CN115838525A - Preparation process of phenolic resin coated nano silicon dioxide modified ABS resin - Google Patents
Preparation process of phenolic resin coated nano silicon dioxide modified ABS resin Download PDFInfo
- Publication number
- CN115838525A CN115838525A CN202310160562.1A CN202310160562A CN115838525A CN 115838525 A CN115838525 A CN 115838525A CN 202310160562 A CN202310160562 A CN 202310160562A CN 115838525 A CN115838525 A CN 115838525A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- silicon dioxide
- coated nano
- abs resin
- preparation process
- 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.)
- Granted
Links
Images
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of silicon dioxide flame retardants, and discloses a preparation process of a phenolic resin coated nano silicon dioxide modified ABS resin, wherein 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and alkenyl of maleimide phenolic resin are subjected to addition reaction to obtain nitrogen-phosphorus phenolic resin, nano silicon dioxide is generated in a nitrogen-phosphorus phenolic resin matrix through a sol-gel method to obtain the phenolic resin coated nano silicon dioxide, the phenolic resin coated nano silicon dioxide is used as a composite flame retardant to fill and modify the ABS resin, an expanded carbon layer is formed in the ABS resin matrix during combustion, the nano silicon dioxide is distributed in the carbon layer to form stable support, the stability and barrier property of the carbon layer are improved, better effects of heat insulation, oxygen insulation and smoke suppression are achieved, the heat release rate and total heat release quantity of the ABS resin are reduced, and excellent combustion char formation and flame retardant properties are shown.
Description
Technical Field
The invention relates to the technical field of silicon dioxide flame retardants, in particular to a preparation process of phenolic resin coated nano silicon dioxide modified ABS resin.
Background
The nano silicon dioxide has small particle size, large specific surface area, high surface performance and a plurality of unique properties, can be used as a toughening agent, a flame retardant, a reinforcing agent and the like, is widely applied to high polymer materials such as epoxy resin, ABS resin and the like, and can improve the performances such as flame retardance, mechanical strength and the like of the materials. For example, patent application No. 201310189706.2, a preparation method of a SiO2/ABS composite material, discloses that the SiO2 microspheres in the prepared SiO2/ABS composite material have good dispersion effect, can achieve the purpose of reinforcement, and can also play a role of toughening, thereby enhancing the mechanical properties of the ABS composite material.
Acrylonitrile-butadiene-styrene copolymer (ABS resin) is a thermoplastic resin, has the advantages of high strength, good toughness, easy processing and the like, but the ABS resin has the defects of poor flame retardance, flammability and the like, and the development of a novel flame retardant for the ABS resin is a research hotspot, for example, in the document TPP/TPPFR (thermoplastic phenol formaldehyde resin/TPPFR) research on the mechanism of charing and flame retarding of the ABS resin, the report that the thermoplastic phenol formaldehyde resin and triphenyl phosphate are compounded to be added into the ABS resin as a halogen-free flame retardant, so that the charing property and the flame retarding performance of the ABS are improved. The invention aims to prepare novel phenolic resin coated nano silicon dioxide as a flame retardant, and enhance the char forming property and flame retardance of ABS resin.
Disclosure of Invention
Technical problem to be solved
The invention provides a preparation process of phenolic resin coated nano silicon dioxide modified ABS resin with excellent flame retardance.
(II) technical scheme
A preparation process of phenolic resin coated nano silicon dioxide modified ABS resin comprises the following steps:
s1: adding maleimide phenolic resin into a solvent, stirring and dissolving, then sequentially adding 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 0.8-1.5% triethylamine which are 60-120% of the weight of the maleimide phenolic resin, heating to 50-70 ℃ for reaction for 4-12 h, adding deionized water after the reaction for precipitation, filtering the solvent, and sequentially washing with the deionized water and acetone to obtain the nitrogen-phosphorous phenolic resin.
