• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention provides a hydrophobic flame retardant and a preparation method thereof, and relates to the technical field of flame retardant modification. The hydrophobic flame retardant includes 70 to 95 mass percent of a flame retardant and 5 to 5 30 mass percent of a modifier. The flame retardant is one or more of an inorganic flame retardant, a compound intumescent flame retardant component and an elementary intumescent flame retardant. The modifier is one or more of tetraethyl orthosilicate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tri(2—methoxyethoxy)silane, octaphenylpolyoxyethyiene—10, dodecyltrimethoxysilane, dodecyltriethoxysilane, l hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and O octadecyltriethoxysilane. The present invention prepares the hydrophobic flame retardant by multiple surface modification. The flame—retardant performance of the flame retardant is improved While high hydrophobicity is given to the flame retardant. The compatibility of the flame retardant With a polymer matrix is good. The preparation method is simple, and the cost is lower. 1 5
    公开号:NL2025769A
    申请号:NL2025769
    申请日:2020-06-08
    公开日:2021-08-30
    发明作者:Jin Die；Yang Jinian；Zhang Xiangfeng；Zhang Xi；Han Chao；Nie Shibin
    申请人:Univ Anhui Sci & Technology；
    IPC主号:
    专利说明:

    P100509NL00 1HYDROPHOBIC FLAME RETARDANT AND PREPARATIONMETHOD THEREOF
    BACKGROUND Technical Field The present invention relates to the technical field of flame retardant modification, and more particularly to a hydrophobic flame retardant and a preparation method thereof. Related Art Combustible polymer materials widely used in modern life have become one of the main ignition materials for fires, especially urban fires and building fires, and its fire hazard danger is increasingly concerned and valued by people.
    Halogen flame retardants (mainly bromine flame retardants and chlorine flame retardants) have a high flame-retardant efficiency, but in the flame-retardant process, the halogen flame retardants can produce acidic substances, dioxins and the like which have adverse effects on human beings and environments. Inorganic flame retardants mainly including aluminum hydroxides and magnesium hydroxides, and intumescent flame retardants using phosphorus and nitrogen compounds as main components do not contain halogen, and belong to relatively environment-friendly flame retardants. However, at present, the intumescent flame retardants and the inorganic flame retardants have high hydrophilicity, and can migrate to surfaces of materials to exude under the condition of high humidity, thus reducing the flame-retardant performance and other performance of the materials.
    Microencapsulation treatment or surface modification on the flame retardants is an effective method to solve the above problems. According to the introduction of Applied Surface Science, 258:2404-2409, 2012 in the Netherlands, when polymethyl methacrylate is grafted to a surface of nanometer magnesium aluminum hydroxides through a phosphate coupling agent DN-27, the hydrophobicity of the magnesium aluminum hydroxides can be obviously improved, and a water contact angle is increased from less than 10° before modification to 108°. According to the introduction of Polymer Degradation and Stability, 105:150-159, 2014 in England, microencapsulation treatment on ammonium polyphosphate by melamine formaldehyde resin can reduce water solubility of ammonium polyphosphate and improve its compatibility with polymer materials.
    P100509NL00 2 However, the hydrophobic effect of the flame retardants obtained above is still not ideal. A good hydrophobic effect can be obtained by using a fluorine-containing modifier, but the cost is very high, and the fluorine-containing modifier is not suitable for large-scale application.
