Modified magnesium flame retardant as well as preparation method and application thereof

Abstract

The invention discloses a modified magnesium flame retardant as well as a preparation method and application thereof. The preparation method comprises the following steps: by taking a fluorine-containing surface modifier as a modifier, carrying out modification reaction on a magnesium-containing inorganic compound to obtain the modified magnesium-based flame retardant. The invention also discloses a preparation method of the organic polymer composite material, which comprises the following steps: uniformly mixing the organic polymer material and the modified magnesium flame retardant to obtain a first component; mixing the first component with a light curing agent serving as a second component, and then carrying out light curing to prepare the organic polymer composite material. The modified magnesium flame retardant is prepared by using a surface modification method, the operation is simple, the modification effect is good, and the cost is easy to control. The prepared organic polymer composite material has high flame retardance and low dielectric constant performance, can be widely applied to the field of 5G communication, and is particularly applied to 5G chip packaging or 5G communication equipment shell materials.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and specifically relates to a modified magnesium-based flame retardant and a preparation method and application thereof. Background Art

[0002] 5G communication is a microwave-based communication technology that has a larger theoretical communication bandwidth than 4G technology, but it also brings about greater power consumption and weak microwave signal penetration. Therefore, a 5G chip package and 5G communication equipment housing material that can meet both flame retardancy and low dielectric constant is needed.

[0003] As a commonly used packaging material, polymer materials have advantages such as good mechanical properties and less shrinkage during curing, but their dielectric constant is relatively high and cannot meet the dielectric constant requirements of 5G communication packaging materials. At the same time, as a polymer material, it is inherently flammable. Taking epoxy resin materials as an example, epoxy resin is a commonly used packaging material with advantages such as good mechanical properties and less shrinkage during curing, but the dielectric constants of existing epoxy resin materials are mostly between 3.5 and 5, which is difficult to meet the requirements of existing 5G communication materials that the dielectric constant is less than 3 and the smaller the better. In addition, epoxy resin is flammable as a polymer material and has the risk of causing fire when used as a packaging material outside high-heat devices (such as 5G chips).

[0004] As for the flammability of polymer materials, flame retardants are usually added to improve the flame retardancy of the overall composite material. Common flame retardants can be divided into halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, boron flame retardants, silicon flame retardants, intumescent flame retardants, hydroxide flame retardants and magnesium flame retardants. Magnesium flame retardants are high-end flame retardants with environmental protection, smoke suppression and droplet suppression effects, but their addition to polymer materials will have a negative impact on the dielectric constant of polymer materials.

[0005] There are usually three methods to reduce the dielectric constant of polymer materials. One is to introduce a large amount of fluorine or silicon into the material monomer to form carbon-fluorine bonds or carbon-silicon bonds to reduce the molecular polarity, thereby reducing the dielectric constant of the composite material. The second is to introduce pores to reduce the material density, thereby reducing the dielectric constant of the composite material. However, since the uniformity of the void distribution and the removal of the porogen are generally difficult to ensure, it is generally achieved by introducing hollow inorganic particles. The third is to add fillers with low dielectric constants to reduce the overall dielectric constant of the composite material. However, the monomer modification, hollow filler modification and other methods of regulating the dielectric constant of polymer materials have the problems of high synthesis cost and complex synthesis process.

[0006] The commonly used additive flame retardants in polymer materials have little effect on regulating the dielectric constant of the material as a whole, and there are few reports. There are also few reports on the commonly used methods for regulating the dielectric constant of polymer composite materials to improve the flame retardant ability of polymer composite materials. For highly polar magnesium-containing inorganic compound powders, there are currently no reports on methods for regulating the dielectric constant of polymer composite materials. Therefore, how to provide a modified magnesium-based flame retardant to reduce the dielectric constant of organic polymer composites is a technical problem that needs to be solved urgently. Summary of the invention

[0007] The main purpose of the present invention is to provide a modified magnesium-based flame retardant and a preparation method and application thereof, and to overcome the deficiencies of the prior art by adding the modified magnesium-based flame retardant to an organic polymer composite material to improve the flame retardancy of the organic polymer composite material while reducing the dielectric constant of the organic polymer composite material.

