CN108070072A - A kind of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring and preparation method thereof - Google Patents
A kind of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring and preparation method thereof Download PDFInfo
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- CN108070072A CN108070072A CN201610969754.7A CN201610969754A CN108070072A CN 108070072 A CN108070072 A CN 108070072A CN 201610969754 A CN201610969754 A CN 201610969754A CN 108070072 A CN108070072 A CN 108070072A
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- phosphonitrile
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- epoxy resin
- curing agent
- latent curing
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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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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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
- C08G59/5046—Amines heterocyclic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring and preparation method thereof, belong to the preparing technical field of epoxy resin latent curing agent.The preparation method of the epoxy resin latent curing agent, includes the following steps：Step 1, hexachlorocyclotriph,sphazene occur nucleophilic substitution with parahydroxyben-zaldehyde, obtain six in organic solvent（To aldehyde radical phenoxy group）Three phosphonitrile of ring；Step 2, by six（To aldehyde radical phenoxy group）Three phosphonitrile of ring aoxidizes, and obtains six（To carboxyphenoxy）Three phosphonitrile of ring；Step 3, at a certain temperature, by six（To carboxyphenoxy）With glyoxaline compound according to certain mol proportion salt-forming reaction occurs in a solvent for three phosphonitrile of ring, obtains the imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring.The epoxy resin latent curing agent of the present invention has good compatibility with epoxy resin, and processing performance is good；It can steadily in the long term be stored at room temperature with epoxy resin, and effectively can carry out curing reaction rapidly by catalyzed epoxies when heated.
Description
Technical field
The present invention relates to a kind of epoxy resin latent curing agents, are specifically a kind of imidazoles epoxy based on three phosphonitrile of ring
Resin latent curing agent.The invention further relates to the preparation methods of the epoxy resin latent curing agent.The invention belongs to
In the preparing technical field of epoxy resin latent curing agent.
Background technology
Epoxy resin have excellent adhesive property, electrical insulation capability, corrosion resistance and mechanical property, as coating,
Composite material, casting material, adhesive, moulding material and injecting forming material are widely used in the every field of national economy.
In the application of epoxy resin, curing agent occupies essential critical role, and imidazole and its derivants are wherein highly important
One based epoxy resin curing agent, the particularly development recently as electronics industry, imidazoles based epoxy resin curing agent dosage are every
Year is incremented by 15%~20%, and the dosage of this respect has accounted for more than the 90% of imidazole and its derivants total output at present.
Imidazole and its derivants have the characteristics that as epoxy curing agent：
(1) dosage of curing agent is few, generally the 0.5%~10% of epoxy resin dosage；
(2) volatility of imidazole and its derivants is low, small toxicity；
(3) curing activity of imidazoles is higher, at moderate temperatures, you can epoxy resin is made to cure in a short time；
(4) the cured epoxy resin heat distortion temperature of imidazoles is high, and chemical mediator-resitant property is good, and electrical insulation capability is strong, mechanical property
It is excellent.
However, glyoxaline compound is generally solid powder, there are fusing point it is high, asked with liquid-state epoxy resin poor compatibility etc.
Topic, difficult so as to cause mixing, processing performance is poor.In addition, imidazole curing agent is commonly used since curing activity is higher, with epoxy
Working life is shorter after resin mixing, it is impossible to be stored as the single-component system long period.In order to overcome common imidazoles asphalt mixtures modified by epoxy resin
Simple imidazolium compounds is modified or synthesize new pattern imdazole derivatives, makes it to epoxy by the shortcomings that fat curing agent and deficiency
The accelerative action in curing of resin has low temperature " latency ", is the effective way to solve the above problems.