S2: adding a hydrochloric acid aqueous solution into an ethyl orthosilicate ethanol solution, standing and aging to form sol, then adding nitrogen-phosphorus phenolic resin which accounts for 200-600% of the weight of the ethyl orthosilicate, stirring uniformly, standing and aging for 6-12 h, and finally drying and curing the material at 130-180 ℃ for 4-8 h to obtain the phenolic resin coated nano silicon dioxide.
S3: adding ABS resin and phenolic resin coated nano silicon dioxide accounting for 1-8% of the weight of the ABS resin into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, and extruding and granulating to obtain the phenolic resin coated nano silicon dioxide modified ABS resin.
Preferably, the solvent in S1 includes any one of dimethyl sulfoxide, N-dimethylformamide, toluene, 1, 4-dioxane or tetrahydrofuran.
Preferably, the mass fraction of the ethyl orthosilicate ethanol solution in the S2 is 30-60%.
Preferably, the mass fraction of the hydrochloric acid aqueous solution in the S2 is 0.4-0.8%.
Preferably, the 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]The preparation process of octane comprises the following steps: adding mercaptoacetic acid and 180-260 wt% of 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] relative to the weight of the mercaptoacetic acid into the reaction solvent]Octane, stirring to dissolve, adding catalyst p-toluenesulfonic acid, heating to 100-130 ℃, stirring to react for 6-18 h, removing the solvent by rotary evaporation after the reaction, washing with petroleum ether, and recrystallizing the crude product in ethyl acetate to obtain 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]Octane of the structural formula
。
Preferably, the reaction solvent includes any one of toluene, xylene or N, N-dimethylformamide.
Preferably, the p-toluenesulfonic acid is used in an amount of 0.8 to 1.5% by mass of the total mass of 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and mercaptoacetic acid.
(III) advantageous technical effects
With mercaptoacetic acid and 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]Octane is subjected to esterification reaction to obtain novel 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]Octane and then carrying out addition reaction with alkenyl of the maleimide phenolic resin to obtain nitrogen-phosphorus phenolic resin, so that a nitrogen-containing heterocycle and a phosphate ester structure are introduced into a side chain of the phenolic resin; 1492 cm in infrared spectrum of nitrogen-phosphated phenolic resin NP-PF -1 Is characterized by a characteristic absorption peak of a benzene ring skeleton in the phenolic resin, 1459 cm -1 Is located at 1326 cm of an absorption peak of maleimide ring C-O-C -1 Peak of stretching vibration at P = O bond, 1117 cm -1 The stretching vibration peak at the P-O bond proves that 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]The octane reacts with the maleimide phenolic resin to obtain nitrogen-phosphorus phenolic resin; nano silicon dioxide NP-PF-SiO coated by phenolic resin 2 In the infrared spectrum of (1), 1009 cm -1 Is located at 1509cm which is the stretching vibration peak of Si-O in silicon dioxide -1 Is characterized by a characteristic absorption peak of a benzene ring skeleton in the phenolic resin, 1480 cm -1 Is located at the absorption peak of maleimide ring C-O-C, 1319 cm -1 Stretching vibration peak at P = O bond, 1113 cm -1 Is the stretching vibration peak of the P-O bond.
And further generating nano silicon dioxide in a nitrogen-phosphorus phenolic resin matrix by a sol-gel method to obtain phenolic resin coated nano silicon dioxide, and filling and modifying the ABS resin as a composite flame retardant. After being coated by phenolic resin, the nano silicon dioxide has good compatibility with ABS resin and excellent dispersibility, is favorable for reducing the agglomeration of silicon dioxide nano particles, the nitrogen-phosphorus phenolic resin forms an expansion flame-retardant system, an expansion carbon layer is formed on the ABS resin matrix during combustion, the nano silicon dioxide is distributed in the carbon layer to form stable support, the stability and the barrier property of the carbon layer are improved, better heat insulation, oxygen insulation and smoke suppression effects are achieved, the heat release rate and the total heat release amount of the ABS resin are reduced, and excellent combustion char formation property and flame retardant property are shown.