    SUMMARY In view of the above problems, the present invention provides a hydrophobic flame retardant and a preparation method thereof. The hydrophobic flame retardant is prepared by multiple surface modification. The flame-retardant performance of the flame retardant is improved while high hydrophobicity is given to the flame retardant. The compatibility of the flame retardant with a polymer matrix is favorably improved. The adverse impact of the flame retardant on materials 1s reduced. Meanwhile, the preparation method related by the present invention is simple, is low in cost, and is suitable for large-scale application. In order to achieve the above objectives, the present invention is realized through the following technical solution: The hydrophobic flame retardant includes 70 to 95 mass percent of a flame retardant and 5 to 30 mass percent of a modifier. The flame retardant is one or more of an inorganic flame retardant, a compound intumescent flame retardant component and an elementary intumescent flame retardant. The modifier is one or more of tetraethyl orthosilicate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tri(2-methoxyethoxy)silane, octaphenylpolyoxyethyiene-10, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane. Preferably, the inorganic flame retardant is selected from one or more of aluminum hydroxides, magnesium hydroxides and magnesium aluminum hydroxides. Preferably, the compound intumescent flame retardant component includes an acid source and a carbon source. Preferably, the acid source is one or more of ammonium polyphosphate, melamine ammonium polyphosphate and melamine ammonium phosphate. The carbon source is one or two of dipentaerythritol and a macromolecular triazine charring agent. Preferably, a proportion of the acid source to the carbon source is 1-5:1. Preferably, the elementary intumescent flame retardant is one or two of
    P100509NL00 3 3,9-dihydroxy-3,9-dioxo-2,4,8, 10-tetraoxa-3,9-diphosphaspiro[ 5,5 Jundecane-3,9-dimela mine, and bis(2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-1-ox0-4-methylene) acid melamine phosphate. The preparation method of the hydrophobic flame retardant of the present invention includes the following steps: firstly dispersing a flame retardant into a mixed solution of ethyl alcohol and water; performing stirring heating to 30 to 50°C; regulating a pH value of the solution to 8 to 12; adding a modifier; performing reaction at the temperature for 1 to 3 h; then, raising the temperature to 55 to 80°C; next, adding the modifier again; continuously performing reaction at the temperature for 1 to 3 h; finally, performing cooling to a room temperature; performing suction filtration and washing; and performing drying to a constant weight to obtain the hydrophobic flame retardant. The present invention has the following beneficial effects: The hydrophobic flame retardant of the present invention can be applicable to flame retardance on polyolefin including polyethylene, polypropylene, ethylene-vinyl acetate copolymers, polyurethane or polylactic acid, and can also be used for flame retardance on coatings and colloids. The compatibility of the hydrophobic flame retardant with a polymer matrix is good. By using the hydrophobic flame retardant of the present invention, the problems of poor hydrophobicity and the like of an existing flame retardant are solved, the impact of the moisture absorption performance of the flame retardant on the water-resistant performance of the materials is reduced, and meanwhile, the flame-retardant performance is improved. Additionally, production raw materials have no pollution, the production cost is lower, and the preparation method is simple.
    BRIEF DESCRIPTION OF THE DRAWINGS To describe the technical solutions in embodiments of this application or in the existing technology more clearly, the following briefly describes the accompanying drawings required for describing the embodiments or the existing technology. Apparently, the accompanying drawings in the following description show merely some embodiments of the present disclosure, and a person of ordinary skill in the art may derive other drawings from the accompanying drawings without creative efforts. Figure 1 is a schematic diagram of a water contact angle of a hydrophobic flame
    P100509NL00 4 retardant in Embodiment 1. Figure 2 is a schematic diagram of a water contact angle of a hydrophobic flame retardant in Embodiment 2. Figure 3 is a schematic diagram of a water contact angle of a hydrophobic flame retardant in Embodiment 3. Figure 4 is a schematic diagram of a water contact angle of a hydrophobic flame retardant in Embodiment 4. Figure 5 is a schematic diagram of a water contact angle of a hydrophobic flame retardant in Embodiment 5.
    DETAILED DESCRIPTION In order to make the objectives, technical solutions, and advantages of the present invention more comprehensible, the technical solutions according to embodiments of the present invention are clearly and completely described in the following with reference to the embodiments of the present invention. Apparently, the embodiments in the following description are merely some rather than all of the embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. The present invention provides a hydrophobic flame retardant, including 70 to 95 mass percent of a flame retardant and 5 to 30 mass percent of a modifier. The flame retardant is one or more of an inorganic flame retardant, a compound intumescent flame retardant component and an elementary intumescent flame retardant. The modifier is one or more of tetraethyl orthosilicate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tri(2-methoxyethoxy)silane, octaphenylpolyoxyethyiene-10, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane. The inorganic flame retardant is selected from one or more of aluminum hydroxides, magnesium hydroxides and magnesium aluminum hydroxides. The elementary intumescent flame retardant is one or two of 3,9-dihydroxy-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5Jundecane-3,9-dimela mine, and bis(2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-1-ox0-4-methylene) acid melamine phosphate.
