CN113652005A - Polyborosiloxane modified ammonium polyphosphate and preparation method thereof - Google Patents
Polyborosiloxane modified ammonium polyphosphate and preparation method thereof Download PDFInfo
- Publication number
- CN113652005A CN113652005A CN202111013499.6A CN202111013499A CN113652005A CN 113652005 A CN113652005 A CN 113652005A CN 202111013499 A CN202111013499 A CN 202111013499A CN 113652005 A CN113652005 A CN 113652005A
- Authority
- CN
- China
- Prior art keywords
- ammonium polyphosphate
- polyborosiloxane
- stirring
- modified
- preparation
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/56—Boron-containing linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides polyborosiloxane modified ammonium polyphosphate and a preparation method thereof. The polyborosiloxane modified ammonium polyphosphate comprises ammonium polyphosphate and polyborosiloxane coated on the surface of the ammonium polyphosphate. The preparation method comprises the following steps: under an acidic condition, boric acid and a silane coupling agent undergo a polycondensation reaction in a solvent, and a viscous liquid polyborosiloxane is obtained through post-treatment; and mixing the obtained polyborosiloxane with ammonium polyphosphate, stirring for modification, and drying to obtain polyborosiloxane modified ammonium polyphosphate. In the modified ammonium polyphosphate, the unsaturated organic chain segment in the polyborosiloxane reduces the water solubility of the ammonium polyphosphate, improves the compatibility with a polymer matrix, reduces the mechanical damage of a flame retardant to the polymer, further obviously improves the heat resistance, and has good P-N-Si-B synergistic flame retardant effect. The ammonium polyphosphate is coated with a compact and uniform polyborosiloxane film layer by simple high-speed stirring, so that the flame retardant property is effectively improved.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to polyborosiloxane modified ammonium polyphosphate and a preparation method thereof.
Background
Ammonium polyphosphate is used as a halogen-free environment-friendly flame retardant with high phosphorus and nitrogen content, has low toxicity, low smoke and other properties, can be usually used as an acid source, is compounded with a carbon source and a gas source to form an intumescent flame retardant system, and has wide application in the fields of plastics, rubber, coatings and the like. However, ammonium polyphosphate has some defects, such as water solubility, poor compatibility with a polymer, and easy migration from the interior of a matrix to the surface under a damp and hot environment, which causes the phenomena of 'back frost' and the like, and affects the mechanical properties of the polymer. In addition, ammonium polyphosphate has the characteristics of low thermal stability and the like. Therefore, in order to improve the performance of ammonium polyphosphate, it needs to be modified.
Usually, high molecular resins, such as melamine resin, polyurethane resin, epoxy resin, etc., are used to perform microcapsule coating modification on ammonium polyphosphate, but the resin has relatively poor thermal stability, complex coating process and high production cost, and for example, free formaldehyde exists after the melamine resin is coated. In addition, the ammonium polyphosphate is in a damp and hot environment in the coating process, ammonia gas is easy to remove, and the structure is damaged to a certain extent. Therefore, the development of a new method for modifying the ammonium polyphosphate reduces the water solubility of the ammonium polyphosphate, improves the thermal stability and the flame retardant efficiency of the ammonium polyphosphate, and has certain practical significance.
Patent document CN 109251386 a discloses an impact-resistant flame-retardant material, in which a flame retardant, which is a mixture of polyborosiloxane resin, ammonium polyphosphate and wood flour, is added. In the document, the polyborosiloxane resin, the ammonium polyphosphate and the wood powder are directly mixed, and the polyborosiloxane resin and the ammonium polyphosphate are simply mixed, so that the flame retardance and the compatibility of the ammonium polyphosphate cannot be improved, the addition amount of the flame retardant is too large, and the impact strength and the tensile strength are reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides polyborosiloxane modified ammonium polyphosphate and a preparation method thereof. The bond energy of Si-O-B in the molecular structure of the polyborosiloxane is far higher than that of Si-O-Si, so that the polyborosiloxane has excellent high temperature resistance, oxidation resistance and better caking property. The modified ammonium polyphosphate has improved thermal stability due to the existence of Si-O-B bonds, obviously increased carbon residue at high temperature, and oxidation resistance to isolate external oxygen to make the carbon residue more compact.