[0008] In order to realize the aforementioned invention, the technical solution of the present invention includes:

[0009] One aspect of the present invention provides a method for preparing a modified magnesium-based flame retardant, comprising using a fluorine-containing surface modifier as a modifier to perform a modification reaction on a magnesium-containing inorganic compound to obtain the modified magnesium-based flame retardant.

[0010] One aspect of the present invention provides a modified magnesium-based flame retardant obtained by the aforementioned preparation method.

[0011] Another aspect of the present invention also provides a method for preparing an organic polymer composite material, comprising uniformly mixing an organic polymer material and the aforementioned modified magnesium-based flame retardant to obtain a first component; mixing the first component with a photocuring agent as a second component, and then performing photocuring to obtain an organic polymer composite material.

[0012] Another aspect of the present invention also provides an organic polymer composite material obtained by the above-mentioned preparation method, wherein the dielectric constant of the organic polymer composite material is 2.1-2.8.

[0013] Another aspect of the present invention also provides the application of the organic polymer composite material obtained by the aforementioned preparation method in the field of 5G communications.

[0014] Compared with the prior art, the present invention has at least the following beneficial effects:

[0015] (1) The present invention utilizes a modified magnesium-based flame retardant to effectively regulate the dielectric constant of an organic polymer composite material, has low synthesis and operation costs, and has a small amount of addition, low filler cost, and little effect on the mechanical properties, adhesion and other properties of the organic polymer; at the same time, the organic polymer composite material has both high flame retardancy and low dielectric constant properties, has great development potential and market application value, and is of great significance to the development of magnesium resources;

[0016] (2) The present invention uses a surface modification method for magnesium-based flame retardants, which is simple to operate, has a good modification effect, and is easy to control costs. DETAILED DESCRIPTION

[0017] In view of the problems existing in the above-mentioned prior art, the inventors of the present invention have conducted extensive and in-depth research and have provided a modified magnesium-based flame retardant and a preparation method and application thereof. A fluorine-containing surface modifier is used as a modifier to carry out a modification reaction on a magnesium-containing inorganic compound to obtain a modified magnesium-based flame retardant. By adding the modified magnesium-based flame retardant to an organic polymer composite material, the flame retardancy of the organic polymer composite material is improved while the dielectric constant of the organic polymer composite material is reduced.

[0018] The technical solution, its implementation process and principle will be further explained as follows.

[0019] As one aspect of the technical solution of the present invention, a method for preparing a modified magnesium-based flame retardant is provided, which comprises using a fluorine-containing surface modifier as a modifier to perform a modification reaction on a magnesium-containing inorganic compound to obtain the modified magnesium-based flame retardant.

[0020] In some embodiments, the preparation method of the modified magnesium-based flame retardant comprises mixing a magnesium-containing inorganic compound, water optionally added or not added, and ethanol optionally added or not added to form a slurry; mixing a fluorine-containing surface modifier with the slurry, stirring to carry out a modification reaction, and obtaining the modified magnesium-based flame retardant.

[0021] In some embodiments, the mass ratio of the magnesium-containing inorganic compound, water, ethanol and fluorine-containing surface modifier is 89-125:0-715:0-715:1-10.

[0022] In some embodiments, the temperature of the modification reaction is 40-90° C., and the time of the modification reaction is 1-7 h.

[0023] In some embodiments, the stirring speed is 100-600 rpm.

[0024] In some embodiments, the magnesium-containing inorganic compound includes at least any one of magnesium hydroxide, magnesium aluminum hydrotalcite, magnesium carbonate, hydromagnesite, attapulgite, brucite, serpentine, dolomite and talc, but is not limited thereto.