    P100509NL00
    The compound intumescent flame retardant component includes an acid source and a carbon source.
    The flame retardant in the present invention may be the acid source and/or the carbon source in the compound intumescent flame retardant component.
    The acid source is one or more of ammonium polyphosphate, melamine ammonium 5 polyphosphate and melamine ammonium phosphate.
    The carbon source is one or two of dipentaerythritol and a macromolecular triazine charring agent.
    When the flame retardant is the acid source and the carbon source, a proportion of the acid source to the carbon source is 1-5:1. A preparation method of the hydrophobic flame retardant of the present invention includes the following steps: The flame retardant is firstly dispersed into a mixed solution of ethyl alcohol and water.
    Stirring heating to 30 to 50°C is performed.
    A pH value of the solution is regulated to 8 to 12. The modifier is added.
    Reaction is performed at the temperature for 1 to 3 h.
    Then, the temperature is raised to 55 to 80°C.
    The modifier is added again.
    Reaction is continuously performed at the temperature for 1 to 3 h.
    Finally, cooling is performed to a room temperature, suction filtration and washing are performed, and drying is performed to a constant weight.
    The hydrophobic flame retardant is obtained.
    Specific embodiments: Embodiment 1: A preparation method of a hydrophobic flame retardant includes the following steps: 50 g of magnesium hydroxides were firstly dispersed into a mixed solution of 150 ml of ethyl alcohol and 50 ml of water.
    Stirring heating to 40°C was performed.
    A pH value of the solution was regulated to 9. 10 g of tetraethyl orthosilicate was added.
    Reaction was performed at the temperature for 2 h.
    Then, the temperature was raised to 55°C. 2.5 g of vinyltrimethoxysilane was added again.
    Reaction was continuously performed at the temperature for 1 h.
    Finally, cooling was performed to a room temperature, suction filtration and washing were performed, and drying was performed to a constant weight.
    The hydrophobic flame retardant was obtained.
    The hydrophobic flame retardant of the present embodiment was subjected to hydrophobicity test: a water contact angle of the hydrophobic flame retardant prepared according to Embodiment 1 was 138.16° (as shown in Figure 1). Embodiment 2:
    P100509NL00 6 A preparation method of a hydrophobic flame retardant includes the following steps: 50 g of magnesium hydroxides were firstly dispersed into a mixed solution of 150 ml of ethyl alcohol and 50 ml of water. Stirring heating to 40°C was performed. A pH value of the solution was regulated to 9. 10 g of tetraethyl orthosilicate was added. Reaction was performed at the temperature for 2 h. Then, the temperature was raised to 60°C. 2 g of dodecyltriethoxysilane was added again. Reaction was continuously performed at the temperature for 1.5 h. Finally, cooling was performed to a room temperature, suction filtration and washing were performed, and drying was performed to a constant weight.
    The hydrophobic flame retardant of the present invention was obtained.
    The hydrophobic flame retardant of the present embodiment was subjected to hydrophobicity test: a water contact angle of the hydrophobic flame retardant prepared according to Embodiment 2 was 134.58° (as shown in Figure 2).
    Embodiment 3: A preparation method of a hydrophobic flame retardant includes the following steps: 55 g of a macromolecular triazine charring agent was firstly dispersed into a mixed solution of 150 ml of ethyl alcohol and 50 ml of water. Stirring heating to 35°C was performed. A pH value of the solution was regulated to 10. 10.4 g of tetraethyl orthosilicate was added. Reaction was performed at the temperature for 3 h. Then, the temperature was raised to 55°C. 2.6 g of vinyltrimethoxysilane was added again. Reaction was continuously performed at the temperature for 0.5 h. Finally, cooling was performed to a room temperature, suction filtration and washing were performed, and drying was performed to a constant weight. The hydrophobic flame retardant of the present invention was obtained.
