Polystyrene composite material and preparation method thereof

Abstract

The invention discloses a polystyrene composite material and a preparation method thereof, and belongs to the technical field of composite materials, the composite material comprises the following raw materials by weight: 60-80 parts of syndiotactic polystyrene, 20-40 parts of nylon 66, 25-30 parts of glass fiber, 5-10 parts of hyperbranched polyether epoxy resin, 3-5 parts of a flame retardant, 0.3-0.5 part of an antioxidant, and 0.3-0.5 part of a lubricant. The hyperbranched polyether epoxy resin anchors syndiotactic polystyrene through a pi-pi effect, an epoxy group of the hyperbranched polyether epoxy resin reacts with an amino-terminated group of nylon 66 for compatibilization, and a three-dimensional spherical structure dissipates energy for toughening; quaternary phosphonium salt cations and hydroxyl groups on the surfaces of the glass fibers form an ion-dipole effect and hydrogen bonds, interface bonding is strengthened, nitrogen and phosphorus elements in the molecular structure generate a phosphorus-nitrogen synergistic flame retardant effect, and the composite material is endowed with excellent mechanical properties and flame retardant properties under the combined action of the nitrogen, the phosphorus, the flame retardant and the glass fibers.

Description

A polystyrene composite material and its preparation method Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a polystyrene composite material and its preparation method. Background Technology

[0002] Polystyrene (PS) includes ordinary polystyrene, expanded polystyrene (EPS), high-impact polystyrene (HIPS), and syndiotactic polystyrene (SPS). Among them, syndiotactic polystyrene has a syndiotactic structure, is produced using metallocene catalysts, and is a newly developed variety of polystyrene with good performance, belonging to engineering plastics.

[0003] Syndiotactic polystyrene (SPS) has a rigid benzene ring structure. The benzene rings are regularly arranged on both sides of the molecular chain, exhibiting crystallization and restricting the movement of the molecular chain, thus giving SPS its rigid structure. This rigid structure endows SPS with high strength, high hardness, and strong corrosion resistance. However, when used alone, SPS does not exhibit any plastic micro-deformation before fracture, limiting its use due to its high brittleness.

[0004] Currently, blending nylon 66 with SPS is a common method. Nylon 66 has a similar melting point to SPS and also exhibits good crystallinity, which allows the nylon 66 / SPS blend to maintain good structural stability at high temperatures. Furthermore, blending SPS with PA66 not only improves the impact resistance of SPS but also enhances the heat resistance of PA66. The two materials mutually promote each other, leveraging their respective advantages to create PA66 / SPS blends with excellent overall performance.

[0005] However, Nylon 66 is a polar polymer and SPS is a non-polar polymer. The two are not compatible and it is difficult to form a uniform blend, resulting in poor mechanical properties of the composite material. Summary of the Invention

[0006] The purpose of this invention is to provide a polystyrene composite material and its preparation method, so as to solve the problem of poor mechanical properties of composite materials made from nylon 66 and SPS.

[0007] The objective of this invention can be achieved through the following technical solution: a polystyrene composite material comprising the following parts by weight of raw materials: 60-80 parts of syndiotactic polystyrene, 20-40 parts of nylon 66, 25-30 parts of glass fiber, 5-10 parts of hyperbranched polyether epoxy resin, 3-5 parts of flame retardant, 0.3-0.5 parts of antioxidant, and 0.3-0.5 parts of lubricant.

[0008] The raw materials for preparing the hyperbranched polyether epoxy resin include quaternary phosphonium salt diol and 1,3,5-triglycidyl-S-triazine trione, wherein the quaternary phosphonium salt diol is an A2 type monomer, where A is a hydroxyl group, and 5-triglycidyl-S-triazine trione is a B3 type monomer, where B is an epoxy group. The hyperbranched polyether epoxy resin is synthesized by the A2+B3 method.