The invention provides polyborosiloxane modified ammonium polyphosphate, which comprises ammonium polyphosphate and polyborosiloxane coated on the surface of the ammonium polyphosphate.
The excellent cohesiveness of the polyborosiloxane can not only form good coating on the ammonium polyphosphate, but also obviously improve the interfacial compatibility of the ammonium polyphosphate and a polymer matrix. In addition, the presence of hydrophobic C ═ C in the molecular chain segment of the polyborosiloxane can further reduce the water solubility of the ammonium polyphosphate.
The invention also provides a preparation method of the polyborosiloxane modified ammonium polyphosphate, which comprises the following steps:
(1) under an acidic condition, boric acid and a silane coupling agent are subjected to a polycondensation reaction in a solvent, and after the reaction is finished, the polyborosiloxane in a viscous liquid state is obtained through post-treatment;
(2) and mixing the obtained viscous liquid polyborosiloxane with ammonium polyphosphate, stirring for modification, and drying to obtain the polyborosiloxane modified ammonium polyphosphate.
In the above technical scheme, in the step (1):
preferably, the molar ratio of the boric acid to the silane coupling agent is (0.2-1): 1.
preferably, the silane coupling agent is one or two of vinyltrimethoxysilane and vinyltriethoxysilane.
Preferably, the pH value of the polycondensation reaction is 1-3.
Preferably, the pH of the polycondensation is adjusted with hydrochloric acid to a concentration of 37%.
Preferably, the solvent is diethylene glycol dimethyl ether.
Preferably, the mass ratio of the solvent to the reactant (sum of the mass of the boric acid and the silane coupling agent) is 1: (0.5-2). More preferably 1: 1.
preferably, the reaction temperature of the polycondensation reaction is 80-180 ℃, and the reaction time is 2-8 h. As a further preferable scheme, the reaction temperature is 80-140 ℃, and the reaction time is 2-6 h.
Preferably, the solvent content of the viscous liquid polyborosiloxane obtained in the step is 3-50 wt%. More preferably, the content of the solvent in the viscous liquid polyborosiloxane is 10 to 30 wt%.
In the above technical solution, in the step (2):
preferably, the mass ratio of the polyborosiloxane to the ammonium polyphosphate is 1: (5-20). More preferably 1: (5-10).
Preferably, the stirring speed for stirring modification is 20000-30000 rpm/min, and the stirring time is 10-40 min.
More preferably, the stirring speed for stirring modification is 23000-26000 rpm/min.
Specifically, the preparation method of the polyborosiloxane modified ammonium polyphosphate comprises the following steps:
(1) preparation of polyborosiloxane: dispersing boric acid and a silane coupling agent in a solvent in a reaction kettle with a stirring and refluxing device, dropwise adding a hydrochloric acid solution to adjust the pH value, subsequently heating and stirring for reaction, and after the reaction is finished, decompressing to remove the solvent and byproducts to obtain viscous liquid polyborosiloxane with a small amount of residual solvent;
(2) polyborosiloxane modified ammonium polyphosphate: and (2) mixing the polyborosiloxane prepared in the step (1) with ammonium polyphosphate, stirring at a high speed in a crusher for modification, and drying to obtain the polyborosiloxane modified ammonium polyphosphate.
In the preparation method, the vinyl silane coupling agent is utilized to remove the methanol/ethanol micromolecules under the conditions of high temperature and acidity, and then the B-OH of boric acid and the Si-OH of siloxane are subjected to polycondensation at high temperature to generate Si-O-B bonds and H2And O. Removing solvent and by-product under reduced pressure to obtain viscous liquid polyborosiloxane with small amount of residual solvent, mixing with ammonium polyphosphate, stirring at high speed to make polyborosiloxane contact with ammonium polyphosphate sufficiently, and collecting residual partThe solvent is completely volatilized, and the polyborosiloxane forms a layer of uniform and compact coating film on the surface of the ammonium polyphosphate and then is cured, so that the modification is completed.
