Antistatic functional plastic and preparation method thereof

Abstract

The invention relates to an antistatic functional plastic and a preparation method thereof, and belongs to the technical field of high polymer materials. The plastic with the antistatic function comprises the following components in parts by weight: 80-100 parts of polystyrene resin, 10-20 parts of glass fibers, 1-5 parts of an antioxidant, 2-8 parts of a light stabilizer, 5-10 parts of a modified antistatic agent and 0.3-0.6 part of a modified flame retardant, anhydride groups in the modified antistatic agent are dehydrated at a high temperature to form a conductive layer, static accumulation is effectively reduced, the anhydride groups and quaternary ammonium salt have a synergistic effect on static elimination characteristics and strong adsorption capacity, and meanwhile, the combustion speed is remarkably slowed down through heat absorption and catalysis of maleic anhydride; in the modified flame retardant, an alpha-amino alkyl phosphonate compound is decomposed to generate phosphorus-containing free radicals, a combustion chain is interrupted, nitrogen is released to inhibit combustion, the alpha-amino alkyl phosphonate compound and DOPO cooperate for flame retardance, the flame retardant efficiency is improved, and the prepared antistatic functional plastic has a good antistatic function and also has excellent flame retardant and tensile properties.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to an antistatic functional plastic and a preparation method thereof. Background Art

[0002] Plastics are widely used in household appliances, transportation, electrical and electronic, and defense industries due to their excellent comprehensive properties. However, with the improvement of environmental awareness, the environmental protection and safety issues of plastics are receiving increasing attention.

[0003] As a good electrical insulating material, plastic easily accumulates static electricity during use and is difficult to eliminate. This will not only cause the plastic to absorb dust in the air, affecting its appearance, but also cause adhesion problems during the plastic manufacturing process. In addition, the accumulation of static electricity may not only cause electric shock and equipment failure, but may also cause safety hazards such as fire. Therefore, the anti-static problem of plastic becomes crucial; in addition, the molecular structure of plastic contains a large amount of combustible elements such as carbon and hydrogen, which makes plastic easy to burn when exposed to fire. The combustion is rapid and accompanied by the release of a large amount of toxic gases and smoke, causing serious harm to the environment and human health. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an antistatic functional plastic and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An antistatic functional plastic comprises the following raw materials in parts by weight: 80-100 parts of polystyrene resin, 10-20 parts of glass fiber, 1-5 parts of antioxidant, 2-8 parts of light stabilizer, 5-10 parts of modified antistatic agent, and 0.3-0.6 parts of modified flame retardant;

[0007] The antioxidant is diphenylamine;

[0008] The light stabilizer is phenyl salicylate.

[0009] The modified antistatic agent is prepared by the following method:

[0010] Step A1: 4-dimethylaminostyrene, 1-chlorohexane and methanol are mixed and reacted for 12 hours. After cooling to room temperature, the mixture is dried under nitrogen protection to obtain an intermediate product. The reaction route can be expressed as follows:

[0011]

[0012] Furthermore, the dosage ratio of 4-dimethylaminostyrene, 1-chlorohexane and methanol is 1-2 mol: 2-4 mol: 2 mL;

[0013] Step A2: maleic anhydride and isoamyl acetate are mixed and reacted for 3 hours. Under nitrogen protection, azobisisobutyronitrile, toluene and the intermediate product are added and stirred evenly. The mixture is reacted at 70°C for 6 hours, centrifuged, filtered, washed, and dried in vacuo at 45°C to obtain a modified antistatic agent. The reaction route can be expressed as follows:

[0014]

[0015] Furthermore, the usage ratio of maleic anhydride, isoamyl acetate, azobisisobutyronitrile, toluene and intermediate product is 0.2-1.5 mol: 1.18-2.05 g: 0.25-0.36 g: 10 mL: 1.04-3.02 g.

