CN106519192A - Curing agent used for epoxy resin system and application method thereof - Google Patents
Curing agent used for epoxy resin system and application method thereof Download PDFInfo
- Publication number
- CN106519192A CN106519192A CN201610948611.8A CN201610948611A CN106519192A CN 106519192 A CN106519192 A CN 106519192A CN 201610948611 A CN201610948611 A CN 201610948611A CN 106519192 A CN106519192 A CN 106519192A
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- Prior art keywords
- epoxy
- resin
- firming agent
- epoxy resin
- application process
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Classifications
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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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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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 curing agent used for an epoxy resin system and an application thereof. The structural formula of the curing agent is shown as follows (the structural formula is defined in the specifications) and is named 1, 5-di-trimellitic anhydride glutaric ester. A novel epoxy curing agent 1, 5-di-trimellitic anhydride glutaric ester is used for reducing a curing temperature of an acid anhydride compound as the epoxy resin curing agent, and thus the curing time is shortened, molding usability is improved, and favorable use stability of the epoxy resin curing agent is maintained. The novel curing agent can be practically applied to embedment and splice of the epoxy resin, fiber-reinforcing the molding process of epoxy resin composite materials and the like, and curing materials have excellent heat resistance and mechanical performance.
Description
Technical field
The present invention relates to the invention belongs to epoxide resin material technical field, more particularly to a kind of it is used for epoxy-resin systems
Firming agent and its application process.
Background technology
Anhydride compound can be used for epoxy curing agent, with volatility it is low, easy to operate, shrinkage factor is low and electrical property is excellent
Good the advantages of.But anhydride compound fusing point is high, easily because high temperature produces internal stress during cured epoxy resin, to material power
Learn performance to adversely affect.Used as epoxy curing agent, its epoxy resin cured product has excellent resistance to trimellitic anhydride
Hot, electrical property, mechanical performance and drug resistance moral character energy, foreign countries have been used for high temperature insulation laminate, heat proof cable insullac, powder
In coating and casting material.But, trimellitic anhydride is separately as solidification temperature during epoxy curing agent too high (180～200
DEG C), material forming process is poor, and the properties of material are adversely affected, while hardening time is long, causes using not
Just.
The content of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art, there is provided a kind of to be used for epoxy
The firming agent and its application process of resin system, to reduce trimellitic anhydride as epoxy curing agent solidification temperature,
Shorten hardening time, and its original mechanical performance and heat stability can be kept.
The present invention by solve the problems, such as the technical scheme for adopting set forth above for：
A kind of firming agent for epoxy-resin systems, its molecular formula are C23H16O10, structural formula as shown in Equation 1, name
For bis- trimellitic anhydrides of 1,5-, penta diester.
Above-mentioned firming agent is comprised the following steps in the application process of epoxy-resin systems：
(1), in the case of being not added with accelerator, it is the 50～70% of epoxy resin quality according to hardener dose, both is mixed
Close uniform, and after molding, be heated to 100～120 DEG C of 3～5h of solidification；
(2) solidify 1～2h during by primary solidification product obtained by step (1) prior to 130～150 DEG C, then in 150～160
DEG C when solidify 1～2h, the epoxide resin material after being solidified.
Above-mentioned firming agent is comprised the following steps in another kind of application process of epoxy-resin systems：
1), in the case of adding accelerator, it is the 1～3% of epoxy resin quality according to the consumption of accelerator, firming agent
Consumption is the 50～70% of epoxy resin quality, is got the raw materials ready, and after firming agent and epoxy resin are dissolved with organic solvent, adds and promotes
Agent and/or filler mix homogeneously, after molding, 5～7h of cold curing；
2) by step 1) primary solidification product is obtained prior to 120～130 DEG C of 1～2h of solidification, it is then solid in 140～150 DEG C
Change 1～2h, the epoxide resin material after being solidified.
By such scheme, the accelerator is triethylamine, DMP-30 etc..
By such scheme, during the organic solvent is acetone, dehydrated alcohol, dibutyl phthalate, ethyl acetate etc.
It is one or any several.
By such scheme, depending on practical situation, the consumption of organic solvent of the present invention is preferred for the consumption of the organic solvent
For the 2～5% of epoxy resin quality.
By such scheme, described filler is Pulvis Talci, titanium dioxide, aerosil, precipitated calcium carbonate, aluminium hydroxide
Deng, concrete consumption depending on practical situation, the consumption of filler of the present invention is the 1～10% of epoxy resin quality.
It is in above two application process, described to be shaped to moulding by casting, injection moulding, resin transfer molding, handss paste
Any one in molding etc..
