A flame retardant and anti-aging high temperature resistant nylon material and preparation method thereof

Abstract

The present invention discloses a flame retardant and anti-aging high temperature resistant nylon material and a preparation method thereof, wherein the flame retardant and anti-aging high temperature resistant nylon material comprises nylon resin, modified flame retardant, heat resistant macromolecular antioxidant, antimony trioxide, lubricant and compatibilizer; the modified flame retardant is prepared by surface modification of boric acid melamine by aminosilane coupling agent. The present invention selects and matches each component of the nylon material, so that the prepared nylon material has excellent high temperature resistance and mechanical properties, as well as excellent flame retardancy and anti-aging ability.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a flame-retardant, anti-aging, high-temperature-resistant nylon material and a preparation method thereof. Background Art

[0002] With the development of industrial technology, especially in the automotive industry, the requirements for improving engine efficiency, significantly reducing automobile fuel consumption, and the requirements for exhaust emissions are getting higher and higher; at the same time, the development of surface mounting technology in the electronics industry has put higher and higher requirements on the high temperature resistance of materials; in order to solve such problems, the materials are required to have properties such as lightness, heat resistance, high strength, dimensional stability, and flame retardancy. High temperature resistant nylon has become one of the more ideal materials.

[0003] Nylon, also known as polyamide, mainly includes PA6 and PA66. Polyamide materials have a wide range of applications in electronic communications, aerospace, automobiles and other fields due to their excellent mechanical strength and good heat resistance. Among them, the development of high-temperature resistant nylon makes it possible to miniaturize, lighten and strengthen the power of products. High-temperature resistant nylon can bring higher temperature resistance to certain parts or directly replace metal materials to produce parts.

[0004] However, as one of the commonly used thermoplastics, nylon material is flammable and produces a large number of flammable droplets when burning. The flammable droplets will further lead to the expansion of fire hazards, resulting in the potential safety hazard of PA in certain application areas that may lead to fire. In addition, the aging of nylon is an irreversible problem. During the use of nylon materials, the influence of the external environment will accelerate the aging of the material. Especially during long-term storage, under the damage of external factors such as light and heat, a serious aging process will occur inside it. The essence is the breakage of the main chain, the cross-linking bond of the polymer chain of the nylon material, which leads to the breakage of the polymer chain and the destruction of the internal structure of the material, which is manifested as the stickiness and hardening of the material surface and the deterioration of various performance properties, thereby making the material lose its use value.

[0005] Therefore, in order to broaden the application scope of high temperature resistant nylon and further expand the use field of high temperature resistant nylon, flame retardants and antioxidants are widely used in the modification of high temperature resistant nylon. However, the modification of high temperature resistant nylon in the prior art often results in a loss of one thing while gaining another. Even if the flame retardant and anti-aging properties of high temperature resistant nylon are improved, its mechanical properties and heat deformation temperature are not improved or even worse.

[0006] Therefore, there is an urgent need for a high-temperature resistant nylon material that has excellent flame retardancy and anti-aging capabilities as well as excellent mechanical properties. Summary of the invention

[0007] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide a flame retardant and anti-aging high temperature resistant nylon material having excellent flame retardancy and anti-aging ability and excellent mechanical properties and a preparation method thereof.

[0008] Technical solution:

[0009] A flame-retardant and anti-aging high-temperature resistant nylon material, comprising nylon resin, a modified flame retardant, a heat-resistant macromolecular antioxidant, antimony trioxide, a lubricant and a compatibilizer;

[0010] The modified flame retardant is prepared by surface modification of boric acid melamine by using an aminosilane coupling agent.

[0011] The invention adds modified flame retardant, heat-resistant macromolecular antioxidant and antimony trioxide into nylon resin and mixes lubricant and compatibilizer, so that the prepared nylon material has excellent high temperature resistance and mechanical properties as well as excellent flame retardancy and anti-aging ability.

[0012] Furthermore, the nylon resin is selected from at least one of PA6, PA66, PA610 or PA612.

[0013] Furthermore, the compatibilizer is selected from at least one of PPE-g-MAH, SEBS-g-MAH or PS-g-MAH.

[0014] Furthermore, the lubricant is selected from at least one of calcium stearate, lithium stearate or stearic acid amide.

[0015] Furthermore, the modified flame retardant is prepared by the following steps: adding boric acid melamine into a high-speed mixer, heating to 110-120° C., adding an aminosilane coupling agent and deionized water, stirring at a high speed for 20-30 minutes, cooling, and drying to obtain the modified flame retardant.