[0016] The modified flame retardant is prepared by the following method:

[0017] Step B1: dimethyl phosphite, diethylamine and acryloyl chloride were mixed, stirred at 40°C for 30 min, tetrahydrofuran and iodine were added under nitrogen atmosphere, the oil bath was heated to 60°C, filtered and washed to obtain a compound;

[0018] Furthermore, the usage ratio of dimethyl phosphite, diethylamine, acryloyl chloride, tetrahydrofuran and iodine is 1.2-1.5 mol: 0.5-0.6 mol: 0.3 g: 30 mL: 0.1-0.2 g;

[0019] Step B2: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide and the compound are mixed, stirred at 150° C. for 9 hours, filtered, washed, and vacuum dried at 60° C. for 24 hours to obtain a modified flame retardant;

[0020] Furthermore, the usage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide, and the compound is 0.15-0.25 mol:40-60 mL:0.03-0.05 mol.

[0021] A method for preparing an antistatic functional plastic comprises the following steps:

[0022] S1: Weighing raw materials by weight, mixing polystyrene resin and glass fiber to prepare a premixed material;

[0023] S2: adding an antioxidant, a light stabilizer, a modified antistatic agent and a modified flame retardant to the premixed material, mixing and stirring the mixture evenly to obtain a mixed base material;

[0024] S3: The mixed base material is moved to a grinder for grinding, and then placed in a twin-screw extruder at 200°C-240°C for granulation to obtain an antistatic functional plastic.

[0025] Beneficial effects of the present invention:

[0026] The modified antistatic agent prepared by the present invention has the advantage of a macromolecular polymer and exhibits antistatic performance that exceeds that of a traditional small molecule antistatic agent. In the modified antistatic agent, firstly, under the action of a catalyst methanol, the chlorine atom of 1-chlorohexane is used to cause 4-dimethylaminostyrene to undergo a quaternary ammonium salt reaction to form a positively charged intermediate product, which not only enhances hydrophilicity and hygroscopicity, but also can effectively eliminate static electricity of plastics due to the static elimination characteristics and strong adsorption of the quaternary ammonium salt; secondly, maleic anhydride and isoamyl acetate are mixed, and an initiator azobisisobutyronitrile is used to cause ethylene in the intermediate product to react with maleic anhydride to synthesize the modified antistatic agent. In the prepared modified antistatic agent, the anhydride group of maleic anhydride can undergo a dehydration reaction with the active group on the plastic surface at high temperature to form a conductive layer, which significantly improves the conductivity of the plastic surface, allows the charge to be quickly released from the plastic surface, and effectively reduces static electricity accumulation. In addition, maleic anhydride can also improve the hydrophilicity of the plastic surface and promote moisture absorption. The ions in the water film formed after moisture absorption act as a conductive medium, further enhancing the conductivity efficiency of the surface ions, accelerating the transfer and dissipation of charges, thereby effectively avoiding the negative impact of static electricity on the production process and product quality. In addition, during combustion, maleic anhydride reduces the combustion temperature and smoke generation of the material through heat absorption and catalysis, effectively slowing down the combustion speed, and further inhibiting the progress of combustion.

[0027] In the modified flame retardant prepared by the present invention, the phosphonic acid diester of dimethyl phosphite, the amine of diethylamine and the carbonyl condensation reaction of acryloyl chloride are firstly used, and then the catalyst iodine is used to form a compound with α-aminoalkyl phosphonate; secondly, the carbon-carbon double bond of the compound and the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide flame retardant are combined to form the modified flame retardant; during the combustion process, the α-aminoalkyl phosphonate compound will decompose to generate phosphorus-containing free radicals, interrupt the combustion chain reaction, prevent the flame from spreading, and achieve the flame retardant effect. In addition, the α-aminoalkyl phosphonate compound will be used to generate phosphorus-containing free radicals, interrupt the combustion chain reaction, prevent the flame from spreading, and achieve the flame retardant effect. The 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the modified flame retardant can promote the formation of a dense and continuous carbon layer during the combustion process, prevent the exchange of heat and combustible gas, and cooperate with the α-aminoalkylphosphonate compound to further improve the flame retardant efficiency. In addition, the modified flame retardant prepared by the present invention is halogen-free, helps to reduce environmental pollution and damage to the ecosystem, is harmless to human health, and achieves sustainable development.

