Phosphorus-containing flame retardant composition, application and flame retardant product

Abstract

The invention discloses a phosphorus-containing flame retardant composition, application and flame retardant products, belonging to the field of flame retardant technology. The provided phosphorus-containing flame retardant composition comprises the following components in parts by weight: 20-60 parts of phosphorus-containing compounds, 1-10 parts of polysiloxanes, 0.1-5 parts of polyalkyl alcohols, 10-30 parts of nitrogen-phosphorus compounds and 1-20 parts of inorganic salts. The above components are coordinated to obtain a novel flame retardant composition with low dielectric constant, high flame retardancy, heat resistance and good stability. The obtained phosphorus-containing flame retardant composition is applied to materials such as nylon, flexible circuit boards, epoxy resins, etc., and can show excellent flame retardant properties.

Description

Technical Field

[0001] The invention relates to the field of flame retardant technology, and in particular to a phosphorus-containing flame retardant composition and application thereof and a flame retardant product. Background Art

[0002] In the traditional 4G communication era, for epoxy resin materials that are widely used, in order to achieve flame retardant function, organic phosphorus flame retardants are added to achieve the corresponding flame retardant level and maintain a certain dielectric constant. However, the existing phosphorus flame retardants do not meet the requirements of 5G era materials in terms of heat resistance stability. At the same time, the organic phosphorus flame retardants sold on the market have a certain hygroscopicity. Moisture absorption of the material will cause the dielectric constant to increase. Since 5G materials require low dielectric constant and high flame retardancy, it is necessary to develop new flame retardants with low dielectric constant and high flame retardancy.

[0003] In view of the above problems, it is necessary to provide a phosphorus-containing flame retardant composition, application and flame retardant product. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the above-mentioned prior art and provide a phosphorus-containing flame retardant composition and its application and flame retardant product.

[0005] The present invention solves the technical problem by adopting the following technical solutions.

[0006] The present invention provides a phosphorus-containing flame retardant composition, comprising the following components in parts by weight:

[0007] Phosphorus-containing compounds 20-60 parts

[0008] Polysiloxane 1-10 parts

[0009] Polyalkyl alcohol 0.1-5 parts

[0010] 10-30 parts of nitrogen-phosphorus compounds and

[0011] 1-20 parts of inorganic salt, wherein:

[0012] The phosphorus-containing compound comprises component I, component II and component III:

[0013] The structural formula of component I is:

[0014] The structural formula of component II is:

[0015] Component III is: phosphite.

[0016] The present invention also provides an application of the phosphorus-containing flame retardant composition in the preparation of flame-retardant products.

[0017] The present invention also provides a flame retardant product, which is made from the phosphorus-containing flame retardant composition.

[0018] The present invention has the following beneficial effects:

[0019] The present invention provides a phosphorus-containing flame retardant composition, application and flame-retardant products. The phosphorus-containing flame retardant composition comprises: 20-60 parts of a phosphorus-containing compound, 1-10 parts of a polysiloxane, 0.1-5 parts of a polyalkyl alcohol, 10-30 parts of a nitrogen-containing phosphorus compound and 1-20 parts of an inorganic salt, wherein the phosphorus-containing compound comprises component I, component II and component III, wherein p-xylyldiphenylphosphine oxide with excellent symmetry is used as component I, which can reduce the dielectric properties of the entire material; component II polyphenylphosphine oxide and component III phosphite synergist are used in combination to effectively improve the flame retardant properties of the entire phosphorus-containing compound; and other components such as polysiloxane, polyalkyl alcohol and the like are used in combination to obtain a phosphorus-containing flame retardant composition with good heat resistance, excellent flame retardancy and low dielectric constant, and the flame retardant products made from the phosphorus-containing flame retardant composition have broad application prospects. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0021] The following is a detailed description of a phosphorus-containing flame retardant composition, application and flame retardant product provided in an embodiment of the present invention.