In above two application process, the epoxy resin includes the rings such as E51, E-44, WSR615, DER330, CYD128
Oxygen tree fat.
Curing mechanism such as Fig. 1 institute of bis- trimellitic anhydrides of firming agent 1,5-, penta diester that the present invention is provided to epoxy resin
Show, the anhydride group of 1,5-, bis- trimellitic anhydrides, penta diester forms negative oxygen ion with accelerator open loop in the first stage first；
Second stage, the negative oxygen ion of generation are pressed nucleophilic mechanism attack epoxy radicals and form crosslinking.
Compared with prior art, beneficial effect of the present invention is：
1st, the present invention is by a kind of new epoxy curing agent 1, bis- trimellitic anhydrides of 5-, penta diester, to reduce acid
Solidification temperature of the anhydridization compound as epoxy curing agent, and the stability in use for keeping which good, this kind of Novel curing agent
Epoxy resin encapsulated, bonding can be applied to；Moulding process of fibre reinforced epoxy resin composite etc., with protrusion
Use value.
2nd, the present invention starts with from MOLECULE DESIGN, there is provided one kind carries out chemistry to chlorination trimellitic anhydride with 1,5-PD
A kind of modified method, so as to obtain Novel curing agent, to reduce trimellitic anhydride as the solidification of epoxy curing agent
Temperature, shorten hardening time, and its original mechanical performance and heat stability can be kept.
Description of the drawings
Fig. 1 is bis- trimellitic anhydrides of 1,5-, penta diester epoxy-resin systems curing mechanism.
Fig. 2 is the infrared spectrogram of bis- trimellitic anhydrides of 1,5-, penta diester prepared in embodiment 1.
Fig. 3 is the nucleus magnetic hydrogen spectrum of bis- trimellitic anhydrides of 1,5-, penta 2 ester molecule prepared in embodiment 1.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to example, but the present invention is not only
It is limited only to the following examples.
Bis- trimellitic anhydrides of raw material 1,5-, penta diester that the present invention is used prepares as follows：Trimellitic Anhydride Chloride, 1,5- penta
The mol ratio of glycol and alkali is 1：(0.6～1.0)：(1.5～2.5), and in -5～0 DEG C of isothermal reaction 3 under the catalysis of weak base
～5h, obtains 1,5-, bis- trimellitic anhydrides, penta diester Jing after remove impurity.
Embodiment 1
Compound 1, bis- trimellitic anhydrides of 5-, penta diester, its molecular structural formula are as follows：
Above-claimed cpd 1, the synthetic method of bis- trimellitic anhydrides of 5-, penta diester, comprises the following steps that：
(1) compare ice according to quality：Calcium chloride=100：20 prepare cryosel, are 1 in molar ratio：0.6：1.5 take trimellitic acid
Acid anhydride acyl chlorides, 1,5-PD, DBU, 5～6 times for reactant volume of solvent ethyl acetate consumption；
The Trimellitic Anhydride Chloride for weighing and solvent ethyl acetate are mixed in there-necked flask, ice are added toward water-bath
Salt, there-necked flask are placed in water-bath and start magnetic stirring apparatuss, first make Trimellitic Anhydride Chloride be dissolved in ethyl acetate, then will
The 1,5-PD for weighing is placed in minim pipette, slowly drips off in 25min, obtains reactant liquor；DBU is added in 30min above-mentioned
In reactant liquor, then controlling reaction temperature is -5～0 DEG C, reacts 3h, and resulting solution is white, bis- trimellitic anhydrides of as 1,5-
Penta diester crude product；
(2) remove impurity is processed：Add and its isopyknic distilled water in crude product, remove water layer to remove DBU salt after shaking up；So
Afterwards, add and its isopyknic 1,5-PD in gained surplus solution, remove oil reservoir to remove what major part did not replaced completely
1,5- pentadiol esters；Continue, add and its isopyknic 1,5-PD toward gained raffinate, after mixing, be poured slowly into saturation
In sodium carbonate liquor, stand the product Jing for separating out and filter, as pure 1,5-, bis- trimellitic anhydrides, penta diester.
The present embodiment is processed by remove impurity and obtains pure white solid, bis- trimellitic anhydrides of as 1,5-, penta diester, in vacuum
It is dried to constant weight in drying baker, yield is 81.8%.
Fig. 2 is the infrared spectrogram of 1,5-, bis- trimellitic anhydrides, penta 2 ester molecule, is analyzed as follows table, it is therefore evident that according to this
The product that invention methods described is obtained is bis- trimellitic anhydrides of 1,5-, penta diester.
