CN115838525B - Preparation process of phenolic resin coated nano silicon dioxide modified ABS resin - Google Patents
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Abstract
The invention relates to the technical field of silica flame retardants, and discloses a preparation process of a phenolic resin coated nano silica modified ABS resin, wherein 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and alkenyl of maleimide phenolic resin are subjected to addition reaction to obtain nitrogen-phosphating phenolic resin, nano silica is generated in a nitrogen-phosphating phenolic resin matrix through a sol-gel method, the phenolic resin coated nano silica is obtained 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 silica is distributed in the carbon layer to form stable support, the stability and the barrier property of the carbon layer are improved, the effects of better heat insulation, oxygen isolation and smoke suppression are achieved, the heat release rate and the total heat release amount of the ABS resin are reduced, and excellent combustion char formation and flame retardant performance are shown.
Description
Technical Field
The invention relates to the technical field of silica flame retardants, in particular to a preparation process of a phenolic resin coated nano silica modified ABS resin.
Background
The nano silicon dioxide has small particle size, large specific surface area and high surface performance, has a plurality of unique properties, can be used as a toughening agent, a flame retardant, a reinforcing agent and the like, can be 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 number 201310189706.2, a preparation method of SiO2/ABS composite material, discloses that SiO2 microspheres in the prepared SiO2/ABS composite material have good dispersing effect, can achieve the purpose of reinforcing, can play a role of toughening, and can enhance the mechanical property of the ABS composite material.
The acrylonitrile-butadiene-styrene copolymer (ABS resin) is 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, inflammability and the like, the development of a novel flame retardant is a research hot spot in the ABS resin, and as in the literature on the study of the flame retardant mechanism of the ABS resin on the char formation of TPP/TPPFR, the compounding of thermoplastic phenolic resin and triphenyl phosphate as a halogen-free flame retardant is reported to be added into the ABS resin, so that the char formation and flame retardant performance of the ABS are improved. The invention aims to prepare novel phenolic resin coated nano silicon dioxide serving as a flame retardant, and enhance the char formation and flame retardance of ABS resin.
Disclosure of Invention
(one) solving the technical problems
The invention provides a preparation process of a phenolic resin coated nano silicon dioxide modified ABS resin with excellent flame retardance.
(II) technical scheme
The preparation process of the phenolic resin coated nano silicon dioxide modified ABS resin comprises the following steps:
s1: adding maleimide phenolic resin into solvent, stirring and dissolving, then adding 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and triethylamine which are 60-120% of the weight of the maleimide phenolic resin into the solvent in sequence, heating to 50-70 ℃ to react 4-12 h, adding deionized water to precipitate after the reaction, filtering the solvent, and washing the solvent with deionized water and acetone in sequence to obtain the nitrogen-phosphorus phenolic resin.
S2: adding aqueous hydrochloric acid into ethyl orthosilicate ethanol solution, standing and aging to form sol, then adding 200-600% of nitrogen-phosphorus phenolic resin by 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 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 for uniform mixing, and adding the materials into a double-screw extruder for extrusion granulation 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, and tetrahydrofuran.
Preferably, the mass fraction of the ethanol solution of the ethyl orthosilicate 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-thioglycolate ester-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]The preparation process of the octane comprises the following steps: adding thioglycollic acid and 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] in an amount of 180-260% by weight of the thioglycollic acid to the reaction solvent]Octane is stirred and dissolved, p-toluenesulfonic acid catalyst is added, the temperature is raised to 100-130 ℃ and stirred for reaction 6-18 h, solvent is removed by rotary evaporation after the reaction, the crude product is recrystallized in ethyl acetate after petroleum ether is washed, and 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2.2 is obtained]Octane of the structural formula
。
Preferably, the reaction solvent includes any one of toluene, xylene or N, N-dimethylformamide.
Preferably, the dosage of the p-toluenesulfonic acid is 0.8-1.5% of the total mass of 1-oxo-4-thioglycolate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and thioglycollic acid.