Drawings
FIG. 1 is a heat release rate curve of a phenolic resin coated nano silica modified ABS resin.
FIG. 2 is a total heat release curve of the phenolic resin coated nano-silica modified ABS resin.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
FIG. 4 shows NPN phenolic resin NP-PF and phenolic resin coated nano-silica NP-PF-SiO 2 An infrared spectrum.
Detailed Description
Nano silicon dioxide: the model is as follows: XH-SiO2-30; the average grain diameter is 30 nm; the purity is more than 99.9 percent.
Phenolic resin: the content of the product is not less than 98.0 percent, and the product is PR-4582L.
ABS resin: the brand PA-756, injection molding grade, the content is not less than 99.0%.
The maleimide Phenolic resin is prepared according to Journal of Polymer Science, part A. Polymer Chemistry Vol.38, 641-652 (2000), phenolic resins bearing macromolecular compounds groups, synthesis and characterization, DOI: 10.1002/(SICI) 1099-0518 (20000201) 38 are in a range of 641: AID-POLA28>3.0.CO 2-Z.
Uniformly mixing 80 g of phenol, 20 g of 4-maleimide phenol and 5 g of oxalic acid, dropwise adding 63 mL of formaldehyde aqueous solution with the mass fraction of 34% at 75 ℃, reacting for 10 h, adding acetone for dilution after the reaction, then adding methanol aqueous solution for precipitation, filtering the solvent, washing with acetone and drying to obtain the maleimide phenolic resin (PMF resin).
Example 1
(1) To 60 mL of N, N-dimethylformamide solvent were added 1.5 g of thioglycolic acid, 2.7 g of 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]Octane, stirring to dissolve, adding 42mg of catalyst p-toluenesulfonic acid, heating to 120 ℃, stirring to react for 6 hours, and removing by rotary evaporation after reactionRemoving solvent, washing with petroleum ether, recrystallizing the crude product with ethyl acetate to obtain 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Octane, molecular formula: c 7 H 11 O 6 PS， 1 H NMR(400MHz，CDCl 3 )：δ 4.48-4.15 (m, 6H)，3.89-3.73(m, 2H)，3.68-3.51(m, 2H)，2.19(s, 1H)。
(2) Adding 5 g of maleimide phenolic resin into 150 mL of toluene solvent, stirring and dissolving, then sequentially adding 4 g of 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 50 mg of triethylamine, heating to 70 ℃ for reaction for 4 hours, adding deionized water after the reaction for precipitation, filtering the solvent, and sequentially washing with deionized water and acetone to obtain the NPS phenolic resin NP-PF.
(3) Adding 10 mL of 0.4% hydrochloric acid aqueous solution into 10 mL of 30% ethyl orthosilicate ethanol solution, standing and aging to form sol, then adding 6 g of nitrogen-phosphorus phenolic resin, stirring uniformly, standing and aging for 10 h, and finally drying and curing the material at 130 ℃ for 8 h to obtain the phenolic resin coated nano-silica NP-PF-SiO 2 。
(4) Adding 2 kg of ABS resin and 20 g of phenolic resin coated nano-silica into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, and extruding and granulating, wherein the temperature of a 1-6 area of the extruder is 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ in sequence to obtain the phenolic resin coated nano-silica modified ABS resin.
Example 2
(1) 1.5 g of mercaptoacetic acid and 3.9 g of 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane are added into 100 mL of toluene solvent, stirred and dissolved, 81 mg of catalyst p-toluenesulfonic acid is added, the temperature is raised to 130 ℃, stirred and reacted for 12 hours, after the reaction, the solvent is removed by rotary evaporation, after petroleum ether washing, the crude product is recrystallized in ethyl acetate, and 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane is obtained.