[0016] The modified flame retardant added in the present invention is prepared by surface modification of boric acid melamine by an aminosilane coupling agent. The boric acid melamine has excellent flame retardancy and has a synergistic effect with nitrogen, phosphorus and silicon compounds. After the surface of the boric acid melamine is modified by an aminosilane coupling agent, on the one hand, it has a synergistic effect with nitrogen and silicon elements, further enhancing the flame retardant effect; on the other hand, the coupling agent can reduce the surface polarity, enhance the compatibility with nylon materials, and further reduce the influence of the flame retardant on the mechanical properties of the material.

[0017] Furthermore, the aminosilane coupling agent is selected from one of 3-aminopropyltriethoxysilane and 3-(2-aminoethylamino)propyltrimethoxysilane.

[0018] Furthermore, the mass ratio of the boric acid melamine to the aminosilane coupling agent is 30-40:1.

[0019] Furthermore, the heat-resistant macromolecular antioxidant has a structure as shown in the following formula A:

[0020]

[0021] Among them, a:b=(5-10):(1-3), and the molecular weight is 5000-8000.

[0022] The heat-resistant macromolecular antioxidant added in the present invention is obtained by grafting an antioxidant monomer onto an acrylamide and maleic anhydride copolymer, wherein the antioxidant monomer contains a large number of antioxidant group amino groups, and provides protons through the structure of aromatic amine to replace the attack of the polymer chain, thereby protecting the polymer chain from degradation and inhibiting aging. In addition, the structures of the naphthalene ring and the benzene ring can further improve the heat resistance of the antioxidant, thereby significantly improving its heat-oxidative aging resistance.

[0023] Furthermore, the heat-resistant macromolecular antioxidant is prepared by the following steps:

[0024] (1) Add 7-methoxy-2-naphthol and p-phenylenediamine into a reactor, mix well, heat to 120-130° C., add a catalyst, keep warm for 8-12 hours, and then vacuum filter, rectify, and dry to obtain the antioxidant monomer;

[0025] (2) Adding acrylamide, maleic anhydride and water into a reactor, stirring and dissolving, introducing nitrogen, heating to 75-85° C., adding an initiator, reacting for 4-6 hours, filtering, washing and drying to obtain the copolymer;

[0026] (3) Adding antioxidant monomer, copolymer and organic solvent into the reactor, stirring and dissolving, heating to 120-130° C., reacting for 8-12 hours, filtering, washing and drying to obtain the heat-resistant macromolecular antioxidant.

[0027] Furthermore, based on the total mass fraction being 100%, the mass percentage of each component is:

[0028]

[0029] The preparation method of any of the above-mentioned flame-retardant, anti-aging and high-temperature resistant nylon materials comprises the following steps: nylon resin, modified flame retardant, heat-resistant macromolecular antioxidant and compatibilizer are mixed in proportion in a high-speed mixer for 10-20 minutes and then placed in the main feeding port of a twin-screw extruder, while antimony trioxide and lubricant are placed in the side feeding port of the twin-screw extruder, the temperature of the twin-screw extruder is controlled to be 270-310°C, and the flame-retardant, anti-aging and high-temperature resistant nylon material is obtained by extrusion, pulling and pelletizing through the twin-screw extruder.

[0030] Beneficial effects:

[0031] (1) The flame-retardant and anti-aging high-temperature resistant nylon material provided by the present invention is prepared by adding a modified flame retardant, a heat-resistant macromolecular antioxidant and antimony trioxide to the nylon resin and formulating a lubricant and a compatibilizer, so that the prepared nylon material has excellent high-temperature resistance and mechanical properties, as well as excellent flame retardancy and anti-aging capabilities.

[0032] (2) The modified flame retardant added to the flame-retardant and anti-aging high-temperature resistant nylon material provided by the present invention is obtained by surface modification of boric acid melamine with an aminosilane coupling agent. Boric acid melamine has excellent flame retardancy and has a synergistic effect with nitrogen, phosphorus and silicon compounds. After its surface is modified by an aminosilane coupling agent, on the one hand, it has a synergistic effect with nitrogen and silicon elements, further enhancing the flame retardant effect; on the other hand, the coupling agent can reduce the surface polarity, enhance the compatibility with the nylon material, and thereby reduce the influence of the flame retardant on the mechanical properties of the material.