[0025] In some preferred embodiments, the particle diameter of the magnesium hydroxide is 200-500 nm.

[0026] In some embodiments, the fluorine-containing surface modifier includes at least any one of sodium perfluorooctanoate, potassium perfluorohexylethylsulfonate, perfluorooctyltriethoxysilane, etc., but is not limited thereto.

[0027] For example, the coating modification of magnesium-containing inorganic compounds by sodium perfluorooctanoate and potassium perfluorohexylethylsulfonate in fluorine-containing surface modifiers; and the coupling modification of perfluorooctyltriethoxysilane and magnesium-containing inorganic compounds.

[0028] In some specific embodiments, the preparation method of the modified magnesium flame retardant specifically comprises the following steps:

[0029] Calculated by weight, 89-125 parts of magnesium hydroxide, 0-715 parts of water and 0-715 parts of ethanol are mixed to form a slurry; 1-10 parts of a fluorine-containing surface modifier is mixed with the slurry, stirred at 100-600 rpm, and then a modification reaction is carried out at 40-90° C. for 1-7 hours to obtain the modified magnesium flame retardant.

[0030] As one aspect of the technical solution of the present invention, a modified magnesium-based flame retardant obtained by the above-mentioned preparation method is provided.

[0031] As another aspect of the technical solution of the present invention, a method for preparing an organic polymer composite material is provided, which comprises uniformly mixing an organic polymer material and the aforementioned modified magnesium-based flame retardant to obtain a first component; mixing the first component with a photocuring agent as a second component, and then performing a photocuring reaction to obtain an organic polymer composite material.

[0032] In some embodiments, the mass ratio of the organic polymer material, the modified magnesium flame retardant and the photocuring agent is 90-110:1.8-10.3:0.5-10.2.

[0033] In some embodiments, the method for preparing the organic polymer composite material comprises:

[0034] The organic polymer material and the modified magnesium flame retardant are uniformly mixed by a first stirring process, and then subjected to a first high-temperature defoaming process to obtain a first component.

[0035] In some preferred embodiments, the organic polymer material includes epoxy resin, and is particularly preferably E-44 epoxy resin.

[0036] In some preferred embodiments, the temperature of the first stirring is 75-93° C., the time of the first stirring is 2-8 h, and the rotation speed of the first stirring is 100-600 rpm.

[0037] In some preferred embodiments, the temperature of the first high-temperature defoaming is 75-93° C., and the time of the first high-temperature defoaming is 12-18 hours.

[0038] In some embodiments, the method for preparing the organic polymer composite material further comprises:

[0039] The first component and the photocuring agent are mixed evenly by a second stirring, and then a second high-temperature degassing is performed, and then photocuring is performed to obtain the organic polymer composite material.

[0040] In some preferred embodiments, the temperature of the second stirring is 75-93° C., the time of the second stirring is 4-15 min, and the rotation speed of the second stirring is 100-600 rpm.

[0041] In some preferred embodiments, the temperature of the second high-temperature defoaming is 75-93° C., and the time of the second high-temperature defoaming is 30-150 min.

[0042] In some preferred embodiments, the photocuring agent includes a fluorine-containing photocuring agent, and 6976 photocuring agent is particularly preferred.

[0043] In some preferred embodiments, the light used for the photocuring includes ultraviolet light, and the photocuring time is 5-20 minutes.

[0044] In some specific embodiments, the method for preparing the organic polymer composite material specifically comprises the following steps:

[0045] The organic polymer material and the modified magnesium flame retardant are stirred at 100-600 rpm and 75-93° C. for 2-8 hours to mix evenly, and then high-temperature defoaming is performed at 75-93° C. for 12-18 hours to obtain a first component;

[0046] The first component and the photocuring agent as the second component are stirred at 100-600 rpm and 75-93° C. for 4-15 minutes to be uniformly mixed, then high-temperature defoaming is performed at 75-93° C. for 30-150 minutes, and then photocuring is performed to obtain the organic polymer composite material.