[0028] The antistatic functional plastic prepared by the present invention not only has excellent antistatic function, but also has good flame retardant performance. The antistatic functional plastic can reduce the accumulation of static electricity on the surface of the material, avoid electric shock and dust absorption caused by static electricity, reduce the release of toxic substances, and improve safety. Among them, glass fiber can enhance the molecular structure of plastic, thereby improving the tensile strength of plastic, so that the plastic with glass fiber added can withstand greater load and pressure. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Example 1

[0031] A method for preparing an antistatic functional plastic comprises the following steps:

[0032] S1: Weigh the raw materials by weight, including 80 parts of polystyrene resin, 10 parts of glass fiber, 1 part of diphenylamine, 2 parts of phenyl salicylate, 5 parts of modified antistatic agent (prepared in this example), and 0.3 parts of modified flame retardant (prepared in this example), mix the polystyrene resin and the glass fiber, and prepare a premixed material;

[0033] S2: adding diphenylamine, phenyl salicylate, modified antistatic agent and modified flame retardant into the premixed material, mixing and stirring evenly to obtain a mixed base material;

[0034] S3: The mixed base material is moved to a grinder for grinding, and then placed in a twin-screw extruder at 200°C for granulation to obtain an antistatic functional plastic;

[0035] The modified antistatic agent is prepared by the following method:

[0036] Step A1: 1 mol 4-dimethylaminostyrene, 2 mol 1-chlorohexane and 2 mL methanol were mixed, reacted for 12 h, cooled to room temperature, and dried under nitrogen protection to obtain an intermediate product;

[0037] Step A2: 0.2 mol maleic anhydride and 1.18 g isoamyl acetate were mixed and reacted for 3 h. Under nitrogen protection, 0.25 g azobisisobutyronitrile, 10 mL toluene and 1.04 g intermediate product were added and stirred evenly. The mixture was reacted at 70° C. for 6 h. The mixture was centrifuged, filtered, washed and dried under vacuum at 45° C. to obtain a modified antistatic agent.

[0038] The modified flame retardant is prepared by the following method:

[0039] Step B1: 1.2 mol dimethyl phosphite, 0.5 mol diethylamine, and 0.3 g acryloyl chloride were mixed, stirred at 40°C for 30 min, 30 mL tetrahydrofuran and 0.1 g iodine were added under nitrogen atmosphere, the oil bath was heated to 60°C, filtered, and washed to obtain a compound;

[0040] Step B2: 0.15 mol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 mL N,N-dimethylformamide and 0.03 mol compound were mixed, stirred at 150° C. for 9 h, filtered, washed, and vacuum dried at 60° C. for 24 h to obtain a modified flame retardant.

[0041] Example 2

[0042] A method for preparing an antistatic functional plastic comprises the following steps:

[0043] S1: Weigh the raw materials by weight, including 90 parts of polystyrene resin, 15 parts of glass fiber, 3 parts of diphenylamine, 5 parts of phenyl salicylate, 7 parts of modified antistatic agent (prepared in this example), and 0.45 parts of modified flame retardant (prepared in this example), mix the polystyrene resin and the glass fiber, and prepare a premixed material;

[0044] S2: adding diphenylamine, phenyl salicylate, modified antistatic agent and modified flame retardant into the premixed material, mixing and stirring evenly to obtain a mixed base material;

[0045] S3: The mixed base material is moved to a grinder for grinding, and then placed in a twin-screw extruder at 220°C for granulation to obtain an antistatic functional plastic;

[0046] The modified antistatic agent is prepared by the following method:

[0047] Step A1: 1.5 mol 4-dimethylaminostyrene, 3 mol 1-chlorohexane and 2 mL methanol were mixed, reacted for 12 h, cooled to room temperature, and dried under nitrogen protection to obtain an intermediate product;

[0048] Step A2: 0.8 mol maleic anhydride and 1.51 g isoamyl acetate were mixed and reacted for 3 h. Under nitrogen protection, 0.3 g azobisisobutyronitrile, 10 mL toluene and 2.01 g intermediate product were added and stirred evenly. The mixture was reacted at 70° C. for 6 h. The mixture was centrifuged, filtered, washed and dried under vacuum at 45° C. to obtain a modified antistatic agent.