[0022] In a first aspect, an embodiment of the present invention provides a phosphorus-containing flame retardant composition, comprising the following components in parts by weight:

[0023] Phosphorus-containing compounds 20-60 parts

[0024] Polysiloxane 1-10 parts

[0025] Polyalkyl alcohol 0.1-5 parts

[0026] 10-30 parts of nitrogen-phosphorus compounds and

[0027] 1-20 parts of inorganic salt, wherein:

[0028] The phosphorus-containing compound comprises component I, component II and component III:

[0029] The structural formula of component I is:

[0030] The structural formula of component II is:

[0031] Component III is: phosphite.

[0032] Preferably, the phosphorus-containing flame retardant composition comprises the following components in parts by weight: 30-50 parts of phosphorus-containing compounds, 2-6 parts of polysiloxane, 0.1-3 parts of polyalkyl alcohol, 15-25 parts of nitrogen-phosphorus-containing compounds and 5-10 parts of inorganic salts.

[0033] In an optional embodiment, component I accounts for 1-50% of the phosphorus-containing compound; component II accounts for 0.01-5% of the phosphorus-containing compound; and component III accounts for 1-40% of the phosphorus-containing compound.

[0034] The above phosphorus-containing compounds, component I is p-xylylbisdiphenylphosphine oxide, which contains a multi-benzene ring structure. The delocalized large π bonds on the benzene rings are conducive to the uniform distribution of the electron cloud, so the symmetry of the molecular structure is better and the dielectric constant of the material is lower;

[0035] The polyphenyl phosphorus oxide compound in component II has a stable PC bond in the polyphenyl structure, a low dielectric constant, a structure similar to component I, and a miscible molecular structure, which can fill the molecular gaps in component I and can be used as a synergist of component I to improve the flame retardant properties of component I;

[0036] The phosphite of component III includes one or more of aluminum phosphite, zinc phosphite, and tin phosphite; phosphite is a flame retardant synergist with excellent flame retardant effect: when mixed with components I and II, the small molecules of phosphite can enter the gaps between macromolecules, further filling the gaps between components I and II, making the effective flame retardant components in the effective space higher, and at the same time, phosphite is a good synergist, which helps to improve the overall flame retardant properties of the composition.

[0037] It can be seen that the phosphorus-containing flame retardant composition provided in the embodiment of the present invention selects a flame retardant with a symmetrical structure: p-xylylbisdiphenylphosphine oxide, which has high symmetry, stable P-C bonds, and a small dielectric constant; it is combined with polyphenyl phosphorus oxides and phosphite synergists to effectively improve the overall flame retardant properties of the phosphorus-containing compounds; and it is combined with polysiloxanes, polyalkyl alcohols, nitrogen-phosphorus compounds and inorganic salts to improve the flame retardant properties of the composition from multiple dimensions such as cooling, smoke suppression, and temperature resistance, and finally a phosphorus-containing flame retardant composition with good heat resistance, excellent flame retardancy and a low dielectric constant is obtained.

[0038] In an optional embodiment, the polysiloxane includes one or both of polydimethylsiloxane and polymethylphenylsiloxane; the polysiloxane has a structure similar to an interpenetrating network and has binding properties, which can limit the fluidity of each component, so that the flame retardant composition does not migrate to the surface of the material, and helps to form a carbon layer, which on the one hand improves the oxygen index and on the other hand reduces the flame propagation speed.

[0039] In an optional embodiment, the polyalkylene glycol includes one or more of polyethylene glycol 400, polyethylene glycol 600, polypropylene glycol 400 and polypropylene glycol 600; the polyalkylene glycol is stable in nature, has good heat resistance, does not decompose at 260°C, and the polymer molecular chains are interspersed between the components, which can improve the overall thermal stability of the composition.

[0040] In an optional embodiment, the nitrogen-phosphorus compound includes one or more of ammonium polyphosphate, di(melamine) pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate and melon polyphosphate; the nitrogen-phosphorus compound is an intumescent flame retardant that can effectively suppress the amount of smoke generated, and when used in combination with the phosphorus-containing compound, it can enhance the flame retardant effect of the flame retardant composition.