(2) Adding 5 g of maleimide phenolic resin into 200 mL of N, N-dimethylformamide solvent, stirring for dissolving, then sequentially adding 3 g of 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 40 mg of triethylamine, heating to 60 ℃ for reaction for 12 hours, adding deionized water for precipitation after the reaction, filtering the solvent, and sequentially washing with deionized water and acetone to obtain the nitrogen-phosphorus phenolic resin.
(3) Adding 10 mL of 0.6% hydrochloric acid aqueous solution into 10 mL of 50% ethyl orthosilicate ethanol solution, standing and aging to form sol, then adding 22 g of nitrogen-phosphorus phenolic resin, stirring uniformly, standing and aging for 6 h, and finally drying and curing the material at 180 ℃ for 4 h to obtain the phenolic resin coated nano silicon dioxide.
(4) Adding 2 kg of ABS resin and 100 g of phenolic resin coated nano-silica into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, and extruding and granulating, wherein the temperature of a 1-6 area of the extruder is 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ in sequence to obtain the phenolic resin coated nano-silica modified ABS resin.
Example 3
(1) Adding 1.5 g of mercaptoacetic acid and 3 g of 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane into 80 mL of xylene solvent, stirring for dissolving, adding 60 mg of catalyst p-toluenesulfonic acid, heating to 120 ℃, stirring for reacting for 18 h, removing the solvent by rotary evaporation after the reaction, washing with petroleum ether, and recrystallizing the crude product in ethyl acetate to obtain 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
(2) Adding 5 g of maleimide phenolic resin into 150 mL of dimethyl sulfoxide solvent, stirring and dissolving, then sequentially adding 6 g of 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 75 mg of triethylamine, heating to 50 ℃ for reacting for 8 h, adding deionized water after the reaction for precipitation, filtering the solvent, and sequentially washing with deionized water and acetone to obtain the nitrogen-phosphorus phenolic resin.
(3) Adding 10 mL of 0.8% hydrochloric acid aqueous solution into 10 mL of 60% ethyl orthosilicate ethanol solution, standing and aging to form sol, then adding 36 g of nitrogen-phosphorus phenolic resin, stirring uniformly, standing and aging for 12 h, and finally drying and curing the material at 150 ℃ for 6 h to obtain the phenolic resin coated nano silicon dioxide.
(4) Adding 2 kg of ABS resin and 160 g of phenolic resin coated nano-silica into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, and extruding and granulating, wherein the temperature of a 1-6 area of the extruder is 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ in sequence to obtain the phenolic resin coated nano-silica modified ABS resin.
Comparative example 1
(1) Adding 1.5 g of mercaptoacetic acid and 3.9 g of 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane into 80 mL of xylene solvent, stirring to dissolve, adding 81 mg of catalyst p-toluenesulfonic acid, heating to 130 ℃, stirring to react for 6 hours, removing the solvent by rotary evaporation after the reaction, washing with petroleum ether, and recrystallizing the crude product in ethyl acetate to obtain 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
(2) Adding 5 g of maleimide phenolic resin into 100 mL of tetrahydrofuran solvent, stirring and dissolving, then sequentially adding 6 g of 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 75 mg of triethylamine, heating to 70 ℃ for reaction for 4 hours, adding deionized water after the reaction for precipitation, filtering the solvent, and sequentially washing with deionized water and acetone to obtain the nitrogen-phosphorus phenolic resin.
(3) Adding 2 kg of ABS resin and 20 g of nitrogen-phosphorus phenolic resin into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, and extruding and granulating, wherein the temperature of a 1-6 area of the extruder is 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ in sequence to obtain the phenolic resin modified ABS resin.
