Flame-retardant nylon material as well as preparation method and application thereof

Abstract

The invention provides a flame-retardant nylon material and a preparation method and application thereof.The flame-retardant nylon material comprises nylon resin, brominated polystyrene, a synergistic flame retardant and a quaternary ammonium salt compound, the components are reasonably matched, especially the quaternary ammonium salt compound is introduced, the flame-retardant nylon material can replace a conventional fluorine-containing anti-dripping agent, and the flame-retardant nylon material has the advantages that the flame-retardant nylon material is high in flame-retardant performance and low in cost; the fluorine-containing anti-dripping agent is added into the nylon material, so that the flame-retardant efficiency of the nylon material can be effectively improved, the obtained nylon material has a relatively high flame-retardant grade, excellent ignition molten drop resistance and relatively high CTI (Comparative Tracking Index) and is very environment-friendly, and the problem that the fluidity of the obtained flame-retardant nylon material becomes poor due to the addition of a conventional fluorine-containing anti-dripping agent is effectively avoided.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and in particular relates to a flame retardant nylon material and a preparation method and application thereof. Background Art

[0002] At present, with the increasing popularity of electrical appliances and people's increasing demand for thinner and lighter appliances, the requirement for the thickness of injection molded products is also developing in the direction of becoming thinner and thinner.

[0003] Thin-walled nylon material is one of the most widely used thin-walled materials. In order to achieve good flame retardant properties and a high relative tracking index (CTI), brominated polystyrene is usually used as the main flame retardant, and a synergistic flame retardant is added. At the same time, in order to overcome the problems of easy dripping and ignition of thin-walled brominated polystyrene flame retardant systems, it is also necessary to add polytetrafluoroethylene anti-drip agents to form a network structure during processing to enhance the material's anti-drip ability. However, most polytetrafluoroethylene anti-drip agents are perfluorinated and polyfluoroalkyl substances. These substances will permanently harm the environment and human health and have been restricted to use in certain fields. In addition, the addition of polytetrafluoroethylene anti-drip agents will also affect the fluidity of nylon materials, resulting in too low a melt flow rate of nylon materials, which greatly limits the use of nylon materials in thin-walled injection molded products.

[0004] Therefore, in response to the above technical problems, there is an urgent need to develop a flame retardant nylon material with good fluidity, high flame retardant grade, high CTI and excellent anti-ignition droplet property. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a flame-retardant nylon material and its preparation method and application. By introducing a quaternary ammonium salt compound, it can replace the conventional fluorine-containing anti-drip agent, greatly improving the flame retardant efficiency of the nylon material, so that the obtained flame-retardant nylon material has a high flame retardant grade, excellent anti-ignition droplet performance, a high CTI and a suitable melt flow rate, and is very environmentally friendly.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a flame retardant nylon material, wherein the flame retardant nylon material comprises the following components in parts by weight:

[0008] 40-55 parts by weight of nylon resin;

[0009] 18 to 25 parts by weight of brominated polystyrene;

[0010] 3 to 8 parts by weight of a synergistic flame retardant;

[0011] 0.02 to 1 part by weight of the quaternary ammonium salt compound.

[0012] The flame-retardant nylon material provided by the present invention comprises nylon resin, brominated polystyrene, a synergistic flame retardant and a quaternary ammonium salt compound. By selecting the brominated polystyrene as the flame retardant, it can not only effectively improve the flame retardant properties of the nylon resin, but also, due to its high thermal stability, can effectively improve the tracking index (CTI) of the nylon resin. When combined with the synergistic flame retardant, and by introducing the quaternary ammonium salt compound, the quaternary ammonium salt compound can replace the conventional fluorine-containing anti-drip agent, so that the obtained flame-retardant nylon material can not only have a high flame retardant grade, but also have excellent anti-ignition droplet properties, while complying with environmental protection trends. In addition, the addition of the quaternary ammonium salt compound can also The invention can effectively avoid the problem that the melt flow rate of the flame retardant nylon material obtained by adding a conventional fluorine-containing anti-drip agent is too low and the fluidity becomes poor, so that the melt flow rate of the flame retardant nylon material finally obtained is between 15 and 50 g / 10 min (280°C / 2.16 kg), thereby avoiding the problems that the melt flow rate of the flame retardant nylon material is lower than 15 g / 10 min (280°C / 2.16 kg), resulting in poor fluidity and difficulty in application in thin-walled products, and the melt flow rate of the flame retardant nylon material is higher than 50 g / 10 min (280°C / 2.16 kg), thereby achieving both good fluidity and processing performance.