Through the retrieval discovery to existing scientific and technical literature, the U.S.《ACS MACRO LETTERS》Magazine is in the 4th phase in 2015
Page 1085 ~ 1088（Kudo K., Furutani M., Arimitsu K., Imidazole Derivatives with an
Intramolecular Hydrogen Bond as Thermal Latent Curing Agents for
Thermosetting Resins [J], ACS Macro Letters, 2015, 4 (10): 1085-1088）Report one
The synthetic method of kind of imdazole derivatives with intramolecular hydrogen bond, this imdazole derivatives stable storing at room temperature, at 150 °
There is higher catalytic activity to the curing of resin during C or so.Holland《MATERIAL LETTERS》Magazine is in 2015 the 161st phases
Page 408 ~ 410（Arimitsu K., Fuse S., Kudo K., et al., Imidazole derivatives as
latent curing agents for epoxy thermosetting resins [J], Materials Letters,
2015, 161: 408-410）Report the side that a kind of double bond prepares latent curing agent with imidazoles generation reversal of the Michael addition
Method, the imdazole derivatives are mainly the room temperature latency that imidazoles is realized using the space steric effect of double bond compound.However with
Upper method, general building-up process is cumbersome, and purification step is complicated, is unfavorable for large-scale industrial production.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of epoxy resin latent curing agent and its systems
Preparation Method.The present invention is obtained by the reaction six using hexachlorocyclotriph,sphazene and parahydroxyben-zaldehyde as raw material（To aldehyde radical phenoxy group）Ring three
Phosphonitrile；Its terminal aldehyde groups is oxidized to carboxyl again, is prepared six（To carboxyphenoxy）Three phosphonitrile of ring；Finally by six（To carboxylic
Phenoxyl）Three phosphonitrile of ring is reacted with glyoxaline compound, and imidazole salts are prepared, and cure as epoxy resin resting form
Agent.Prepared epoxy resin latent curing agent and epoxy resin compatibility are good, and catalytic activity is high when heated, and with good
Good long-term room-temperature storage stability.In addition, the latent curing agent contains the alternate phosphonitrile ring structure of phosphorus-nitrogen-atoms, can carry
The heat resistance and anti-flammability of high epoxy resin, are with a wide range of applications.
The present invention is achieved by the following technical solutions, and the present invention relates to a kind of imidazoles epoxies based on three phosphonitrile of ring
Resin latent curing agent, chemical constitution are as follows：
Three substituent group R wherein on each imidazole ring can be identical, can also be different, selected from hydrogen-based, 1 ~ 5 carbon atom
Several alkyl, the hydroxyalkyl of 3 ~ 5 carbon numbers, the alkylene of 3 ~ 4 carbon numbers, cyclohexyl, 6 ~ 10 carbon numbers
One or more of the aralkyl of aryl, 7 ~ 8 carbon numbers.
The preparation method of the epoxy resin latent curing agent, includes the following steps：
Under the conditions of existing for acid binding agent, hexachlorocyclotriph,sphazene is occurred in organic solvent with parahydroxyben-zaldehyde for step 1
Nucleophilic substitution, separating-purifying obtain six（To aldehyde radical phenoxy group）Three phosphonitrile of ring；
Step 2, under the conditions of existing for oxidant, by six（To aldehyde radical phenoxy group）Three phosphonitrile of ring aoxidizes, and separating-purifying obtains six
（To carboxyphenoxy）Three phosphonitrile of ring；
Step 3, at a certain temperature, by six（To carboxyphenoxy）Three phosphonitrile of ring is with glyoxaline compound according to certain mole
Than salt-forming reaction occurs in a solvent, precipitating reagent is added in, obtains the imidazole salts based on three phosphonitrile of ring.
In step 1, the acid binding agent is triethylamine, one kind in tri-n-butylamine, pyridine, potassium carbonate, sodium hydride.
In step 1, the organic solvent for tetrahydrofuran, acetonitrile, acetone, toluene,N ,NIn '-dimethylformamide
One or more of mixed solvents.
In step 2, the oxidant is potassium permanganate, one kind in nitric acid, chromium oxide, potassium bichromate.
In step 3, the certain temperature is 10 ~ 50 °C.
In step 3, the certain mol proportion is 1:5~1:7（Six（To carboxyphenoxy）Three phosphonitrile of ring：Imidazoles chemical combination
Object）.
In step 3, the solvent isN ,NIn '-dimethylformamide, dimethyl sulfoxide, chloroform, dichloromethane, water
One or more of mixed solvents.
In step 3, the precipitating reagent is petroleum ether, one kind in ethyl acetate, acetone, ether, chloroform.
Compared with prior art, the present invention has the advantages that：（1）Epoxy resin resting form of the present invention is consolidated
Agent has good compatibility with epoxy resin；（2）Epoxy resin latent curing agent of the present invention contain abundant phosphorus,
Nitrogen-atoms can improve the heat resistance and anti-flammability of epoxy resin；（3）Epoxy resin latent curing agent of the present invention exists
With higher catalytic activity during heating, at ambient temperature with good extended storage stability；（4）It is of the present invention
The building-up process of epoxy resin latent curing agent is simple, and purification step is few, is conducive to industrial large-scale production.