Fig. 3 is the nucleus magnetic hydrogen spectrum of 1,5-, bis- trimellitic anhydrides, penta 2 ester molecule, is analyzed as follows table, it is therefore evident that according to this
The product that bright methods described is obtained is bis- trimellitic anhydrides of 1,5-, penta diester.
A kind of Novel curing agent 1, application process of bis- trimellitic anhydrides of 5-, penta diester in epoxy-resin systems, its step is such as
Under：
(1) according to the mass fraction, 100 parts of CYD128 epoxy resin is weighed, 60 parts of 1,5- bis- trimellitic anhydride, penta diester is stirred
It is even, then the container for filling mixture is placed in ultrasonic cleaner and is shaken, taking-up is mix homogeneously, cast, row's bubble, heating
To 120 DEG C of solidification 4h；
(2) solidify afterwards：Solidify 2h during by step (1) products therefrom prior to 130 DEG C, then solidify 1h when 150 DEG C, obtain
Epoxide resin material after solidification.
Embodiment 2
A kind of Novel curing agent 1, application process of bis- trimellitic anhydrides of 5-, penta diester in epoxy-resin systems, its step is such as
Under：
(1) according to the mass fraction, 100 parts of E44 epoxy resin is weighed, 50 parts of 1,5- bis- trimellitic anhydride, penta diester uses third
After ketone solvent (acetone consumption for E44 epoxy resin quality 5%) dissolving, 2 parts of accelerator triethylamines are added to close uniform, Jing fibers
After impregnation hand pasting forming, cold curing 7h；
2) solidify afterwards：By step (1) products therefrom prior to 130 DEG C of solidification 2h；Then solidify 2h in 150 DEG C, solidified
Epoxide resin material afterwards.
Embodiment 3
A kind of Novel curing agent 1, application process of bis- trimellitic anhydrides of 5-, penta diester in epoxy-resin systems, its step is such as
Under：
(1) according to the mass fraction, weigh 100 parts of WSR615 epoxy resin, 60 parts of 1,5- bis- trimellitic anhydride, penta diester,
1 part of DMP-30 accelerator is got the raw materials ready, by firming agent 1, bis- trimellitic anhydrides of 5-, penta diester and E51 epoxy resin dehydrated alcohol (nothing
After water-ethanol consumption is for the 5%) dissolving of WSR615 epoxy resin quality, altax P-30, Jing row's bubbles, glass fibre is added to increase
After strong RTM injection mouldings, cold curing 5h；
2) solidify afterwards：By step (1) products therefrom prior to 130 DEG C of solidification 1.5h；Then solidify 1.5h in 150 DEG C, obtain
Epoxide resin material after solidification.
Embodiment 4
A kind of Novel curing agent 1, bis- trimellitic anhydrides of 5-, penta diester make the application process in epoxy-resin systems, its step
It is as follows：
(1) according to the mass fraction, 100 parts of E51 epoxy resin, 70 parts of 1,5- bis- trimellitic anhydride, penta diester, Talcum are weighed
4 parts of powder calcium filler, 1.5 parts of accelerator triethylamine.By bis- trimellitic anhydrides of firming agent 1,5-, penta diester and CYD128 type asphalt mixtures modified by epoxy resin
After fat dibutyl phthalate (dibutyl phthalate consumption for CYD128 mass 5%) dissolving, accelerator is added
Triethylamine is by three's mix homogeneously, and Jing carbon cloths handss paste technological forming, cold curing 5h.
(2) solidify afterwards：By step (1) products therefrom prior to 130 DEG C of solidification 1h；Then solidify 2h in 140 DEG C, solidified
Epoxide resin material afterwards.
From above-described embodiment 4：Novel curing agent of the present invention is compared to trimellitic anhydride cured epoxy resin
Solidification temperature is reduced and is close to 50 DEG C, shortens nearly 40% hardening time, and solidfied material can be made to have excellent resistance to impact
And high intensity, tensile strength is 46Mpa, bending strength 69Mpa, impact strength 38kJ/m2, compare trimellitic anhydride nearly 200
DEG C solidification temperature, the solidification temperature of 1,5- bis- trimellitic anhydride, penta diester significantly reduces.Certainly, in Novel curing agent 1,5- bis-
When penta diester of trimellitic anhydride is applied to epoxy-resin systems, input accelerator and filler can be adjusted according to practical situation
It is whole.