[0041] In an optional embodiment, the inorganic salt includes one or more of antimony trioxide, zinc borate, and aluminum hydroxide; the inorganic salt can play a role in cooling. Antimony trioxide and aluminum hydroxide are both air-type flame retardants. When heated, they undergo endothermic decomposition and have a cooling effect, which can cool the flame-retarded matrix. Zinc borate can lose crystal water at temperatures above 300°C, which plays an endothermic cooling role. At the same time, the inorganic salts are all inorganic small molecules and also have a filler effect, which can increase the bulk density of the composition.

[0042] In an optional embodiment, the phosphorus-containing flame retardant composition provided above has an average particle size D50≤60 μm and a bulk density of 200-800 kg / m 3 .

[0043] In a second aspect, an embodiment of the present invention further provides a use of the above-mentioned phosphorus-containing flame retardant composition in the preparation of flame-retardant products, such as nylon, flexible circuit boards, epoxy resins, and the like.

[0044] In a third aspect, an embodiment of the present invention further provides a flame retardant product made from the above-mentioned phosphorus-containing flame retardant composition.

[0045] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0046] p-Xylylbis(diphenylphosphine) oxide, polyphenylphosphine oxide, aluminum phosphite, Jiangsu Liside New Materials Co., Ltd.;

[0047] Nylon PP66, EPR27 type, Pingdingshan Shenma Engineering Plastics Co., Ltd.

[0048] Glass fiber, ECS301UW, Chongqing International Composite Materials Co., Ltd.

[0049] Polydimethylsiloxane, polymethylphenylsiloxane, polyethylene glycol, polypropylene glycol, melamine polyphosphate, di(melamine) pyrophosphate, melam polyphosphate, zinc borate, aluminum hydroxide, and aluminum hydroxide are all commercially available.

[0050] The formulas of the phosphorus-containing flame retardant compositions of the comparative examples and the examples are shown in Table 1 below:

[0051] Table 1

[0052]

[0053]

[0054] The dielectric constant, particle size distribution and bulk density of the phosphorus-containing flame retardant composition in the examples and comparative examples in Table 1 were tested.

[0055] Dielectric constant test: According to GB / T1409-2006, use LCR digital bridge with a frequency of 1MHz to test the dielectric constant of the sample.

[0056] Particle size distribution test: The phosphorus-containing flame retardant composition is dispersed in water, ethanol or acetone, and tested by laser scattering method.

[0057] Bulk density test: Use a bulk density tester to test the bulk density of each group.

[0058] The test results of the dielectric constant, particle size distribution and bulk density of the phosphorus-containing flame retardant composition of the comparative example and the embodiment are shown in Table 2 below:

[0059] Table 2

[0060] Dielectric constant D50μm <![CDATA[Bulk density kg / m 3 <!-- 5 -->]]> Comparative Example 1 4.9 30.55 450 Comparative Example 2 4.5 29.66 486 Comparative Example 3 4.2 29.12 492 Comparative Example 4 3.4 30.42 313 Comparative Example 5 3.1 31.25 465 Comparative Example 6 3.3 29.48 302 Comparative Example 7 5.1 31.21 475 Comparative Example 8 5.4 32.01 491 Example 1 3.2 25.63 557 Example 2 4.0 23.75 536 Example 3 3.3 21.22 568 Example 4 3.3 24.14 542 Example 5 3.2 24.66 559 Example 6 3.4 25.52 564 Example 7 3.3 24.12 543

[0061] In Table 2 above, the dielectric constant of the phosphorus-containing flame retardant composition in Example 1 is 3.2, and the bulk density is 557 kg / m 3 In Examples 1 to 7, the components cooperate with each other, and the dielectric constant and D50 value of the obtained phosphorus-containing flame retardant composition are low, and the bulk density is large. In Comparative Examples 1 to 5, the phosphorus-containing flame retardant composition lacks one or several of the components, and the dielectric constant and D50 value are high, and the bulk density is large. It can be seen that the amount of component I and component II affects the dielectric constant of the phosphorus-containing flame retardant composition. The more the amount is used, the lower the dielectric constant; the inorganic salt can significantly increase the bulk density; the components cooperate with each other to obtain a phosphorus-containing flame retardant composition with a low dielectric constant and D50 value and a large bulk density.

