CN114989395A - Flame-retardant epoxy resin containing DOPO flame retardant and preparation method thereof - Google Patents
Flame-retardant epoxy resin containing DOPO flame retardant and preparation method thereof Download PDFInfo
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- CN114989395A CN114989395A CN202210817356.9A CN202210817356A CN114989395A CN 114989395 A CN114989395 A CN 114989395A CN 202210817356 A CN202210817356 A CN 202210817356A CN 114989395 A CN114989395 A CN 114989395A
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
Abstract
The invention discloses a flame-retardant epoxy resin containing a DOPO flame retardant, which comprises the following components in parts by weight: 40 parts of epoxy resin, 10-15 parts of DOPO derivative, 30 parts of curing agent and 20-60 parts of flame-retardant synergist, wherein the molecular structural formula of the flame-retardant epoxy resin containing the DOPO flame retardant is as follows:
a preparation method of flame-retardant epoxy resin containing DOPO flame retardant comprises the following steps: s1, weighing 40 parts of epoxy resin, 10-15 parts of DOPO derivative and 20-60 parts of flame retardant synergist according to the weight ratio; 30 parts of a curing agent; s2, putting the raw materials into a stirrer, wherein the stirring speed of the stirrer is 1000RPM/min, and the stirring time is 1 hour; s3, pouring the prepared slurry into a mould, and curing and forming at 100 ℃ for 2 hours; and S4, secondary curing, wherein the curing temperature is 120 ℃, and the curing time is 2 hours. The invention has the advantages that: avoid the migration of flame retardant, improve the flame retardant efficiency and synthesize the chemical engineeringSimple process, short period and easy post-treatment.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to flame-retardant epoxy resin containing a DOPO flame retardant and a preparation method thereof.
Background
Epoxy resins (EP) have excellent physical and mechanical properties, electrical properties, adhesion, thermal stability and good processability, and are widely used in coatings, adhesives, structural composites, electronic and electrical equipment and the like. In general, the limiting oxygen index of EP is about 20%, the EP is extremely easy to burn, the application of the EP in certain fields is influenced, and the flame retardant can be added to improve the flame retardant property of EP, so that the application range of the EP is expanded.
The flame retardant of the epoxy resin comprises an inorganic flame retardant, a halogen flame retardant, an organic phosphorus flame retardant and the like, and people tend to use the halogen-free flame retardant in consideration of the influence of environmental factors, wherein a phosphorus-containing compound is concerned, and the phosphorus-containing compound reacts with the epoxy resin, so that a flame retardant element is introduced into an epoxy molecular framework and is covalently linked to a polymer molecular chain, the migration of the flame retardant can be avoided, and the flame retardant efficiency is improved.
The phosphorus-containing reactive flame retardant DOPO is introduced into the epoxy resin body type macromolecules in various ways, has little influence on the physical and mechanical properties of the epoxy resin, and has high hydrolysis stability and thermal stability of the DOPO, and the obtained phosphorus-containing compound epoxy resin has good comprehensive performance. Because the phosphorus-containing flame retardant is single and is matched with the nitrogen-containing compound, the flame retardant effect is better, the phosphorus-nitrogen synergistic flame retardant effect can be better exerted, and the epoxy resin curing agent can play a role of a nitrogen source.
Thereby providing the flame-retardant epoxy resin containing the DOPO flame retardant and the preparation method thereof.
Disclosure of Invention
Aiming at the problems, the invention provides the flame-retardant epoxy resin containing the DOPO flame retardant and the preparation method thereof, wherein the flame-retardant epoxy resin avoids the migration of the flame retardant, improves the flame-retardant efficiency, has simple synthesis process, short period, easy post-treatment and easy control and industrial production.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the flame-retardant epoxy resin containing the DOPO flame retardant comprises the following components in parts by weight: 40 parts of epoxy resin, 10-15 parts of DOPO derivatives, 30 parts of curing agent and 20-60 parts of flame-retardant synergist, wherein the molecular structural formula of the flame-retardant epoxy resin containing the DOPO flame retardant is as follows:
further, the epoxy resin containing flame retardant DOPO is subjected to addition reaction with p-hydroxybenzophenone through DOPO to obtain a DOPO compound with hydroxyl at two ends, and then is subjected to condensation reaction with the epoxy resin under the action of a catalyst.