The surface energy of a main chain on a polyborosiloxane molecular chain structure is low, the polyborosiloxane molecular chain structure is easy to migrate to the surface of a material when being heated, a borosilicate ceramic material can be formed at high temperature, a synergistic effect is generated between the polyborosiloxane molecular chain structure and P, N element in ammonium polyphosphate, a compact carbon layer is promoted to be formed on a combustion interface, the heat release rate and the total heat release amount can be reduced, and the smoke release rate can also be reduced.
The raw materials adopted by the invention are relatively low in price, the preparation process and the flow are simple, the ammonium polyphosphate coating modification is realized, the thermal stability is improved, the emigration of the ammonium polyphosphate is inhibited, the problem of the compatibility of the ammonium polyphosphate and a polymer is solved, the modified ammonium polyphosphate can play a role in the synergistic flame retardant effect of P-N-Si-B, and the modified ammonium polyphosphate has the characteristics of low production cost, easiness in industrial production and the like.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, polyborosiloxane is used for modifying ammonium polyphosphate, and unsaturated organic chain segments in the polyborosiloxane further reduce the water solubility of the ammonium polyphosphate, improve the compatibility with a polymer matrix, reduce the mechanical damage of a flame retardant to the polymer, further obviously improve the heat resistance of the obtained modified ammonium polyphosphate, and have good P-N-Si-B synergistic flame retardant effect. The preparation method disclosed by the invention enables the surface of the ammonium polyphosphate to be coated with a compact and uniform polyborosiloxane film layer through simple high-speed stirring, effectively improves the flame retardant property, is simple in preparation process, easy to realize experimental conditions, and has wide market prospect and application value.
Drawings
FIG. 1 is a scanning electron microscope image of unmodified ammonium polyphosphate;
FIG. 2 is a scanning electron microscope image of the modified ammonium polyphosphate prepared in example 1;
FIG. 3 is a scanning electron micrograph of the modified ammonium polyphosphate prepared in example 2;
FIG. 4 is a scanning electron micrograph of the modified ammonium polyphosphate prepared in example 3;
FIG. 5 is a scanning electron micrograph of the modified ammonium polyphosphate prepared in example 4;
FIG. 6 is a scanning electron microscope image of the modified ammonium polyphosphate prepared in comparative example 1;
FIG. 7 is a scanning electron microscope cross-sectional view of a flame retardant polyurethane material prepared from unmodified ammonium polyphosphate;
FIG. 8 is a scanning electron microscope cross-sectional view of a flame retardant polyurethane material prepared from the modified ammonium polyphosphate obtained in example 2;
fig. 9 is a scanning electron microscope cross-sectional view of a flame retardant polyurethane material prepared from the modified ammonium polyphosphate obtained in the comparative example.
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to the following examples.
The starting materials used in the examples are all commercially available.
Wherein, the type of the ammonium polyphosphate: TF-201, polymerization degree ≧ 1000, manufacturer: ji37025;
boric acid: high purity, manufacturer: dellboron industry;
vinylsiloxanes (vinyltrimethoxysilane, vinyltriethoxysilane): industrial grade, manufacturer: hubei chemical Limited;
diethylene glycol dimethyl ether: industrial grade, manufacturer: jiangsu Yida chemical Co., Ltd;
polyurethane slurry: the solid content was 50 wt%; the manufacturer: zhejiang Luoxing industries, Ltd.