Preparing a sample with the length of 2cm, the width of 2cm and the width of 0.2 mm by coating nano silicon dioxide with phenolic resin, and then testing the combustion performance in a cone calorimeter with the heat radiation intensity of 35 kW/m 2 。
Examples 1 to 3, in which the nano-silica was coated with the phenolic resin to modify the flame retardancy of the ABS resin, whereas comparative example 1, in which the nano-silica was not coated with the nitrogen-phosphorous phenolic resin but modified with the nitrogen-phosphorous phenolic resin, showed that the peak heat release rate and the total heat release amount of the ABS resin prepared in the comparative example were higher than those of the modified ABS resins prepared in the examples and the flame retardancy thereof was inferior to those of the modified ABS resins prepared in the examples.
Claims (7)
1. A preparation process of phenolic resin coated nano silicon dioxide modified ABS resin is characterized by comprising the following steps: the preparation process comprises the following steps:
s1: adding maleimide phenolic resin into a solvent, stirring and dissolving, then sequentially adding 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 0.8-1.5% triethylamine which are 60-120% of the weight of the maleimide phenolic resin, and heating to 50-70 ℃ for reaction for 4-12 h to obtain nitrogen-phosphorus phenolic resin;
s2: adding a hydrochloric acid aqueous solution into an ethyl orthosilicate ethanol solution, standing and aging to form sol, then adding nitrogen-phosphorus phenolic resin which accounts for 200-600% of the weight of the ethyl orthosilicate, uniformly stirring, standing and aging for 6-12 h, and finally drying and curing the material at 130-180 ℃ for 4-8 h to obtain phenolic resin coated nano silicon dioxide;
s3: adding ABS resin and phenolic resin coated nano silicon dioxide accounting for 1-8% of the weight of the ABS resin into a high-speed mixer, uniformly mixing, adding the materials into a double-screw extruder, and extruding and granulating to obtain the phenolic resin coated nano silicon dioxide modified ABS resin.
2. The preparation process of the phenolic resin coated nano silica modified ABS resin according to claim 1, characterized in that: the solvent in S1 comprises any one of dimethyl sulfoxide, N-dimethylformamide, toluene, 1, 4-dioxane or tetrahydrofuran.
3. The preparation process of the phenolic resin coated nano silica modified ABS resin according to claim 1, characterized in that: the mass fraction of the ethyl orthosilicate ethanol solution in the S2 is 30-60%.
4. The preparation process of the phenolic resin coated nano silica modified ABS resin according to claim 1, characterized in that: the mass fraction of the hydrochloric acid aqueous solution in the S2 is 0.4-0.8%.
5. The preparation process of the phenolic resin coated nano silica modified ABS resin according to claim 1, characterized in that: the 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]The preparation process of octane comprises the following steps: adding mercaptoacetic acid and 180-260 wt% of 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] relative to the weight of the mercaptoacetic acid into the reaction solvent]Octane, stirring to dissolve, adding p-toluenesulfonic acid as catalyst, heating to 100-130 deg.C, stirring, and reacting for 6-18 h to obtain 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]Octane of the structural formula
。
6. The preparation process of the phenolic resin coated nano silica modified ABS resin according to claim 5, characterized in that: the reaction solvent includes any one of toluene, xylene or N, N-dimethylformamide.