[0013] Among them, the content of the nylon resin can be 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight or 55 parts by weight, and the mass percentage of the nylon resin in the flame retardant nylon material is not less than 55%.

[0014] The content of the brominated polystyrene can be 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, or 25 parts by weight.

[0015] The content of the synergistic flame retardant can be 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight or 8 parts by weight, etc.

[0016] The content of the quaternary ammonium salt compound can be 0.02 weight part, 0.15 weight part, 0.2 weight part, 0.25 weight part, 0.3 weight part, 0.35 weight part, 0.4 weight part, 0.45 weight part, 0.5 weight part, 0.6 weight part, 0.7 weight part, 0.8 weight part or 0.9 weight part, etc.; when the content of the quaternary ammonium salt compound is less than 0.02 weight part, the flame retardant nylon material obtained will drip and ignite the absorbent cotton, and when the content of the quaternary ammonium salt compound is higher than 1 weight part, the melt flow rate of the flame retardant nylon material obtained will be higher than 50g / 10min (280℃ / 2.16kg), and the processing performance will be affected.

[0017] Preferably, the nylon resin includes PA66 resin.

[0018] Preferably, the melt index of the PA66 resin under the test conditions of 270°C and 1.2kg is 10-50g / 10min, for example, 10g / 10min, 15g / 10min, 20g / 10min, 25g / 10min, 30g / 10min, 35g / 10min, 40g / 10min, 45g / 10min or 50g / 10min, and more preferably 20-35g / 10min; the melt index of the PA66 resin under the test conditions of 270°C and 1.2kg is further limited to 20-35g / 10min, which can ensure that the melt flow rate of the obtained flame retardant nylon material is between 20 and 40g / 10min (280°C / 2.16kg), thereby having the most suitable fluidity and the best processing performance.

[0019] In the present invention, the melt index of the PA66 resin can be tested with reference to the method provided in ISO 1133-1:2022.

[0020] Preferably, the synergistic flame retardant includes at least one of antimony trioxide, sodium antimonate, sodium pyroantimonate or potassium antimonate.

[0021] Preferably, the mass percentage of the quaternary ammonium salt compound in the flame retardant nylon material is 0.1-1.2%, for example, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1% or 1.2%, etc.; by limiting the mass percentage of the quaternary ammonium salt compound in the flame retardant nylon material to within the range of 0.1-1.2%, it can be ensured that the flame retardant grade of the obtained flame retardant nylon material reaches V0, and all dripping does not ignite, the melt flow rate is between 15 and 50 g / 10 min (280°C / 2.16 kg), and it can have good processing performance and suitable fluidity.

[0022] Preferably, the mass percentage of the quaternary ammonium salt compound in the flame retardant nylon material is 0.2-0.8%; further limiting the mass percentage of the quaternary ammonium salt compound in the flame retardant nylon material to be within the range of 0.2-0.8% can ensure that the flame retardant grade of the obtained flame retardant nylon material is V0, and it does not ignite when dripping, and the melt flow rate is between 20-40g / 10min (280℃ / 2.16kg), combining the best processing performance and the most suitable fluidity.

[0023] Preferably, the chemical formula of the quaternary ammonium salt compound is [R1R2R3R4N] + X - , wherein R1 to R3 are each independently selected from at least one of C1 to C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl, C6 to C20 (e.g., C6, C8, C10, C12, C14, C16, C18, or C20, etc.) aryl, R4 is selected from C10 to C30 (e.g., C10, C14, C18, C22, C24, C26, C28, or C30, etc.) alkyl, and X is halogen (e.g., F, Cl, Br, I, At, etc.).

[0024] Preferably, the quaternary ammonium salt compound includes at least one of dimethyloctadecylbenzylammonium chloride, trimethylhexadecylammonium bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, eicosyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyltriethylammonium chloride, hexacosyltrimethylammonium chloride, octadecyltrimethylammonium chloride, triacontyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, eicosyltrimethylammonium bromide, behenyltrimethylammonium bromide, behenyltriethylammonium bromide, hexacosyltrimethylammonium bromide, octadecyltrimethylammonium bromide or triacontyltrimethylammonium bromide, and is further preferably dimethyloctadecylbenzylammonium chloride.

[0025] Preferably, at least one of R1 to R3 is selected from a C6 to C20 aromatic group, X is selected from Cl or Br, and the quaternary ammonium salt compound is further preferably dimethyl octadecyl benzyl ammonium chloride. The quaternary ammonium salt compound is further limited to dimethyl octadecyl benzyl ammonium chloride, which not only enables the melt flow rate of the final nylon material to be between 20 and 40 g / 10 min (280° C. / 2.16 kg), thereby having both the most suitable fluidity and the best processing performance, but also enables the nylon material to have the highest CTI.

[0026] Preferably, the flame retardant nylon material further comprises an antioxidant.

[0027] Preferably, the content of the antioxidant in the flame retardant nylon material is 0.1 to 1.5 parts by weight, for example, 0.5 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight or 1.5 parts by weight.

[0028] Preferably, the antioxidant includes at least one of a hindered amine antioxidant, a hindered phenol antioxidant, a phosphite antioxidant or a thioester antioxidant.

[0029] In the present invention, there is no particular limitation on the specific selection of the above-mentioned hindered amine antioxidant, hindered phenol antioxidant, phosphite antioxidant or thioester antioxidant.

[0030] Illustratively, the hindered amine antioxidants include antioxidant 5057, antioxidant T534, and the like.

[0031] For example, the hindered phenol antioxidants include antioxidant 1010, antioxidant 1076, antioxidant BHT, antioxidant 1098, antioxidant 2246, bisphenol A, antioxidant 3114, and antioxidant 1135.

[0032] Illustratively, the phosphite antioxidant includes triphenyl phosphite, tri(2-ethylhexyl) phosphite, trilauryl phosphite, and the like.

[0033] For example, the thioester antioxidants include lauryl thiodipropionate, octadecyl thiodipropionate, and the like.

[0034] In addition, for the flame-retardant nylon material provided by the present invention, fillers, colorants, weathering agents and antistatic agents can be added according to actual needs without affecting the technical effects. The present invention has no special requirements for the specific types of the above-mentioned additives or fillers, and conventional additives or fillers in the field can be selected.

[0035] For example, the filler may be glass microbeads, talc, wollastonite or magnesium hydroxide.

[0036] For example, the colorant can be selected from quinacridone red, azo substances (such as azo orange), phthalocyanine blue, phthalocyanine green, naphthoxydibenzoylmethane red, anthrone red, anthrone blue, anthraquinone violet, methylene orange, zinc sulfide, cerium sulfide, carbon black, ultramarine blue, ultramarine violet, etc.

[0037] For example, the weathering agent may be selected from salicylate, benzotriazole, hydroxybenzophenone, and the like.

[0038] Exemplarily, the antistatic agent can be selected from ionic antistatic agents (such as sulfonates, carboxylates), nonionic antistatic agents (such as glycerides, polyoxyethylene ethers, etc.), and conductive filled antistatic agents (such as carbon black, carbon nanotubes, graphene, metals and their oxides).

[0039] In a second aspect, the present invention provides a method for preparing the flame-retardant nylon material as described in the first aspect, the preparation method comprising: mixing the various components, and performing extrusion granulation in an extruder to obtain the flame-retardant nylon material.

[0040] Preferably, the mixing time is 3 to 5 minutes.

[0041] Preferably, the extruder is a twin-screw extruder.

[0042] Preferably, the temperature of the extrusion granulation is 260-300°C, for example, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C or 300°C.

[0043] In a third aspect, the present invention provides a product comprising the flame-retardant nylon material as described in the first aspect.

[0044] Preferably, the manufactured parts include at least one of packaging products, smart home appliance parts, electronic and electrical appliance parts, medical equipment parts, construction equipment parts or automobile parts.

[0045] Preferably, the component comprises an electronic connector or a micro motor coil.

[0046] The numerical range described in the present invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] The flame-retardant nylon material provided by the present invention includes nylon resin, brominated polystyrene, a synergistic flame retardant and a quaternary ammonium salt compound. Through the reasonable combination of the above-mentioned components, in particular, by introducing the quaternary ammonium salt compound, it can replace the conventional fluorinated anti-drip agent, effectively improving the flame retardant efficiency of the obtained nylon material, so that the obtained nylon material has a high flame retardant grade and excellent anti-ignition dripping property, and conforms to the trend of environmental protection. It also effectively avoids the problem that the addition of conventional fluorinated anti-drip agents will cause the fluidity of the obtained nylon material to deteriorate, so that the final flame-retardant nylon material has a suitable melt flow rate, a high flame retardant grade, excellent anti-ignition dripping property and a high CTI, and is very environmentally friendly. DETAILED DESCRIPTION

[0049] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0050] Some of the raw material information involved in the following examples and comparative examples are as follows:

[0051] (1) PA66 resin

[0052] PA66-1: melt index 22 g / 10 min (270°C / 1.2 kg), purchased from Huafeng Group Co., Ltd., brand EP-158;

[0053] PA66-2: melt index 33g / 10min (270℃ / 1.2kg), purchased from Shenma Industrial Co., Ltd., brand EPR27;

[0054] PA66-3: melt index 27 g / 10 min (270°C / 1.2 kg), purchased from INVISTA Technologies Co., Ltd., brand U4800;

[0055] PA66-4: melt index of 12 g / 10 min (270°C / 1.2 kg), purchased from Shenma Industrial Co., Ltd., brand EPR32;

[0056] PA66-5: melt index is 49 g / 10 min (270°C / 1.2 kg), purchased from Shenma Industrial Co., Ltd., brand EPR24.

[0057] (2) Brominated polystyrene: purchased from Albemarle Chemical, brand name Saytex 3010.

[0058] (3) Synergistic flame retardants

[0059] Antimony trioxide: purchased from Hunan Xikuangshan Shanxing Antimony Industry Import and Export Co., Ltd., brand S-12N.

[0060] (4) Quaternary ammonium salt compounds

[0061] Trimethylhexadecyl ammonium bromide: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand CTAB;

[0062] Dimethyloctadecylbenzyl ammonium chloride: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand 1827;

[0063] Dodecyltrimethylammonium chloride: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand DTAC;

[0064] Dodecyltrimethylammonium bromide: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand DTAB.

[0065] (5) Antioxidants

[0066] Antioxidant 1098: commonly available on the market.

[0067] (6) Fluorinated anti-dripping agent

[0068] Polytetrafluoroethylene: purchased from Zhejiang Xin'an Chemical Industry Group Co., Ltd., brand FR-2221.

[0069] (7) Brominated epoxy resin: purchased from Albemarle Chemical, brand CXB-2000H.

[0070] Examples 1 to 12 and Comparative Examples 1 to 4

[0071] Examples 1 to 12 and Comparative Examples 1 to 4 respectively provide a flame retardant nylon material, the components of which are shown in Table 1 and Table 2;

[0072] In Tables 1 and 2, the units of the amounts of each component are "parts by weight";

[0073] Table 1

[0074]

[0075]

[0076] Table 2

[0077]

[0078] The preparation method of the flame-retardant nylon material provided in Examples 1 to 12 and Comparative Examples 1 to 4 includes: mixing the components in the table according to their respective amounts for 4 minutes, placing them in a twin-screw extruder, and extruding and granulating them at 280° C. to obtain the flame-retardant nylon material.

[0079] Performance testing:

[0080] (1) Flame retardant grade: tested in accordance with UL94-2018 standard, with a thickness of 0.8 mm for the burning specimen.

[0081] (2) Anti-drip performance: The test was conducted in accordance with the UL94-2018 standard. The thickness of the burning specimen was 0.8 mm. It was observed whether dripping occurred during the test and whether the dripping would ignite the absorbent cotton.

[0082] (3) Melt flow rate: tested in accordance with ISO 1133-1:2022, under the conditions of 280°C / 2.16 kg.

[0083] (4) Tracking Index (CTI): Tested in accordance with IEC 60112:2023.

[0084] The nylon materials provided in Examples 1 to 12 and Comparative Examples 1 to 4 were tested according to the above test method. The test results are shown in Table 3:

[0085] Table 3

[0086]

[0087] According to the data in Table 3, we can see that:

[0088] The flame retardant grades of the flame retardant nylon materials provided in Examples 1 to 12 can all reach the V-0 level, and the anti-dripping performance can all achieve non-ignition, indicating that they have a high flame retardant grade and excellent anti-ignition dripping performance. At the same time, the melt flow rate of the flame retardant nylon materials provided in Examples 1 to 12 is 16 to 50 g / 10 min, and they have suitable fluidity and excellent processing performance. In addition, the CTI of the flame retardant nylon materials provided in Examples 1 to 12 is not less than 350 V, and they also have a high leakage tracking index.