Example 1
A preparation method of polyborosiloxane modified ammonium polyphosphate comprises the following steps:
(1) preparation of polyborosiloxane: 0.2mol (12.37g) of boric acid and 0.2mol (29.65g) of vinyltrimethoxysilane were dispersed in 42.02g of diethylene glycol dimethyl ether in a reaction vessel equipped with a stirring and refluxing apparatus, and a hydrochloric acid solution was added dropwise to adjust the pH to 3, followed by warming to 80 ℃ and stirring for 6 hours. After the reaction is finished, removing the solvent and the by-product under reduced pressure to obtain viscous liquid polyborosiloxane with a small amount of residual diethylene glycol dimethyl ether, wherein the content of the diethylene glycol dimethyl ether is 10 wt%;
(2) polyborosiloxane modified ammonium polyphosphate: and (2) mixing polyborosiloxane (containing 10g of polyborosiloxane) with a small amount of residual diethylene glycol dimethyl ether prepared in the step (1) with ammonium polyphosphate (100g), stirring at a high speed (the rotating speed of 24000rpm/min) in a grinder for 40min for modification, and drying to obtain polyborosiloxane modified ammonium polyphosphate.
Example 2
A preparation method of polyborosiloxane modified ammonium polyphosphate comprises the following steps:
(1) preparation of polyborosiloxane: 0.1mol (6.18g) of boric acid and 0.2mol (29.65g) of vinyltrimethoxysilane were dispersed in 35.83g of diethylene glycol dimethyl ether in a reaction vessel equipped with a stirring and refluxing apparatus, and a hydrochloric acid solution was added dropwise to adjust the pH to 3, followed by warming to 140 ℃ and stirring for 2 hours. After the reaction is finished, removing the solvent and the by-product under reduced pressure to obtain viscous liquid polyborosiloxane with a small amount of residual diethylene glycol dimethyl ether, wherein the content of the diethylene glycol dimethyl ether is 14 wt%;
(2) polyborosiloxane modified ammonium polyphosphate: and (2) mixing polyborosiloxane (containing 10g of polyborosiloxane) with a small amount of residual diethylene glycol dimethyl ether prepared in the step (1) with ammonium polyphosphate (100g), stirring at a high speed (the rotating speed of 24000rpm/min) in a grinder for 40min for modification, and drying to obtain polyborosiloxane modified ammonium polyphosphate.
Example 3
A preparation method of polyborosiloxane modified ammonium polyphosphate comprises the following steps:
(1) preparation of polyborosiloxane: 0.1mol (6.18g) of boric acid and 0.5mol (95.16g) of vinyltriethoxysilane were dispersed in 101.34g of diethylene glycol dimethyl ether in a reaction vessel equipped with a stirring and refluxing apparatus, and a hydrochloric acid solution was added dropwise to adjust the pH to 1, followed by heating to 120 ℃ and stirring for 5 hours. After the reaction is finished, removing the solvent and the by-product under reduced pressure to obtain viscous liquid polyborosiloxane with a small amount of residual diethylene glycol dimethyl ether, wherein the content of the diethylene glycol dimethyl ether is 18 wt%;
(2) polyborosiloxane modified ammonium polyphosphate: and (2) mixing polyborosiloxane (containing 20g of polyborosiloxane) with a small amount of residual diethylene glycol dimethyl ether prepared in the step (1) with ammonium polyphosphate (100g), stirring at a high speed (the rotating speed of 24000rpm/min) in a crusher for 20min for modification, and drying to obtain polyborosiloxane modified ammonium polyphosphate.
Example 4
A preparation method of polyborosiloxane modified ammonium polyphosphate comprises the following steps:
(1) preparation of polyborosiloxane: 0.1mol (6.18g) of boric acid and 0.2mol (29.65g) of vinyltrimethoxysilane were dispersed in 35.83g of diethylene glycol dimethyl ether in a reaction vessel equipped with a stirring and refluxing apparatus, and a hydrochloric acid solution was added dropwise to adjust the pH to 1, followed by heating to 100 ℃ and stirring for 2 hours. After the reaction is finished, removing the solvent and the by-product under reduced pressure to obtain viscous liquid polyborosiloxane with a small amount of residual diethylene glycol dimethyl ether, wherein the content of the diethylene glycol dimethyl ether is 20 wt%;
(2) polyborosiloxane modified ammonium polyphosphate: and (2) mixing polyborosiloxane (containing 5g of polyborosiloxane) with a small amount of residual diethylene glycol dimethyl ether prepared in the step (1) with ammonium polyphosphate (100g), stirring at a high speed (the rotating speed of 24000rpm/min) in a grinder for 30min for modification, and drying to obtain polyborosiloxane modified ammonium polyphosphate.