7. The preparation process of the phenolic resin coated nano silica modified ABS resin according to claim 5, characterized in that: the dosage of the p-toluenesulfonic acid is 0.8 to 1.5 percent of the total mass of the 1-oxo-4-mercaptoacetate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and the mercaptoacetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310160562.1A CN115838525B (en) | 2023-02-24 | 2023-02-24 | Preparation process of phenolic resin coated nano silicon dioxide modified ABS resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310160562.1A CN115838525B (en) | 2023-02-24 | 2023-02-24 | Preparation process of phenolic resin coated nano silicon dioxide modified ABS resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115838525A true CN115838525A (en) | 2023-03-24 |
| CN115838525B CN115838525B (en) | 2023-04-28 |
Family
ID=85580154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310160562.1A Active CN115838525B (en) | 2023-02-24 | 2023-02-24 | Preparation process of phenolic resin coated nano silicon dioxide modified ABS resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115838525B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118048034A (en) * | 2024-04-16 | 2024-05-17 | 广州豫顺新材料科技有限公司 | Nano silicon dioxide modified ABS alloy composite material and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH552407A (en) * | 1972-03-07 | 1974-08-15 | Ciba Geigy Ag | Bicyclic phosphorus cpds - used as stabilisers for organic materials |
| US3873498A (en) * | 1971-04-22 | 1975-03-25 | Ciba Geigy Corp | Esters of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo {8 2,2,2{9 {0 octane and p-hydroxyphenylcarboxylic acids as stabilizers for organic polymers |
| JPH06240126A (en) * | 1993-02-16 | 1994-08-30 | Denki Kagaku Kogyo Kk | Flame retardant resin composition |
| JP2003171532A (en) * | 2001-12-04 | 2003-06-20 | Mitsui Chemicals Inc | Flame-retardant resin composition, and prepreg and laminate using the same |
| US20030130385A1 (en) * | 1998-09-02 | 2003-07-10 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition containing styrene polymer as compatabilizer and oxaphospholane compound as flame retardant |
| CN102276907A (en) * | 2011-07-26 | 2011-12-14 | 东华大学 | Synergic antiflaming thermoplastic resin and preparation method thereof |
| CN102617645A (en) * | 2012-02-20 | 2012-08-01 | 华中师范大学 | 1-oxo-4-hydroxymethyl-1-phospholane-2, 6, 7-trioxabicyclo [2, 2, 2] octane derivative with flame retardation effect and preparation of derivative |
| US20160333137A1 (en) * | 2015-05-12 | 2016-11-17 | Guangdong Guangshan New Materials Co., Ltd. | Flame retardant compounds, hardeners and polyphenol-based epoxy resins |
| CN110256802A (en) * | 2019-06-10 | 2019-09-20 | 安徽蓝润自动化仪表有限公司 | A kind of potent heat-proof combustion-resistant plastics power control cabinet case material and preparation method thereof |
| CN114685937A (en) * | 2020-12-25 | 2022-07-01 | 深圳光启尖端技术有限责任公司 | Flame-retardant epoxy resin composite material and preparation method thereof |
| CN115521583A (en) * | 2022-11-24 | 2022-12-27 | 广州豫顺新材料有限公司 | Preparation method of modified silicon dioxide and application of modified silicon dioxide in epoxy resin |
-
2023
- 2023-02-24 CN CN202310160562.1A patent/CN115838525B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3873498A (en) * | 1971-04-22 | 1975-03-25 | Ciba Geigy Corp | Esters of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo {8 2,2,2{9 {0 octane and p-hydroxyphenylcarboxylic acids as stabilizers for organic polymers |
| CH552407A (en) * | 1972-03-07 | 1974-08-15 | Ciba Geigy Ag | Bicyclic phosphorus cpds - used as stabilisers for organic materials |
| JPH06240126A (en) * | 1993-02-16 | 1994-08-30 | Denki Kagaku Kogyo Kk | Flame retardant resin composition |
| US20030130385A1 (en) * | 1998-09-02 | 2003-07-10 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition containing styrene polymer as compatabilizer and oxaphospholane compound as flame retardant |
| JP2003171532A (en) * | 2001-12-04 | 2003-06-20 | Mitsui Chemicals Inc | Flame-retardant resin composition, and prepreg and laminate using the same |
| CN102276907A (en) * | 2011-07-26 | 2011-12-14 | 东华大学 | Synergic antiflaming thermoplastic resin and preparation method thereof |