    The hydrophobic flame retardant of the present embodiment was subjected to hydrophobicity test: a water contact angle of the hydrophobic flame retardant prepared according to Embodiment 3 was 137.89° (as shown in Figure 3).
    Embodiment 4: A preparation method of a hydrophobic flame retardant includes the following steps: 45 g of ammonium polyphosphate was firstly dispersed into a mixed solution of 150 ml of ethyl alcohol and 50 ml of water. Stirring heating to 45°C was performed. A pH value of the solution was regulated to 9.5. 10.4 g of tetraethyl orthosilicate was added. Reaction was performed at the temperature for 4 h. Then, the temperature was raised to
    P100509NL00 7 65°C. 2.1 g of vinyltrimethoxysilane was added again. Reaction was continuously performed at the temperature for 2 h. Finally, cooling was performed to a room temperature, suction filtration and washing were performed, and drying was performed to a constant weight. The hydrophobic flame retardant of the present invention was obtained.
    The hydrophobic flame retardant of the present embodiment was subjected to hydrophobicity test: a water contact angle of the hydrophobic flame retardant prepared according to Embodiment 4 was 135.78 (as shown in Figure 4).
    Embodiment 5: A preparation method of a hydrophobic flame retardant includes the following steps: 45 g of ammonium polyphosphate was firstly dispersed into a mixed solution of 150 ml of ethyl alcohol and 50 ml of water. Stirring heating to 45°C was performed. A pH value of the solution was regulated to 9.5. 10 g of tetraethyl orthosilicate was added. Reaction was performed at the temperature for 4 h. Then, the temperature was raised to 60°C. 2.5 g of dodecyltriethoxysilane was added again. Reaction was continuously performed at the temperature for 1.5 h. Finally, cooling was performed to a room temperature, suction filtration and washing were performed, and drying was performed to a constant weight. The hydrophobic flame retardant of the present invention was obtained.
    The hydrophobic flame retardant of the present embodiment was subjected to hydrophobicity test: a water contact angle of the hydrophobic flame retardant prepared according to Embodiment 5 was 131.78° (as shown in Figure 5).
    Performance test: Experimental example: The hydrophobic flame retardant in Embodiment 4 of the present invention was subjected to flame-retardant performance test: firstly, an intumescent flame retardant (prepared from the hydrophobic flame retardant prepared according to Embodiment 4 and trishydroxyethyl isocyanurate according to a mass ratio of 2:1) accounting for 30% of the total mass of a system was subjected to melt blending with polyethylene accounting for 70% of the total mass of the system according to a mass ratio to obtain flame-retardant polyethylene.
    Then, the flame-retardant polyethylene was cut into standard splines of 100 mmx6.5
    P100509NL00 8 mmx3 mm after plate pressing. A limit oxygen index test was performed on an HC-2 type oxygen index instrument according to a standard ASTM D2863-77 to obtain its limit oxygen index of 33.5% through the test. Comparative example: The intumescent flame retardant (the intumescent flame retardant was prepared from ammonium polyphosphate and trishydroxyethyl isocyanurate according to a mass ratio of 2:1) accounting for 30% of the total mass of a system was subjected to melt blending with polyethylene accounting for 70% of the total mass of the system according to a mass ratio to obtain flame-retardant polyethylene.
    Then, after plate pressing, the flame-retardant polyethylene was cut into standard splines of 100 mmx6.5 mmx3 mm to be detected to obtain its limit oxygen index of
    31.2% through the test.
    It can be seen from the above experimental example and comparative example that under the condition of keeping the total addition amount of the intumescent flame retardant unchanged at 30%, the oxygen index of the flame-retardant polyethylene prepared in the embodiments was 2.3 units higher than the oxygen index of the flame-retardant polyethylene prepared in the comparative example. It shows that the hydrophobic flame retardant of the present invention obviously improves the flame-retardant performance of the ammonium polyphosphate.
