CN112194882A - Intrinsic flame-retardant reinforced epoxy resin and preparation method thereof - Google Patents
Intrinsic flame-retardant reinforced epoxy resin and preparation method thereof Download PDFInfo
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- CN112194882A CN112194882A CN202011084792.7A CN202011084792A CN112194882A CN 112194882 A CN112194882 A CN 112194882A CN 202011084792 A CN202011084792 A CN 202011084792A CN 112194882 A CN112194882 A CN 112194882A
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- epoxy resin
- reinforced epoxy
- flame
- retardant reinforced
- retardant
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- 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
- C08K5/5399—Phosphorus bound to nitrogen
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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
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses an essential flame-retardant reinforced epoxy resin and a preparation method thereof. The preparation method comprises the following steps: adding epoxy resin and an essential flame retardant 5-amino-1, 2, 4-triazole-1-neopentyl glycol phosphate amide into a single-neck flask, mechanically stirring and blending for a period of time at a certain blending temperature, adding a curing agent, uniformly stirring and transparentizing, vacuumizing, pouring into a preheated stainless steel mold, and curing by stages to obtain the essential flame-retardant reinforced epoxy resin. Through tests on flame retardance and mechanical properties, the Limit Oxygen Index (LOI) of the prepared epoxy resin can reach 37 percent at most, and the tensile strength and the bending strength can reach 80MPa and 122MPa at most. The preparation method provided by the invention is simple and easy for industrial production, and the prepared epoxy resin has greatly improved flame retardance and mechanical properties.
Description
Technical Field
The invention relates to an essential flame-retardant reinforced epoxy resin and a preparation method thereof.
Background
Epoxy groups of epoxy resins can undergo ring-opening addition reaction with amine type, anhydride type and various latent curing agents under a high-temperature reaction environment, so that three-dimensional space network structures are formed, and excellent mechanical properties, corrosion resistance, adhesion and electric insulation are provided for the materials, so that the epoxy resins are widely concerned in recent years and are applied to the fields of aerospace, electronics, building engineering, food packaging, transportation and the like. However, epoxy resins are extremely flammable and release toxic gases, which limits the development of epoxy resins in various fields, and thus it is very important to solve the problem of flammability.
Commonly used flame retardant modifiers for epoxy resins include: halogen compounds, organic phosphorus compounds, inorganic and nano compounds and the like, but in recent years, the organic phosphorus flame retardant has a dominant position in the market due to the characteristics of high flame retardant efficiency, small smoke generation amount, no toxicity and the like. The method can be divided into an additive type and a reactive type when applied to the epoxy resin, and compared with the two methods, the additive type is easier to destroy the mechanical property of the epoxy resin and has the phenomenon of uneven mixing. Based on the above, the invention provides a preparation method of an essential flame-retardant reinforced epoxy resin, wherein organic phosphorus is used as a reactive flame retardant to be applied to the epoxy resin to prepare a flame-retardant reinforced epoxy resin material.
Disclosure of Invention
The invention aims to solve the problem of flammability of epoxy resin and provides a preparation method of an essential flame-retardant reinforced epoxy resin.
The technical scheme adopted for realizing the purpose of the invention is as follows:
adding epoxy resin and an intrinsic flame retardant 5-amino-1, 2, 4-triazole-1-neopentyl glycol phosphate amide (PATA) into a single-neck flask, magnetically stirring and blending at 100-110 ℃ for a period of time at 1000rpm, adding a certain amount of curing agent, uniformly stirring and transparentizing, vacuumizing, pouring into a preheated stainless steel mold, curing by stages, curing at 85-100 ℃ for 3 hours in the first stage, and curing at 140-150 ℃ for 2 hours in the second stage to obtain the intrinsic flame retardant reinforced epoxy resin.
The epoxy resin prepared by the method is one of E44 and E51.
The structural formula of the intrinsic flame retardant 5-amino-1, 2, 4-triazole-1-neopentyl glycol phosphate amide in the method is as follows:
the mass ratio of the epoxy resin to the curing agent is 5: 1 to 2.