Comparative example
(1) Preparation of polyborosiloxane: 0.1mol (6.18g) of boric acid and 0.2mol (29.65g) of vinyltrimethoxysilane were dispersed in 35.83g of diethylene glycol dimethyl ether in a reaction vessel equipped with a stirring and refluxing apparatus, and a hydrochloric acid solution was added dropwise to adjust the pH to 3, followed by warming to 140 ℃ and stirring for 2 hours. After the reaction is finished, decompressing to remove the solvent and the by-product, and drying to obtain solid polyborosiloxane;
(2) polyborosiloxane modified ammonium polyphosphate: and (2) mixing 10g of polyborosiloxane prepared in the step (1) with 100g of ammonium polyphosphate, stirring at a high speed (the rotating speed of 24000rpm/min) for 40min in a grinder for modification, and drying to obtain the solid polyborosiloxane modified ammonium polyphosphate.
As shown in fig. 1 to 6, fig. 1 is a scanning electron microscope image of unmodified ammonium polyphosphate, fig. 2 to 5 are scanning electron microscope images of polyborosiloxane-modified ammonium polyphosphate prepared in examples 1 to 4, respectively, and fig. 6 is a scanning electron microscope image of solid polyborosiloxane-modified ammonium polyphosphate obtained in a comparative example.
As can be seen from fig. 1, the unmodified ammonium polyphosphate had a smooth surface; as can be seen from fig. 2 to 5, a layer of relatively smooth film exists on the surface of the polyborosiloxane modified ammonium polyphosphate, and the smoothness of the polyborosiloxane film layer increases with the increase of the amount of the polyborosiloxane film. In fig. 4 (example 3), the modified ammonium polyphosphate exhibited a spherical-like morphology, whereas in fig. 5, a dense coating could not be formed due to the relatively small amount of polyborosiloxane. In fig. 6, the shape of the ammonium polyphosphate modified by the solid polyborosiloxane is not significantly changed, and no coating film layer appears, which indicates that the polyborosiloxane with a certain viscosity can form a dense film layer.
Performance testing in flame retardant polyurethane materials:
respectively adding 4g of unmodified ammonium polyphosphate, 4g of modified ammonium polyphosphate prepared in examples 1 to 4 and 1 g of modified ammonium polyphosphate into six parts of 32g of polyurethane slurry (with the solid content of 50 wt%), stirring and dispersing, and drying at 80 ℃ to prepare six groups of flame-retardant polyurethane materials, namely an unmodified group, examples 1 to 4 and a comparative group.
Fig. 7, fig. 8 and fig. 9 are scanning electron microscope cross-sectional views of the flame retardant polyurethane materials prepared in the unmodified group, the example 2 group and the comparative example group, respectively, and it can be seen from fig. 7 that the unmodified ammonium polyphosphate has a large polarity, a large amount of agglomeration occurs in the matrix, and a distinct boundary exists between the ammonium polyphosphate and the matrix. As can be seen from fig. 8, the polyborosiloxane film on the surface of the ammonium polyphosphate after high-speed stirring treatment reduces the surface polarity thereof, improves the compatibility with the matrix, does not have an obvious boundary, and in addition, the presence of the polyborosiloxane film effectively reduces the mutual agglomeration among the ammonium polyphosphates, so that the dispersibility of the ammonium polyphosphate is also improved. In contrast, solid polyborosiloxane modified ammonium polyphosphate exhibited some degree of agglomeration and had no improvement in compatibility with the matrix.
And detecting and analyzing the flame retardant properties of the six groups of flame retardant polyurethane materials, wherein the flame retardant property detection comprises the following steps: limiting Oxygen Index (LOI) and vertical burn. Wherein, the residual carbon amount is obtained by placing sample powder in a muffle furnace (700 ℃), and observing the residual carbon amount before and after heating; the oxygen index of the flame retardant performance test refers to GB/T2406.2-2009; the vertical burning test is referred to GB/T2408-2008.
