CN114349968B - POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof - Google Patents
POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114349968B CN114349968B CN202210050016.8A CN202210050016A CN114349968B CN 114349968 B CN114349968 B CN 114349968B CN 202210050016 A CN202210050016 A CN 202210050016A CN 114349968 B CN114349968 B CN 114349968B
- Authority
- CN
- China
- Prior art keywords
- cyclotriphosphazene
- hexa
- flame retardant
- preparation
- poss
- 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.)
- Active
Links
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a POSS modified phosphazene flame retardant, and a preparation method and application thereof. The structural formula is as follows:
R 1 ‑R 6 same or different, selected from NH 2 Or
Wherein the content of the first and second substances,
Description
Technical Field
The invention relates to a POSS modified phosphazene flame retardant, a preparation method thereof, application of the POSS modified phosphazene flame retardant serving as a flame retardant in a polycarbonate flame-retardant composite material, and a preparation method of the polycarbonate flame-retardant composite material.
Background
With the wide application of polymer materials in the fields with higher fireproof safety requirements, such as vehicles, building materials, electronic appliances, home decoration and the like, the requirement on the flame retardant property of the polymer materials is continuously improved. The flame retardant is an auxiliary agent capable of improving the flame retardant property of the material, so that the material is not easy to ignite, the flame propagation is inhibited, small fire is prevented from developing into catastrophic big fire, the fire hazard is reduced, and various high polymer products are safely used. The flame retardants used in polymer materials are generally classified into halogen-containing flame retardants and halogen-free flame retardants. With the increasing of the environmental protection requirement, the application range and the dosage of the halogen-free flame retardant are continuously expanded, and common halogen-free flame retardants include phosphorus flame retardants, aluminum magnesium flame retardants, nitrogen flame retardants, silicon flame retardants and a small amount of sulfonate flame retardants, wherein the phosphorus-nitrogen-containing flame retardants have better flame retardant effect and are widely applied.
The phosphazene compound is an organic-inorganic compound with a skeleton formed by alternately arranging phosphorus and nitrogen single bonds and side groups formed by organic groups. The phosphazene has high content of phosphorus and nitrogen elements in molecules, so that the flame retardant has excellent flame retardant property. In the combustion process, the phosphazene can be used as a char forming promoter to play a role of coacervate phase flame retardance, and can also be decomposed to generate PO to play a role of gas phase flame retardance. In recent years, cyclotriphosphazene flame retardants are more and more widely used in polymeric flame retardant materials. The cyclotriphosphazene compound mostly takes hexachlorocyclotriphosphazene as an initial reactant, and six chlorine atoms on the hexachlorocyclotriphosphazene are easily substituted by different functional groups, so that the molecular design of the cyclotriphosphazene can be diversified, and the cyclotriphosphazene derivatives containing different groups and different properties can be obtained, thereby being suitable for various polymer matrixes. Although the phosphazene flame retardant has excellent flame retardant effect, the addition of the phosphazene flame retardant can reduce the heat distortion temperature of the material, and limits the application of the phosphazene flame retardant in the field of high temperature resistance.
The cage-shaped oligomeric silsesquioxane (POSS) is a novel organic-inorganic hybrid material with a three-dimensional structure, has the advantages of high strength, high rigidity, good thermal stability and the like of inorganic materials, and has the characteristics of light weight, easiness in processing and the like of organic materials. In recent years, POSS has been added to polymers as flame retardants or synergistic flame retardants for use, exhibiting good flame retardant properties. For example: although the addition of POSS can improve the flame retardant performance of the polymer, the flame retardant efficiency of the polymer is low, and the improvement range of the flame retardant effect of the polymer is limited in China patent application CN 201910234531.
Therefore, the phosphazene and POSS can be combined to prepare the novel flame retardant, so that a good flame retardant synergistic effect can be generated, and the heat resistance of the flame retardant composite material can be improved.
Disclosure of Invention
The invention aims to overcome the defects that the phosphazene flame retardant reduces the heat resistance of the flame-retardant composite material and the flame retardant efficiency of the POSS flame retardant is low, makes up for the defects of strong points and weak points, and provides a novel POSS modified phosphazene flame retardant with high flame retardant efficiency and good heat resistance.
Another aspect of the present invention is to provide a preparation method of POSS modified phosphazene flame retardant, which has the following advantages: the synthesis route is simple and efficient, the target product is prepared by the nucleophilic substitution reaction, the reduction reaction and the ring-opening reaction in sequence, the cost is low, special equipment and harsh conditions are not needed, the large-scale production is easy to realize, and the method has extremely high practical value.
The invention also provides a polycarbonate flame-retardant composite material and a preparation method thereof, and the flame-retardant property, the heat resistance, the mechanical property and the like of the composite material are obviously improved, so that the polycarbonate flame-retardant composite material has a wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a POSS modified phosphazene flame retardant comprising the structure:
R 1 -R 6 same or different, selected from NH 2 Or
Wherein the content of the first and second substances,
the preparation method of the POSS modified phosphazene flame retardant comprises the following steps: firstly, hexachlorocyclotriphosphazene and p-nitrophenol undergo nucleophilic substitution reaction to generate hexa (4-nitrophenoxy) -cyclotriphosphazene, and then hexa (4-nitrophenoxy) -cyclotriphosphazene undergoes reduction reaction under the action of palladium carbon as a catalyst and hydrazine hydrate to generate hexa (4-aminophenoxy) -cyclotriphosphazene; phenyl triethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane are subjected to hydrolysis reaction to generate epoxy oligomeric silsesquioxane; and then carrying out ring-opening reaction on the amino group of the hexa (4-aminophenoxy) -cyclotriphosphazene and the epoxy group of the epoxy group oligomeric silsesquioxane to obtain the target product POSS modified phosphazene flame retardant.
As a preferred scheme, the method for modifying the phosphazene flame retardant by the POSS comprises the following steps:
(1) Synthesis and preparation of hexa (4-nitrophenoxy) -cyclotriphosphazene: dissolving hexachlorocyclotriphosphazene, p-nitrobenzene and potassium carbonate/triethylamine in acetone or benzene at the concentration of 10-35wt%, controlling the temperature at 50-60 ℃ under the catalytic action of sodium iodide or tetrabutylammonium iodide accounting for 1-2% of the total mass of hexachlorocyclotriphosphazene and p-nitrobenzene, carrying out reflux reaction for 2-3 hours, and repeatedly filtering, washing and drying to obtain a hexa (4-nitrophenoxy) -cyclotriphosphazene solid.
In the step, K2CO 3/triethylamine is used as an acid-binding agent. Hydrogen halide is generated in the nucleophilic substitution reaction process of hexachlorocyclotriphosphazene and p-nitrobenzene, the reaction progress is influenced by the excessively high content of the hydrogen halide, and the acid-binding agent can react with the hydrogen halide generated in the reaction to maintain the normal operation of the nucleophilic substitution reaction.
(2) Preparation of hexa (4-aminophenoxy) -cyclotriphosphazene: dissolving hexa (4-nitrophenoxy) -cyclotriphosphazene and palladium carbon as a catalyst in isopropanol, chloroform or DMF at the concentration of 5-25wt%, heating the solution to 80-120 ℃, slowly adding a hydrazine hydrate solution, and carrying out reflux reaction for 10-12 hours under the protection of nitrogen. Then pouring the solution into excessive poor solvent deionized water to obtain flocculent precipitate, repeatedly washing the flocculent precipitate, and freeze-drying at-60-30 ℃ under 80Pa vacuum to obtain hexa (4-aminophenoxy) -cyclotriphosphazene solid.
In the step, hexa (4-nitrophenoxy) -cyclotriphosphazene is subjected to reduction reaction under the action of palladium carbon and hydrazine hydrate serving as catalysts to generate hexa (4-aminophenoxy) -cyclotriphosphazene.
(3) Adding ethanol and hydrochloric acid into a three-neck flask according to the volume ratio of 1; and then the solvent is removed through reduced pressure distillation, and light yellow viscous liquid, namely the target product epoxy group oligomeric silsesquioxane is obtained after repeated washing and filtration.
(4) Preparation of POSS modified phosphazene flame retardant: respectively dissolving hexa (4-aminophenoxy) -cyclotriphosphazene and epoxy oligomeric silsesquioxane in 5-25wt% of DMF, petroleum ether or chloroform; then slowly adding the solution of epoxy group oligomeric silsesquioxane into the solution of hexa (4-aminophenoxy) -cyclotriphosphazene, keeping magnetic stirring at 90-120 ℃, and carrying out reflux reaction for 10-12 hours under the nitrogen protection environment. And finally, repeatedly filtering and washing, and freeze-drying at-60-30 ℃ under 80Pa vacuum to obtain the POSS modified phosphazene flame retardant.
In the step, the amino group of the hexa (4-aminophenoxy) -cyclotriphosphazene and the epoxy group of the epoxy group oligomeric silsesquioxane are subjected to a ring-opening reaction to obtain the target product POSS modified phosphazene flame retardant.
Preferably, in step (1), the molar ratio of hexachlorocyclotriphosphazene: p-nitrobenzene: acid-binding agent =1 (6-8): (2-4), wherein the dosage of the sodium iodide or tetrabutylammonium iodide catalyst is 1% -2% of the total mass of hexachlorocyclotriphosphazene and p-nitrobenzene. .
Preferably, in step (2), the molar ratio of hexa (4-nitrophenoxy) -cyclotriphosphazene: hydrazine hydrate: palladium-carbon = (8-10): 14-18): 1.
Preferably, in step (3), the molar ratio of phenyltriethoxysilane: β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane = 6-10: 1.
preferably, in step (4), the molar ratio of hexa (4-aminophenoxy) -cyclotriphosphazene: epoxy oligomeric silsesquioxane = 1.
A polycarbonate flame retardant composite comprising at least: 85-99 parts by mass of a polycarbonate matrix, 0.1-10 parts by mass of the POSS modified phosphazene flame retardant of the invention, and preferably, 0.3-0.5 part by mass of anti-dripping agent polytetrafluoroethylene, and 0.5-1.5 parts by mass of a toughening agent methacrylic acid-butadiene-styrene terpolymer methyl methacrylate-acrylate-organosilicon terpolymer or ethylene-acrylic acid copolymer.
The preparation method of the polycarbonate flame-retardant composite material comprises the following steps: and premixing the POSS modified phosphazene flame retardant, the PC, the preferable anti-dripping agent and the toughening agent uniformly through a high-speed mixer, and then adding the mixture into a double-screw extruder for melt extrusion and granulation to obtain a sample, wherein preferably, the melt temperature is 280-310 ℃, and the rotating speed of the extruder is 300-900rpm.
Compared with the prior art, the invention has the following remarkable beneficial effects:
(1) The nucleophilic substitution, the reduction reaction and the ring-opening reaction are sequentially utilized to graft the POSS to the phosphazene flame retardant, and the preparation method is simple and efficient, is suitable for large-scale production and has high practical value.
(2) The prepared POSS graft modification phosphazene flame retardant integrates three elements of phosphorus, nitrogen and silicon, and has excellent synergistic flame retardant effect, wherein the phosphorus element can promote the generation of a carbon layer, and the silicon can improve the thermal stability of the carbon layer; in addition, the rigid cage structure of POSS can improve the heat resistance and mechanical property of the flame-retardant composite material.
Detailed Description
The technical scheme of the invention is further fully explained in detail by combining the embodiment, the application example and the comparative example.
Example 1
A preparation method of a POSS modified phosphazene flame retardant comprises the following steps;
(1) Synthesis and preparation of hexa (4-nitrophenoxy) -cyclotriphosphazene: 35g of hexachlorocyclotriphosphazene (0.1 mol), 102g of p-nitrobenzene (0.6 mol) and 28g of potassium carbonate (0.2 mol) are dissolved in 600mL of acetone, 1.4g of a catalyst sodium iodide is added, reflux reaction is carried out for 2.5 hours in a water bath at 60 ℃ with stirring, and a hexa (4-nitrophenoxy) -cyclotriphosphazene solid is obtained after repeated filtration, washing and drying.
(2) Preparation of hexa (4-aminophenoxy) -cyclotriphosphazene: 19g of hexa (4-nitrophenoxy) -cyclotriphosphazene (0.02 mol) prepared above was dissolved in 1L of isopropanol, 2.0g of palladium on carbon (0.025 mol) as a catalyst was added thereto, and after warming to 80 ℃, 30g of hydrazine hydrate solution was slowly added thereto, and the reaction was carried out under reflux for 10 hours under nitrogen protection. After the reaction is finished. Pouring the solution into a poor solvent deionized water to obtain flocculent precipitate, repeatedly washing the flocculent precipitate, and freeze-drying at-40 ℃ under 80Pa to obtain a hexa (4-aminophenoxy) -cyclotriphosphazene solid.
(3) Preparing epoxy group oligomeric silsesquioxane, namely adding 50mL of ethanol and 150mL of hydrochloric acid into a three-neck flask, stirring, heating to 45 ℃, adding a mixed solution of 45g of phenyltriethoxysilane (0.3 mol) and 12.5g of beta-3, 4-epoxy cyclohexyl ethyl trimethoxysilane (0.05 mol) into the flask, keeping stirring, and carrying out hydrolysis reaction for 24 hours; and then carrying out reduced pressure distillation at 85 ℃ and 0.1MPa to remove the solvent, and repeatedly washing and filtering to obtain light yellow viscous liquid, namely the target product epoxy group oligomeric silsesquioxane.
(4) Preparing a POSS modified phosphazene flame retardant: 7.83g of hexa (4-aminophenoxy) -cyclotriphosphazene (0.01 mol) and 64.8g of epoxy oligomeric silsesquioxane (0.06 mol) were dissolved in 100ml of DMF, respectively; then the dissolved DMF solution of the epoxy group oligomeric silsesquioxane is slowly added into the DMF solution of hexa (4-aminophenoxy) -cyclotriphosphazene, magnetic stirring is kept at 120 ℃, and the reaction is refluxed for 12 hours under the nitrogen protection environment. And finally, repeatedly filtering and washing, and freeze-drying at-40 ℃ under the vacuum of 80Pa to obtain the POSS modified phosphazene flame retardant (POSS-PN-1). Through infrared analysis of the target product in a reflection mode by the aid of the Nicolet iS10, the target product iS found to have 1102cm on a spectrogram -1 Asymmetric stretching vibration peak of Si-O-Si of (8), 887 and 1205cm -1 The presence of a phosphazene ring structure, 1153cm -1 The characteristic peak of hydroxyl group is appeared, 910cm is not appeared -1 The characteristic peak of the nearby epoxy group shows that the target product is indeed formed by the reaction of POSS and phosphazene.
Example 2
A preparation method of a POSS modified phosphazene flame retardant comprises the following steps;
(1) Synthesis and preparation of hexa (4-nitrophenoxy) -cyclotriphosphazene: 35g of hexachlorocyclotriphosphazene (0.1 mol), 135g of p-nitrobenzene (0.8 mol) and 42g of potassium carbonate (0.3 mol) are dissolved in 600mL of acetone, 2.5g of catalyst sodium iodide is added, reflux reaction is carried out for 2.5 hours in a water bath at 60 ℃ under stirring, and after repeated filtration, washing and drying, hexa (4-nitrophenoxy) -cyclotriphosphazene solid is obtained.
(2) Preparation of hexa (4-aminophenoxy) -cyclotriphosphazene: 29g of hexa (4-nitrophenoxy) -cyclotriphosphazene (0.03 mol) prepared above was dissolved in 1L of isopropanol, 3.5g of palladium on carbon as a catalyst was added thereto, and after warming to 80 ℃, 60g of hydrazine hydrate solution was slowly added thereto, and the reaction was refluxed for 10 hours under the protection of nitrogen. After the reaction is finished. And pouring the solution into a poor solvent deionized water to obtain flocculent precipitate, repeatedly washing the flocculent precipitate, and freeze-drying to obtain a hexa (4-aminophenoxy) -cyclotriphosphazene solid.
(3) Adding 75mL of ethanol and 200mL of hydrochloric acid into a three-neck flask, stirring, heating to 45 ℃, adding a mixed solution of 120g of phenyltriethoxysilane (0.8 mol) and 24.6g of beta-3, 4-epoxycyclohexylethyltrimethoxysilane (0.1 mol) into the flask, keeping stirring, and carrying out hydrolysis reaction for 24 hours; and then distilling under reduced pressure at 85 ℃ and 0.1MPa to remove the solvent, and repeatedly washing and filtering to obtain light yellow viscous liquid, namely the target product epoxy group oligomeric silsesquioxane.
(4) Preparing a POSS modified phosphazene flame retardant: 7.83g of hexa (4-aminophenoxy) -cyclotriphosphazene (0.01) and 86.4g of epoxy oligomeric silsesquioxane (0.08 mol) were dissolved in 150ml of DMF, respectively; the DMF solution of epoxy oligomeric silsesquioxane was then added slowly to the DMF solution of hexa (4-aminophenoxy) -cyclotriphosphazene, magnetically stirred at 120 ℃ and refluxed under nitrogen for 12 hours. And finally, repeatedly filtering and washing, and freeze-drying at-40 ℃ under 80Pa vacuum to obtain the POSS modified phosphazene flame retardant (POSS-PN-2). Subjecting the target product to infraredAnalyzing, and finding that 1104cm exists on the spectrogram -1 Asymmetric stretching vibration peak of Si-O-Si of (889) and 1203cm -1 The presence of a phosphazene ring structure at 1150cm is indicated by a characteristic peak of -1 The characteristic peak of hydroxyl group is appeared, 910cm is not appeared -1 The characteristic peak of the nearby epoxy group shows that the target product is indeed formed by the reaction of POSS and phosphazene.
Example 3
A preparation method of a POSS modified phosphazene flame retardant comprises the following steps;
(1) Synthesis and preparation of hexa (4-nitrophenoxy) -cyclotriphosphazene: 35g of hexachlorocyclotriphosphazene (0.1 mol), 135g of p-nitrobenzene (0.8 mol) and 56g of potassium carbonate (0.4 mol) are dissolved in 900mL of acetone, 3.3g of catalyst sodium iodide is added, reflux reaction is carried out for 2.5 hours in a water bath at 60 ℃ under stirring, and after repeated filtration, washing and drying, hexa (4-nitrophenoxy) -cyclotriphosphazene solid is obtained.
(2) Preparation of hexa (4-aminophenoxy) -cyclotriphosphazene: 48g of hexa (4-nitrophenoxy) -cyclotriphosphazene (0.05 mol) prepared above was dissolved in 1L of isopropanol, 6g of palladium on carbon (0.09 mol) as a catalyst was added thereto, and after warming to 80 ℃, 105g of hydrazine hydrate solution was slowly added thereto, and the reaction was carried out under reflux for 10 hours under nitrogen protection. And after the reaction is finished, pouring the solution into a poor solvent deionized water to obtain flocculent precipitate, repeatedly washing the flocculent precipitate, and freeze-drying to obtain a hexa (4-aminophenoxy) -cyclotriphosphazene solid.
(3) Adding 75mL of ethanol and 200mL of hydrochloric acid into a three-neck flask, stirring, heating to 45 ℃, adding a mixed solution of 150g of phenyltriethoxysilane (1 mol) and 24.6g of beta-3, 4-epoxycyclohexylethyltrimethoxysilane (0.1 mol) into the flask, keeping stirring, and performing hydrolysis reaction for 24 hours; and then distilling under reduced pressure at 85 ℃ and 0.1MPa to remove the solvent, and repeatedly washing and filtering to obtain light yellow viscous liquid, namely the target product epoxy group oligomeric silsesquioxane.
(4) Preparing a POSS modified phosphazene flame retardant: 7.83g of hexa (4-aminophenoxy) -cyclotriphosphazene (0.01 mol) and 108g of epoxy oligomeric silsesquioxane (0.1 mol) were dissolved in 180ml of DMF, respectively; then making a ringThe DMF solution of the oxyoligomeric silsesquioxane was slowly added to the DMF solution of hexa (4-aminophenoxy) -cyclotriphosphazene, magnetic stirring was maintained at 120 ℃ and the reaction was refluxed for 12 hours under a nitrogen atmosphere. And finally, repeatedly filtering and washing, and freeze-drying at-40 ℃ under 80Pa vacuum to obtain the POSS modified phosphazene flame retardant (POSS-PN-3). Performing infrared analysis on the target product, and finding that 1106cm exists on a spectrogram -1 The asymmetric stretching vibration peak of Si-O-Si of (A), 893 and 1201cm -1 The characteristic peak of (A) indicates the presence of a phosphazene ring structure, 1147cm -1 The characteristic peak of hydroxyl group is appeared, 910cm is not appeared -1 The characteristic peak of the nearby epoxy group shows that the target product is indeed formed by the reaction of POSS and phosphazene.
Application example 1
8 parts of POSS-PN-1 flame retardant prepared according to the embodiment 1, 0.5 part of anti-dripping agent PTFE (large gold fluorine chemical), 1 part of toughening agent MBS (Brillouin chemical) and 90.5 parts of PC are premixed uniformly by a high-speed mixer, and then added into a double-screw extruder for melt extrusion and granulation to obtain a sample. The melt temperature was 280 ℃ and the extruder speed was 300rpm.
Application example 2
8 parts of POSS-PN-2 flame retardant prepared according to the embodiment 2, 0.5 part of anti-dripping agent PTFE, 1 part of toughening agent MBS and 90.5 parts of PC are premixed uniformly by a high-speed mixer, and then added into a double-screw extruder for melt extrusion and granulation to obtain a sample. The melt temperature was 280 ℃ and the extruder speed was 300rpm.
Application example 3
8 parts of POSS-PN-3 flame retardant prepared according to the embodiment 3, 0.5 part of anti-dripping agent PTFE, 1 part of toughening agent MBS and 90.5 parts of PC are premixed uniformly by a high-speed mixer, and then added into a double-screw extruder for melt extrusion and granulation to obtain a sample. The melt temperature was 280 ℃ and the extruder speed was 300rpm.
Comparative example 1
8 parts of hexaphenoxy-cyclotriphosphazene (carbofuran technology) flame retardant, 0.5 part of anti-dripping agent PTFE, 1 part of toughening agent MBS and 90.5 parts of PC are premixed uniformly by a high-speed mixer, and then added into a double-screw extruder for melt extrusion and granulation to obtain a sample. The melt temperature was 280 ℃ and the extruder speed was 300rpm.
Comparative example 2
8 parts of POSS (Allantin reagent), 0.5 part of anti-dripping agent PTFE, 1 part of toughening agent MBS and 90.5 parts of PC are premixed uniformly by a high-speed mixer, and then added into a double-screw extruder for melt extrusion and granulation to obtain a sample. The melt temperature was 280 ℃ and the extruder speed was 300rpm.
Comparative example 3
4 parts of hexaphenoxy-cyclotriphosphazene flame retardant, 4 parts of POSS, 0.5 part of anti-dripping agent PTFE, 1 part of toughening agent MBS and 96.5 parts of PC are premixed uniformly by a high-speed mixer and then added into a double-screw extruder for melt extrusion and granulation to obtain a sample. The melt temperature was 280 ℃ and the extruder speed was 300rpm.
After the polycarbonate alloy resins prepared in application examples 1 to 3 and comparative examples 1 to 3 were dried at 100 ℃ for 4 hours, standard physical property sample strips and flame retardant sample strips were injection molded under the same injection molding conditions according to the ISO standard, and the physical properties and flame retardant properties of the respective resin compositions were tested, and the specific test standards and conditions are shown in table 1.
TABLE 1 physical Properties, flame retardancy and test methods corresponding tables
| Test items | Test conditions | Test method |
| Tensile strength | 23℃ | ISO 527 |
| Elongation at break | 23℃ | ISO 527 |
| Notched impact strength | 23℃ | ISO 180 |
| Heat distortion temperature | 1.80MPa | ISO 75 |
| Flame retardant properties | 1.5mm | UL94 |
The physical properties and flame retardancy test results of the halogen-free flame retardant polycarbonate resins of application examples 1 to 3 and comparative examples 1 to 3 are shown in table 2.
TABLE 2 corresponding tables of physical properties and flame retardancy of application examples and comparative examples
| Performance index | Application example 1 | Application example 2 | Application example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile Strength (MPa) | 66.5 | 67.4 | 66.8 | 58.9 | 67.1 | 64.6 |
| Impact Strength (kJ/m) 2 ) | 58.5 | 57.1 | 59.3 | 58.2 | 59.7 | 56.8 |
| Heat distortion temperature (. Degree. C.) | 126 | 128 | 127 | 117 | 127 | 125 |
| Flame retardant rating | V0 | V0 | V0 | V0 | V1 | V1 |
As can be seen from the data in Table 2, compared with the PC flame-retardant composite material added with pure phosphazene, pure POSS and compound phosphazene/POSS, the PC composite material added with the POSS modified phosphazene flame retardant provided by the invention has the advantages that the flame retardance is obviously improved, and the mechanical property and the heat resistance are obviously improved.
In summary, the following steps: according to the invention, through POSS grafting modification on phosphazene, three elements of phosphorus, nitrogen and silicon are integrated, the synergistic flame-retardant effect is excellent, and the rigid cage-shaped structure of POSS can improve the heat resistance and mechanical properties of the flame-retardant composite material. In addition, the preparation process is economical and practical, the preparation process is simple, the cost is low, large-scale production is easy to realize, the practical value is high, and compared with the prior art, the preparation method has the advantages of remarkable progress and unexpected effect.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be made by those skilled in the art without inventive work within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (12)
1. A POSS modified phosphazene flame retardant characterized in that it comprises the following structure:
R 1 -R 6 same or different, selected from NH 2 Or
And R is 1 -R 6 At least one selected from
Wherein, the first and the second end of the pipe are connected with each other,
。
2. the method of preparing a POSS modified phosphazene flame retardant of claim 1, wherein the method comprises the steps of: comprises the following steps: (1) Carrying out nucleophilic substitution reaction on hexachlorocyclotriphosphazene and p-nitrophenol to generate hexa (4-nitrophenoxy) -cyclotriphosphazene, (2) carrying out reduction reaction on hexa (4-nitrophenoxy) -cyclotriphosphazene under the action of palladium carbon as a catalyst and hydrazine hydrate to generate hexa (4-aminophenoxy) -cyclotriphosphazene; (3) Phenyl triethoxysilane and beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxysilane are subjected to hydrolysis reaction to generate epoxy oligomeric silsesquioxane; (4) Then carrying out a ring-opening reaction on the amino group of the hexa (4-aminophenoxy) -cyclotriphosphazene and the epoxy group of the epoxy group oligomeric silsesquioxane to obtain a target product POSS modified phosphazene flame retardant; wherein the structural formula of the epoxy group oligomeric silsesquioxane is as follows:
and/or, the structural formula of the hexa (4-aminophenoxy) -cyclotriphosphazene is as follows:
3. the preparation method according to claim 2, wherein the preparation of the epoxy-based oligomeric silsesquioxane in the step (3) comprises the steps of adding ethanol and hydrochloric acid into a reactor, stirring and heating to 45-60 ℃, adding a mixed solution of phenyltriethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, keeping stirring, and carrying out hydrolysis reaction for 16-24 hours; and then the solvent is removed through reduced pressure distillation, and light yellow viscous liquid, namely the target product epoxy group oligomeric silsesquioxane is obtained after repeated washing and filtration.
4. The method according to claim 3, wherein the phenyltriethoxysilane and the beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane are mixed in a molar ratio of 6-10: 1, adding.
5. The method of claim 2, wherein the preparation of hexa (4-nitrophenoxy) -cyclotriphosphazene in step (1) comprises the steps of: dissolving hexachlorocyclotriphosphazene and p-nitrobenzene in acetone or benzene, taking potassium carbonate or triethylamine as an acid-binding agent, controlling the temperature at 50-60 ℃ under the catalytic action of sodium iodide or tetrabutylammonium iodide, performing reflux reaction for 2-3 hours, and repeatedly filtering, washing and drying to obtain hexa (4-nitrophenoxy) -cyclotriphosphazene solid.
6. The method according to claim 5, wherein the weight ratio of hexachlorocyclotriphosphazene: p-nitrobenzene: the molar ratio of the acid-binding agent =1 (6-8): (2-4), the dosage of the catalyst is 1% -2% of the total mass of the hexachlorocyclotriphosphazene and the p-nitrobenzene.
7. The method of claim 2, wherein the preparation of hexa (4-aminophenoxy) -cyclotriphosphazene in step (2) comprises the steps of: dissolving hexa (4-nitrophenoxy) -cyclotriphosphazene and a catalyst palladium carbon in isopropanol, chloroform or DMF, heating the solution to 80-120 ℃, slowly adding a hydrazine hydrate solution, carrying out reflux reaction for 10-12 hours under the protection of nitrogen, then pouring the solution into a poor solvent deionized water to obtain flocculent precipitate, repeatedly washing the flocculent precipitate, and carrying out freeze drying to obtain hexa (4-aminophenoxy) -cyclotriphosphazene solid.
8. The method according to claim 7, wherein the hexa (4-nitrophenoxy) -cyclotriphosphazene, hydrazine hydrate and palladium on carbon are fed in a mass ratio of (8-10): 14-18): 1.
9. The method of claim 2, wherein the preparation of the POSS-modified phosphazene flame retardant in step (4) comprises the steps of: respectively dissolving hexa (4-aminophenoxy) -cyclotriphosphazene and epoxy oligomeric silsesquioxane in DMF, petroleum ether or chloroform; and then slowly adding the solution of epoxy group oligomeric silsesquioxane into the solution of hexa (4-aminophenoxy) -cyclotriphosphazene, keeping magnetic stirring at 90-120 ℃, carrying out reflux reaction for 10-12 hours under the nitrogen protection environment, and finally carrying out repeated filtration and washing, and freeze-drying to obtain the target product POSS modified phosphazene flame retardant.
10. The method of claim 9, wherein in step (4), the molar ratio of hexa (4-aminophenoxy) -cyclotriphosphazene to epoxy oligomeric silsesquioxane is 1.
11. A polycarbonate flame retardant composite, comprising at least: 85-99 parts by mass of a polycarbonate matrix, 0.1-10 parts by mass of a POSS modified phosphazene flame retardant of claim 1 or a POSS modified phosphazene flame retardant prepared by the preparation method of any one of claims 2-9, and further comprising 0.3-0.5 part by mass of anti-dripping agent polytetrafluoroethylene, 0.5-1.5 parts by mass of a toughening agent methacrylic acid-butadiene-styrene terpolymer or methyl methacrylate-acrylate-organosilicon terpolymer or ethylene-acrylic acid copolymer.
12. The method for preparing the polycarbonate flame-retardant composite material according to claim 11, comprising the steps of: and premixing the POSS modified phosphazene flame retardant, the PC, the preferable anti-dripping agent and the toughening agent uniformly by a high-speed mixer, and then adding the mixture into a double-screw extruder for melt extrusion and granulation to obtain a sample, wherein the melt temperature is 280-310 ℃, and the rotating speed of the extruder is 300-900rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210050016.8A CN114349968B (en) | 2022-01-17 | 2022-01-17 | POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210050016.8A CN114349968B (en) | 2022-01-17 | 2022-01-17 | POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114349968A CN114349968A (en) | 2022-04-15 |
| CN114349968B true CN114349968B (en) | 2023-03-24 |
Family
ID=81090544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210050016.8A Active CN114349968B (en) | 2022-01-17 | 2022-01-17 | POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114349968B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537969B (en) * | 2022-08-19 | 2024-03-29 | 邵阳深镁科技时尚有限公司 | Flame-retardant wig and preparation method thereof |
| CN116102734B (en) * | 2022-12-29 | 2023-10-24 | 广州硅碳新材料有限公司 | Phosphorus-nitrogen-containing cage polysilsesquioxane, preparation method thereof and application thereof as crusting and carbonizing agent |
| CN116695271A (en) * | 2023-07-05 | 2023-09-05 | 潮州市丹辉婚纱礼服有限公司 | High-elasticity spandex fiber fabric and preparation process thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020059354A (en) * | 1999-08-04 | 2002-07-12 | 하이브리드 플라스틱스 | Process for the formation of polyhedral oligomeric silsesquioxanes |
| CN105670258B (en) * | 2014-11-21 | 2018-11-13 | 合肥杰事杰新材料股份有限公司 | A kind of high transparency halogen-free flameproof scratch resistant polycarbonate composite material and preparation method |
| CN108794751A (en) * | 2017-04-28 | 2018-11-13 | 中蓝晨光化工研究设计院有限公司 | One kind resin fire retardant of structural silicone containing phosphonitrile and preparation method thereof |
| CN107245228B (en) * | 2017-06-22 | 2018-07-24 | 深圳市高科塑化有限公司 | A kind of preparation method and flame-retardant and anti-dripping polyester material of flame-retardant and anti-dripping polyester material |
| CN109943052A (en) * | 2019-03-26 | 2019-06-28 | 北京濮源新材料技术研究院(普通合伙) | POSS modified thermostabilization fire-retardant polycarbonate and preparation method thereof |
| CN110437452B (en) * | 2019-08-30 | 2021-08-06 | 山东大学 | Heteroatom doped phosphazene functionalized POSS-based hybrid porous polymer and preparation method and application thereof |
| CN110591382A (en) * | 2019-10-22 | 2019-12-20 | 广州特种承压设备检测研究院 | Low-density halogen-free flame-retardant graphene heat-conducting silica gel and preparation method thereof |
| CN112873458B (en) * | 2021-01-08 | 2022-05-17 | 山东新港企业集团有限公司 | Flame-retardant environment-friendly solid wood thick-core plywood and preparation method thereof |
-
2022
- 2022-01-17 CN CN202210050016.8A patent/CN114349968B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114349968A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114349968B (en) | POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof | |
| CN111072973B (en) | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant | |
| CN113121885B (en) | Flame retardant, flame-retardant PLA composite material and preparation method thereof | |
| CN109134864B (en) | Trapezoidal polysilsesquioxane derivative and preparation method thereof | |
| CN108659040A (en) | A kind of Phenylphosphine diamide derivative and its synthetic method and application | |
| CN104448830A (en) | Phosphorus-silicon composite flame retardant as well as preparation method and application thereof | |
| CN111635618A (en) | Phosphazene-based organic metal complex flame-retardant epoxy resin and preparation method thereof | |
| CN108250646B (en) | Halogen-free flame retardant composition | |
| CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
| CN109776780B (en) | Phosphorus-containing flame-retardant PTT and preparation method and application thereof | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN116622088A (en) | Nitrogen and phosphorus-containing graphene synergistic flame retardant, and preparation method and application thereof | |
| CN110922637A (en) | DOPO derivative flame-retardant photo-thermal stabilizer and preparation method and application thereof | |
| CN115850708A (en) | Preparation method and application of N-P-Si-containing cage polysilsesquioxane flame retardant | |
| CN114262554A (en) | Nitrogen-phosphorus-containing epoxy resin fireproof coating and preparation method thereof | |
| CN112979951A (en) | Novel flame retardant, flame-retardant transparent polycarbonate resin and preparation method thereof | |
| CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
| CN112321800A (en) | Preparation method of flame-retardant epoxy resin | |
| CN117551338B (en) | Flame-retardant cold-resistant and damp-heat-resistant polyester composition and preparation method thereof | |
| CN114213710B (en) | Flame retardant and high-temperature-resistant flame-retardant transparent polycarbonate resin | |
| CN113773416B (en) | Intrinsic flame-retardant modified natural rubber and preparation method thereof | |
| CN114716669B (en) | Polyphosphazene grafted polyamide 6 flame retardant, and preparation method and application thereof | |
| CN117089095B (en) | Preparation method of flame-retardant polyamide 6 film | |
| CN113278203B (en) | Preparation method and application of efficient halogen-free flame retardant for polypropylene | |
| KR101469270B1 (en) | Polyphosphonate copolymer, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same |
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 |