Description of the drawings
Fig. 1 is the route schematic diagram of synthetic epoxy resin latent curing agent；
Fig. 2 is the digital photograph figure for the epoxy resin latent curing agent that embodiment 1 synthesizes；
Fig. 3 is the pot life at room temperature figure for the epoxy resin latent curing agent that embodiment 1 synthesizes.
Specific embodiment
Following instance will the invention will be further described with reference to attached drawing.The present embodiment using technical solution of the present invention before
It puts and is implemented, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments.
The experimental method of actual conditions is not specified in the following example, usually according to normal condition or according to proposed by manufacturer
Condition.
Embodiment 1
In the three-necked flask of the 250 mL dryings equipped with magneton, thermometer, constant pressure funnel and condensation reflux unit, add
Enter 50 mL of 14.76 g of parahydroxyben-zaldehyde and tetrahydrofuran, add triethylamine（TEA） 20 mL.After being heated to 60 DEG C,
Stirring is lower to be added dropwise hexachlorocyclotriph,sphazene（6.95 g）Tetrahydrofuran（40 mL）Solution is kept stirring lower 8 h of back flow reaction knots
Beam.Six are obtained after being recrystallized in ethyl acetate（To aldehyde radical phenoxy group）Three phosphonitrile of ring.
Six are sequentially added in the single-necked flask of 250 mL（To aldehyde radical phenoxy group）Three phosphonitrile of ring, 4.31 g, tetrahydrofuran
60 mL, 7 g of potassium permanganate, 1.5 g of sodium hydroxide, and stir evenly.24 h are reacted at a reflux temperature.Revolving removes solvent
Afterwards, pH to 5 ~ 6 is adjusted, filters to obtain white powder, six are obtained after drying 24 h in an oven（To carboxyphenoxy）Three phosphonitrile of ring.
Weigh 2 g six（To carboxyphenoxy）Three phosphonitrile of ring, 1.03 g 2-methylimidazoles are dissolved in 100 mLN ,N'-two
In methylformamide, when reaction 2 is small under 50 °C, adds 200 mL ether and precipitate to obtain imidazole salts, and be used as epoxy
Resin latent curing agent.10 g epoxy resin, the imidazole salts of Different adding amount are weighed, are stirred evenly, obtain single-component epoxy tree
Fat.
The implementation result of the present embodiment：
Fig. 1 is the route schematic diagram of synthetic epoxy resin latent curing agent.
Fig. 2 is the digital photograph figure for the epoxy resin latent curing agent that embodiment 1 synthesizes.As seen from the figure, it is prepared
Epoxy resin latent curing agent at room temperature for liquid, and reactant six（To carboxyphenoxy）Three phosphonitrile of ring is white powder
End, 2-methylimidazole are similarly crystalline solid, therefore show the successful synthesis of epoxy resin latent curing agent.
Fig. 3 is the pot life at room temperature figure for the epoxy resin latent curing agent that embodiment 1 synthesizes, it can be seen that with
The additive amount of latent curing agent increases, and the room temperature storage time of single component epoxy is declined slightly, but still higher than 40 days,
Illustrate that the epoxy resin latent curing agent being prepared has good latent effect.
Embodiment 2
In the three-necked flask of the 250 mL dryings equipped with magneton, thermometer, constant pressure funnel and condensation reflux unit, add
Enter 50 mL of 14.76 g of parahydroxyben-zaldehyde and tetrahydrofuran, add triethylamine（TEA） 20 mL.After being heated to 60 DEG C,
Stirring is lower to be added dropwise hexachlorocyclotriph,sphazene（6.95 g）Tetrahydrofuran（40 mL）Solution is kept stirring lower 8 h of back flow reaction knots
Beam.Six are obtained after being recrystallized in ethyl acetate（To aldehyde radical phenoxy group）Three phosphonitrile of ring.
Six are sequentially added in the single-necked flask of 250 mL（To aldehyde radical phenoxy group）Three phosphonitrile of ring, 4.31 g, tetrahydrofuran
60 mL, 7 g of potassium permanganate, 1.5 g of sodium hydroxide, and stir evenly.24 h are reacted at a reflux temperature.Revolving removes solvent
Afterwards, pH to 5 ~ 6 is adjusted, filters to obtain white powder, six are obtained after drying 24 h in an oven（To carboxyphenoxy）Three phosphonitrile of ring.