(III) beneficial technical effects
Thioglycollic acid and 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Esterification reaction of octane to obtain novel 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]]Performing addition reaction on the octane and alkenyl of the maleimide phenolic resin to obtain nitrogen-phosphide phenolic resin, so that a nitrogen-containing heterocycle and phosphate structure are introduced into the side chain of the phenolic resin; 1492 and cm in infrared spectrum of nitrogen-phosphorus phenolic resin NP-PF -1 Is characterized by the characteristic absorption peak of benzene ring skeleton in phenolic resin, 1459 cm -1 The peak of the maleimide ring C-O-C is 1326 cm -1 A stretching vibration peak of P=O bond, 1117 cm -1 The stretching vibration peak of the P-O bond proves that 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]The octane reacts with the maleimide phenolic resin,obtaining the nitrogen-phosphorus phenolic resin; phenolic resin coated nano silicon dioxide NP-PF-SiO 2 1009, cm in the infrared spectrum of (a) -1 The position is the stretching vibration peak of Si-O in silicon dioxide, 1509cm -1 Is characterized by the characteristic absorption peak of benzene ring skeleton in phenolic resin, 1480 and 1480 cm -1 Is the absorption peak of maleimide ring C-O-C, 1319 cm -1 A stretching vibration peak of P=O bond, 1113 cm -1 The stretching vibration peak of the P-O bond is shown.
Further generating nano silicon dioxide in the nitrogen phosphating 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 the nano silicon dioxide is coated by the phenolic resin, the nano silicon dioxide has good compatibility with the ABS resin and excellent dispersibility, is favorable for reducing agglomeration of silicon dioxide nano particles, the nitrogen-phosphorus phenolic resin forms an intumescent flame-retardant system, an intumescent carbon layer is formed on an 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 effects of heat insulation, oxygen isolation and smoke suppression are achieved, the heat release rate and total heat release amount of the ABS resin are reduced, and excellent combustion char formation and flame retardance are shown.
Drawings
FIG. 1 is a graph of the heat release rate of a phenolic resin coated nano silica modified ABS resin.
FIG. 2 is a graph of total heat release of phenolic resin coated nano silica modified ABS resin.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 1-oxo-4-thioglycolate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
FIG. 4 is a schematic illustration of a nitrogen-phosphated phenolic resin NP-PF and a phenolic resin coated nanosilicon NP-PF-SiO 2 And (5) infrared spectrogram.
Detailed Description
Nano silicon dioxide: model: XH-SiO2-30; average particle diameter 30 nm; the purity is more than 99.9 percent.
Phenolic resin: the content of the brand PR-4582L is not less than 98.0 percent.
ABS resin: the brand PA-756, injection grade, content is not less than 99.0%.
The preparation process of maleimide phenolic resins is described in journal Journal of Polymer Science, part A Polymer Chemistry, vol. 38, 641-652 (2000), document Phenolic resins bearing maleimide groups: synthesis and characterization, DOI No.: 10.1002/(SICI) 1099-0518 (20000201) 38:3< 641:AID-POLA 28>3.0.CO;2-Z.
Mixing 80 g phenol, 20 g 4-maleimidophenol and 5 g oxalic acid uniformly, dropwise adding 63 mL volume percent formaldehyde aqueous solution with the mass fraction of 34% at 75 ℃, reacting 10 h, adding acetone for dilution after the reaction, adding methanol aqueous solution for precipitation, filtering the solvent, washing with acetone and drying to obtain maleimide phenolic resin (PMF resin).
Example 1
(1) 1.5 g thioglycollic acid, 2.7 g 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2.2 ] are added to 60 mL N, N-dimethylformamide solvent]Octane, stirring to dissolve, adding 42mg of catalyst p-toluenesulfonic acid, heating to 120 ℃ to stir for reaction 6 h, removing solvent by rotary evaporation after the reaction, washing the crude product by petroleum ether, and recrystallizing the crude product in ethyl acetate to obtain 1-oxo-4-thioglycolate-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2.2 ]]Octane, molecular formula: c (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 toluene solvent, stirring and dissolving, then sequentially adding 4 g 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 50 mg triethylamine, heating to 70 ℃ to react 4 h, adding deionized water to precipitate after the reaction, filtering the solvent, and washing with deionized water and acetone in sequence to obtain the nitrogen-phosphorus phenolic resin NP-PF.