| CN102617645A (en) * | 2012-02-20 | 2012-08-01 | 华中师范大学 | 1-oxo-4-hydroxymethyl-1-phospholane-2, 6, 7-trioxabicyclo [2, 2, 2] octane derivative with flame retardation effect and preparation of derivative |
| US20160333137A1 (en) * | 2015-05-12 | 2016-11-17 | Guangdong Guangshan New Materials Co., Ltd. | Flame retardant compounds, hardeners and polyphenol-based epoxy resins |
| CN110256802A (en) * | 2019-06-10 | 2019-09-20 | 安徽蓝润自动化仪表有限公司 | A kind of potent heat-proof combustion-resistant plastics power control cabinet case material and preparation method thereof |
| CN114685937A (en) * | 2020-12-25 | 2022-07-01 | 深圳光启尖端技术有限责任公司 | Flame-retardant epoxy resin composite material and preparation method thereof |
| CN115521583A (en) * | 2022-11-24 | 2022-12-27 | 广州豫顺新材料有限公司 | Preparation method of modified silicon dioxide and application of modified silicon dioxide in epoxy resin |
Non-Patent Citations (1)
| Title |
|---|
| 魏晓莹等: "马来酰亚胺改性酚醛树脂研究进展" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118048034A (en) * | 2024-04-16 | 2024-05-17 | 广州豫顺新材料科技有限公司 | Nano silicon dioxide modified ABS alloy composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115838525B (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021023226A1 (en) | Nitrogen-rich group functionalized graphene, preparation method, and application | |
| CN109912650B (en) | Phosphorus-nitrogen series bio-based flame retardant and synthetic method and application thereof | |
| CN108659228B (en) | Modified lignin flame retardant and preparation method thereof | |
| CN115838525B (en) | Preparation process of phenolic resin coated nano silicon dioxide modified ABS resin | |
| CN110423353B (en) | Polysiloxane, maleopimaric acid modified polysiloxane and maleopimaric acid modified polysiloxane flame-retardant polyurethane foam | |
| CN110591157B (en) | Preparation method and application of polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses | |
| CN116515119B (en) | All-bio-based aryl diamine flame retardant, and preparation method and application thereof | |
| CN109337161A (en) | A kind of graphene flame-retardant master batch and preparation method improving dispersion by core-shell structure | |
| EP2883896A1 (en) | Multifunctional epoxy resin with enhanced flame resistance | |
| CN112341495B (en) | Rosinyl silicon-phosphorus synergistic flame retardant, preparation method thereof and polyurethane foam prepared from rosinyl silicon-phosphorus synergistic flame retardant | |
| CN110483577A (en) | A kind of P, N, Si ternary hybrid fire retardant and preparation method | |
| Wang et al. | Recycling of waste melamine formaldehyde foam as flame-retardant filler for polyurethane foam | |
| CN102796283B (en) | Compound intumescent flame retardant and preparation method thereof | |
| CN110951029A (en) | Organic silicon modified vegetable oil-based polyol and preparation method and application thereof | |
| CN112175198A (en) | Novel reactive lignin-based flame retardant and preparation method and application thereof | |
| Feng et al. | POSS‐modified ammonium polyphosphate for improving flame retardant of epoxy resins | |
| CN112194822B (en) | Phosphorus-containing flame retardant, preparation method and modified epoxy resin | |
| Niu et al. | High biomass content, anti-flammable and degradable epoxy thermosets by curing a tyramine-derived epoxy monomer with a furan-derived diamine for non-destructively recyclable carbon fiber composite application | |
| CN112080038A (en) | Modified phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN115850708B (en) | Preparation method and application of N-P-Si-containing caged polysilsesquioxane flame retardant | |
| CN115160523B (en) | Low-temperature-brittleness-resistant modified melamine resin and preparation method thereof | |
| Zhang et al. | Construction of thermoplastic cellulose esters matrix composites with enhanced flame retardancy and mechanical properties by embedding hydrophobic magnesium hydroxide | |
| CN113801283B (en) | High heat-resistant Gao Cantan benzoxazine resin and preparation method thereof | |
| CN116023761A (en) | Recyclable flame-retardant carbon fiber/epoxy resin composite material and preparation method thereof | |
| CN115353632A (en) | Polyhydroxy cyclic polymer/polysiloxane double-modified phenolic resin and preparation method and application 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |