CN109161000A - A kind of application of new compound DOPO-MA in epoxy-resin systems - Google Patents
A kind of application of new compound DOPO-MA in epoxy-resin systems Download PDFInfo
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- CN109161000A CN109161000A CN201810845237.8A CN201810845237A CN109161000A CN 109161000 A CN109161000 A CN 109161000A CN 201810845237 A CN201810845237 A CN 201810845237A CN 109161000 A CN109161000 A CN 109161000A
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- epoxy resin
- dopo
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- curing agent
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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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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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
本发明公开了化合物DOPO‑MA作为新型阻燃环氧树脂固化剂在环氧树脂体系的应用方法，该方法包括如下步骤：(1)以一定比例将固化剂与环氧树脂混合，并加入有机溶剂促进剂，搅拌使之混合均匀；(2)将上述混合物注入模具当中，并在50‑60℃下预固化4‑8h，使之成型；(3)固化阶段：在80～100℃下，固化2‑6h，使固化剂充分固化环氧树脂；(4)后固化阶段：在130～160℃下，继续固化2‑4h，完成固化，成为交联网状固化物。本发明所采用的新型固化剂既可固化环氧树脂又能用于环氧树脂阻燃，并且固化效果、相容性均较好，由于不含卤素因此低烟低毒，符合新型绿色环保型固化剂的要求。The invention discloses an application method of compound DOPO-MA as a novel flame retardant epoxy resin curing agent in an epoxy resin system. The method includes the following steps: (1) mixing the curing agent and epoxy resin in a certain proportion, and adding organic Solvent accelerator, stir to make it evenly mixed; (2) Inject the above mixture into the mold, and pre-cure it at 50-60°C for 4-8h to make it into shape; (3) Curing stage: at 80-100°C, Curing for 2-6h to make the curing agent fully cure the epoxy resin; (4) Post-curing stage: at 130-160°C, continue curing for 2-4h to complete the curing and become a cross-linked cured product. The novel curing agent adopted in the present invention can not only cure epoxy resin but also be used for flame retardancy of epoxy resin, and has good curing effect and compatibility. Because it does not contain halogen, it has low smoke and low toxicity, and conforms to the new green environmental protection type. Curing agent requirements.
Description
Technical field
The present invention relates to a kind of new compound DOPO-MA epoxy-resin systems application.
Background technique
Epoxy resin has excellent mechanical performance, chemical corrosion resistance, electrical insulating property, processing performance, adhesive property, and
And shrinking percentage is low, is widely used in social all trades and professions.Epoxy curing agent is indispensable one in epoxy-resin systems
Part, epoxy curing agent is various in style currently on the market, and performance is also different.Forefathers have carried out many grind in this regard
Study carefully, the shortcomings that mainly for epoxy resin and different purposes, its curing agent is modified, common are toughening, fire-retardant
Deng, or for low temperature, increase viscosity etc..
Epoxy resin limit oxygen index (LOI) only has 19.8%, belongs to combustible material, will limit it in certain special occasions
Using.And 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.
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 novel compounds
Object DOPO-MA improves the not good enough weakness of the anti-flammability of epoxy resin, applied to epoxy resin in the application of epoxy-resin systems
In solidification, the anti-flammability of reinforced epoxy solidfied material.
In order to solve the above technical problem, the present invention provides a kind of new compound DOPO- MA in epoxy-resin systems
Application, comprise the following steps:
DOPO-MA is mixed with epoxy resin, adds organic solvent, promotor, is uniformly mixed to obtain mixture；
It injects the mixture into precuring in mold to form, solidify after heating, continue to solidify after the completion of heating, it is solid to finally obtain crosslinking net
Compound；
The molecular formula of the compound DOPO-MA is C16H12O5P, molecular structural formula are shown below:
As a preferred embodiment of the above technical solution, new compound DOPO- MA provided by the invention is in epoxy-resin systems
Application further comprise some or all of following technical characteristic:
As an improvement of the above technical solution, the dosage of the DOPO-MA is the 70~80% 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 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 promotor is one of DMP-30 or imidazoles.
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 50-60 DEG C, required time 4-8h.
As an improvement of the above technical solution, the solidification temperature is 80-100 DEG C, required time 2-6h.
As an improvement of the above technical solution, the rear solidification temperature is 130-160 DEG C, required time 2-4h.
The DOPO-MA that the present invention is prepared is as follows to the curing mechanism of epoxy resin: first under conditions of no promotor
The epoxy group of the carboxyl and resin that dissociated in the hydroxyl in resin and acid anhydrides either acid anhydrides before this starts to react, the list of generation
Ester or hydroxyl continuation and epoxy reaction, ultimately produce three-dimensional reticular structure.In the presence of Tertiary amine accelerators, tertiary amine attack
Acid anhydrides, generates carboanion, and the reaction was continued generates alcoxyl anion, alcoxyl anion for the carboanion and epoxy group of generation
Carboanion is regenerated with anhydride reaction.Reaction successively goes on, final curing epoxy resin.
Compared with prior art, the invention has the benefit that new reaction-type flame-retarding epoxy resin cure used in (1)
Agent both curable epoxy, also can be used for the fire-retardant of epoxy resin；(2) new reaction-type flame-retarding epoxy resin cure used in
Phenyl ring is introduced in agent, improves the not good enough weakness of the toughness of epoxy resin, applied in the solidification of epoxy resin, makes epoxy resin body
System has good intensity and heat resistance；；(3) new reaction-type flame-retarding epoxy curing agent used in is halogen-free, low cigarette
Low toxicity meets the requirement of new green environment protection type 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 infrared spectrogram of DOPO-MA molecule prepared by the specific embodiment of the invention；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of DOPO-MA molecule prepared by the specific embodiment of the invention.
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.
The preparation method of Novel curing agent DOPO-MA of the present invention includes the following steps:
1. in N2Under atmosphere, to equipped with dropping funel, condensing reflux, magnetic agitation and N2The 250mL three-necked flask being passed through
Middle addition DOPO (0.3mol) and toluene (160 mL), stirring makes it completely dissolved, and maleic anhydride is then added
(0.3mol), and 100 DEG C are warming up to, in N212h is reacted under protection atmosphere.
2. being cooled to room temperature to after reaction, filter, then rinsed with ethyl alcohol, repeats 3 times, finally in vacuum oven
In at 100 DEG C drying obtain product for 24 hours.
Fig. 1 is the infrared spectrogram of DOPO-MA molecule prepared by the specific embodiment of the invention, and analysis is as shown in table 1.
The infrared spectrum of 1 DOPO-MA of table is analyzed
Fig. 2 is the 1H-NMR spectrogram of compound DOPO-MA, and analysis is as shown in table 2.
2 DOPO-MA's of table1H-NMR spectrum resolution table
Embodiment 1
A kind of new compound DOPO-MA is in the application method of epoxy-resin systems, and its step are as follows:
(1) epoxy resin E51 is chosen, by the DMP-30 or imidazoles of itself and the compound DOPO-MA, 1wt% of 80wt%
(in terms of epoxy resin quality, similarly hereinafter) and organic solvent DMF are uniformly mixed；
(2) above-mentioned mixed liquor is injected in homemade silica gel mould, is heated to 50 DEG C of precuring 4h, is allowed to form；
(3) 100 DEG C of solidification 4h are heated the mixture to, makes the abundant cured epoxy resin of curing agent, then proceedes to be warming up to
Solidify 2h after 130 DEG C, to eliminate the comprehensive performance that internal stress improves glue-joint strength and epoxy resin cured product.
Embodiment 2
(1) epoxy resin E44 is chosen, by the DMP-30 or imidazoles of itself and the compound DOPO-MA, 3wt% of 70wt%,
Organic solvent DMF is uniformly mixed；
(2) above-mentioned mixed liquor is injected in homemade silica gel mould, is heated to 50 DEG C of precuring 4h, is allowed to form；Heating
To 120 DEG C of solidification 4h, solidify 2h after being continuously heating to 180 DEG C.
Embodiment 3
(1) epoxy resin CYD128 is chosen, by the DMP-30 or miaow of itself and compound the DOPO- MA, 3wt% of 75wt%
Azoles, organic solvent DMF are uniformly mixed；
(2) above-mentioned mixed liquor is injected in homemade silica gel mould, is heated to 60 DEG C of precuring 4h, is allowed to form；Heating
To 100 DEG C of solidification 4h, solidify 2h after being continuously heating to 160 DEG C.
Embodiment 4
(1) epoxy resin E51 is chosen, by the DMP-30 or imidazoles of itself and compound the DOPO- MA, 3wt% of 80wt%,
Organic solvent DMF is uniformly mixed；
(2) above-mentioned mixed liquor is injected in homemade silica gel mould, is heated to 60 DEG C of precuring 8h, is allowed to form；Heating
To 100 DEG C of solidification 6h, solidify 4h after being continuously heating to 160 DEG C.
The solidfied material of above embodiments is prepared into having a size of 130mm × 13mm × 3.2mm standard batten each 5, is surveyed
Examination UL94 rank and limit oxygen index take its average value, and test result is as shown in table 3.
The UL94 rank and limit oxygen index test result table of each batten of table 3
As seen from the above table, new compound DOPO-MA is applied in epoxy resin as curing agent can be improved asphalt mixtures modified by epoxy resin
The flame retardant property of rouge.
Novel curing agent of the present invention not only curable epoxy but also can be used for ethoxyline resin antiflaming, and solidify
Effect, compatibility are preferable, due to being halogen-free therefore low-smoke low-toxicity, meet the requirement of new green environment protection type curing agent.
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 (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810845237.8A CN109161000A (en) | 2018-07-27 | 2018-07-27 | A kind of application of new compound DOPO-MA in epoxy-resin systems |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810845237.8A CN109161000A (en) | 2018-07-27 | 2018-07-27 | A kind of application of new compound DOPO-MA in epoxy-resin systems |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275308A (en) * | 2013-06-26 | 2013-09-04 | 兰州理工大学 | Phosphorous flame-retardant water-based alkyd resin and preparation method thereof |
| CN103408903A (en) * | 2013-08-28 | 2013-11-27 | 四川迪弗电工科技有限公司 | High-strength insulating support beam and preparation method thereof |
| WO2014179688A1 (en) * | 2013-05-03 | 2014-11-06 | Albemarle Corporation | Butadien2,3-diyl linked di-dopo derivatives as flame retardants |
-
2018
- 2018-07-27 CN CN201810845237.8A patent/CN109161000A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014179688A1 (en) * | 2013-05-03 | 2014-11-06 | Albemarle Corporation | Butadien2,3-diyl linked di-dopo derivatives as flame retardants |
| CN103275308A (en) * | 2013-06-26 | 2013-09-04 | 兰州理工大学 | Phosphorous flame-retardant water-based alkyd resin and preparation method thereof |
| CN103408903A (en) * | 2013-08-28 | 2013-11-27 | 四川迪弗电工科技有限公司 | High-strength insulating support beam and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王昱等: "阻燃型DOPO-马来酸酐改性的环氧树脂研究", 《绝缘材料》 * |
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