CN117843680A - Phosphorus-containing flame retardant for epoxy resin and preparation method thereof - Google Patents
Phosphorus-containing flame retardant for epoxy resin and preparation method thereof Download PDFInfo
- Publication number
- CN117843680A CN117843680A CN202410049773.2A CN202410049773A CN117843680A CN 117843680 A CN117843680 A CN 117843680A CN 202410049773 A CN202410049773 A CN 202410049773A CN 117843680 A CN117843680 A CN 117843680A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphorus
- containing flame
- reaction
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 55
- 239000011574 phosphorus Substances 0.000 title claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 6
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical class C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 monosubstituted benzene rings Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
Abstract
The invention discloses a phosphorus-containing flame retardant for epoxy resin and a preparation method thereof, belonging to the field of flame retardants. The preparation method of the phosphorus-containing flame retardant comprises the following steps: mixing diphenyl phosphine oxide and 4-aminoacetophenone, and heating to a reaction temperature; then adding a catalyst to perform heat preservation reaction, and obtaining the phosphorus-containing flame retardant after the reaction is completed. The phosphorus-containing flame retardant designed and synthesized by the invention contains primary amine groups and phosphorus-containing flame retardant groups, the primary amine groups provide protons to react with epoxy groups to play a role in curing and crosslinking, and the carbon layer and free radicals generated by the thermal decomposition of the phosphorus-containing flame retardant groups can realize the flame retardant function. No additional initiator is needed, and primary amine is located in the polymer molecular chain after curing, so that no migration problem exists. Meanwhile, the phosphorus-containing flame retardant can be used for obtaining the epoxy resin flame retardant material with the advantages of low odor, low toxicity, good stability, good hardness and the like.
Description
Technical Field
The invention relates to the field of flame retardants, in particular to a phosphorus-containing flame retardant for epoxy resin and a preparation method of the phosphorus-containing flame retardant.
Background
Epoxy resins are an important polymeric material that is widely used in industrial applications such as coatings, adhesives, composites, and the like. However, epoxy resins face flame retardant performance challenges in applications. Flame retardant performance is a key performance index of materials, especially under high temperature conditions, such as when a fire occurs. The reactive flame retardant is a compound with a reaction functional group at the tail end and low relative molecular mass, and has the dual functions of curing, crosslinking and flame retardance.
The reactive phosphorus-containing flame retardant is prepared by reacting a reactive functional group at the tail end with epoxy resin to open a ring so as to achieve the aim of connecting flame retardant molecules into the main chain of the epoxy resin, wherein the flame retardant molecules are decomposed at high temperature to promote the carbonization of the material at high temperature, so that a stable carbon-shaped layer is formed. When the material is heated, the phosphorus-containing flame retardant decomposes and releases phosphorus compounds that react at high temperatures to form char. After the carbonization layer is formed, flame and oxygen can be effectively isolated, and fire spreading is prevented. Some non-flammable gases such as ammonia, ammonia compounds, etc. may also be produced. These gases help dilute the oxygen in the combustion area in the event of a fire, reducing the fire while inhibiting the spread of the flame.
Disclosure of Invention
The invention aims to provide a phosphorus-containing flame retardant for epoxy resin and a preparation method of the phosphorus-containing flame retardant.
The technical scheme adopted by the invention is as follows:
a phosphorus-containing flame retardant for epoxy resins, which is a compound having the structure:
the preparation method of the phosphorus-containing flame retardant comprises the following steps:
(1) Diphenyl phosphine oxide and 4-aminoacetophenone are selected as reaction raw materials;
(2) Mixing diphenyl phosphine oxide and 4-aminoacetophenone, and heating to a reaction temperature; then adding a catalyst to perform heat preservation reaction, and obtaining the phosphorus-containing flame retardant after the reaction is completed.
Preferably, the mass ratio of the diphenyl phosphine oxide and the 4-amino acetophenone is (1-2.5) to (1-2).
Preferably, the mass ratio of the diphenyl phosphine oxide to the catalyst is (1-2.5) to (0.03-0.2).
Preferably, the catalyst is p-toluenesulfonic acid.
Preferably, the ratio of the amounts of diphenylphosphines, 4-aminoacetophenone and p-toluenesulfonic acid is 2.1:1:0.05.
Preferably, the reaction temperature is 100-160 ℃, and the reaction time is 10-24h. More preferably, the reaction temperature is 125℃and the reaction time is 12 hours.
Preferably, the method further comprises a separation and purification step after the reaction is finished, ethyl acetate is added into the crude product generated by the reaction, the adding amount of the ethyl acetate is 5-10 times of the weight of the crude product, and then the reaction is carried out for 1-6 hours at a low temperature, so that the product is fully crystallized and separated out, and the phosphorus-containing flame retardant is obtained.