(3) Adding 10 mL of 0.4% hydrochloric acid aqueous solution into 10 mL mass percent of ethanol solution of 30% ethyl orthosilicate, standing and aging to form sol, then adding 6 g of nitrogen-phosphorus phenolic resin, stirring uniformly, standing and aging for 10h, finally drying and curing the material at 130 ℃ to obtain the phenolic resin coated nano silicon dioxide NP-PF-SiO 8 h 2 。
(4) Adding the ABS resin of 2 kg and the phenolic resin coated nano silica of 20 g into a high-speed mixer for uniform mixing, adding the materials into a double-screw extruder for extrusion granulation, and obtaining the phenolic resin coated nano silica modified ABS resin at the temperature of 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ in sequence in the 1-6 region of the extruder.
Example 2
(1) 1.5 g thioglycollic acid and 3.9 g 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane are added into 100 mL toluene solvent, stirred and dissolved, 81 mg catalyst p-toluenesulfonic acid is added, the temperature is raised to 130 ℃ and stirred for reaction, 12 h is obtained after the reaction, the solvent is removed by rotary evaporation, petroleum ether is washed, and the crude product is recrystallized from ethyl acetate to obtain 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
(2) Adding 5 g maleimide phenolic resin into 200 mL N, N-dimethylformamide solvent, stirring and dissolving, then sequentially adding 3 g 1-oxo-4-thioglycolate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 40 mg triethylamine, heating to 60 ℃ to react 12 h, adding deionized water to precipitate, 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 mass percent of 50% ethyl orthosilicate ethanol solution, standing and ageing to form sol, then adding 22 g of nitrogen-phosphorus phenolic resin, uniformly stirring, standing and ageing 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 the ABS resin of 2 kg and the phenolic resin coated nano silica of 100 g into a high-speed mixer for uniform mixing, adding the materials into a double-screw extruder for extrusion granulation, and obtaining the phenolic resin coated nano silica modified ABS resin at the temperature of 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ in sequence in the 1-6 region of the extruder.
Example 3
(1) 1.5 g thioglycollic acid and 3 g 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane are added into 80 mL dimethylbenzene solvent, stirred and dissolved, 60 mg catalyst p-toluenesulfonic acid is added, the temperature is raised to 120 ℃ and stirred for reaction, 18 h is obtained, the solvent is removed by rotary evaporation after the reaction, petroleum ether is washed, and the crude product is recrystallized from ethyl acetate to obtain 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
(2) Adding 5 g maleimide phenolic resin into 150 mL dimethyl sulfoxide solvent, stirring and dissolving, then sequentially adding 6 g 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 75 mg triethylamine, heating to 50 ℃ to react 8 h, adding deionized water to precipitate after the reaction, filtering the solvent, and washing with deionized water and acetone in sequence to obtain the nitrogen-phosphated phenolic resin.
(3) Adding 10 mL of 0.8% hydrochloric acid aqueous solution into 10 mL of 60% ethyl orthosilicate ethanol solution, standing and ageing to form sol, then adding 36 g of nitrogen-phosphorus phenolic resin, uniformly stirring, standing and ageing 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 the ABS resin of 2 kg and the phenolic resin coated nano silica of 160 g into a high-speed mixer for uniform mixing, adding the materials into a double-screw extruder for extrusion granulation, and obtaining the phenolic resin coated nano silica modified ABS resin at the temperature of 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ in sequence in the 1-6 region of the extruder.
Comparative example 1
(1) 1.5 g thioglycollic acid and 3.9 g 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane are added into 80 mL dimethylbenzene solvent, stirring is carried out to dissolve, 81 mg catalyst p-toluenesulfonic acid is added, the temperature is raised to 130 ℃, stirring is carried out to react 6 h, the solvent is removed after the reaction by rotary evaporation, petroleum ether is washed, and the crude product is recrystallized from ethyl acetate to obtain 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.
(2) Adding 5 g of maleimide phenolic resin into 100 mL tetrahydrofuran solvent, stirring and dissolving, then sequentially adding 6 g of 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and 75 mg of triethylamine, heating to 70 ℃ to react 4 h, adding deionized water to precipitate after the reaction, filtering the solvent, and washing with deionized water and acetone in sequence to obtain the nitrogen-phosphated phenolic resin.
(3) Adding the ABS resin of 2 kg and the nitrogen-phosphorus phenolic resin of 20 g into a high-speed mixer for uniform mixing, adding the materials into a double-screw extruder for extrusion granulation, and obtaining the phenolic resin modified ABS resin by sequentially heating the materials in the 1-6 region of the extruder to 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃.
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 performing combustion performance test in a cone calorimeter, wherein the heat radiation intensity is 35 KW/m 2 。
Examples 1-3 flame-retardant modified ABS resins with phenolic resin coated with nanosilica, whereas comparative example 1 without the nitrided phenolic resin coated with nanosilica, only modified ABS resins with nitrided phenolic resin, and the ABS resins prepared in comparative examples were higher in peak heat release rate and total heat release than the modified ABS resins prepared in examples, and had inferior flame-retardant properties to the modified ABS resins prepared in examples, through a combustion performance test.
Claims (7)
1. A preparation process of phenolic resin coated nano silicon dioxide modified ABS resin is characterized in that: the preparation process comprises the following steps:
s1: taking phenol, 4-maleimido phenol, oxalic acid and formaldehyde aqueous solution as reaction raw materials to react, so as to prepare maleimide phenolic resin; adding maleimide phenolic resin into a solvent, stirring and dissolving, then sequentially adding 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and triethylamine accounting for 0.8-1.5 percent of the weight of the maleimide phenolic resin, heating to 50-70 ℃ to react for 4-12 h, and obtaining nitrogen-phosphating phenolic resin;
s2: adding an aqueous solution of hydrochloric acid into an ethanol solution of ethyl orthosilicate, standing and aging to form sol, then adding 200-600% of nitrogen-phosphorus phenolic resin by 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, and then adding the materials into a double-screw extruder for extrusion granulation to obtain the phenolic resin coated nano silicon dioxide modified ABS resin.
2. The process for preparing the phenolic resin coated nano silica modified ABS resin according to claim 1, wherein the process is characterized in that: the solvent in S1 comprises any one of dimethyl sulfoxide, N-dimethylformamide, toluene, 1, 4-dioxane or tetrahydrofuran.
3. The process for preparing the phenolic resin coated nano silica modified ABS resin according to claim 1, wherein the process is characterized in that: the mass fraction of the ethanol solution of the ethyl orthosilicate in the S2 is 30-60%.
4. The process for preparing the phenolic resin coated nano silica modified ABS resin according to claim 1, wherein the process is characterized in that: the mass fraction of the hydrochloric acid aqueous solution in the S2 is 0.4-0.8%.
5. The process for preparing the phenolic resin coated nano silica modified ABS resin according to claim 1, wherein the process is characterized in that: the 1-oxo-4-thioglycolate ester-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]The preparation process of the octane comprises the following steps: adding thioglycollic acid and 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] in an amount of 180-260% by weight of the thioglycollic acid to the reaction solvent]Octane, stirring to dissolve and adding catalyst p-tolueneSulfonic acid is heated to 100-130 ℃ and stirred for reaction of 6-18 h to obtain 1-oxo-4-thioglycollate-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2.2]Octane of the structural formula
。
6. The process for preparing the phenolic resin coated nano silica modified ABS resin according to claim 5, wherein the process is characterized in that: the reaction solvent comprises any one of toluene, xylene or N, N-dimethylformamide.
7. The process for preparing the phenolic resin coated nano silica modified ABS resin according to claim 5, wherein the process is characterized in that: the dosage of the p-toluenesulfonic acid is 0.8-1.5% of the total mass of the 1-oxo-4-thioglycolate-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and the thioglycollic acid.
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| CH552407A (en) * | 1972-03-07 | 1974-08-15 | Ciba Geigy Ag | Bicyclic phosphorus cpds - used as stabilisers for organic materials |
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| JP3278079B2 (en) * | 1993-02-16 | 2002-04-30 | 電気化学工業株式会社 | Flame retardant resin composition |
| US6838497B2 (en) * | 1998-09-02 | 2005-01-04 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition containing styrene polymer as compatabilizer and oxaphospholane compound as flame retardant |
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