[0033] (3) The heat-resistant macromolecular antioxidant added to the flame-retardant and anti-aging high-temperature resistant nylon material provided by the present invention is obtained by grafting an antioxidant monomer onto an acrylamide and maleic anhydride copolymer, wherein the antioxidant monomer contains a large number of antioxidant group amino groups, and the structure of the aromatic amine provides protons to replace the polymer chain from being attacked, thereby protecting the polymer chain from degradation and inhibiting aging. In addition, the structure of the naphthalene ring and the benzene ring can further improve the heat resistance of the antioxidant, thereby significantly improving its resistance to heat-oxidative aging. DETAILED DESCRIPTION

[0034] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0035] The commercially available high temperature resistant nylon material was TE250F6 purchased from Dongguan Kaiwan Engineering Plastic Raw Materials Co., Ltd.; the platinum catalyst was 965005 purchased from Bailingwei Technology Co., Ltd. and diluted to a mass fraction of 4.0×10 -3 ; The commercially available antioxidant 4020 is the antioxidant 6PPD (4020) purchased from Zhonghe Chemical (Shandong) Co., Ltd.; the remaining reagents and equipment are conventional reagents and equipment in the technical field.

[0036] Preparation of modified flame retardant-1

[0037] The modified flame retardant-1 was prepared by the following steps:

[0038] 15 g of boric acid melamine was added to a high-speed mixer, and after heating to 120° C., 0.5 g of 3-aminopropyltriethoxysilane and 30 ml of deionized water were added. After high-speed stirring for 30 minutes, the mixture was cooled and dried to obtain the modified flame retardant-1.

[0039] Preparation of modified flame retardant-2

[0040] The preparation method is basically the same as that of modified flame retardant-1, except that 3-aminopropyltriethoxysilane is replaced by an equal amount of 3-(methacryloyloxy)propyltrimethoxysilane.

[0041] Preparation of heat-resistant macromolecular antioxidant:

[0042] The heat-resistant macromolecular antioxidant is prepared by the following steps:

[0043] (1) In a reactor, 0.12 mol of 7-methoxy-2-naphthol and 0.1 mol of p-phenylenediamine were added, mixed evenly, and then heated to 130° C., 0.1 g of platinum catalyst was added, and the mixture was kept warm for 12 hours, and then vacuum filtered, rectified, and dried to obtain an antioxidant monomer;

[0044] Mass spectrometry data of the antioxidant monomer: The product was analyzed by LC-MS, and the m / z of the product was 264.13 (100.0%), 265.14 (19.5%), and 266.13 (1.8%);

[0045] (2) In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen protection device, 0.3 mol of acrylamide, 0.08 mol of maleic anhydride and 50 ml of water were added, and nitrogen was introduced after stirring and dissolving. The temperature was raised to 80° C., and 0.5 g of dibenzoyl peroxide was added. The reaction was carried out for 6 hours, and a copolymer was obtained after filtering, washing and drying.

[0046] (3) In a single-necked flask equipped with a condenser, 3 g of antioxidant monomer, 12 g of copolymer and 50 ml of xylene were added, stirred to dissolve and then heated to 130° C., reacted for 12 hours, filtered, washed and dried to obtain the heat-resistant macromolecular antioxidant.

[0047] Example 1

[0048] The flame retardant, anti-aging, high temperature resistant nylon material is prepared by the following steps:

[0049] PA66, modified flame retardant-1, heat-resistant macromolecular antioxidant and PPE-g-MAH are mixed in a high-speed mixer in proportion for 20 minutes and then placed in the main feeding port of a twin-screw extruder. Antimony trioxide and calcium stearate are placed in the side feeding port of the twin-screw extruder. The temperature of the twin-screw extruder is controlled to be 300° C. The flame-retardant and anti-aging high-temperature resistant nylon material is obtained through extrusion, strip drawing and pelletizing by the twin-screw extruder.

[0050] Taking the total mass fraction as 100%, the mass percentage of each component is:

[0051]

[0052] Example 2

[0053] The same as Example 1, except that the total mass fraction is 100%, and the components and their mass percentages are:

[0054]

[0055]

[0056] Example 3

[0057] Basically the same as Example 1, except that based on the total mass fraction being 100%, the components and their mass percentages are:

[0058]

[0059] Comparative Example 1

[0060] Commercially available high temperature resistant nylon material.

[0061] Comparative Example 2

[0062] The process is basically the same as Example 1, except that the heat-resistant macromolecular antioxidant is replaced by an equal amount of commercially available antioxidant 4020.

[0063] Comparative Example 3

[0064] The method is basically the same as Example 1, except that the modified flame retardant-1 is replaced by an equal amount of boric acid melamine.

[0065] Comparative Example 4

[0066] The method is basically the same as Example 1, except that the modified flame retardant-1 is replaced by an equal amount of modified flame retardant-2.