Table 1 shows the comparison of the performance tests of six groups of flame-retardant polyurethane materials
The results in Table 1 show that the polyborosiloxane coated on the surface of the ammonium polyphosphate can obviously improve the residual carbon amount of the ammonium polyphosphate at high temperature, the flame retardant property of the ammonium polyphosphate is obviously improved when the polyborosiloxane is applied to a polyurethane composite material, the limiting oxygen index is improved to more than 28 percent from 25.3 percent (unmodified ammonium polyphosphate), and the ammonium polyphosphate can pass the V-0 grade of vertical combustion. The polyborosiloxane forms a layer of compact protective film on the surface of the ammonium polyphosphate, so that the compatibility of the ammonium polyphosphate in a polymer matrix can be improved, the thermal stability of the ammonium polyphosphate is improved, the carbonization of the polymer matrix is promoted, and the flame retardant property is improved.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and it should be understood that any person skilled in the art can make modifications and equivalents of the above-described embodiments without departing from the scope of the present invention.
Claims (10)
1. The polyborosiloxane modified ammonium polyphosphate is characterized by comprising ammonium polyphosphate and polyborosiloxane coated on the surface of the ammonium polyphosphate.
2. The method for preparing polyborosiloxane-modified ammonium polyphosphate according to claim 1, comprising the steps of:
(1) under an acidic condition, boric acid and a silane coupling agent are subjected to a polycondensation reaction in a solvent, and after the reaction is finished, the polyborosiloxane in a viscous liquid state is obtained through post-treatment;
(2) and mixing the obtained viscous liquid polyborosiloxane with ammonium polyphosphate, stirring for modification, and drying to obtain the polyborosiloxane modified ammonium polyphosphate.
3. The production method according to claim 2, wherein in the step (1), the molar ratio of the boric acid to the silane coupling agent is (0.2 to 1): 1.
4. the method according to claim 2, wherein in the step (1), the silane coupling agent is one or both of vinyltrimethoxysilane and vinyltriethoxysilane.
5. The method according to claim 2, wherein in the step (1), the pH value of the polycondensation reaction is 1 to 3.
6. The production method according to claim 2, wherein in the step (1), the solvent is diethylene glycol dimethyl ether.
7. The method according to claim 2, wherein in the step (1), the reaction temperature of the polycondensation is 80 to 180 ℃ and the reaction time is 2 to 8 hours.
8. The method according to claim 2, wherein the solvent content of the viscous liquid polyborosiloxane obtained in step (1) is 3 to 50 wt%.
9. The preparation method according to claim 2, wherein in the step (2), the mass ratio of the polyborosiloxane to the ammonium polyphosphate is 1: (5-20).
10. The preparation method according to claim 2, wherein in the step (2), the stirring speed for stirring modification is 20000 to 30000rpm/min, and the stirring time is 10 to 40 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111013499.6A CN113652005B (en) | 2021-08-31 | 2021-08-31 | Polyborosiloxane modified ammonium polyphosphate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111013499.6A CN113652005B (en) | 2021-08-31 | 2021-08-31 | Polyborosiloxane modified ammonium polyphosphate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113652005A true CN113652005A (en) | 2021-11-16 |
| CN113652005B CN113652005B (en) | 2023-04-18 |
Family
ID=78482517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111013499.6A Active CN113652005B (en) | 2021-08-31 | 2021-08-31 | Polyborosiloxane modified ammonium polyphosphate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113652005B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117327347A (en) * | 2023-09-19 | 2024-01-02 | 江苏海聚新材料科技有限公司 | Flame-retardant polypropylene and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570246A (en) * | 2018-01-24 | 2018-09-25 | 北京化工大学 | A kind of preparation method of the ammonium polyphosphate with activity of cross-linking reaction group |