Further, the DOPO and p-hydroxybenzophenone are subjected to addition reaction to obtain a DOPO compound with hydroxyl at two ends, wherein the reaction condition is that the reaction temperature is 190 ℃, and the reaction time is 3 hours.
Further, the curing agent is at least one of imidazoles, imidazolines, trialkyl phosphorus, quaternary ammonium salts, quaternary phosphonium salts and organic urea, and the flame-retardant synergist is at least one of diammonium hydrogen phosphate, melamine cyanurate, sodium tripolyphosphate, ammonium dihydrogen phosphate, magnesium hydroxide, aluminum hydroxide and aluminum oxalate.
A preparation method of flame-retardant epoxy resin containing DOPO flame retardant comprises the following steps:
s1, weighing 40 parts of epoxy resin, 10-15 parts of DOPO derivative and 20-60 parts of flame retardant synergist according to the weight ratio; 30 parts of a curing agent;
s2, putting the raw materials into a stirrer, wherein the stirring speed of the stirrer is 1000RPM/min, and the stirring time is 1 hour;
s3, pouring the prepared slurry into a mould, and curing and forming at 100 ℃ for 2 hours;
and S4, secondary curing, wherein the curing temperature is 120 ℃, and the curing time is 2 hours.
Furthermore, the fire-retardant epoxy resin prepared has the fire-retardant rating of UL94 and the fire-retardant rating of V-0.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, a phosphorus-containing compound DOPO is introduced into an epoxy molecular chain, so that the migration of a flame retardant can be avoided, and the flame retardant efficiency is improved;
2. the synthesis process of the DOPO derivative with the hydroxyl at the two ends of the DOPO is simple, the period is short, the post-treatment is easy, and the control and the industrial production are easy.
Drawings
FIG. 1 is a diagram showing a synthesis route of a DOPO derivative having hydroxyl groups at both ends according to an example of the present invention.
FIG. 2 is a schematic diagram of a synthesis scheme of an epoxy resin containing a flame retardant according to an embodiment of the present invention.
FIG. 3 is a diagram of the mechanism of cure for an embodiment of the present invention.
Detailed Description
Examples
DOPO and p-hydroxybenzophenone are subjected to addition reaction to obtain a DOPO derivative with hydroxyl at two ends, the reaction temperature is 190 ℃, the reaction time is 3h, and the reaction formula is shown in figure 1;
carrying out condensation reaction on the DOPO derivative with hydroxyl at two ends and epoxy resin under the action of a catalyst to obtain the epoxy resin containing flame retardant DOPO, wherein the catalyst adopts trimethyl benzyl ammonium chloride, the dosage of the catalyst is 1 wt% of the hydroxyl DOPO derivative, the reaction temperature is 170 ℃, and the reaction time is 2 hours; the reaction formula is shown in figure 2;
heating the obtained epoxy resin to 90-120 ℃, keeping the temperature for 20-40 min, adding a curing agent, stirring and mixing uniformly, then removing bubbles in vacuum, pouring the mixture into a preheated mold, and curing to obtain the flame-retardant epoxy resin with a nitrogen-phosphorus containing structure, wherein the curing action mechanism is shown in figure 3.
Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and it is intended to cover in the claims the invention as defined in the appended claims.
Claims (6)
1. The flame-retardant epoxy resin containing the DOPO flame retardant is characterized by comprising the following components in parts by weight: 40 parts of epoxy resin, 10-15 parts of DOPO derivative, 30 parts of curing agent and 20-60 parts of flame-retardant synergist, wherein the molecular structural formula of the flame-retardant epoxy resin containing the DOPO flame retardant is as follows:
2. the flame retardant epoxy resin containing DOPO flame retardant according to claim 1, wherein: the epoxy resin containing flame retardant DOPO is subjected to addition reaction of DOPO and p-hydroxybenzophenone to obtain a DOPO compound with hydroxyl at two ends, and then the DOPO compound and the epoxy resin are subjected to condensation reaction under the action of a catalyst.
3. The flame retardant epoxy resin containing DOPO flame retardant according to claim 2, wherein: and carrying out addition reaction on the DOPO and p-hydroxybenzophenone to obtain a DOPO compound with two ends provided with hydroxyl, wherein the reaction condition is that the reaction temperature is 190 ℃, and the reaction time is 3 hours.
4. The flame retardant epoxy resin containing DOPO flame retardant according to claim 1, wherein: the curing agent is at least one of imidazoles, imidazolines, trialkyl phosphorus, quaternary ammonium salts, quaternary phosphonium salts and organic urea, and the flame-retardant synergist is at least one of diammonium hydrogen phosphate, melamine cyanurate, sodium tripolyphosphate, ammonium dihydrogen phosphate, magnesium hydroxide, aluminum hydroxide and aluminum oxalate.
5. The preparation method of the flame-retardant epoxy resin containing the DOPO flame retardant is characterized by comprising the following steps of:
s1, weighing 40 parts of epoxy resin, 10-15 parts of DOPO derivative and 20-60 parts of flame retardant synergist according to the weight ratio; 30 parts of a curing agent;
s2, putting the raw materials into a stirrer, wherein the stirring speed of the stirrer is 1000RPM/min, and the stirring time is 1 hour;
s3, pouring the prepared slurry into a mould, and curing and forming at 100 ℃ for 2 hours;
and S4, secondary curing, wherein the curing temperature is 120 ℃, and the curing time is 2 hours.
6. The flame-retardant epoxy resin prepared by the method for preparing the flame-retardant epoxy resin containing the DOPO flame retardant according to claim 5, wherein the method comprises the following steps: the fire-retardant rating is UL94, and the flame-retardant rating is V-0.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210817356.9A CN114989395A (en) | 2022-07-12 | 2022-07-12 | Flame-retardant epoxy resin containing DOPO flame retardant and preparation method thereof |
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| CN202210817356.9A CN114989395A (en) | 2022-07-12 | 2022-07-12 | Flame-retardant epoxy resin containing DOPO flame retardant and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117363299A (en) * | 2023-11-02 | 2024-01-09 | 东莞市皓彩塑胶科技有限公司 | Hot melt adhesive and preparation method thereof |
| CN117363299B (en) * | 2023-11-02 | 2024-04-30 | 广东合力化工科技有限公司 | Hot melt adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090258997A1 (en) * | 2008-04-11 | 2009-10-15 | Chang Chun Plastics Co., Ltd. | Novel phosphorus-containing compounds and their preparing process and use |
| CN103073746A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Reactive phosphorus flame retardant containing DOPO and active double bond and preparation method and application thereof |
| CN108250675A (en) * | 2016-12-28 | 2018-07-06 | 广东生益科技股份有限公司 | A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate |
-
2022
- 2022-07-12 CN CN202210817356.9A patent/CN114989395A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090258997A1 (en) * | 2008-04-11 | 2009-10-15 | Chang Chun Plastics Co., Ltd. | Novel phosphorus-containing compounds and their preparing process and use |
| CN103073746A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Reactive phosphorus flame retardant containing DOPO and active double bond and preparation method and application thereof |
| CN108250675A (en) * | 2016-12-28 | 2018-07-06 | 广东生益科技股份有限公司 | A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate |
Non-Patent Citations (1)
| Title |
|---|
| YING LING LIU: "Epoxy Resins from Novel Monomers with a Bis-(9, 10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl-) Substituent", 《JOURNAL OF POLYMER SCIENCE PART A POLYMER CHEMISTRY》, vol. 40, no. 3, pages 359 - 368 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117363299A (en) * | 2023-11-02 | 2024-01-09 | 东莞市皓彩塑胶科技有限公司 | Hot melt adhesive and preparation method thereof |
| CN117363299B (en) * | 2023-11-02 | 2024-04-30 | 广东合力化工科技有限公司 | Hot melt adhesive and preparation method thereof |
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