[0062] Application Examples

[0063] The phosphorus-containing flame retardant composition prepared in Examples 1-7 and Comparative Examples 1-8 was mixed with nylon 66 and glass fiber, and the phosphorus-containing flame retardant composition (20%) was mixed with nylon 66 (50%) and glass fiber (30%), extruded into pellets using a twin-screw extruder, and injection molded in an injection molding machine to obtain standard specimens, and the relevant material properties were tested. The main performance indicators of concern are as follows:

[0064] Impact strength test: ISO179-1 was used to test the simply supported beam notched impact strength of the prepared specimens.

[0065] Tensile strength: For the prepared specimens, the tensile strength was tested with reference to GB / T 1040.1-2018.

[0066] Flame retardant properties: The flame retardant properties of the prepared specimens were tested by UL94 V0 (0.8 mm) method, with 5 to 6 specimens in each group.

[0067] Heat aging performance: With reference to GB / T 7141-2008, the tensile strength of the prepared specimens was measured after heating at 200°C for 300h.

[0068] Smoke density: refer to GB / T 8627, for the prepared specimens, use the smoke density tester XP-2 to test the smoke density of each group of materials.

[0069] Oxygen index: refer to GB / T 2406. For the prepared specimens, use the oxygen index tester LOI to test the oxygen index of each group of specimens.

[0070] The nylon performance test results of the phosphorus-containing flame retardant compositions of the comparative examples and the examples are shown in Table 3 below:

[0071] Table 3

[0072]

[0073]

[0074] It can be seen from the data in Table 3 above that the phosphorus-containing flame retardant composition provided in Comparative Examples 1-5 lacks one or two components, and its synergistic effect will be reduced, and the overall effect will be weakened. Comparative Examples 1-8 failed the flame retardant test. It can be seen from the oxygen index data: in Comparative Examples 1-8, the oxygen index is around 24, which belongs to the flammable category, among which the oxygen index of Comparative Example 1 is the smallest, only 24.0. However, after adding the phosphorus-containing flame retardant composition provided by the present invention, the oxygen index of nylon is significantly increased. For example, in Examples 1-7, the oxygen index is all greater than 27.0, which belongs to the flame retardant category, among which the oxygen index of Example 1 is the highest, reaching 29.2. Therefore, in the embodiments of the present invention, each component cooperates with each other to obtain a phosphorus-containing flame retardant composition with excellent flame retardant properties.

[0075] It can also be seen from Table 3 above that the amount of polyalkyl alcohol used will affect the overall thermal stability of the phosphorus-containing flame retardant composition. Increasing the amount of polyalkyl alcohol used can improve the heat resistance of the material. In Comparative Example 3, no polyalkyl alcohol was added, and its tensile strength decreased significantly after thermal aging. Similarly, in Example 3, the amount of polyalkyl alcohol added was small, and thermal aging had a significant effect on the tensile strength. In Example 1, the amount of polyalkyl alcohol added was relatively large, and thermal aging had no significant effect on the tensile strength.

[0076] At the same time, in the phosphorus-containing flame retardant composition, when no inorganic salt is added, the impact strength and tensile strength of the material are not good; compared with polypropylene glycol 600, polyethylene glycol 400 has better effect; in comparative example 5, no nitrogen-phosphorus compounds are added, and its smoke density is as high as 528, and the smoke density decreases with the increase of the amount of nitrogen-phosphorus compounds added. Among them, compared with melamine polyphosphate, ammonium polyphosphate, di(melamine) pyrophosphate, and melam polyphosphate, melamine polyphosphate has better smoke suppression effect than the others.