[0089] Comparing the data of Example 1 and Comparative Example 1, it can be seen that not adding the quaternary ammonium salt compound will lead to a decrease in the flame retardancy of the obtained nylon material, and the flame retardancy level is only V-2 level, and the flame retardancy performance is very poor.

[0090] Comparing the data of Example 1 and Comparative Example 2, it can be seen that the use of conventional polytetrafluoroethylene as an anti-dripping agent can ensure that the resulting flame-retardant nylon material has a high flame retardant grade and excellent anti-melt dripping performance, but its melt flow rate is very low, only 12g / 10min, and its fluidity is very poor. At the same time, its safety and environmental protection are poor.

[0091] Further comparison of the data of Example 1 and Comparative Example 3 shows that the flame retardant grade of the nylon material obtained without adding the synergistic flame retardant is NR, that is, it has no flame retardant performance and the anti-dripping performance is poor.

[0092] Finally, by comparing the data of Example 1 and Comparative Example 4, it can be seen that using brominated epoxy resin instead of brominated polystyrene as a flame retardant will result in a lower CTI of the resulting nylon material, which cannot meet the use requirements of electronic and electrical equipment.

[0093] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A flame retardant nylon material, characterized in that: The flame retardant nylon material comprises the following components in parts by weight: 40-55 parts by weight of nylon resin; 18 to 25 parts by weight of brominated polystyrene; 3 to 8 parts by weight of a synergistic flame retardant; 0.02 to 1 part by weight of quaternary ammonium salt compound.

2. The flame retardant nylon material according to claim 1, characterized in that: The nylon resin includes PA66 resin; Preferably, the PA66 resin has a melt index of 10 to 50 g / 10 min, more preferably 20 to 35 g / 10 min, under test conditions of 270° C. and 1.2 kg.

3. The flame retardant nylon material according to claim 1 or 2, characterized in that: The synergistic flame retardant includes at least one of antimony trioxide, sodium antimonate, sodium pyroantimonate or potassium antimonate.

4. The flame retardant nylon material according to any one of claims 1 to 3, characterized in that: The chemical formula of the quaternary ammonium salt compound is [R1R2R3R4N] + X - , wherein R1 to R3 are each independently selected from at least one of C1 to C6 alkyl and C6 to C20 aryl, R4 is selected from C10 to C30 alkyl, and X is halogen.

5. The flame retardant nylon material according to claim 4, characterized in that: The quaternary ammonium salt compound includes at least one of dimethyloctadecylbenzylammonium chloride, trimethylhexadecylammonium bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, eicosyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyltriethylammonium chloride, hexacosyltrimethylammonium chloride, octadecyltrimethylammonium chloride, triacontyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, eicosyltrimethylammonium bromide, behenyltrimethylammonium bromide, behenyltriethylammonium bromide, hexacosyltrimethylammonium bromide, octadecyltrimethylammonium bromide or triacontyltrimethylammonium bromide, preferably dimethyloctadecylbenzylammonium chloride.

6. The flame retardant nylon material according to claim 4, characterized in that: At least one of R1 to R3 is selected from C6 to C20 aryl groups, X is selected from Cl or Br, and the quaternary ammonium salt compound is preferably dimethyloctadecylbenzylammonium chloride.

7. The flame retardant nylon material according to any one of claims 1 to 6, characterized in that: The flame retardant nylon material also includes an antioxidant; Preferably, the content of the antioxidant in the flame retardant nylon material is 0.1 to 1.5 parts by weight.

8. A method for preparing the flame-retardant nylon material according to any one of claims 1 to 7, characterized in that: The preparation method comprises: mixing various components, and performing extrusion granulation in an extruder to obtain the flame retardant nylon material.

9. A manufactured article, characterized in that: The article comprises the flame-retardant nylon material according to any one of claims 1 to 7.

10. The article according to claim 9, characterized in that The manufactured parts include at least one of packaging products, smart home appliance parts, electronic and electrical parts, medical equipment parts, construction equipment parts or automobile parts.

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