[0067] Performance Testing

[0068] Tensile strength test: According to GB / T 1040.1-2006, the tensile strength of the products of Examples 1-3 and Comparative Examples 1-4 was tested.

[0069] Anti-aging ability test: After the products of Examples 1-3 and Comparative Examples 1-4 were aged at an aging temperature of 100° C. and an aging time of 48 h, the tensile strength of the products was tested.

[0070] High temperature resistance test: According to GB / T 1634.1-2004 standard for determination of load deformation temperature of plastics, the thermal degeneration temperature of the products of Examples 1-3 and Comparative Examples 1-4 was tested under a bending stress of 0.45 MPa.

[0071] Flame retardant ability test: According to the UL94 vertical combustion test standard, the combustion levels of the products of Examples 1-3 and Comparative Examples 1-4 were tested.

[0072] The test results are shown in the following table:

[0073]

[0074] According to the comparison of the test results of Examples 1-3 with those of Comparative Example 1, the flame-retardant and anti-aging high-temperature resistant nylon material provided by the present invention has better mechanical strength, anti-aging ability and flame retardant properties than the high-temperature resistant nylon material in the prior art.

[0075] According to the comparison of the test results of Examples 1-3 with those of Comparative Example 2, adding a heat-resistant macromolecular antioxidant to the flame-retardant and anti-aging high-temperature resistant nylon material provided by the present invention can improve the high-temperature resistance and anti-aging ability of the nylon material.

[0076] According to the comparison of the test results of Examples 1-3 with Comparative Examples 3 and 4, it can be seen that the modified flame retardant is added to the flame-retardant and anti-aging high-temperature resistant nylon material provided by the present invention. On the one hand, it has excellent flame retardancy through synergistic effect; on the other hand, the coupling agent can reduce the surface polarity of the flame retardant, enhance the compatibility with the nylon material, and thus reduce the influence of the flame retardant on the mechanical properties of the material.

[0077] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A flame retardant, anti-aging, high temperature resistant nylon material. It is characterized in that Taking the total mass fraction as 100%, the mass percentage of each component is: Modified flame retardant 5-10% Heat-resistant macromolecular antioxidant 1-3% Antimony trioxide 2-3% Lubricant 0.3-0.5% Compatibilizer 3-5% The balance is nylon resin; The modified flame retardant is prepared by surface modification of boric acid melamine with an aminosilane coupling agent; The heat-resistant macromolecular antioxidant has a structure shown in the following formula A: ， Among them, a:b=(5-10):(1-3), and the molecular weight is 5000-8000.

2. The flame retardant, anti-aging, high temperature resistant nylon material according to claim 1, It is characterized in that The nylon resin is selected from at least one of PA6, PA66, PA610 and PA612.

3. The flame retardant, anti-aging and high temperature resistant nylon material according to claim 1, It is characterized in that The compatibilizer is selected from at least one of PPE-g-MAH, SEBS-g-MAH or PS-g-MAH.

4. The flame retardant, anti-aging and high temperature resistant nylon material according to claim 1, It is characterized in that The lubricant is selected from at least one of calcium stearate, lithium stearate or stearic acid amide.

5. The flame retardant, anti-aging and high temperature resistant nylon material according to claim 1, It is characterized in that The modified flame retardant is prepared by the following steps: adding boric acid melamine into a high-speed mixer, heating to 110-120° C., adding an aminosilane coupling agent and deionized water, stirring at a high speed for 20-30 minutes, cooling, and drying to obtain the modified flame retardant.

6. The flame retardant, anti-aging and high temperature resistant nylon material according to claim 5, It is characterized in that The aminosilane coupling agent is selected from 3-aminopropyltriethoxysilane or 3-(2-aminoethylamino)propyltrimethoxysilane.

7. The flame retardant, anti-aging, high temperature resistant nylon material according to claim 5, It is characterized in that The mass ratio of the boric acid melamine to the aminosilane coupling agent is 30-40:

1.

8. A method for preparing the flame-retardant, anti-aging, high-temperature resistant nylon material according to any one of claims 1 to 7, It is characterized in that The following steps are involved: Nylon resin, modified flame retardant, heat-resistant macromolecular antioxidant and compatibilizer are mixed in a high-speed mixer in proportion for 10-20 minutes and then placed in the main feeding port of a twin-screw extruder. Meanwhile, antimony trioxide and a lubricant are placed in the side feeding port of the twin-screw extruder. The temperature of the twin-screw extruder is controlled at 270-310°C. The flame-retardant, anti-aging and high-temperature resistant nylon material is obtained through extrusion, strip drawing and pelletizing.

Images