[0047] As another aspect of the technical solution of the present invention, an organic polymer composite material obtained by the above-mentioned preparation method is provided.

[0048] Furthermore, the dielectric constant of the organic polymer composite material is 2.1-2.8.

[0049] As another aspect of the technical solution of the present invention, an application of the aforementioned organic polymer composite material in the field of 5G communications is provided.

[0050] In some preferred embodiments, the application includes: application of the organic polymer composite material in 5G chip packaging or 5G communication equipment housing materials.

[0051] In summary, the present invention utilizes modified magnesium-based flame retardants to effectively regulate the dielectric constant of organic polymer composite materials, has low synthesis and operation costs, and has a small amount of addition, low filler cost, and little effect on the mechanical, adhesion and other properties of organic polymers; at the same time, the organic polymer composite materials have both high flame retardancy and low dielectric constant properties, have great development potential and market application value, and are of great significance to the development of magnesium resources.

[0052] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment.It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.Those skilled in the art can make modifications or equivalent substitutions based on the understanding of the technical scheme of the present invention without departing from the spirit and scope of the technical scheme of the present invention, and all should be included in the protection scope of the present invention.

[0053] If the specific experimental steps or conditions are not specified in the embodiment, the operation or conditions of the conventional experimental steps described in the literature in this field can be carried out. The reagents or instruments used without indicating the manufacturer are all conventional reagent products that can be obtained commercially. Exemplarily, the dielectric constant test of the present invention is determined using AS2853A of Shanghai Aiyi Electronic Equipment Co., Ltd., and the flame retardant test is tested using iCone mini cone calorimeter of FIRE TESTING TECHNOLOGY, UK. The commercial selection of the remaining raw materials or instruments not mentioned is all conventional selection, and does not involve the core technical means of the present invention.

[0054] Example 1

[0055] (1) Take 103 parts of magnesium hydroxide, add 611 parts of water and 0 parts of ethanol to make a slurry, add 7 parts of sodium perfluorooctanoate as a modifier, control the reaction temperature to 61°C, control the stirring speed to 175 rpm, react for 5 hours, filter, and obtain a modified magnesium hydroxide flame retardant;

[0056] (2) Take 96 parts of E-44 epoxy resin, add 3.9 parts of modified magnesium hydroxide flame retardant, control the stirring temperature to 80°C, the stirring time to 5h, the stirring speed to 595rpm, then defoam at high temperature, the temperature to 81°C, the time to 16h, obtain component A, 1 part of 6976 photocuring agent, recorded as component B, after component B is added to component A, the stirring speed is controlled at 595rpm, the stirring temperature to 80°C, the stirring time to 12min, then defoam at high temperature for 35min, the temperature to 81°C, and then immediately carry out photocuring reaction to obtain an epoxy resin composite material.

[0057] The parts in step (1) and step (2) are all parts by mass, and 1 part by mass in step (1) is not equal to 1 part by mass in (2). The dielectric constant test results and flame retardancy test results of epoxy resin are shown in Table 1. Except for the dielectric constant, the other data in the table are given by the cone calorimeter.

[0058] Example 2

[0059] The operation steps are the same as those in Example 1, wherein in step (1): 99 parts of magnesium hydroxide; 503 parts of water; 0 parts of ethanol; 9 parts of potassium perfluorohexylethylsulfonate; reaction temperature 58° C.; stirring speed 195 rpm; reaction time 5 h;

[0060] In step (2), component A includes: 95 parts of E-44 epoxy resin; 3.9 parts of modified magnesium hydroxide; stirring temperature of 81°C; stirring time of 5h; stirring speed of 555rpm; defoaming temperature of 82°C; defoaming time of 14h; component B includes: 1 part of 6976 photocuring agent; after component B is added to component A: stirring temperature of 81°C; stirring speed of 555rpm; stirring time of 10min; defoaming temperature of 82°C; defoaming time of 65min.