Weigh 2 g six（To carboxyphenoxy）Three phosphonitrile of ring, 0.84 g imidazoles are dissolved in 100 mLN ,N'-dimethyl methyl
In amide, when reaction 2 is small under 50 °C, adds 200 mL ether and precipitate to obtain imidazole salts, and be used as epoxy resin and dive
Volt type curing agent.10 g epoxy resin, the imidazole salts of Different adding amount are weighed, stirs evenly, obtains single component epoxy.
Embodiment 3
In the three-necked flask of the 250 mL dryings equipped with magneton, thermometer, constant pressure funnel and condensation reflux unit, add
Enter 50 mL of 14.76 g of parahydroxyben-zaldehyde and tetrahydrofuran, add triethylamine（TEA） 20 mL.After being heated to 60 DEG C,
Stirring is lower to be added dropwise hexachlorocyclotriph,sphazene（6.95 g）Tetrahydrofuran（40 mL）Solution is kept stirring lower 8 h of back flow reaction knots
Beam.Six are obtained after being recrystallized in ethyl acetate（To aldehyde radical phenoxy group）Three phosphonitrile of ring.
Six are sequentially added in the single-necked flask of 250 mL（To aldehyde radical phenoxy group）Three phosphonitrile of ring, 4.31 g, tetrahydrofuran
60 mL, 7 g of permanganic acid agent, 1.5 g of sodium hydroxide, and stir evenly.24 h are reacted at a reflux temperature.Revolving removes solvent
Afterwards, pH to 5 ~ 6 is adjusted, filters to obtain white powder, six are obtained after drying 24 h in an oven（To carboxyphenoxy）Three phosphonitrile of ring.
Weigh 2 g six（To carboxyphenoxy）Three phosphonitrile of ring, 1.03 g 2-methylimidazoles are dissolved in 100 mLN ,N'-two
In methylformamide, when reaction 2 is small under 50 °C, adds 200 mL ethyl acetate and precipitate to obtain imidazole salts, and be used as
Epoxy resin latent curing agent.10 g epoxy resin, the imidazole salts of Different adding amount are weighed, are stirred evenly, obtain one-component ring
Oxygen resin.
Embodiment 4
In the three-necked flask of the 250 mL dryings equipped with magneton, thermometer, constant pressure funnel and condensation reflux unit, add
Enter 50 mL of 14.76 g of parahydroxyben-zaldehyde and tetrahydrofuran, add triethylamine（TEA） 20 mL.After being heated to 60 DEG C,
Stirring is lower to be added dropwise hexachlorocyclotriph,sphazene（6.95 g）Tetrahydrofuran（40 mL）Solution is kept stirring lower 8 h of back flow reaction knots
Beam.Six are obtained after being recrystallized in ethyl acetate（To aldehyde radical phenoxy group）Three phosphonitrile of ring.
Six are sequentially added in the single-necked flask of 250 mL（To aldehyde radical phenoxy group）Three phosphonitrile of ring, 4.31 g, tetrahydrofuran
60 mL, 7 g of potassium permanganate, 1.5 g of sodium hydroxide, and stir evenly.24 h are reacted at a reflux temperature.Revolving removes solvent
Afterwards, pH to 5 ~ 6 is adjusted, filters to obtain white powder, six are obtained after drying 24 h in an oven（To carboxyphenoxy）Three phosphonitrile of ring.
Weigh 2 g six（To carboxyphenoxy）Three phosphonitrile of ring, 1.20 g 2-methylimidazoles are dissolved in 100 mLN ,N'-two
In methylformamide, when reaction 2 is small under 50 °C, adds 200 mL ether and precipitate to obtain imidazole salts, and be used as epoxy
Resin latent curing agent.10 g epoxy resin, the imidazole salts of Different adding amount are weighed, are stirred evenly, obtain single-component epoxy tree
Fat.
Claims (6)
1. a kind of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring, which is characterized in that its chemical constitution is as follows
It is shown：
Three substituent group R wherein on each imidazole ring can be identical, can also be different, selected from hydrogen-based, 1 ~ 5 carbon atom
Several alkyl, the hydroxyalkyl of 3 ~ 5 carbon numbers, the alkylene of 3 ~ 4 carbon numbers, cyclohexyl, 6 ~ 10 carbon numbers
One or more of the aralkyl of aryl, 7 ~ 8 carbon numbers.