After recrystallization, further washing with methanol is performed to remove impurities and purify the product.
The application of the phosphorus-containing flame retardant in preparing flame retardant materials.
A flame-retardant epoxy resin comprises the phosphorus-containing flame retardant, 4' -diaminodiphenyl sulfone and epoxy resin, wherein the phosphorus-containing flame retardant accounts for 0.1-1.5% of the mass of the epoxy resin.
The beneficial technical effects of the invention are as follows:
the phosphorus-containing flame retardant (named DPO) designed and synthesized by the invention 2 -NH 2 ) Contains primary amine groups and phosphorus-containing flame retardant groups. The phosphorus-containing flame retardant can play a role in curing and crosslinking by providing protons through primary amine groups to react with epoxy groups, and can realize a flame retardant function through a carbon layer and free radicals generated by the thermal decomposition of the phosphorus-containing flame retardant groups. In the process, no auxiliary initiator is added, primary amine is positioned in a polymer molecular chain after curing, and the migration problem is avoided. Meanwhile, the phosphorus-containing flame retardant disclosed by the invention can be used for obtaining the epoxy resin flame retardant material with the advantages of low odor, low toxicity, good stability, good hardness and the like.
Drawings
FIG. 1 is an MS diagram of a phosphorus-containing flame retardant prepared in example 1 of the present invention;
FIG. 2 is a schematic representation of a phosphorus-containing flame retardant prepared in example 1 of the present invention 1 H NMR chart;
FIG. 3 is a schematic representation of a phosphorus-containing flame retardant prepared in example 1 of the present invention 13 C NMR chart;
FIG. 4 shows a phosphorus-containing flame retardant prepared in example 1 of the present invention 31 P NMR chart.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
Example 1
DPO (0.2 mol,40.4 g), 4-aminoacetophenone (0.1 mol,13.5 g) and p-toluenesulfonic acid (0.005 mol,0.86 g) were weighed out separately as reaction raw materials.
DPO and 4-aminoacetophenone were first placed in a three-necked flask with a capacity of 1000 mL. The flask was equipped with a mechanical stirrer, reflux condenser and thermometer to control and monitor the reaction process.
The temperature was raised to 150 ℃, then stirring mixing was started, and this reaction condition was maintained for 12 hours.
After the reaction was completed, 500mL of ethyl acetate was added to the crude reaction product, which helped dissolve the product in the mixture, to obtain a reaction solution.
The reaction solution was cooled to room temperature. Recrystallization was performed at room temperature to recrystallize the resulting material into a solid.
The recrystallized mixture is filtered to separate the product. Then washed with methanol to remove impurities and purify the product. Finally 20.78g of DPO was collected 2 -NH 2 It was a pale yellow powder with a yield of 39.9%.
Example 2
DPO (0.21 mol,42.42 g), 4-aminoacetophenone (0.1 mol,13.5 g) and p-toluenesulfonic acid (0.05 mol,8.6 g) were weighed out separately as reaction raw materials.
DPO and 4-aminoacetophenone were first placed in a three-necked flask with a capacity of 1000 mL.
The temperature was raised to 120℃and stirring mixing was then started and the reaction conditions were maintained for 12 hours.
After the completion of the reaction, 500mL of ethyl acetate was added to the crude reaction product to obtain a reaction solution.
The reaction solution was cooled to room temperature. Recrystallization was performed at room temperature to recrystallize the resulting material into a solid.
The recrystallized mixture is filtered to separate the product. Then washed with methanol to remove impurities and purify the product. Finally, 33.08g of DPO was collected 2 -NH 2 It was pale yellow powder in 63.5% yield.
Example 3
DPO (0.1 mol,20.2 g), 4-aminoacetophenone (0.1 mol,13.5 g) and p-toluenesulfonic acid (0.05 mol,8.6 g) were weighed out separately as reaction raw materials.
DPO and 4-aminoacetophenone were first placed in a three-necked flask with a capacity of 1000 mL.
The temperature was raised to 160℃and stirring mixing was then started and the reaction conditions were maintained for 20 hours.
After the completion of the reaction, 500mL of ethyl acetate was added to the crude reaction product to obtain a reaction solution.
The reaction solution was cooled to room temperature. Recrystallization was performed at room temperature to recrystallize the resulting material into a solid.
After recrystallization ofThe mixture was filtered to isolate the product. Then washed with methanol to remove impurities and purify the product. Finally 22.35g of DPO was collected 2 -NH 2 It was pale yellow powder in 42.9% yield.
Example 4
DPO (0.15 mol,30.3 g), 4-aminoacetophenone (0.1 mol,13.5 g) and p-toluenesulfonic acid (0.1 mol,17.2 g) were weighed out separately as reaction raw materials.