[0061] Example 3

[0062] The operation steps are the same as those in Example 1, wherein in step (1): 110 parts of magnesium hydroxide; 105 parts of water; 231 parts of ethanol; 3 parts of perfluorooctyltriethoxysilane; reaction temperature 73°C; stirring speed 150 rpm; reaction time 4 h;

[0063] In step (2), component A includes: 103 parts of E-44 epoxy resin; 2.1 parts of modified magnesium hydroxide; stirring temperature of 85°C; stirring time of 4 hours; stirring speed of 500 rpm; defoaming temperature of 86°C; defoaming time of 18 hours; component B includes: 1 part of 6976 photocuring agent; after component B is added to component A: stirring temperature of 85°C; stirring speed of 520 rpm; stirring time of 9 minutes; defoaming temperature of 86°C; defoaming time of 75 minutes.

[0064] Example 4

[0065] The operation steps are the same as those in Example 1, except that: in step (2), component A: the modified magnesium hydroxide is 1.9 parts.

[0066] Example 5

[0067] The operation steps are the same as those of Example 2, except that in step (2), component A: the modified magnesium hydroxide is 6.1 parts.

[0068] Example 6

[0069] The operation steps are the same as those of Example 3, except that in step (2), component A: the modified magnesium hydroxide is 4.1 parts.

[0070] Comparative Example 1

[0071] No modified magnesium hydroxide flame retardant is added, and only fluorine-containing photocuring agent 6976 is used to cure the epoxy resin, 99.2 parts of E-44 epoxy resin and 1.1 parts of 6976 photocuring agent; stirring temperature is 80°C; stirring speed is 500 rpm; stirring time is 9 minutes; defoaming temperature is 81°C; and defoaming time is 30 minutes.

[0072] Comparative Example 2

[0073] The operation steps are the same as those of Example 1, except that in step (2), component A: unmodified magnesium hydroxide is 1.9 parts.

[0074] Table 1 Dielectric constant test results and flame retardant test results of epoxy resin composite materials in Examples 1-6 and Comparative Examples 1-2

[0075]

[0076]

[0077] Notes:

[0078] 1. Fire development index = maximum heat release rate / time to reach maximum heat release rate

[0079] 2. Fire performance index = ignition time / maximum heat release rate

[0080] 3. Lower fire development index and higher fire performance index mean higher fire safety

[0081] Compared with Example 4, Example 3 of the present invention has little difference in the amount of modified magnesium hydroxide flame retardant added, but the dielectric constant and fire development index are significantly different. The reason is that the fluorine-containing surface modifiers used in the two examples are different. This also illustrates the regulatory effect of the modification method in the present invention on the dielectric and flame retardant properties of epoxy resin composite materials.

[0082] Comparative Example 1 of the present invention does not add modified magnesium hydroxide flame retardant, and its dielectric constant is not much different from the results of the embodiment and embodiments 4 and 6, and its flame retardant performance is obviously worse than that of embodiments 4 and 6.

[0083] From the above, it can be seen that Examples 1-6 reflect the ability of the modified magnesium flame retardant of the present invention to regulate different dielectric constants of organic polymer composite materials, and at the same time, compared with the control example, it shows better flame retardancy and smoke suppression capabilities. Adding modified magnesium flame retardant can greatly reduce the dielectric constant of organic polymers.

[0084] In summary, the organic polymer composite material prepared by the present invention has both high flame retardancy and low dielectric constant properties, and can be widely used in the field of 5G communications. The present invention can reduce the dielectric constant of the organic polymer composite material by modifying the magnesium-based flame retardant, which is of great significance to the development of huge magnesium resources in my country's salt lake areas and the construction of salt lake science and technology highland.

[0085] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all aspects and are not intended to limit the present invention, the scope of the present invention is defined only by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

[0086] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0087] Although the present invention has been described with reference to illustrative embodiments, it will be appreciated by those skilled in the art that various other changes, omissions and / or additions may be made without departing from the spirit and scope of the present invention and that the elements of the embodiments may be replaced by substantial equivalents. In addition, many modifications may be made without departing from the scope of the present invention to adapt specific circumstances or materials to the teachings of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for performing the present invention, but it is intended that the present invention will include all embodiments within the scope of the appended claims. In addition, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. A method for preparing a modified magnesium flame retardant, characterized in that: include: A fluorine-containing surface modifier is used as a modifier to carry out a modification reaction on a magnesium-containing inorganic compound to obtain a modified magnesium-based flame retardant.

2. The preparation method according to claim 1, characterized in that: include: Mixing a magnesium-containing inorganic compound, water optionally added or not added, and ethanol optionally added or not added to form a slurry; The fluorine-containing surface modifier is mixed with the slurry, and stirred to carry out a modification reaction to obtain the modified magnesium-based flame retardant.

3. The preparation method according to claim 2, characterized in that: The mass ratio of the magnesium-containing inorganic compound, water, ethanol and fluorine-containing surface modifier is 89-125:0-715:0-715:1-10.

4. The preparation method according to claim 2, characterized in that: The temperature of the modification reaction is 40-90°C, and the time of the modification reaction is 1-7h; And / or, the magnesium-containing inorganic compound includes at least any one of magnesium hydroxide, magnesium aluminum hydrotalcite, magnesium carbonate, hydromagnesite, attapulgite, brucite, serpentine, dolomite and talc; Preferably, the particle diameter of the magnesium hydroxide is 200-500 nm; And / or, the fluorine-containing surface modifier includes at least any one of sodium perfluorooctanoate, potassium perfluorohexylethylsulfonate, and perfluorooctyltriethoxysilane; And / or, the stirring speed is 100-600 rpm.

5. The modified magnesium flame retardant obtained by the preparation method according to any one of claims 1 to 4.

6. A method for preparing an organic polymer composite material, characterized in that: include: The organic polymer material and the modified magnesium flame retardant according to claim 5 are mixed uniformly to obtain a first component; The first component is mixed with a light curing agent as a second component, and then light-cured to obtain an organic polymer composite material.

7. The preparation method according to claim 6, characterized in that: The mass ratio of the organic polymer material, the modified magnesium flame retardant and the light curing agent is 90-110:1.8-10.3:0.5-10.

2.

8. The preparation method according to claim 6, characterized in that: include: The organic polymer material and the modified magnesium flame retardant are uniformly mixed by a first stirring process, and then a first high-temperature defoaming process is performed to obtain a first component; Preferably, the organic polymer material comprises epoxy resin, and is particularly preferably E-44 epoxy resin; Preferably, the temperature of the first stirring is 75-93° C., the time of the first stirring is 2-8 h, and the speed of the first stirring is 100-600 rpm; Preferably, the temperature of the first high-temperature degassing is 75-93°C, and the time of the first high-temperature degassing is 12-18h; And / or, the preparation method further comprises: uniformly mixing the first component and the photocuring agent by a second stirring, then performing a second high-temperature degassing, and then performing photocuring to obtain the organic polymer composite material; Preferably, the temperature of the second stirring is 75-93°C, the time of the second stirring is 4-15min, and the speed of the second stirring is 100-600rpm; Preferably, the temperature of the second high-temperature degassing is 75-93°C, and the time of the second high-temperature degassing is 30-150min; Preferably, the photocuring agent includes a fluorine-containing photocuring agent, and 6976 photocuring agent is particularly preferred; Preferably, the light used for the photocuring includes ultraviolet light, and the photocuring time is 5-20 minutes.

9. The organic polymer composite material obtained by the preparation method according to any one of claims 6 to 8, characterized in that: The dielectric constant of the organic polymer composite material is 2.1-2.

8.

10. Application of the organic polymer composite material according to claim 9 in the field of 5G communications, preferably, the application includes: The organic polymer composite material is used in 5G chip packaging or 5G communication equipment housing materials.

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