CN108912307A - It is a kind of for the DOPO type curing agent of epoxy-resin systems and its application - Google Patents
It is a kind of for the DOPO type curing agent of epoxy-resin systems and its application Download PDFInfo
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- CN108912307A CN108912307A CN201810843338.1A CN201810843338A CN108912307A CN 108912307 A CN108912307 A CN 108912307A CN 201810843338 A CN201810843338 A CN 201810843338A CN 108912307 A CN108912307 A CN 108912307A
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- Prior art keywords
- epoxy
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- type curing
- resin systems
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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
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
A kind of application method the invention discloses new compound D-DICY as curing agent, fire retardant in epoxy-resin systems, this method are specially：It is mixed with epoxy resin, and promotor and filler is added, stirring is allowed to uniformly mixed；It heats the mixture to 100 DEG C of precuring 1-2h to be allowed to form, continues to be heated to 115 DEG C of solidification 4-6h, make the abundant cured epoxy resin of curing agent, be finally warming up to 135 DEG C and continue to solidify 2h completion solidification, ultimately form crosslinking net solidfied material.The new compound and epoxy resin have preferable compatibility, not only curable epoxy but also can be used for the fire-retardant of epoxy resin, and be halogen-free, low-smoke low-toxicity, meet the requirement of new green environment protection type curing agent.
Description
Technical field
The present invention relates to epoxide resin material technical fields, and in particular to DOPO type compound D-DICY and its in asphalt mixtures modified by epoxy resin
Application in resin system.
Background technique
Epoxy resin has specific strength and specific stiffness height, corrosion resistance as a kind of important thermoset macromolecule material
Can be good, structure size is stable, good insulating and caking property are strong the advantages that, it is widely used in adhesive, coating, aviation and electronics
Emerging composite material in industry.
Epoxy resin belongs to flammable material, and untreated epoxy resin limit oxygen index (LOI) only has 19.8%, because
And need to improve its flame retardant property in numerous applications, but existing curing agent does not have flame retardant property generally at present.Therefore
Need a kind of Novel curing agent, application of the fire retardant in epoxy-resin systems.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of new compound D-
DICY, and its application as Novel curing agent, fire retardant in epoxy-resin systems.
DOPO is new flame retardant intermediate, and P-H key is contained in structure, to alkene, epoxy bond and the great activity of carbonyl,
It can react and generate many derivatives.Therefore, by DOPO and the above functional group reactions, preparation can response type epoxy curing agent,
On the one hand it can be used for the solidification of epoxy resin, on the other hand also can be used for the fire-retardant of epoxy resin.
The structural formula of new compound D-DICY is as follows：
In order to solve the above technical problem, the present invention provides a kind of answering for DOPO type curing agent for epoxy-resin systems
With, it is characterised in that：
The curing agent is compound D-DICY, and structural formula is as follows：
Compound D-DICY is applied in epoxy-resin systems as curing agent, fire retardant.
As a preferred embodiment of the above technical solution, answering provided by the present invention for the DOPO type curing agent of epoxy-resin systems
With further comprising some or all of following technical characteristic：
As an improvement of the above technical solution, the application method of the DOPO type curing agent is as follows：
D-DICY is mixed with epoxy resin, organic solvent, promotor and filler is added, is uniformly mixed；It will mixing
Object injects precuring molding in mold, solidifies after heating, continues to solidify after the completion of heating, finally obtains crosslinking net solidfied material.
As an improvement of the above technical solution, the dosage of the D-DICY is the 10~15% of epoxy resin quality.
As an improvement of the above technical solution, the dosage of the promotor is the 1~3% of epoxy resin quality.
As an improvement of the above technical solution, the promotor is one of DMP-30 or imidazoles.
As an improvement of the above technical solution, the epoxy resin is in E44, E51, CYD127, CYD128, E20, E12
Any one or in which several mixtures being mixed to form in any proportion.
As an improvement of the above technical solution, the organic solvent is ethyl alcohol, acetone, dimethylbenzene, tetrahydrofuran, N ' N- bis-
One of methylformamide.
As an improvement of the above technical solution, the precuring forming temperature is 90 DEG C~100 DEG C, required time 1-2h.
The molding main purpose of precuring is to be allowed to form.
As an improvement of the above technical solution, the solidification temperature is 110 DEG C~115 DEG C, required time 4-6h.Solidify rank
The main purpose of section is to make the abundant cured epoxy resin of reaction-type flame-retarding epoxy curing agent.
As an improvement of the above technical solution, the rear solidification temperature is 125 DEG C~135 DEG C, required time 2h.After solidify
The main purpose in stage is to eliminate internal stress, improves adhesive strength, improves the comprehensive performance of epoxy resin cured product.
Compared with prior art, technical solution of the present invention has the advantages that：
(1) used compound D-DICY both curable epoxy, also can be used for ethoxyline resin antiflaming；(2) compound
D-DICY is preferable with epoxy resin compatibility；(3) the compound D-DICY used in is halogen-free, low-smoke low-toxicity, is met novel green
The requirement of color environment-friendly curing agent.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues.
Fig. 1 is the mechanism figure of D-DICY cured epoxy resin；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of D-DICY cured epoxy resin.
Specific embodiment
The following detailed description of a specific embodiment of the invention, as part of this specification, by embodiment come
Illustrate that the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Reaction involved by prepare compound D-DICY of the present invention is as follows：
The synthetic method of compound D-DICY, specific step is as follows：
Suitable DOPO is added in reaction flask under an inert atmosphere and is heated until DOPO is completely melt, then will be fitted
Amount dicyandiamide, which is added in reaction flask, forms mixture, and reaction temperature is higher than 110 DEG C, to ensure that mixture is in molten
State, then temperature is increased to 175 DEG C, 6-12h is reacted, reaction product is washed with tetrahydrofuran is filtered to remove unreacted DOPO,
Then it is dried in vacuum drying oven after washing filtering with hot deionized water, obtains final product.
The nucleus magnetic hydrogen spectrum figure of products therefrom is as shown in Fig. 2.Analyzing the product that susceptible of proof obtains by table 1 is D-DICY.
Table 1
Embodiment 1
The application method of new compound D-DICY in the epoxy, specific step is as follows：
1. epoxy resin CYD127 is chosen, by the DMP-30 or imidazoles of itself and the compound D-DICY, 1wt% of 10wt%
(in terms of epoxy resin quality, similarly hereinafter) and filler are uniformly mixed；
2. above-mentioned mixed liquor is injected in homemade silica gel mould, 100 DEG C of precuring 1h are heated to, are allowed to form；
3. heating the mixture to 115 DEG C of solidification 4h, makes the abundant cured epoxy resin of curing agent, then proceed to be warming up to
Solidify 2h after 135 DEG C, to eliminate the comprehensive performance that internal stress improves glue-joint strength and epoxy resin cured product.
Using the mechanism of D-DICY cured epoxy resin referring to Fig. 1.The primary amino group on D-DICY is first under suitable condition
Elder generation and epoxy reaction, epoxy ring-opening are reacted into hydroxyl, and primary amine loses an active H into secondary amine, then secondary amino group continue with
Epoxy reaction generates tertiary amino, and the hydroxyl of generation also has with epoxy reaction, the lasting progress of reaction, the hydroxyl of generation simultaneously
Accelerate cured tendency.
Embodiment 2
1. choose epoxy resin E51, by its DMP-30 or imidazoles with the compound D-DICY, 3wt% of 15wt% and fill out
Material is uniformly mixed；
2. above-mentioned mixed liquor is injected in homemade silica gel mould, 100 DEG C of precuring 2h are heated to, are allowed to form；Heating
To 115 DEG C of solidification 4h, solidify 2h after being continuously heating to 135 DEG C.
Embodiment 3
1. choose epoxy resin CYD128, by its DMP-30 or imidazoles with the compound D-DICY, 3wt% of 15wt% and
Filler is uniformly mixed；
2. above-mentioned mixed liquor is injected in homemade silica gel mould, 100 DEG C of precuring 2h are heated to, are allowed to form；Heating
To 115 DEG C of solidification 6h, solidify 2h after being continuously heating to 135 DEG C.
Comparative example 1
1. epoxy resin E51 is chosen, by the compound aniline of itself and 15wt%, the DMP-30 or imidazoles of 3wt%, You Jirong
Agent DMF and filler are uniformly mixed；
2. above-mentioned mixed liquor is injected in homemade silica gel mould, 100 DEG C of precuring 2h are heated to, are allowed to form；Heating
To 115 DEG C of solidification 6h, solidify 2h after being continuously heating to 135 DEG C.
The above various embodiments and comparative example solidfied material are prepared into having a size of 130mm × 13mm × 3.2mm standard batten
It each 5, tests UL94 rank and limit oxygen index and takes its average value, test result is as follows table：
The UL94 rank and limit oxygen index test result table of each batten of table 1
It tests by contrast, reaction-type flame-retarding epoxy curing agent flame retardant property synthesized by the present invention has obtained biggish
It is promoted, UL94 flame retardant rating has reached fire retardant rank up to 29% or more up to V-0 rank, limit oxygen index LOI.Explanation
New compound of the present invention and epoxy resin have preferable compatibility, not only curable epoxy but also can be used for epoxy
Resin it is fire-retardant, and be halogen-free, low-smoke low-toxicity, meet the requirement of new green environment protection type curing agent, as novel solid
The application of agent, fire retardant in epoxy-resin systems is that green is feasible.
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of application of the DOPO type curing agent for epoxy-resin systems, it is characterised in that：
The curing agent is compound D-DICY, and structural formula is as follows：
Compound D-DICY is applied in epoxy-resin systems as curing agent, fire retardant.
2. the application for the DOPO type curing agent of epoxy-resin systems as described in claim 1, which is characterized in that described
The application method of DOPO type curing agent is as follows：
D-DICY is mixed with epoxy resin, organic solvent, promotor and filler is added, is uniformly mixed；Mixture is infused
Enter precuring in mold to form, solidify after heating, continues to solidify after the completion of heating, finally obtain crosslinking net solidfied material.
3. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 2, it is characterised in that：The D-
The dosage of DICY is the 10~15% of epoxy resin quality.
4. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 2, it is characterised in that：The rush
Dosage into agent is the 1~3% of epoxy resin quality.
5. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 3, it is characterised in that：The rush
It is one of DMP-30 or imidazoles into agent.
6. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 2, it is characterised in that：The ring
Oxygen resin be in E44, E51, CYD127, CYD128, E20, E12 any one or in which several mix shape in any proportion
At mixture.
7. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 2, it is characterised in that：It is described to have
Solvent is one of ethyl alcohol, acetone, dimethylbenzene, tetrahydrofuran, N ' dinethylformamide.
8. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 2, it is characterised in that：It is described pre-
Curing molding temperature is 90 DEG C~100 DEG C, required time 1-2h.
9. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 2, it is characterised in that：It is described solid
Changing temperature is 110 DEG C~115 DEG C, required time 4-6h.
10. the application for the DOPO type curing agent of epoxy-resin systems as claimed in claim 2, it is characterised in that：It is described
Solidification temperature is 125 DEG C~135 DEG C afterwards, required time 2h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810843338.1A CN108912307A (en) | 2018-07-27 | 2018-07-27 | It is a kind of for the DOPO type curing agent of epoxy-resin systems and its application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810843338.1A CN108912307A (en) | 2018-07-27 | 2018-07-27 | It is a kind of for the DOPO type curing agent of epoxy-resin systems and its application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838730A (en) * | 2011-06-24 | 2012-12-26 | 都宝科技有限公司 | Epoxy resin hardener with flame retardant property and resin material |
| CN105482452A (en) * | 2015-12-25 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition as well as prepreg, laminated board and printed circuit board containing halogen-free resin composition |
| CN107501859A (en) * | 2017-08-04 | 2017-12-22 | 武汉工程大学 | It is a kind of for the DOPO types curing agent of epoxy-resin systems and its application |
-
2018
- 2018-07-27 CN CN201810843338.1A patent/CN108912307A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838730A (en) * | 2011-06-24 | 2012-12-26 | 都宝科技有限公司 | Epoxy resin hardener with flame retardant property and resin material |
| US20120329960A1 (en) * | 2011-06-24 | 2012-12-27 | Chien-Hong Chen | Flame-retardant hardner for epoxy resin and flame-retardant resin material comprising the same |
| CN105482452A (en) * | 2015-12-25 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition as well as prepreg, laminated board and printed circuit board containing halogen-free resin composition |
| CN107501859A (en) * | 2017-08-04 | 2017-12-22 | 武汉工程大学 | It is a kind of for the DOPO types curing agent of epoxy-resin systems and its application |
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Application publication date: 20181130 |