[0049] The modified flame retardant is prepared by the following method:

[0050] Step B1: 1.35 mol dimethyl phosphite, 0.55 mol diethylamine, and 0.3 g acryloyl chloride were mixed, stirred at 40°C for 30 min, 30 mL tetrahydrofuran and 0.15 g iodine were added under nitrogen atmosphere, the oil bath was heated to 60°C, filtered, and washed to obtain a compound;

[0051] Step B2: Mix 0.2 mol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 50 mL N,N-dimethylformamide and 0.04 mol compound, stir at 150°C for 9 h, filter, wash, and vacuum dry at 60°C for 24 h to obtain a modified flame retardant.

[0052] Example 3

[0053] A method for preparing an antistatic functional plastic comprises the following steps:

[0054] S1: Weigh the raw materials by weight, including 100 parts of polystyrene resin, 20 parts of glass fiber, 5 parts of diphenylamine, 8 parts of phenyl salicylate, 10 parts of modified antistatic agent (prepared in this embodiment), and 0.6 parts of modified flame retardant (prepared in this embodiment), mix the polystyrene resin and the glass fiber, and prepare a premixed material;

[0055] S2: adding diphenylamine, phenyl salicylate, modified antistatic agent and modified flame retardant into the premixed material, mixing and stirring evenly to obtain a mixed base material;

[0056] S3: The mixed base material is moved to a grinder for grinding, and then placed in a twin-screw extruder at 240°C for granulation to obtain an antistatic functional plastic;

[0057] The modified antistatic agent is prepared by the following method:

[0058] Step A1: 2 mol 4-dimethylaminostyrene, 4 mol 1-chlorohexane and 2 mL methanol were mixed, reacted for 12 h, cooled to room temperature, and dried under nitrogen protection to obtain an intermediate product;

[0059] Step A2: 1.5 mol maleic anhydride and 2.05 g isoamyl acetate were mixed and reacted for 3 h. Under nitrogen protection, 0.36 g azobisisobutyronitrile, 10 mL toluene and 3.02 g intermediate product were added and stirred evenly. The mixture was reacted at 70° C. for 6 h. The mixture was centrifuged, filtered, washed and dried under vacuum at 45° C. to obtain a modified antistatic agent.

[0060] The modified flame retardant is prepared by the following method:

[0061] Step B1: 1.5 mol dimethyl phosphite, 0.6 mol diethylamine, and 0.3 g acryloyl chloride were mixed, stirred at 40°C for 30 min, 30 mL tetrahydrofuran and 0.2 g iodine were added under nitrogen atmosphere, the oil bath was heated to 60°C, filtered, and washed to obtain a compound;

[0062] Step B2: 0.25 mol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 60 mL N,N-dimethylformamide and 0.05 mol compound were mixed, stirred at 150° C. for 9 h, filtered, washed, and vacuum dried at 60° C. for 24 h to obtain a modified flame retardant.

[0063] Comparative Example 1

[0064] This comparative example is an antistatic functional plastic, which differs from Example 3 in that an equal amount of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate is used to replace the modified antistatic agent prepared in Example 3, and the rest are the same.

[0065] Comparative Example 2

[0066] This comparative example is an antistatic functional plastic, which differs from Example 3 in that an equal amount of ammonium polyphosphate is used to replace the modified flame retardant prepared in Example 3, and the rest are the same.