2. a kind of preparation side of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring according to claim 1
Method, which is characterized in that include the following steps：
Under the conditions of existing for acid binding agent, hexachlorocyclotriph,sphazene is occurred in organic solvent with parahydroxyben-zaldehyde for step 1
Nucleophilic substitution, separating-purifying obtain six（To aldehyde radical phenoxy group）Three phosphonitrile of ring；
Step 2, under the conditions of existing for oxidant, by six（To aldehyde radical phenoxy group）Three phosphonitrile of ring aoxidizes, and separating-purifying obtains six
（To carboxyphenoxy）Three phosphonitrile of ring；
Step 3, at a certain temperature, by six（To carboxyphenoxy）Three phosphonitrile of ring is with glyoxaline compound according to certain mole
Than salt-forming reaction occurs in a solvent, precipitating reagent is added in, obtains the imidazole salts based on three phosphonitrile of ring；
In step 1, the acid binding agent is triethylamine, one kind in tri-n-butylamine, pyridine, potassium carbonate, sodium hydride；
In step 1, the organic solvent for tetrahydrofuran, acetonitrile, acetone, toluene,N ,NOne in '-dimethylformamide
Kind or several mixed solvents；
In step 2, the oxidant is potassium permanganate, one kind in nitric acid, chromium oxide, potassium bichromate.
3. a kind of preparation side of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring according to claim 2
Method, which is characterized in that in step 3, the certain temperature is 10 ~ 50 °C.
4. a kind of preparation side of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring according to claim 2
Method, which is characterized in that in step 3, the certain mol proportion is 1:5~1:7（Six（To carboxyphenoxy）Three phosphonitrile of ring：Imidazoles
Class compound）.
5. a kind of preparation side of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring according to claim 2
Method, which is characterized in that in step 3, the solvent isN ,N'-dimethylformamide, dimethyl sulfoxide, chloroform, dichloromethane,
The mixed solvent of one or more of water.
6. a kind of preparation side of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring according to claim 2
Method, which is characterized in that in step 3, the precipitating reagent is petroleum ether, one kind in ethyl acetate, acetone, ether, chloroform.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181377A (en) * | 2021-12-02 | 2022-03-15 | 常州百思通复合材料有限公司 | Cyclotriphosphazene-based flame-retardant imidazole curing agent and preparation method and application thereof |
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|---|---|---|---|---|
| EP0514335A2 (en) * | 1991-05-17 | 1992-11-19 | Ciba-Geigy Ag | Curable epoxy resin mixtures containing a latent curing agent, an amine and a dithiol |
| JP2002088137A (en) * | 2000-09-14 | 2002-03-27 | Sanwa Chemical Industry Co Ltd | Low-temperature curing latent curable agent for epoxy resin |
| CN101906206A (en) * | 2009-04-29 | 2010-12-08 | 气体产品与化学公司 | Contain imidazoles-and the fast curable epoxy compositions of 1-(aminoalkyl group) imidazoles-isocyanate adduct |
| CN103087295A (en) * | 2013-02-06 | 2013-05-08 | 中南民族大学 | Latent hyperbranched polymer curing agent and its preparation method |
| CN104927308A (en) * | 2015-06-30 | 2015-09-23 | 江南大学 | Epoxy resin toughening agent based on cyclotriphosphazene six-arm star polymer and preparation method for epoxy resin toughening agent |
-
2016
- 2016-11-07 CN CN201610969754.7A patent/CN108070072A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0514335A2 (en) * | 1991-05-17 | 1992-11-19 | Ciba-Geigy Ag | Curable epoxy resin mixtures containing a latent curing agent, an amine and a dithiol |
| JP2002088137A (en) * | 2000-09-14 | 2002-03-27 | Sanwa Chemical Industry Co Ltd | Low-temperature curing latent curable agent for epoxy resin |
| CN101906206A (en) * | 2009-04-29 | 2010-12-08 | 气体产品与化学公司 | Contain imidazoles-and the fast curable epoxy compositions of 1-(aminoalkyl group) imidazoles-isocyanate adduct |
| CN103087295A (en) * | 2013-02-06 | 2013-05-08 | 中南民族大学 | Latent hyperbranched polymer curing agent and its preparation method |
| CN104927308A (en) * | 2015-06-30 | 2015-09-23 | 江南大学 | Epoxy resin toughening agent based on cyclotriphosphazene six-arm star polymer and preparation method for epoxy resin toughening agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181377A (en) * | 2021-12-02 | 2022-03-15 | 常州百思通复合材料有限公司 | Cyclotriphosphazene-based flame-retardant imidazole curing agent and preparation method and application thereof |
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Application publication date: 20180525 |