    The water contact angle of the hydrophobic flame retardant prepared in Embodiment 4 of the present invention was 135.78°. The water contact angle of the ammonium polyphosphate not subjected to modification treatment was 24.7°. The hydrophobic performance of the ammonium polyphosphate was quite obviously improved.
    The above embodiments are merely provided for describing the technical solutions of the present disclosure, but are not intended to limit the present disclosure. It should be understood by a person of ordinary skill in the art that although the present disclosure has been described in detail with reference to the foregoing embodiments, modifications can be made to the technical solutions described in the foregoing embodiments, or equivalent replacements can be made to some technical features in the technical solutions, as long as such modifications or replacements do not cause the essence of corresponding technical solutions to depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
    权利要求:
    Claims (8)
    [1]
    A hydrophobic flame retardant, characterized in that it comprises 70-95% by weight flame retardant and 5-30% by weight modifier; the flame retardant comprising one or more of an inorganic flame retardant, a component of a compound expanded flame retardant and an elemental expanded flame retardant; the modifying agent comprising one or more of tetraethylsilicate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, polyoxyethyleneoctylphenol ether-10, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyloctyl-triethoxysilane, and octadecyloctyl-triethoxysilane.
    [2]
    A hydrophobic flame retardant according to claim 1, characterized in that the inorganic flame retardant is selected from one or more of aluminum hydroxide, magnesium hydroxide and magnesium aluminum hydroxide.
    [3]
    The hydrophobic flame retardant according to claim 1, characterized in that the components of the composite expanded flame retardant comprise an acid source and a carbon source.
    [4]
    A hydrophobic flame retardant according to claim 3, characterized in that the acid source is selected from one or more of ammonium polyphosphate, melamine ammonium polyphosphate and melamine ammonium phosphate.
    [5]
    A hydrophobic flame retardant according to claim 3, characterized in that the carbon source is selected from one or two of dipentaerythritol and macromolecular triazine-based carbon-forming agent.
    [6]
    A hydrophobic flame retardant according to claim 3, characterized in that the ratio of the acid source to the carbon source is 1-5:1.
    [7]
    The hydrophobic flame retardant according to claim 1, characterized in that the elemental expanded flame retardant is selected from one or two of 3,9-dihydroxy-3,9-dioxO-2,4,8, 10-tetraoxa-3, 9-Diphosfaspiro[5,5]undecane-3,9-dimelamine and bis(2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane-1-oxy-4-methylene) acid phosphate melamine.
    [8]
    Method of preparation of the hydrophobic flame retardant according to any one of claims 1 to 7, characterized in that it comprises the following steps: - first disperse the flame retardant in the mixture of ethanol and water, - stir and increase the temperature to 30 -50°C, 9
    P100509EN00 10 - adjust the pH of the solution to 8-12, - add the modifier, - react at this temperature for 1-3 hours, then increase the temperature to 55-80°C, - add the modifier again - react at this temperature for 1-3 hours and finally cool to room temperature, and - suction filter, wash and dry to constant weight to obtain the hydrophobic flame retardant.
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    同族专利:
    公开号 | 公开日
    CN111154142A|2020-05-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN100357394C|2006-05-29|2007-12-26|太原理工大学|Preparation method of hydrophobic ultrafine nanometer fire retardant magnesium hydroxide|
    JP2010059298A|2008-09-03|2010-03-18|Shin-Etsu Chemical Co Ltd|Room-temperature curing organopolysiloxane composition and heat foaming fire-resistant coating material|
    CN102850824B|2012-10-16|2014-03-12|河北大学|Modification preparation method of hydrophobic low-water-solubility ammonium polyphosphate |
    CN106381714B|2016-09-14|2019-04-02|南通纺织丝绸产业技术研究院|Preparation method with fire-retardant and hydrophobic function fabric|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CN201910816815|2019-08-30|
    CN202010006423.XA|CN111154142A|2019-08-30|2020-01-03|Hydrophobic flame retardant and preparation method thereof|
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