[0009] Further, the preparation steps of the hyperbranched polyether epoxy resin are as follows: 1,3,5-triglycidyl-S-triazine trione and tetrabutylammonium bromide are added to N,N-dimethylformamide, and stirred at 130°C for 8-12 min under nitrogen protection. Then, quaternary phosphonium diol is added, and the mixture is stirred at 150-155°C for 2-4 h. After the reaction is completed, the mixture is cooled to room temperature, and N,N-dimethylformamide is removed by vacuum distillation to obtain the hyperbranched polyether epoxy resin.

[0010] Furthermore, the mass ratio of 1,3,5-triglycidyl-S-triazine trione to quaternary phosphonium diol is 2.97:4.91, and the amount of tetrabutylammonium bromide is 1-2% of the total mass of 1,3,5-triglycidyl-S-triazine trione and quaternary phosphonium diol.

[0011] Furthermore, the raw materials for preparing the quaternary phosphonium salt diol include allyltriphenylphosphine bromide and 3-mercapto-1,2-propanediol, which are used to prepare the quaternary phosphonium salt diol via a mercapto-olefin click reaction.

[0012] Further, the preparation steps of the quaternary phosphonium base diol are as follows: allyltriphenylphosphine bromide, 3-mercapto-1,2-propanediol, benzoin dimethyl ether and dichloromethane are added to a flask, stirred for 0.5-1 h, sealed under nitrogen protection and placed under ultraviolet light irradiation for 1-2 h. After the reaction is completed, dichloromethane is removed by rotary evaporation, washed with tetrahydrofuran and dried to obtain the quaternary phosphonium base diol.

[0013] Furthermore, the ratio of allyltriphenylphosphine bromide, 3-mercapto-1,2-propanediol, benzoin dimethyl ether, and dichloromethane is 3.83 g: 1.08-2.16 g: 0.05 g: 30-50 mL.

[0014] Furthermore, the glass fiber is a short-cut glass fiber with a diameter of 9-15 μm and a length of 3-6 mm.

[0015] Furthermore, the flame retardant is ammonium polyphosphate and / or zinc borate.

[0016] Furthermore, the antioxidant is at least one of antioxidant 1010, antioxidant 168, and antioxidant 1076.

[0017] Furthermore, the lubricant is at least one selected from zinc stearate, calcium stearate, polyethylene wax, and polypropylene wax.

[0018] Furthermore, the method for preparing the polystyrene composite material includes the following steps: placing syndiotactic polystyrene and nylon 66 in a blower box and drying them at 120°C for 3 hours, cooling them to room temperature and then adding them to a mixer, then adding hyperbranched polyether epoxy resin, flame retardant, antioxidant and lubricant to the mixer, mixing them evenly and then transferring them to a twin-screw extruder, and feeding glass fiber into the twin-screw extruder through a side feeder, extruding and granulating to obtain the polystyrene composite material.

[0019] Furthermore, the mixer speed is 300-500 r / min, and the mixing time is 1-2 h.

[0020] Furthermore, the temperatures of zones 1-10 of the twin-screw extruder are set to 130-140℃, 260-265℃, 260-265℃, 245-250℃, 245-250℃, 245-250℃, 245-250℃, 245-250℃, 250-255℃, and 260-265℃, the die head temperature is 231℃, and the screw speed is 280-320 r / min.