| CN109251386A (en) * | 2018-07-02 | 2019-01-22 | 广东安普智信电气有限公司 | The resistance to fire proofing of shock resistance, preparation method and the application in cable protection pipe |
| CN112143034A (en) * | 2020-08-14 | 2020-12-29 | 杭州师范大学 | Preparation method and application of hydrogen-containing polyborosiloxane modified white carbon black |
| CN112552696A (en) * | 2020-11-28 | 2021-03-26 | 重庆交通大学 | Low-smoke flame-retardant modified asphalt suitable for paving extra-long tunnel and preparation method thereof |
-
2021
- 2021-08-31 CN CN202111013499.6A patent/CN113652005B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570246A (en) * | 2018-01-24 | 2018-09-25 | 北京化工大学 | A kind of preparation method of the ammonium polyphosphate with activity of cross-linking reaction group |
| CN109251386A (en) * | 2018-07-02 | 2019-01-22 | 广东安普智信电气有限公司 | The resistance to fire proofing of shock resistance, preparation method and the application in cable protection pipe |
| CN112143034A (en) * | 2020-08-14 | 2020-12-29 | 杭州师范大学 | Preparation method and application of hydrogen-containing polyborosiloxane modified white carbon black |
| CN112552696A (en) * | 2020-11-28 | 2021-03-26 | 重庆交通大学 | Low-smoke flame-retardant modified asphalt suitable for paving extra-long tunnel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 冉国文: ""膨胀型阻燃剂的表面改性及其在聚丙烯和聚乳酸中的应用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117327347A (en) * | 2023-09-19 | 2024-01-02 | 江苏海聚新材料科技有限公司 | Flame-retardant polypropylene and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113652005B (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113462127B (en) | Modified boron nitride, composite material containing modified boron nitride, and preparation method and application of modified boron nitride | |
| CN110093680B (en) | Graphene/cage type polysilsesquioxane modified polyester fiber and preparation method thereof | |
| CN109851759B (en) | Organic silicon modified epoxy resin, preparation method thereof and organic silicon modified epoxy resin adhesive | |
| CN109265912B (en) | Titanium modified boron phenolic resin and preparation method and application thereof | |
| CN102504271A (en) | Method for preparing hyperbranched polyester modified organic silicon resin | |
| CN109912804B (en) | Preparation method of phosphorus-nitrogen modified lignin-based intumescent flame retardant | |
| CN112980372B (en) | Adhesive and preparation method thereof | |
| CN109369958B (en) | Preparation method and application of organically modified zirconium phosphate | |
| CN113652005B (en) | Polyborosiloxane modified ammonium polyphosphate and preparation method thereof | |
| CN109135650B (en) | Single-component silane modified polyether sealant and preparation method thereof | |
| CN111205487A (en) | Preparation method of organic silicon coated polytetrafluoroethylene anti-dripping agent | |
| CN117487509A (en) | Ceramic flame-retardant fireproof silicone sealant | |
| CN114836060A (en) | Anti-cracking inorganic ceramic building coating and preparation method thereof | |
| CN110670414B (en) | Heat-resistant waterproof wallpaper and preparation method thereof | |
| CN109401710A (en) | Dual-component silicane modified polyether seal glue and preparation method thereof | |
| CN101974290B (en) | Transparent flame-retardant organic silicon coating solution and preparation method thereof | |
| CN111849290B (en) | High-thermal-conductivity flame-retardant acrylic resin coating and preparation method thereof | |
| CN109880566A (en) | One kind having high thermal stability electronics new material and preparation method thereof | |
| CN110628170B (en) | Graphene oxide-phenolic aerogel material based on silane modification and preparation method thereof | |
| CN117070180A (en) | Reactive polyurethane hot melt adhesive and preparation method thereof | |
| CN111234598A (en) | Alcohol-resistant flame-retardant ink | |
| CN115772264A (en) | Alkoxy-terminated polysiloxane with self-adhesive property and preparation method and application thereof | |
| CN108084930A (en) | A kind of LED display binding agent and preparation method thereof | |
| CN112063181A (en) | Mixing silicone rubber and preparation method thereof | |
| CN111234770A (en) | Silicon rubber 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 |