DPO and 4-aminoacetophenone were first placed in a three-necked flask with a capacity of 1000 mL.
The temperature was raised to 100 ℃, then stirring mixing was started, and this reaction condition was maintained for 18 hours.
After the completion of the reaction, 700mL of ethyl acetate was added to the crude reaction product to obtain a reaction solution.
The reaction solution was cooled to room temperature. Recrystallization was performed at room temperature to recrystallize the resulting material into a solid.
The recrystallized mixture is filtered to separate the product. Then washed with methanol to remove impurities and purify the product. Finally, 21.15g of DPO was collected 2 -NH 2 It was a pale yellow powder with a yield of 40.6%.
FIG. 1 is an MS diagram of the phosphorus-containing flame retardant prepared in example 1, wherein the relative molecular mass 521.2 of the phosphorus-containing flame retardant is calculated, and 522.2 of the diagram is analyzed to be an excimer ion peak, namely the mass (M+H) of hydrogenation of the molecular mass of a sample.
FIG. 2 is a phosphorus-containing flame retardant prepared in example 1 1 H NMR charts, where δ=8.32-8.76 (m, 20H) ppm is the chemical shift of H on 4 monosubstituted benzene rings, δ=7.38 (d, 2H) ppm is the chemical shift of two H's on the disubstituted benzene rings near the amino group, δ=7.96 (d, 2H) ppm is the chemical shift of 2H's on the disubstituted benzene rings near the tertiary carbon atom, and δ=4.44 (s, 3H) ppm is the chemical shift of three H's on the methyl group.
FIG. 3 is a schematic representation of a phosphorus-containing flame retardant prepared in example 1 of the present invention 13 C NMR chart; FIG. 4 shows a phosphorus-containing flame retardant prepared in example 1 of the present invention 31 P NMR chart.
Combining MS with 1 H NMR chart and the like prove that the synthetic substance is a phosphorus-containing flame retardant.
In addition, the physical object of the phosphorus-containing flame retardant prepared by the invention has better fluidity. The phosphorus-containing flame retardant is further used for preparing flame-retardant epoxy resin.
Example 5
Preparing an epoxy resin sample:
the formulations of the epoxy cured samples are shown in table 1. First, DGEBA and DPO are combined 2 -NH 2 Heat to 150 ℃ and stir until DPO 2 -NH 2 Completely dissolved in DGEBA. Then, DDS was added for mixing. After DDS was dissolved in DGEBA, the mixture was poured into a preheated mold, cured for 2 hours at 125 ℃ and then cured for 2 hours at 180 ℃. The prepared sample is marked according to the flame retardant property and the mass content of phosphorus (P) element in the epoxy thermosetting resin. For example, EP/DPO 2 -NH 2 P-0.9 represents the flame retardant DPO 2 -NH 2 The mass content of the phosphorus element in the thermosetting material is 0.9wt%.
Comparative example 1
Preparation of epoxy resin samples
The formulation of the UV cured samples is shown in table 1. DGEBA and DDS were heated to 150℃and mixed, stirred to transparency. After DDS was dissolved in DGEBA, the mixture was poured into a preheated mold, cured for 2 hours at 125 ℃ and then cured for 2 hours at 180 ℃.
Flame retardant rating test
The flame retardant rating results are shown in Table 2, respectively, according to UL-94.
Table 1 is a formulation of epoxy thermosetting materials.
TABLE 1
Table 2 shows the UL-94 test results.
TABLE 2
As can be seen from tables 1 and 2, the phosphorus-containing flame retardant prepared by the invention can obviously improve the flame retardant property of the epoxy resin.
The parts not described in the above modes can be realized by adopting or referring to the prior art.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A phosphorus-containing flame retardant for epoxy resins, characterized by being a compound having the structure:
2. the method for preparing the phosphorus-containing flame retardant according to claim 1, comprising the steps of:
(1) Diphenyl phosphine oxide and 4-aminoacetophenone are selected as reaction raw materials;
(2) Mixing diphenyl phosphine oxide and 4-aminoacetophenone, and heating to a reaction temperature; then adding a catalyst to perform heat preservation reaction, and obtaining the phosphorus-containing flame retardant after the reaction is completed.
3. The method for preparing the phosphorus-containing flame retardant according to claim 2, wherein: the mass ratio of the diphenyl phosphine oxide to the 4-amino acetophenone is (1-2.5) to (1-2).
4. The method for preparing the phosphorus-containing flame retardant according to claim 2, wherein: the mass ratio of the diphenyl phosphine oxide to the catalyst is (1-2.5) to (0.03-0.2).
5. The method for preparing the phosphorus-containing flame retardant according to claim 2, wherein: the catalyst is p-toluenesulfonic acid.