The above is only the preferred embodiment of the present invention, it is noted that for one of ordinary skill in the art comes
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
1. a kind of firming agent for epoxy-resin systems, it is characterised in that its molecular formula is C23H16O10, structural formula such as formula 1
It is shown：
It is named as bis- trimellitic anhydrides of 1,5-, penta diester.
2. application process of the firming agent described in claim 1 in epoxy-resin systems, it is characterised in that the firming agent is added
Enter in epoxy-resin systems mix homogeneously, and Jing after molding, solidification, solidify afterwards, obtain epoxy resin cured product.
3. application process of the firming agent described in claim 1 in epoxy-resin systems, it is characterised in that it comprises the following steps：
(1), in the case of being not added with accelerator, it is the 50～70% of epoxy resin quality according to hardener dose, both is mixed
It is even, and after molding, it is heated to 100～120 DEG C of 3～5h of solidification；
(2) solidify 1～2h during by primary solidification product obtained by step (1) prior to 130～150 DEG C, then when 150～160 DEG C
1～2h of solidification, the epoxide resin material after being solidified.
4. application process of the firming agent described in claim 1 in epoxy-resin systems, it is characterised in that it comprises the following steps：
1), in the case of adding accelerator, it is the 1～3% of epoxy resin quality according to the consumption of accelerator, the consumption of firming agent
Be the 50～70% of epoxy resin quality, get the raw materials ready, by firming agent and epoxy resin with organic solvent dissolving after, add accelerator and
Or filler mix homogeneously, after molding, 5～7h of cold curing；
2) by step 1) obtain primary solidification product prior to 120～130 DEG C solidification 1～2h, then in 140～150 DEG C solidify 1～
2h, the epoxide resin material after being solidified.
5. application process of the firming agent according to claim 4 in epoxy-resin systems, it is characterised in that the accelerator
For triethylamine or DMP-30.
6. application process of the firming agent according to claim 4 in epoxy-resin systems, it is characterised in that described organic molten
Agent is acetone, dehydrated alcohol, dibutyl phthalate, one or any several in ethyl acetate；The organic solvent
Consumption for epoxy resin quality 2～5%.
7. application process of the firming agent according to claim 4 in epoxy-resin systems, it is characterised in that described filler is
One kind in Pulvis Talci, titanium dioxide, aerosil, precipitated calcium carbonate, aluminium hydroxide, the consumption of filler is asphalt mixtures modified by epoxy resin lipid
The 1～10% of amount.
8. application process of the firming agent according to Claims 2 or 3 or 4 in epoxy-resin systems, it is characterised in that described
It is shaped to moulding by casting, injection moulding, resin transfer molding, any one in hand pasting forming.
9. application process of the firming agent according to Claims 2 or 3 or 4 in epoxy-resin systems, it is characterised in that described
Epoxy resin includes one or any several in E51, E-44, WSR615, DER330, CYD128..
10. the epoxy-resin systems of Novel curing agent described in claim 1 are included.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610948611.8A CN106519192A (en) | 2016-11-02 | 2016-11-02 | Curing agent used for epoxy resin system and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610948611.8A CN106519192A (en) | 2016-11-02 | 2016-11-02 | Curing agent used for epoxy resin system and application method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106519192A true CN106519192A (en) | 2017-03-22 |
Family
ID=58292932
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610948611.8A Pending CN106519192A (en) | 2016-11-02 | 2016-11-02 | Curing agent used for epoxy resin system and application method thereof |
Country Status (1)
| Country | Link |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005213189A (en) * | 2004-01-29 | 2005-08-11 | Mitsubishi Chemicals Corp | Method for producing trimellitic anhydride ester |
| CN101663344A (en) * | 2007-04-03 | 2010-03-03 | Abb研究有限公司 | Curable epoxy resin composition |
| JP2014031422A (en) * | 2012-08-02 | 2014-02-20 | Hitachi Chemical Co Ltd | Method for producing bonded product, method for forming adhesive pattern, and adhesive |
-
2016
- 2016-11-02 CN CN201610948611.8A patent/CN106519192A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005213189A (en) * | 2004-01-29 | 2005-08-11 | Mitsubishi Chemicals Corp | Method for producing trimellitic anhydride ester |
| CN101663344A (en) * | 2007-04-03 | 2010-03-03 | Abb研究有限公司 | Curable epoxy resin composition |
| JP2014031422A (en) * | 2012-08-02 | 2014-02-20 | Hitachi Chemical Co Ltd | Method for producing bonded product, method for forming adhesive pattern, and adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 王德中: "《环氧树脂生产与应用》", 30 June 2001, 化学工业出版社 * |
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Application publication date: 20170322 |