[0077] The phosphorus-containing flame retardant composition provided in Comparative Example 6 has component dosages different from those in the examples. Under this ratio, the flame retardancy test fails, the strength test effect is poor, and the oxygen index is low.

[0078] The phosphorus-containing flame retardant composition provided in Comparative Example 7 uses zinc phosphite instead of aluminum phosphite, and melamine instead of melamine polyphosphate. It can be seen from the data in Tables 2 and 3 that after the components are replaced, the dielectric constant of the composition increases. After being applied to the material, the strength test results are not ideal, and the flame retardancy fails, the smoke density is large, and the oxygen index is small, which proves that this combination is not an excellent flame retardant composition.

[0079] The phosphorus-containing flame retardant composition provided in Comparative Example 8 uses bisphenol A bis(diphenyl phosphate) instead of component I. Bisphenol A bis(diphenyl phosphate) also has a symmetrical structure, but when used in this composition, the dielectric test results are not good, proving that not all symmetrical flame retardants can be applied to the flame retardant composition of the present invention.

[0080] In summary, the embodiments of the present invention provide a phosphorus-containing flame retardant composition, its application and flame retardant products. The provided phosphorus-containing flame retardant composition comprises: 20-60 parts of phosphorus-containing compounds, 1-10 parts of polysiloxanes, 0.1-5 parts of polyalkyl alcohols, 10-30 parts of nitrogen-phosphorus compounds and 1-20 parts of inorganic salts, wherein the phosphorus-containing compound comprises three components, with p-xylyldiphenylphosphine oxide having excellent symmetry as the main component, which can reduce the overall dielectric properties of the material; the components of polyphenylphosphine oxide and phosphite synergist are combined to effectively improve the overall flame retardant properties of the phosphorus-containing compound; and other components such as polysiloxanes, polyalkyl alcohols, etc. are combined to obtain a phosphorus-containing flame retardant composition with good heat resistance, excellent flame retardancy and low dielectric constant.

[0081] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A phosphorus-containing flame retardant composition, characterized in that: Contains the following components in parts by weight: Phosphorus-containing compounds 20-60 parts Polysiloxane 1-10 parts Polyalkyl alcohol 0.1-5 parts 10-30 parts of nitrogen-phosphorus compounds and 1-20 parts of inorganic salt, wherein: The phosphorus-containing compound comprises component I, component II and component III: The structural formula of component I is: The structural formula of component II is: Component III is: phosphite; The proportion of component I in the phosphorus-containing flame retardant composition is 27.5-50%; the proportion of component II in the phosphorus-containing flame retardant composition is 0.01-5%; the proportion of component III in the phosphorus-containing flame retardant composition is 1-40%; The inorganic salt includes one or more of antimony trioxide, zinc borate and aluminum hydroxide.

2. The phosphorus-containing flame retardant composition according to claim 1, characterized in that: The component III includes one or more of aluminum phosphite, zinc phosphite and tin phosphite.

3. The phosphorus-containing flame retardant composition according to claim 1, characterized in that: The polysiloxane includes one or both of polydimethylsiloxane and polymethylphenylsiloxane.

4. The phosphorus-containing flame retardant composition according to claim 1, characterized in that The polyalkyl alcohol includes one or more of polyethylene glycol 400, polyethylene glycol 600, polypropylene glycol 400 and polypropylene glycol 600.

5. The phosphorus-containing flame retardant composition according to claim 1, characterized in that: The nitrogen-phosphorus compound includes one or more of ammonium polyphosphate, di(melamine) pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate and melon polyphosphate.

6. The phosphorus-containing flame retardant composition according to any one of claims 1 to 5, characterized in that: The phosphorus-containing flame retardant composition has an average particle size D50≤60 μm and a bulk density of 200-800 kg / m 3 .

7. Use of the phosphorus-containing flame retardant composition according to any one of claims 1 to 6 in the preparation of flame-retardant products.

8. A flame retardant product, characterized in that: Made from the phosphorus-containing flame retardant composition described in any one of claims 1-6.

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