The mass of the intrinsic flame retardant (PATA) in the method accounts for 2.5-20% of the total mass of the intrinsic flame retardant reinforced epoxy resin.
The epoxy resin and the intrinsic flame retardant (PATA) are blended in the method, and the blending time is 0.5-2 hours.
The curing agent described in the above method is 4, 4' -diaminodiphenylmethane (DDM).
The Limiting Oxygen Index (LOI) of the intrinsic flame-retardant reinforced epoxy resin prepared by the method can reach 37 percent at most, and the tensile strength and the bending strength can reach 80MPa and 122MPa at most respectively.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method of the essential flame-retardant reinforced epoxy resin provided by the invention is simple to operate and easy for industrial production.
(2) According to the preparation method of the essential flame-retardant reinforced epoxy resin, the prepared epoxy resin is improved in flame retardance and mechanical property.
Detailed Description
The preparation example of the essential flame-retardant reinforced epoxy resin provided by the invention is as follows:
comparative example 1
Adding 100g E44 type epoxy resin and 25g DDM curing agent into a 250ml single-neck flask, magnetically stirring uniformly at 110 ℃ through 1000rpm and making transparent, vacuumizing, pouring into a preheated stainless steel mold, curing at 90 ℃ for 3 hours, curing at 150 ℃ for 2 hours to obtain the flame-retardant reinforced epoxy resin, wherein the measured Limiting Oxygen Index (LOI) is 25.0%, and the tensile strength and bending strength are 62MPa and 82 MPa.
Comparative example 2
100g E51 type epoxy resin and 32g DDM curing agent are added into a 250ml single-neck flask, the mixture is magnetically stirred uniformly and transparent at 110 ℃ through 1000rpm, vacuumized, poured into a preheated stainless steel mold, cured for 3 hours at 100 ℃ and cured for 2 hours at 145 ℃ to obtain the flame-retardant reinforced epoxy resin, the measured Limiting Oxygen Index (LOI) is 25.8%, and the tensile strength and the bending strength are 64MPa and 85 MPa.
Example 1
100g E44 type epoxy resin and 3.2g PATA (2.5%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 15min at 110 ℃ through 1000rpm, 25g DDM curing agent is added, stirring is uniform and transparent, vacuum pumping treatment is carried out, then the mixture is poured into a preheated stainless steel mold, curing is carried out for 3 hours at 90 ℃ and 2 hours at 150 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 28.8%, and the tensile strength and the bending strength are 65MPa and 92 MPa.
Example 2
100g E51 type epoxy resin and 3.4g PATA (2.5%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 30min at 100 ℃ through 1000rpm, 33g DDM curing agent is added, stirring is uniform and transparent, vacuum pumping treatment is carried out, then the mixture is poured into a preheated stainless steel mold, curing is carried out for 3 hours at 100 ℃ and 2 hours at 140 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 29.0%, and the tensile strength and the bending strength are 64MPa and 95 MPa.
Example 3
100g E44 type epoxy resin and 6.7g PATA (5%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 20min at 100 ℃ through 1000rpm, 28g DDM curing agent is added, the mixture is stirred uniformly and is transparent, vacuum treatment is carried out, then the mixture is cast into a preheated stainless steel mold, curing is carried out for 3 hours at 85 ℃ and 2 hours at 140 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 31.4%, and the tensile strength and the bending strength are 71MPa and 98 MPa.
Example 4
100g E51 type epoxy resin and 7.2g PATA (5%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 35min at 110 ℃ through 1000rpm, 38g DDM curing agent is added, the mixture is stirred uniformly and is transparent, vacuum pumping treatment is carried out, then the mixture is cast into a preheated stainless steel mold, curing is carried out for 3 hours at 100 ℃ and 2 hours at 150 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 31.2%, and the tensile strength and the bending strength are 69MPa and 98 MPa.
Example 5
100g E44 type epoxy resin and 10.1g PATA (7.5%) are added into a 250ml single-neck flask, mechanically stirred for 35min at 110 ℃, then 25g DDM curing agent is added, the mixture is uniformly stirred and transparent, vacuumized, poured into a preheated stainless steel mold, cured for 3 hours at 85 ℃ and 2 hours at 150 ℃ to obtain the flame-retardant reinforced epoxy resin, the measured Limiting Oxygen Index (LOI) is 32.8%, and the tensile strength and bending strength are 74MPa and 104 MPa.
Example 6
100g E44 type epoxy resin and 13.8g PATA (10%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 42min at 110 ℃ through 1000rpm, 24g DDM curing agent is added, the mixture is stirred uniformly and is transparent, vacuum pumping treatment is carried out, then the mixture is cast into a preheated stainless steel mold, curing is carried out for 3 hours at 110 ℃ and 2 hours at 140 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 33.5%, and the tensile strength and the bending strength are 75MPa and 107 MPa.
Example 7
100g E51 type epoxy resin and 15.6g PATA (10%) are added into a 250ml single-neck flask, mechanically stirred for 50min at 110 ℃, 40g DDM curing agent is added, the mixture is uniformly stirred and transparent, vacuumized, poured into a preheated stainless steel mold, cured for 3 hours at 100 ℃ and 2 hours at 145 ℃ to obtain the flame-retardant reinforced epoxy resin, the measured Limiting Oxygen Index (LOI) is 33.8%, and the tensile strength and bending strength are 76MPa and 110 MPa.
Example 8
100g E44 type epoxy resin and 21.9g PATA (15%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 40min at 100 ℃ through 1000rpm, 20g DDM curing agent is added, the mixture is stirred uniformly and is transparent, vacuum treatment is carried out, then the mixture is cast into a preheated stainless steel mold, curing is carried out for 3 hours at 85 ℃ and 2 hours at 140 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 35%, and the tensile strength and the bending strength are 78MPa and 115 MPa.
Example 9
100g E51 type epoxy resin and 25.6g PATA (15%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 1h at 110 ℃ through 1000rpm, 37g DDM curing agent is added, the mixture is stirred uniformly and is transparent, vacuum pumping treatment is carried out, then the mixture is cast into a preheated stainless steel mold, curing is carried out for 3 hours at 100 ℃ and 2 hours at 150 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 37.0%, and the tensile strength and the bending strength are 80MPa and 122 MPa.
Example 10
100g E44 type epoxy resin and 26.9g PATA (17.5%) are added into a 250ml single-neck flask, mechanically stirred for 1h 15min at 100 ℃, then 27g DDM curing agent is added, the mixture is uniformly stirred and transparent, vacuumized, poured into a preheated stainless steel mold, cured for 3 hours at 85 ℃ and 2 hours at 150 ℃ to obtain the flame-retardant reinforced epoxy resin, the measured Limiting Oxygen Index (LOI) is 37.0%, and the tensile strength and bending strength are 78MPa and 117 MPa.
Example 11
100g E44 type epoxy resin and 30.3g PATA (20%) are added into a 250ml single-neck flask, magnetic stirring is carried out for 1h 33min at 110 ℃ through 1000rpm, then 21g DDM curing agent is added, stirring is carried out uniformly and transparently, vacuum pumping treatment is carried out, then the mixture is poured into a preheated stainless steel mold, curing is carried out for 3 hours at 90 ℃ and 2 hours at 150 ℃, finally the flame-retardant reinforced epoxy resin is obtained, the measured Limiting Oxygen Index (LOI) is 37.3%, and the tensile strength and the bending strength are 76MPa and 118 MPa.
Claims (7)
1. A preparation method of an essential flame-retardant reinforced epoxy resin is characterized by comprising the following steps:
adding epoxy resin and an intrinsic flame retardant (PATA) into a single-neck flask, magnetically stirring and blending at the temperature of 100-110 ℃ for a period of time at 1000rpm, adding a curing agent, uniformly stirring and transparentizing, vacuumizing, pouring into a preheated stainless steel mold, curing by stages, wherein the first stage is curing at 85-100 ℃ for 3 hours, and the second stage is curing at 140-150 ℃ for 2 hours, so as to obtain the intrinsic flame-retardant reinforced epoxy resin.