[0021] The beneficial effects of this invention are as follows: This invention provides a polystyrene composite material prepared from syndiotactic polystyrene, nylon 66, glass fiber, and hyperbranched polyether epoxy resin, which possesses high mechanical properties and flame retardant properties. The hyperbranched polyether epoxy resin utilizes the π-π interaction between the benzene ring and syndiotactic polystyrene, and achieves compatibilization through the reaction of epoxy groups with the terminal amino groups of nylon 66, thereby strengthening the interfacial adhesion between syndiotactic polystyrene and nylon 66 to improve their compatibility. Furthermore, it utilizes the inherent three-dimensional spherical molecular structure of its hyperbranched polymer. When the composite material is subjected to external force, it dissipates energy, thereby enhancing the toughness of the composite material. In addition, the positively charged quaternary phosphonium salt structure in the hyperbranched polyether epoxy resin can form ion-dipole interactions and hydrogen bonds with the anionic groups (numerous -OH) on the surface of the glass fiber, promoting wetting and thus improving the compatibility between the matrix resin and between the glass fiber and the matrix resin. This results in increased interfacial bonding force, tensile strength, and impact performance of the composite material. In addition to the above advantages, the molecular design of this hyperbranched polyether epoxy resin makes it a highly efficient intrinsic flame retardant component. The nitrogen element (derived from the triazine trione unit) and phosphorus element (derived from the quaternary phosphonium salt unit) introduced into its molecular structure can produce a significant "phosphorus-nitrogen synergistic" flame retardant effect, working together with the flame retardant and glass fiber in the system to exert a flame retardant effect. Detailed Implementation

[0022] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0023] Obviously, the following description is merely some examples or embodiments of this application. Those skilled in the art can apply this application to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this application, any changes to design, manufacturing, or production based on the technical content disclosed in this application are merely conventional technical means and should not be construed as insufficient disclosure of the content of this application.

[0024] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structure may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter of the claims.

[0025] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions, and all technical features and optional technical features of this application can be combined to form new technical solutions.

[0026] In this application, the nylon 66, model EPR27, was purchased from Shenma Industrial Co., Ltd., and the syndiotactic polystyrene (SPS), model 90ZC, was manufactured by Idemitsu Corporation of Japan. The following is a detailed description in conjunction with the embodiments.

[0027] Preparation Example 1

[0028] A hyperbranched polyether epoxy resin is prepared by the following steps: 2.97 g of 1,3,5-triglycidyl-S-triazine trione and 0.08 g of tetrabutylammonium bromide are added to 80 mL of N,N-dimethylformamide. Under nitrogen protection, the mixture is stirred at 130 °C for 8 min. Then, 4.91 g of quaternary phosphonium diol is added, and the mixture is stirred at 150 °C for 2 h. After the reaction is completed, the mixture is cooled to room temperature, and N,N-dimethylformamide is removed by vacuum distillation to obtain the hyperbranched polyether epoxy resin.

[0029] The preparation steps of quaternary phosphonium base diol are as follows: 3.83 g allyltriphenylphosphine bromide, 1.08 g 3-mercapto-1,2-propanediol, 0.05 g benzoin dimethyl ether and 30 mL dichloromethane were added to a flask. After stirring for 0.5 h, the mixture was sealed under nitrogen protection and placed under ultraviolet light for 1 h. After the reaction was completed, the dichloromethane was removed by rotary evaporation, and the mixture was washed with tetrahydrofuran and dried to obtain quaternary phosphonium base diol.

[0030] Preparation Example 2

[0031] A hyperbranched polyether epoxy resin is prepared by the following steps: 2.97 g of 1,3,5-triglycidyl-S-triazine trione and 0.16 g of tetrabutylammonium bromide are added to 100 mL of N,N-dimethylformamide. Under nitrogen protection, the mixture is stirred at 130 °C for 12 min. Then, 4.91 g of quaternary phosphonium diol is added, and the mixture is stirred at 155 °C for 4 h. After the reaction is completed, the mixture is cooled to room temperature, and N,N-dimethylformamide is removed by vacuum distillation to obtain the hyperbranched polyether epoxy resin.

[0032] The preparation steps of quaternary phosphonium base diol are as follows: 3.83 g allyltriphenylphosphine bromide, 2.16 g 3-mercapto-1,2-propanediol, 0.05 g benzoin dimethyl ether and 50 mL dichloromethane were added to a flask. After stirring for 1 h, the mixture was sealed under nitrogen protection and placed under ultraviolet light for 2 h. After the reaction was completed, the dichloromethane was removed by rotary evaporation, and the mixture was washed with tetrahydrofuran and dried to obtain quaternary phosphonium base diol.

[0033] Compare with Example 1

[0034] A hyperbranched polyether epoxy resin, compared with Preparation Example 1, differs only in that the quaternary phosphonium diol in Preparation Example 1 is replaced with 0.01 mol of ethylene glycol.

[0035] Compare with Example 2

[0036] A hyperbranched polyether epoxy resin, which differs from Preparation Example 1 only in that 1,3,5-triglycidyl-S-triazine trione in Preparation Example 1 is replaced with an equimolar amount of glycerol triglycidyl ether.

[0037] Compare with Example 3

[0038] This comparative example uses maleic anhydride-grafted polyphenylene ether, model FB820, with a grafting rate of 1.0%, purchased from Jia Yi Rong Polymer (Shanghai) Co., Ltd.

[0039] Example 1

[0040] A polystyrene composite material comprises the following raw materials in parts by weight: 60 parts of syndiotactic polystyrene, 40 parts of nylon 66, 25 parts of glass fiber, 5 parts of hyperbranched polyether epoxy resin of Preparation Example 1, 3 parts of flame retardant, 0.3 parts of antioxidant, and 0.3 parts of lubricant.

[0041] The glass fiber is chopped glass fiber with a diameter of 9-15μm and a length of 3-6mm. The flame retardant is ammonium polyphosphate, the antioxidant is antioxidant 1010, and the lubricant is zinc stearate.

[0042] The above-mentioned method for preparing polystyrene composite material includes the following steps: syndiotactic polystyrene and nylon 66 are placed in a blower box and dried at 120°C for 3 hours. After cooling to room temperature, they are added to a mixer. Hyperbranched polyether epoxy resin, flame retardant, antioxidant, and lubricant are then added to the mixer. The mixing speed is 300 r / min, and the mixing time is 1 hour. The mixture is then transferred to a twin-screw extruder. Glass fiber is fed into the twin-screw extruder through a side feeder. The mixture is then extruded and granulated. The temperatures of zones 1-10 of the twin-screw extruder are set to 130°C, 260°C, 260°C, 250°C, 250°C, 250°C, 250°C, 255°C, and 265°C, respectively. The die head temperature is 231°C, and the screw speed is 320 r / min, thus obtaining the polystyrene composite material.

[0043] Example 2

[0044] A polystyrene composite material comprises the following raw materials in parts by weight: 70 parts of syndiotactic polystyrene, 30 parts of nylon 66, 28 parts of glass fiber, 8 parts of hyperbranched polyether epoxy resin of Preparation Example 1, 4 parts of flame retardant, 0.4 parts of antioxidant, and 0.4 parts of lubricant.

[0045] The glass fiber is chopped glass fiber with a diameter of 9-15μm and a length of 3-6mm. The flame retardant is ammonium polyphosphate, the antioxidant is antioxidant 1010, and the lubricant is zinc stearate.

[0046] The above-mentioned method for preparing polystyrene composite material includes the following steps: syndiotactic polystyrene and nylon 66 are placed in a blower box and dried at 120°C for 3 hours. After cooling to room temperature, they are added to a mixer. Hyperbranched polyether epoxy resin, flame retardant, antioxidant, and lubricant are then added to the mixer. The mixing speed is 400 r / min, and the mixing time is 1.5 hours. The mixture is then transferred to a twin-screw extruder. Glass fiber is fed into the twin-screw extruder through a side feeder. The mixture is then extruded and granulated. The temperatures of zones 1-10 of the twin-screw extruder are set to 130°C, 260°C, 260°C, 250°C, 250°C, 250°C, 250°C, 255°C, and 265°C, the die head temperature is 231°C, and the screw speed is 320 r / min, thus obtaining the polystyrene composite material.

[0047] Example 3

[0048] A polystyrene composite material comprises the following raw materials in parts by weight: 80 parts of syndiotactic polystyrene, 20 parts of nylon 66, 30 parts of glass fiber, 5 parts of hyperbranched polyether epoxy resin of Preparation Example 1, 3 parts of flame retardant, 0.3 parts of antioxidant, and 0.3 parts of lubricant.

[0049] The glass fiber is chopped glass fiber with a diameter of 9-15μm and a length of 3-6mm. The flame retardant is ammonium polyphosphate, the antioxidant is antioxidant 1010, and the lubricant is zinc stearate.

[0050] The above-mentioned method for preparing polystyrene composite material includes the following steps: syndiotactic polystyrene and nylon 66 are placed in a blower box and dried at 120°C for 3 hours. After cooling to room temperature, they are added to a mixer. Hyperbranched polyether epoxy resin, flame retardant, antioxidant, and lubricant are then added to the mixer. The mixing speed is 500 r / min, and the mixing time is 2 hours. The mixture is then transferred to a twin-screw extruder. Glass fiber is fed into the twin-screw extruder through a side feeder. The mixture is then extruded and granulated. The temperatures of zones 1-10 of the twin-screw extruder are set to 130°C, 260°C, 260°C, 250°C, 250°C, 250°C, 250°C, 255°C, and 265°C, respectively. The die head temperature is 231°C, and the screw speed is 320 r / min, thus obtaining the polystyrene composite material.

[0051] Example 4

[0052] A polystyrene composite material, which differs from Example 1 only in that the hyperbranched polyether epoxy resin in Example 1 is replaced with an equal weight of the product obtained in Example 2.

[0053] Example 5

[0054] A polystyrene composite material, which differs from Example 2 only in that the hyperbranched polyether epoxy resin in Example 2 is replaced with an equal weight of the product obtained in Example 2.

[0055] Example 6

[0056] A polystyrene composite material, which differs from Example 3 only in that the hyperbranched polyether epoxy resin in Example 3 is replaced with an equal weight of the product obtained in Preparation Example 2.

[0057] Comparative Example 1

[0058] A polystyrene composite material, which differs from Example 1 only in that the hyperbranched polyether epoxy resin in Example 1 is replaced with an equal weight of the product obtained in Comparative Example 1.

[0059] Comparative Example 2

[0060] A polystyrene composite material, which differs from Example 1 only in that the hyperbranched polyether epoxy resin in Example 1 is replaced with an equal weight of the product obtained in Comparative Example 2.

[0061] Comparative Example 3

[0062] A polystyrene composite material, which differs from Example 1 only in that the hyperbranched polyether epoxy resin in Example 1 is replaced with an equal weight of the product obtained in Comparative Example 3.

[0063] The polystyrene composite materials obtained in Examples 1-6 and Comparative Examples 1-3 were dried at 120°C for 2 hours. Test specimens were then prepared using an injection molding machine. The injection molding process was as follows: melt temperature 290°C, mold temperature 50°C, injection pressure 80 MPa, holding pressure 80 MPa, and holding time 3 seconds. Finally, the injection-molded specimens were allowed to stand at room temperature for 24 hours before performance testing. The testing procedures were as follows: Tensile strength: tested according to GB / T 1040.2-2006, with a tensile rate of 10 mm / min; Notched beam impact strength: tested according to GB / T 1043.1-2008, with a test temperature of 23°C and a pendulum energy of 1 J; LOI test: tested according to ISO-4589-2:2017, with all specimens measuring 100.0 mm × 6.5 mm × 3.2 mm.

[0064] The results are shown in Table 1: Table 1

[0065] As can be seen from the data recorded in Table 1, the tensile strength of the polystyrene composite materials obtained in Examples 1-6 is 186.2-188.1 MPa, and the notched impact strength is 14.5-16.0 kJ / m. 2 The LOI is 28.2-30.5, indicating that the polystyrene composite material prepared by this invention has both good mechanical properties and flame retardant properties.

[0066] Specifically, as can be seen from the test results of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, changing the raw materials used to prepare the hyperbranched polyether epoxy resin in this application or replacing them with conventional compatibilizers significantly reduces the notched impact strength and flame retardant properties of the obtained polystyrene composite material.

[0067] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0068] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A polystyrene composite material, characterized in that, The raw materials include the following parts by weight: 60-80 parts of syndiotactic polystyrene, 20-40 parts of nylon 66, 25-30 parts of glass fiber, 5-10 parts of hyperbranched polyether epoxy resin, 3-5 parts of flame retardant, 0.3-0.5 parts of antioxidant, and 0.3-0.5 parts of lubricant.

2. The polystyrene composite material according to claim 1, characterized in that, The raw materials for preparing the hyperbranched polyether epoxy resin include quaternary phosphonium salt diol and 1,3,5-triglycidyl-S-triazine trione.

3. The polystyrene composite material according to claim 1, characterized in that, The preparation steps of the hyperbranched polyether epoxy resin are as follows: 1,3,5-triglycidyl-S-triazine trione and tetrabutylammonium bromide are added to N,N-dimethylformamide, and stirred at 130°C for 8-12 min under nitrogen protection. Then, quaternary phosphonium diol is added, and the mixture is stirred at 150-155°C for 2-4 h. After the reaction is completed, the temperature is lowered to room temperature, and N,N-dimethylformamide is removed by vacuum distillation to obtain the hyperbranched polyether epoxy resin.

4. A polystyrene composite material according to claim 3, characterized in that, The mass ratio of 1,3,5-triglycidyl-S-triazine trione to quaternary phosphonium diol is 2.98:4.91, and the amount of tetrabutylammonium bromide is 1-2% of the total mass of 1,3,5-triglycidyl-S-triazine trione and quaternary phosphonium diol.

5. A polystyrene composite material according to claim 3, characterized in that, The raw materials for preparing the quaternary phosphonium salt diol include allyltriphenylphosphine bromide and 3-mercapto-1,2-propanediol, which are prepared by a mercapto-olefin click reaction.

6. A polystyrene composite material according to claim 3, characterized in that, The preparation steps of the quaternary phosphonium base diol are as follows: allyltriphenylphosphine bromide, 3-mercapto-1,2-propanediol, benzoin dimethyl ether and dichloromethane are added to a flask, stirred for 0.5-1 h, sealed under nitrogen protection and placed under ultraviolet light irradiation for 1-2 h. After the reaction is completed, dichloromethane is removed by rotary evaporation, washed with tetrahydrofuran and dried to obtain the quaternary phosphonium base diol.

7. A polystyrene composite material according to claim 6, characterized in that, The ratio of allyltriphenylphosphine bromide, 3-mercapto-1,2-propanediol, benzoin dimethyl ether and dichloromethane is 3.83 g: 1.08-2.16 g: 0.05 g: 30-50 mL.

8. A polystyrene composite material according to claim 1, characterized in that, The flame retardant is ammonium polyphosphate and / or zinc borate.

9. A method for preparing a polystyrene composite material, characterized in that, The preparation of the polystyrene composite material according to any one of claims 1-8 includes the following steps: placing syndiotactic polystyrene and nylon 66 in a blower box and drying at 120°C for 3 hours, cooling to room temperature and then adding them to a mixer, then adding hyperbranched polyether epoxy resin, flame retardant, antioxidant and lubricant to the mixer, mixing evenly and then transferring to a twin-screw extruder, glass fiber entering the twin-screw extruder through a side feeder, extruding and granulating to obtain the polystyrene composite material.

10. A method for preparing a polystyrene composite material according to claim 9, characterized in that, The temperature settings for zones 1-10 of the twin-screw extruder are 130-140℃, 260-265℃, 260-265℃, 245-250℃, 245-250℃, 245-250℃, 245-250℃, 245-250℃, 250-255℃, and 260-265℃.

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