[0067] Performance test: The antistatic functional plastics prepared in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes, and the surface resistivity was tested according to GB / T1410-2006. The vertical burning performance was tested using the GB / T2048-1996 plastic burning performance test method. The tensile strength was tested according to GB / T1040.1-2006 (the tensile strength of polystyrene plastic is 48.3 Mpa). The test results are shown in the following table:

[0068] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Surface resistivity / Ω <![CDATA[2.1×10 5 ]]> <![CDATA[2.2×10 5 ]]> <![CDATA[2×10 5 ]]> <![CDATA[2×10 6 ]]> <![CDATA[2.3×10 5 ]]> Vertical burning level V-1 V-1 V-1 V-1 V-2 Tensile strength / Mpa 54 58 53 56 52

[0069] It can be seen from the test data in the table that the antistatic functional plastic prepared in Example 1 has an excellent antistatic effect. It can also be seen from the above table that the antistatic functional plastic prepared in the present invention has a good flame retardant effect and tensile strength.

[0070] The above contents are merely examples and explanations of the concept of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing an antistatic functional plastic, characterized in that: The following steps are involved: S1: mixing and stirring polystyrene resin and glass fiber to prepare a premixed material; S2: adding an antioxidant, a light stabilizer, a modified antistatic agent and a modified flame retardant to the premixed material, mixing and stirring the mixture evenly to obtain a mixed base material; S3: The mixed base material is moved to a grinder for grinding, and then placed in a twin-screw extruder at 200°C-240°C for granulation to obtain an antistatic functional plastic.

2. The method for preparing an antistatic functional plastic according to claim 1, characterized in that: The modified antistatic agent is prepared by the following method: Step A1: 4-dimethylaminostyrene, 1-chlorohexane and methanol are mixed, reacted for 12 hours, cooled to room temperature, and dried under nitrogen protection to obtain an intermediate product; Step A2: maleic anhydride and isoamyl acetate are mixed and reacted for 3 hours. Under nitrogen protection, azobisisobutyronitrile, toluene and the intermediate product are added and stirred evenly. The mixture is reacted at 70° C. for 6 hours, centrifuged, filtered, washed, and dried in vacuo at 45° C. to obtain a modified antistatic agent.

3. The method for preparing an antistatic functional plastic according to claim 2, characterized in that: In step A1, the usage ratio of 4-dimethylaminostyrene, 1-chlorohexane and methanol is 1-2 mol: 2-4 mol: 2 mL.

4. The method for preparing an antistatic functional plastic according to claim 2, characterized in that: In step A2, the usage ratio of maleic anhydride, isoamyl acetate, azobisisobutyronitrile, toluene and the intermediate product is 0.2-1.5 mol: 1.18-2.05 g: 0.25-0.36 g: 10 mL: 1.04-3.02 g.

5. The method for preparing an antistatic functional plastic according to claim 1, characterized in that: The modified flame retardant is prepared by the following method: Step B1: dimethyl phosphite, diethylamine and acryloyl chloride were mixed, stirred at 40°C for 30 min, tetrahydrofuran and iodine were added under nitrogen atmosphere, the oil bath was heated to 60°C, filtered and washed to obtain a compound; Step B2: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide and the compound are mixed, stirred at 150° C. for 9 hours, filtered, washed, and vacuum dried at 60° C. for 24 hours to obtain a modified flame retardant.

6. The method for preparing an antistatic functional plastic according to claim 5, characterized in that: In step B1, the usage ratio of dimethyl phosphite, diethylamine, acryloyl chloride, tetrahydrofuran and iodine is 1.2-1.5 mol: 0.5-0.6 mol: 0.3 g: 30 mL: 0.1-0.2 g.

7. The method for preparing an antistatic functional plastic according to claim 5, characterized in that: In step B2, the usage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide, and compound is 0.15-0.25 mol:40-60 mL:0.03-0.05 mol.

8. The method for preparing an antistatic functional plastic according to claim 1, characterized in that: The antioxidant is diphenylamine.

9. The method for preparing an antistatic functional plastic according to claim 1, characterized in that: The light stabilizer is phenyl salicylate.

10. An antistatic functional plastic, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 9.

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