6. The method for preparing the phosphorus-containing flame retardant according to claim 5, wherein: the mass ratio of the diphenyl phosphine oxide, the 4-aminoacetophenone and the p-toluenesulfonic acid substance is 2.1:1:0.05.
7. The method for preparing the phosphorus-containing flame retardant according to claim 2, wherein: the reaction temperature is 100-160 ℃, and the reaction time is 10-24h.
8. The method for preparing the phosphorus-containing flame retardant according to claim 2, wherein: after the reaction is finished, the method also comprises a separation and purification step, wherein ethyl acetate is added into the crude product generated by the reaction, the addition amount of the ethyl acetate is 5-10 times of the weight of the crude product, and then the reaction is placed at a low temperature for 1-6 hours, so that the product is fully crystallized and separated out, and the phosphorus-containing flame retardant is obtained.
9. Use of the phosphorus-containing flame retardant according to claim 1 for the preparation of flame retardant materials.
10. A flame retardant epoxy resin, characterized in that: comprising the phosphorus-containing flame retardant, 4' -diaminodiphenyl sulfone and epoxy resin as claimed in claim 1, wherein the phosphorus-containing flame retardant accounts for 0.1-1.5% of the mass of the epoxy resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202410049773.2A CN117843680A (en) | 2024-01-13 | 2024-01-13 | Phosphorus-containing flame retardant for epoxy resin and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202410049773.2A CN117843680A (en) | 2024-01-13 | 2024-01-13 | Phosphorus-containing flame retardant for epoxy resin and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117843680A true CN117843680A (en) | 2024-04-09 |
Family
ID=90528861
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202410049773.2A Pending CN117843680A (en) | 2024-01-13 | 2024-01-13 | Phosphorus-containing flame retardant for epoxy resin and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117843680A (en) |
-
2024
- 2024-01-13 CN CN202410049773.2A patent/CN117843680A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Phosphorus‐containing epoxy for flame retardant. III: Using phosphorylated diamines as curing agents | |
Lin et al. | Novel phosphorus-containing epoxy resins Part I. Synthesis and properties | |
Wang et al. | Synthesis and properties of epoxy resins containing 2-(6-oxid-6H-dibenz< c, e>< 1, 2> oxaphosphorin-6-yl) 1, 4-benzenediol | |
Schäfer et al. | Synthesis and properties of flame‐retardant epoxy resins based on DOPO and one of its analog DPPO | |
Wang et al. | Synthesis and properties of phosphorus‐containing epoxy resins by novel method | |
CN104277223B (en) | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant | |
WO2017071161A1 (en) | Cyclotriphosphazene halogen-free flame retardant containing imide structure, and preparation method and use | |
CN104086593A (en) | DOPO derivatives as well as preparation method and application thereof | |
CN109135189B (en) | P/N/Si-containing multi-element polyphosphazene silazane flame retardant for epoxy resin and preparation method thereof | |
CN109467574B (en) | Reactive flame retardant based on vanillin as well as preparation and application thereof | |
CN106432340A (en) | Composite structural phosphorus fire retardant containing poly-DOPO cyclic phosphate and preparation method thereof | |
KR20140024000A (en) | Phosphorus-containing compounds useful for making halogen-free, ignition-resistant polymers | |
TWI460186B (en) | Phosphinated amino and phenolic-containing multifunctional epoxy curing agents and their preparation and use | |
JP2001323268A (en) | Organophosphorus-based flame retardant, method for producing the same and resin composition comprising the same | |
CN111303483A (en) | Nitrogen-phosphorus efficient flame retardant containing p-hydroxybenzaldehyde and tryptamine structures, preparation method and application | |
CN103012847A (en) | Efficient nitrogen and phosphorus fire retardant for epoxy resin and preparation method of efficient nitrogen and phosphorus fire retardant | |
CN110643066B (en) | Phosphorus-nitrogen flame retardant and preparation method thereof | |
CN110981912B (en) | Phosphoric acid triester DOPO derivative flame retardant and preparation method thereof | |
CN106633673A (en) | Compounding flame-retardant epoxy resin based on phosphaphenanthrene derivant and inorganic flame retardant and preparation method thereof | |
CN116478357A (en) | DOPO-based reactive flame retardant containing terminal isocyanate groups, and preparation method and application thereof | |
Tian et al. | Effect of char-forming agents rich in tertiary carbon on flame retardant properties of polypropylene | |
CN117843680A (en) | Phosphorus-containing flame retardant for epoxy resin and preparation method thereof | |
CN114409827B (en) | Synthesis and performance of transparent epoxy resin material with high flame retardant performance based on chitosan derivative | |
US4308218A (en) | Aryl phosphonites and thiophosphonites useful as antioxidants | |
CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |