CN114316370B - Preparation method of POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant - Google Patents
Preparation method of POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant Download PDFInfo
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- CN114316370B CN114316370B CN202111471326.9A CN202111471326A CN114316370B CN 114316370 B CN114316370 B CN 114316370B CN 202111471326 A CN202111471326 A CN 202111471326A CN 114316370 B CN114316370 B CN 114316370B
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Abstract
The invention provides a preparation method of a POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant. And (3) reacting melamine, POSS-NH2 and formaldehyde at pH 8-9 to obtain a prepolymer, dropwise adding the prepolymer into an ethanol water solution of ammonium polyphosphate which is uniformly stirred and dispersed, and adjusting the pH to 5-6 to obtain the POSS modified melamine resin coated ammonium polyphosphate flame retardant. The method provides the ammonium polyphosphate microcapsule flame retardant which is prepared by coating the ammonium polyphosphate with the resin containing the POSS structure serving as a wall material, and improves the structural stability of the wall material of the microcapsule flame retardant. The prepared flame retardant has good dispersibility, enhances the compatibility with materials, reduces the water solubility, does not influence the mechanical properties of the materials, exerts the synergistic flame retardance of phosphorus, nitrogen and silicon, improves the flame retardance, and has good application prospect.
Description
Technical Field
The invention relates to a POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant and a preparation method thereof, belonging to the technical field of preparation of intumescent flame retardants.
Background
Ammonium polyphosphate (APP) has good flame retardant property, less smoke, no toxic gas generation under the conditions of high temperature and combustion, low price and wide application range, and is an environment-friendly flame retardant. But APP has stronger hydrophilicity and is easy to hydrolyze under the conditions of high temperature and high humidity; poor compatibility with the base material, easy occurrence of dialysis phenomenon and damage of mechanical properties of the material. In order to reduce the water solubility of APP, improve the compatibility with the substrate, APP is modified by microencapsulation techniques. Coating APP with melamine formaldehyde resin to obtain melamine formaldehyde resin microencapsulated APP in a patent CN 1216679C; CN106279771 coats APP with epoxy resin to obtain epoxy resin microencapsulated APP; CN103980541 activates APP at high temperature, then grafts melamine surface, and then reacts with formaldehyde to obtain coated APP; CN101492881 is prepared by preparing melamine, a silane coupling agent and an epoxy resin coated APP, and then forming a multi-layer coated APP under the action of an emulsifying agent and polyurethane, wherein the wall material formed by the resin used in the above patent has low temperature resistance level and low softening point, so that the microcapsule formed by coating the APP can not be applied to a substrate with higher processing temperature. CN101760049 coats APP with silicon dioxide to obtain silicon dioxide microencapsulated APP; CN110606990 reports that the preparation of hyperbranched polysiloxane coated ammonium polyphosphate by using tetraethoxysilane, phenylsiloxane and amino-terminated siloxane as monomers has poor compatibility between wall materials and materials formed by the resin used in the above patent, and influences the mechanical properties of the materials. POSS is a novel organic-inorganic hybrid material, is formed by connecting inorganic Si-O, has a cage-shaped structure with nanoscale size and regularity, is formed by connecting organic functional groups with Si atoms through covalent bonds, introduces one or more reactive functional groups into a molecular structure, has excellent organic compatibility, and is widely used for modifying high polymer materials.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and prepare the amino-oligomeric silsesquioxane (POSS-NH) 2 ) And the prepolymer is reacted with melamine and formaldehyde under alkaline condition to provide a polymer with a POSS structure in a polymer structure, and under acidic condition, the polymer with a stable structure is formed and ammonium polyphosphate is coated to prepare the POSS modified microcapsule coated ammonium polyphosphate flame retardant, so that the strength of the wall material and the compatibility with materials such as polypropylene, polyurethane, epoxy resin and the like are improved, the water solubility is reduced, the phosphorus-nitrogen-silicon synergistic flame retardance is exerted, and the flame retardant property is improved.
The technical problem to be solved by the invention is realized by the following scheme:
the preparation method of the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant comprises the following steps:
(1) Adding melamine, POSS-NH into a reactor with a stirrer and a condensing reflux device 2 Formaldehyde solution and distilled water, wherein the mass concentration of Na is 10 percent 2 CO 3 Regulating pH to 8-9, 60-70 deg.c and 400-500 rStirring for 1h in the reaction kettle/min to obtain POSS modified melamine resin.
The POSS modified melamine resin has the following structure:
wherein R is a cyclohexyl group or a phenyl group, and n is 2 to 8.
(2) Adding ethanol, distilled water and ammonium polyphosphate powder into a reactor with a stirrer and a condensing reflux device, stirring and dispersing at 70-80 ℃ and 500-700 r/min, regulating pH to 5-6 by adopting sulfuric acid with the mass concentration of 10%, dropwise adding POSS modified melamine resin by a constant flow pump, continuing to react for 2-3h after the dropwise adding, carrying out suction filtration, washing by deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
Melamine, POSS-NH in step (1) 2 The mass ratio of the formaldehyde to the formaldehyde is 1:0.01-0.1: 3 to 4.
The mass fraction of formaldehyde is 35-37%.
The mass ratio of the POSS modified melamine resin to the ammonium polyphosphate powder is 1:6-20.
The POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant obtained by the technical scheme of the invention has the technical effects of uniform distribution, uniform and compact coating, stable phosphorus content of 29+/-1 and obvious phosphorus-nitrogen-silicon synergistic flame retardant effect, and the solubility of the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant is below 0.08g/100mL under the pure water condition of 25 ℃.
Drawings
FIG. 1 is a scanning electron microscope image of a raw material ammonium polyphosphate.
FIG. 2 is a scanning electron microscope image of a POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
Detailed Description
The material melamine (CAS: 108-78-1) used in the examples of the present invention was purchased from the national pharmaceutical group chemical reagent company.
Ammonium polyphosphate (CAS: 68333-79-9) was purchased from Hangzhou Jieshi flame retardant chemical Co., ltd.
POSS-NH2 (self-made) has the following structural formula:
example 1
In a flask with stirrer and a condensate reflux, melamine (0.04 mol,5.04 g), POSS-NH 2 (0.0004 mol,0.416 g) (R is phenyl, n is 6), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL), 10% Na 2 CO 3 Adjusting the pH to 8.6, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
Adding ethanol (100 mL), distilled water (200 mL), APP powder (135 g), stirring and dispersing at 80 ℃ and 700r/min for 0.5h, adjusting the pH of the solution to 5.5 by using 10% sulfuric acid, adding a prepolymer by a constant flow pump, dropwise adding for about 2h, continuing to react for 2h, performing suction filtration, washing by using deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
Example 2
Melamine (0.04 mol,5.04 g) was charged into a flask with stirrer and a condensate reflux apparatus, POSS-NH 2 (0.0004 mol,0.433 g) (R is cyclohexyl and n is 6), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL), 10% Na 2 CO 3 The pH is adjusted to 8.7, and the mixture is stirred for 1h at 70 ℃ and 500r/min to obtain a prepolymer.
Adding ethanol (100 mL), distilled water (200 mL), APP powder (135 g), stirring and dispersing at 80 ℃ and 700r/min for 0.5h, adjusting the pH of the solution to 5.2 by using 10% sulfuric acid, adding a prepolymer by a constant flow pump, dropwise adding for about 2h, continuing to react for 2h, performing suction filtration, washing by using deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
Example 3
Melamine (0.04 mol,5.04 g) was charged into a flask with stirrer and a condensate reflux apparatus, POSS-NH 2 (0.0004 mol,0.404 g) (R is phenyl, n is 4), 37% formaldehyde solution (0.13 mol,3.9 g)Distilled water (50 mL) with 10% Na 2 CO 3 Adjusting the pH to 8.5, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
Ethanol (100 mL), distilled water (200 mL) and APP powder (135 g) are added into a flask with a stirrer and a condensation reflux device, after stirring and dispersing for 0.5h at 80 ℃ and 700r/min, 10% sulfuric acid is used for adjusting the pH value of the solution to 5.6, a prepolymer is added through a constant flow pump, after about 2h of dropwise addition is completed, the reaction is continued for 2h, suction filtration is carried out, deionized water is used for washing, and the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant is obtained after drying.
Example 4
Melamine (0.04 mol,5.04 g) was charged into a flask with stirrer and a condensate reflux apparatus, POSS-NH 2 (0.0004 mol, 0.390 g) (R is phenyl, n is 2), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL), 10% Na 2 CO 3 Adjusting the pH to 8.6, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
Ethanol (100 mL), distilled water (200 mL) and APP powder (135 g) are added into a flask with a stirrer and a condensation reflux device, after stirring and dispersing for 0.5h at 80 ℃ and 700r/min, 10% sulfuric acid is used for adjusting the pH value of the solution to 5.5, a prepolymer is added through a constant flow pump, after about 2h of dropwise addition is completed, the reaction is continued for 2h, suction filtration is carried out, deionized water is used for washing, and the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant is obtained after drying.
Example 5
In a flask equipped with a stirrer and a condensate reflux apparatus, melamine (0.04 mol,5.04 g), POSS-NH2 (0.0008 mol,0.834 g) (R is phenyl, n is 6), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL), and 10% Na were added 2 CO 3 Adjusting the pH to 8.4, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
Adding ethanol (100 mL), distilled water (200 mL) and APP powder (135 g) into a flask with a stirrer and a condensation reflux device, stirring and dispersing at 80 ℃ and 700r/min for 0.5h, regulating the pH of the solution to 5.7 by using 10% sulfuric acid, adding a prepolymer by using a constant flow pump, dropwise adding for about 2h, continuing to react for 2h, filtering, washing by using deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
Example 6
In a flask equipped with a stirrer and a condensing reflux, melamine (0.04 mol,5.04 g), POSS-NH2 (0.0012 mol,1.248 g) (R is phenyl and n is 6), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL), and 10% Na were added 2 CO 3 Adjusting the pH to 8.8, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
In a flask with stirrer and a condensing reflux device, ethanol (100 mL), distilled water (200 mL), APP powder (135 g) were added, and dispersed in a four-necked flask at 80℃and 500r/min for 0.5h with stirring, followed by adjusting pH to 5.4 with a 10% sulfuric acid solution. Adding the prepolymer by a constant flow pump, after the dripping is finished for about 2 hours, continuing to react for 2 hours, carrying out suction filtration, cleaning filter residues by deionized water, and drying at 60 ℃.
Example 7
Melamine (0.04 mol,5.04 g) was charged into a flask with stirrer and a condensate reflux apparatus, POSS-NH 2 (0.0008 mol,0.834 g) (R is phenyl, n is 6), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL), 10% Na 2 CO 3 Adjusting the pH to 8.8, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
Adding ethanol (100 mL), distilled water (200 mL) and APP powder (90 g) into a flask with a stirrer and a condensation reflux device, stirring and dispersing at 80 ℃ and 700r/min for 0.5h, regulating the pH of the solution to 5.5 by using 10% sulfuric acid, adding a prepolymer by a constant flow pump, dropwise adding for about 2h, continuing to react for 2h, filtering, washing by using deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
Example 8
Melamine (0.04 mol,5.04 g) was charged into a flask with stirrer and a condensate reflux apparatus, POSS-NH 2 (0.0008 mol,0.834 g) (R is phenyl, n is 6), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL), 10% Na 2 CO 3 Adjusting the pH to 8.0, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
Adding ethanol (100 mL), distilled water (200 mL) and APP powder (180 g) into a flask with a stirrer and a condensation reflux device, stirring and dispersing at 80 ℃ and 700r/min for 0.5h, regulating the pH of the solution to 5.6 by using 10% sulfuric acid, adding a prepolymer by using a constant flow pump, dropwise adding for about 2h, continuing to react for 2h, filtering, washing by using deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
Example 9
In a flask equipped with a stirrer and a condensing reflux, melamine (0.04 mol,5.04 g), 37% formaldehyde solution (0.13 mol,3.9 g), distilled water (50 mL) and 10% Na were added 2 CO 3 Adjusting the pH to 9, stirring at 70 ℃ and 500r/min for 1h to obtain the prepolymer.
Adding ethanol (100 mL), distilled water (200 mL) and APP powder (135 g) into a flask with a stirrer and a condensation reflux device, stirring and dispersing at 80 ℃ and 700r/min for 0.5h, adjusting the pH of the solution to 6 by using 10% sulfuric acid, adding a prepolymer into the solution by a constant flow pump, dropwise adding for about 2h, continuing to react for 2h, filtering, washing with deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant.
The test results of examples 1 to 9 are shown in Table 1.
TABLE 1
Fig. 1 is a scanning electron microscope image of a raw material ammonium polyphosphate, and fig. 2 is a scanning electron microscope image of a POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant of example 9. From the figure, it can be seen that the particles are uniformly distributed and the coating is dense. The topographical maps of examples 1, 2, 3, 5, 6, 7 are substantially similar to example 9, with only particle size differences, and are not provided.
Claims (4)
- The preparation method of the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant is characterized by comprising the following steps:(1) With stirringAdding melamine and POSS-NH into a reactor of a stirrer and a condensation reflux device 2 Regulating pH to 8-9 with formaldehyde solution and distilled water, and stirring at 60-70 ℃ and 400-500 r/min for 1h to obtain POSS modified melamine resin;the POSS modified melamine resin has the following structure:
wherein R is cyclohexyl or phenyl, and n is 2-8;(2) Adding ethanol, distilled water and ammonium polyphosphate powder into a reactor with a stirrer and a condensing reflux device, stirring and dispersing at 70-80 ℃ and 500-700 r/min, regulating the pH to 5-6, dropwise adding POSS modified melamine resin by a constant flow pump, continuing to react for 2-3h after the dropwise adding, carrying out suction filtration, washing by deionized water, and drying to obtain the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant. - 2. The method for preparing POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant according to claim 1, wherein in the step (1), melamine and POSS-NH are used 2 The mass ratio of the formaldehyde to the formaldehyde is 1:0.01-0.1: 3 to 4.
- 3. The method for preparing the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant according to claim 2, wherein the mass fraction of formaldehyde is 35-37%.
- 4. The preparation method of the POSS modified melamine resin coated ammonium polyphosphate microcapsule flame retardant according to claim 2, wherein the mass ratio of the POSS modified melamine resin to the ammonium polyphosphate powder is 1:6-20.
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| JPH09302243A (en) * | 1996-05-10 | 1997-11-25 | Chisso Corp | Flame-retardant thermosetting resin composition and flame-retardant molded item produced therefrom |
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