2. The method of claim 1, wherein the epoxy resin is one of E44 and E51.
3. The method for preparing an intrinsic flame retardant reinforced epoxy resin as claimed in claim 1, wherein the intrinsic flame retardant (PATA) has the following structure:
4. the method for preparing the intrinsic flame-retardant reinforced epoxy resin as claimed in claim 1, wherein the mass ratio of the epoxy resin to the curing agent is 5: 1 to 2.
5. The method for preparing the intrinsic flame-retardant reinforced epoxy resin as claimed in claim 1, wherein the mass of the intrinsic flame retardant PATA accounts for 2.5-20% of the total mass of the intrinsic flame-retardant reinforced epoxy resin.
6. The method for preparing the intrinsic flame retardant reinforced epoxy resin as claimed in claim 1, wherein the epoxy resin and the intrinsic flame retardant PATA are blended for 0.5-2 hours.
7. The method for preparing an intrinsic flame retardant reinforced epoxy resin as claimed in claim 1, wherein said curing agent is 4, 4' -diaminodiphenylmethane DDM.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011084792.7A CN112194882A (en) | 2020-10-12 | 2020-10-12 | Intrinsic flame-retardant reinforced epoxy resin and preparation method thereof |
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| CN202011084792.7A CN112194882A (en) | 2020-10-12 | 2020-10-12 | Intrinsic flame-retardant reinforced epoxy resin and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248541A (en) * | 2021-05-14 | 2021-08-13 | 青岛大学 | Phosphorus-nitrogen type flame retardant and preparation method and application thereof |
| CN113388090A (en) * | 2021-06-28 | 2021-09-14 | 福建师范大学 | Phosphorus-nitrogen-rich compound flame-retardant reinforced epoxy resin and preparation method thereof |
| CN117255474A (en) * | 2023-09-26 | 2023-12-19 | 广东格斯泰科技有限公司 | High-temperature-resistant resin-based copper-clad laminate and preparation method thereof |
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| US20040247881A1 (en) * | 2003-06-06 | 2004-12-09 | Dean Jennifer M. | Curable flame retardant epoxy resin compositions |
| CN109400649A (en) * | 2018-10-26 | 2019-03-01 | 福建师范大学 | A kind of one pack system expansion type flame retardant preparation and its application in fire retarding epoxide resin |
| CN109438754A (en) * | 2018-10-26 | 2019-03-08 | 福建师范大学 | It a kind of phosphorous 3-triazole compounds preparation method and its is applied on flame-proof polylactic acid |
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2020
- 2020-10-12 CN CN202011084792.7A patent/CN112194882A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040247881A1 (en) * | 2003-06-06 | 2004-12-09 | Dean Jennifer M. | Curable flame retardant epoxy resin compositions |
| CN109400649A (en) * | 2018-10-26 | 2019-03-01 | 福建师范大学 | A kind of one pack system expansion type flame retardant preparation and its application in fire retarding epoxide resin |
| CN109438754A (en) * | 2018-10-26 | 2019-03-08 | 福建师范大学 | It a kind of phosphorous 3-triazole compounds preparation method and its is applied on flame-proof polylactic acid |
Non-Patent Citations (1)
| Title |
|---|
| AI YUAN-FANG等: "Multifunctional Phosphorus-Containing Triazolyl Amine toward Self-Intumescent Flame-Retardant and Mechanically Strong Epoxy Resin with High Transparency", 《IND. ENG. CHEM. RES.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248541A (en) * | 2021-05-14 | 2021-08-13 | 青岛大学 | Phosphorus-nitrogen type flame retardant and preparation method and application thereof |
| CN113388090A (en) * | 2021-06-28 | 2021-09-14 | 福建师范大学 | Phosphorus-nitrogen-rich compound flame-retardant reinforced epoxy resin and preparation method thereof |
| CN117255474A (en) * | 2023-09-26 | 2023-12-19 | 广东格斯泰科技有限公司 | High-temperature-resistant resin-based copper-clad laminate and preparation method thereof |
| CN117255474B (en) * | 2023-09-26 | 2024-03-26 | 广东格斯泰科技有限公司 | High-temperature-resistant resin-based copper-clad laminate and preparation method thereof |
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Application publication date: 20210108 |