucidated, but the present invention is not only
It is limited only to the following examples.
The preparation method of Novel curing agent 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene of the present invention, specifically
Process is as follows:
A. suitable thiocarbamide and dimethythiotoluene diamine investment are weighed with thermometer, agitating device and vent gas treatment dress
In the four-hole boiling flask set, wherein thiocarbamide: dimethythiotoluene diamine=1:5 is passed through nitrogen protection, in 130 under stirring
It DEG C is reacted, after reacting 8h, after reaction, cooling discharge；
B. the resulting product of step a is mixed with toluene, is extracted by extractant of toluene, vibrated, to stratification
Afterwards, it extracts upper liquid to move in container, after rotary evaporation, obtains yellow oily liquid, as bis- (first of 2- ghiourea group -3,5-
Sulfenyl) -4- amino toluene.
Embodiment 1
Bis- (methyl mercapto) -4- amino toluene of Novel curing agent 2- ghiourea group -3,5- epoxy-resin systems application method,
Its step are as follows:
(1) as mass fraction, 100 parts of E-51 epoxy resin, 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino are weighed
35 parts of toluene, epoxy resin is preheated to 80 DEG C, 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene is added, is stirred
Uniformly, it is poured, excludes bubble, gained resin compound is heated to 100 DEG C of solidification 3h；
(2) solidify afterwards: by step (1) products therefrom in 130 DEG C of solidification 4h, obtaining epoxy resin cured product.
Embodiment 2
Bis- (methyl mercapto) -4- amino toluene of Novel curing agent 2- ghiourea group -3,5- epoxy-resin systems application method,
Its step are as follows:
(1) as mass fraction, 100 parts of E-44 epoxy resin, 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino are weighed
25 parts of toluene, boron trifluoride~2 parts of mono aminoethane complex compound after three is mixed evenly, exclude bubble, glass fiber dipped
Compression molding, solidifies 8h for gained resin compound after molding at room temperature；
(2) solidify afterwards: step (1) being first warming up to 110 DEG C of solidification 2h, 130 DEG C of solidification 3h is continuously heating to, obtains epoxy
Resin cured matter.
Embodiment 3
Bis- (methyl mercapto) -4- amino toluene of Novel curing agent 2- ghiourea group -3,5- epoxy-resin systems application method,
Its step are as follows:
(1) as mass fraction, 100 parts of CYD128 epoxy resin, 2- ghiourea group -3,5- bis- (methyl mercapto) -4- ammonia are weighed
30 parts of base toluene, 4 parts of precipitated calcium carbonate filler after three is mixed evenly, exclude bubble, and glass fiber reinforcement is injected into
Gained resin compound after molding is heated to 95 DEG C of solidification 3h, is continuously heating to 110 DEG C of solidification 3h by type；
(2) solidify afterwards: by step (1) products therefrom in 130 DEG C of solidification 3h, obtaining epoxy resin cured product.
Embodiment 4
Bis- (methyl mercapto) -4- amino toluene of Novel curing agent 2- ghiourea group -3,5- epoxy-resin systems application method,
Its step are as follows:
(1) as mass fraction, 100 parts of E-51 epoxy resin, 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino are weighed
40 parts of toluene, epoxy resin is preheated to 80 DEG C, 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene is added, is stirred
After uniformly, bubble is excluded, gained resin compound after molding is heated to 100 DEG C of solidification 4h by glass fibre pultrusion；
(2) solidify afterwards: by step (1) products therefrom in 130 DEG C of solidification 3h, obtaining epoxy resin cured product.
As can be seen from the above embodiments: Novel curing agent of the present invention is compared to dimethythiotoluene diamine cured epoxy tree
The solidification temperature of rouge is reduced close to 40 DEG C, and solidfied material can be made to have excellent heat resistance, impact resistance and high intensity.When
So, when Novel curing agent 2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene is applied to epoxy-resin systems, promotor
It can be added according to the actual situation with filler, additional amount and subsequent cure temperature slightly adjust.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (3)
1. application method of bis- (the methyl mercapto) -4- amino toluene of curing agent 2- ghiourea group -3,5- in epoxy-resin systems, feature
Be the following steps are included:
1) according to 2- ghiourea group -3,5- two (methyl mercapto) -4- amino toluene dosage be epoxy resin quality 20 ~ 40% stock；It will
2- ghiourea group -3,5- bis- (methyl mercapto) -4- amino toluene is added in epoxy resin, and promotor and/or filler is then added, stirs
It mixes and is uniformly mixed and forms, gained mixture after molding is solidified into 6 ~ 8h at room temperature；
2) afterwards solidify: step 1) products therefrom is warming up to 100 ~ 110 DEG C of 2 ~ 4h of solidification, then then at 120 ~ 130 DEG C solidify 2 ~
4h obtains epoxy resin cured product；
The promotor is one or more of boron trifluoride~mono aminoethane complex compound, triethylamine, triethylamine alcohol, DMP-30
Mixture in any proportion, accelerator dosage are the 1 ~ 3% of epoxy resin quality；The filler is lightweight calcium silicates, gas phase
The mixture of one or more of silica, talcum powder in any proportion, the dosage of filler be epoxy resin quality 2 ~
10%。
2. two (methyl mercapto) -4- amino toluene of curing agent 2- ghiourea group -3,5- according to claim 1 is in epoxy resin body
The application method of system, it is characterised in that it is described be shaped to compression molding, moulding by casting, hand pasting forming, it is Wrapping formed in it is any
It is a kind of.
3. two (methyl mercapto) -4- amino toluene of curing agent 2- ghiourea group -3,5- according to claim 1 is in epoxy resin body
The application method of system, it is characterised in that the epoxy resin is E-54, E-51, E-44, E-42, CYD127, in CYD128
One or more of mixtures in any proportion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610695747.2A CN106146802B (en) | 2016-08-19 | 2016-08-19 | Application of two (the methyl mercapto) -4- amino toluene of compound 2- ghiourea group -3,5- in epoxy-resin systems |
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| CN201610695747.2A CN106146802B (en) | 2016-08-19 | 2016-08-19 | Application of two (the methyl mercapto) -4- amino toluene of compound 2- ghiourea group -3,5- in epoxy-resin systems |
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| CN106146802B true CN106146802B (en) | 2019-05-03 |
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|---|---|---|---|---|
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2016
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| CN1143661A (en) * | 1996-01-17 | 1997-02-26 | 青岛化工学院 | Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive |
| 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 |
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