High-performance PPE / PS alloy material as well as preparation method and application thereof

Abstract

The invention discloses a high-performance PPE / PS alloy material as well as a preparation method and application thereof. The high-performance PPE / PS alloy material is prepared from the following raw materials in parts by weight: 10-84.98% of bulk flame-retardant MPPE resin; 5-35% of polystyrene resin; 10 to 40% of flame-retardant glass fiber; 0.01 to 10% of a flame retardant; 0.01-2% of a synergistic flame retardant, and 0-3% of other auxiliary agents. The PPE / PS alloy material prepared by the invention has excellent mechanical properties, processability and flame retardance, and can be applied to products such as electronic and electrical products, household appliances, automobiles and the like.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a high-performance PPE / PS alloy material and a preparation method and application thereof. Background Art

[0002] Plastic alloys are obtained by physical blending or chemical grafting. They have the characteristics of high performance, functionality and specialization. They can be widely used in the fields of automobiles, electronics, precision instruments, office equipment, packaging materials, building materials, etc. The purpose of preparing this material is to make the components of different plastics complement each other better. Some properties even exceed the performance of any single component. The performance advantages of plastic alloys are mainly reflected in their excellent physical properties, chemical properties and processing properties. According to the functionality, they are divided into two specifications: flame retardant and non-flame retardant.

[0003] PPE / PS alloy combines polystyrene (PS) with polyphenylene ether (PPE) and utilizes the internal plasticizing effect of PS to significantly improve the melt fluidity of PPE, thereby improving its molding processability. This alloy not only solves the problem of high melt viscosity and difficult processing of PPE, but also gives the blend excellent melt flow characteristics, which significantly improves the processing performance of PPE. In general, the development and utilization of PPE / PS alloy not only solves the difficulties of PPO in the processing process, but also enhances the comprehensive performance of the material by combining the characteristics of PS, making it have a wider application potential in the field of engineering plastics.

[0004] Chinese patent CN202011522160.4 relates to a flame-retardant high-rigidity PS / PPE composite material and its preparation method and application. The continuous long glass fiber is used to synergize with a specific flame retardant synergist and flame retardant, and the glass fiber retention length D90 is adjusted to greatly improve the flame retardancy of the material. The flame retardancy level can reach above 5VB under thin thickness conditions; in addition, through the synergistic effect of glass fiber and coupling agent, the material has high rigidity, toughness and heat resistance, and can be widely used in functional structural injection molding parts of electronic and electrical products or household appliances. Chinese patent CN202011558092.7 discloses a PPE / PS alloy material and its preparation method and application. By adding pentaerythritol ester with an active -OH structure, the processing film-forming property of the PPE / PS alloy material can be significantly improved, and it is easy to make a film. The prepared PPE / PS film has high transparency and good flexibility, which further broadens the application of PPE / PS alloy in the field of food packaging, especially in the field of food soft packaging. Chinese patent CN202011560385.9 discloses a PPE / PS alloy, which is prepared by compounding PPE and PS to make the carbon nanotubes have good dispersion in the alloy resin matrix, the surface resistance of the injection molded parts is greater than E5, it is not easy to decarburize, and the thermal deformation temperature is high. When glass fiber is added, there is no floating fiber on the surface of the parts, which is suitable for preparing ICTRAY disks. The currently disclosed patents increase the functionality of PPE / PS by physical blending, and there is little research on the influence of the difference in terminal functional groups on the performance of alloy materials. For glass fiber reinforced PPE / PS alloy materials, the surface pretreatment of glass fiber has little effect on the performance of alloy materials. The performance improvement of dimensionality is of great research significance for realizing the high performance of PPE / PS alloy materials and increasing their application fields. Summary of the invention

[0005] In order to fill the gap in the prior art, the present invention provides a high-performance PPE / PS alloy material and a preparation method and application thereof. The PPE / PS alloy material is prepared by formula design, and the PPE / PS alloy material prepared by the method has both flame retardant properties and mechanical properties, and can be applied to the performance requirements of materials in the use conditions of electronic and electrical products, household appliances, automobiles, etc.

[0006] The present invention is achieved through the following technical solutions:

[0007] A high-performance PPE / PS alloy material, comprising the following raw materials in percentage by weight:

[0008]

[0009] The bulk flame-retardant MPPE resin is a functionally modified PPE resin, the weight average molecular weight of the PPE resin is 20000-60000, and the melt flow rate (test conditions: 280°C, 5kg) is 0.5-30g / 10min. The functional modification of PPE is prepared in three steps: first, a carboxyl modified PPE resin is prepared by reacting butyl lithium and carbon dioxide in anhydrous toluene solvent; secondly, the carboxyl epoxy phosphate is further esterified to prepare a bulk flame-retardant PPE resin, the structural formula of which is as follows:

[0010]

[0011] The polystyrene resin may be one or more of high impact polystyrene, general purpose polystyrene, SBS resin, etc., with a density of 1.04-1.06 g / cm3, a refractive index of 1.5-1.7, and a weight average molecular weight of 50000-200000. The present invention gives priority to HIPS.

[0012] The flame retardant glass fiber has an alkali content of less than 0.8%, a volume density of 0.6-0.8g / cm3, a single fiber diameter of 7-13μm, a short cut length of 2-5mm, a moisture content of ≤0.05%, and a sizing treatment is performed by spraying a flame retardant solution on the glass fiber surface, and the mass fraction of the sizing agent is greater than 0.3%. The mass fraction of the flame retardant in the flame retardant solution is 1%-10%, and the flame retardant is a compound with a phosphate group, and the structural formula is as follows:

[0013]

[0014] The synergistic flame retardant is prepared by coating the surface of hydroxyapatite with epoxy phenyl phosphate. The chemical formula of hydroxyapatite is Ca10(PO4)6(OH)2, and it is a white powdery solid. The structural formula of epoxy phenyl phosphate is as follows:

[0015]

[0016] The other auxiliary agents may be one or more of antioxidants, lubricants, and colorants.

[0017] The preparation method of the above-mentioned high-performance PPE / PS alloy material comprises the following steps:

[0018] (1) Weigh various dried raw materials according to the formula ratio; mix the flame retardant MPPE resin, polystyrene resin, flame retardant, synergistic flame retardant and other additives uniformly by high-speed mixer, and set aside; weigh the flame retardant glass fiber according to the ratio, and set aside;

[0019] (2) The resin and additive mixture is added through the main feed port of a twin-screw extruder, and flame-retardant glass fiber is added from the side feed port of the twin-screw extruder. After melt extrusion, granulation, drying and other processes, the PPE / PS alloy material is obtained.

[0020] The above-mentioned PPE / PS alloy materials can be applied to electronic and electrical products, household appliances, automobiles and the like.

[0021] The technical advantage of the present invention is that the PPE / PS alloy material prepared by formula design has excellent flame retardant properties and mechanical properties. According to the structural characteristics and flame retardant principle of the PPE / PS alloy material, the formula design selects a flame-retardant PPE resin, and at the same time, the flame retardant is loaded on the surface of the glass fiber and the surface of the synergistic flame retardant. Compared with simple physical blending, the distribution of the flame retardant in the PPE / PS alloy material and the compatibility of the various components of the formula are increased, and a higher flame retardant efficiency is obtained. To achieve the same flame retardant effect, the amount of flame retardant added can be greatly reduced, and the influence of the high amount of flame retardant added and the poor compatibility on the mechanical properties of the PPE / PS alloy material is solved. The prepared high-performance PPE / PS alloy material has both mechanical properties and flame retardant properties.

[0022] The beneficial effects of the present invention are:

[0023] 1) The present invention selects the functional modification of the PPE resin terminal with epoxyphenyl phosphate, so that the MPPE has the flame retardant performance of the body, and at the same time increases the compatibility of the MPPE with glass fiber and flame retardant, thereby increasing the mechanical properties of the PPE / PS alloy material.

[0024] 2) The surface of the glass fiber selected by the present invention is sizing treated with a flame retardant solution to load the flame retardant on the surface of the glass fiber. During the alloy material processing, the glass fiber is evenly distributed in the resin. On the one hand, the dispersion of the flame retardant in the resin and the compatibility of the glass fiber and the resin are increased. On the other hand, the flame retardant loading on the surface of the glass fiber can eliminate the "wick effect" of the flame-retardant glass fiber during the combustion process, thereby improving the flame retardant efficiency. Compared with simple physical blending, the amount of flame retardant added can be greatly reduced.

[0025] 3) The present invention selects epoxy phenyl phosphate-coated hydroxyapatite as a synergistic flame retardant. The synergistic flame retardant can promote the carbonization reaction and increase the flame retardant properties of the material. Compared with simple physical blending, the epoxy phosphate coating increases the flame retardant efficiency of the synergistic flame retardant and the compatibility of the resin, thereby making the PPE / PS alloy material have more excellent mechanical properties.

[0026] 4) The PPE / PS alloy material prepared by the present invention can achieve excellent flame retardant effect with a small amount of flame retardant added, and the material has excellent mechanical properties and processing properties, thereby realizing the application of the PPE / PS alloy material in electronic and electrical products, household appliances, automobiles and the like.

[0027] The above beneficial effects achieve excellent mechanical properties, processing properties and flame retardant properties of the PPE / PS alloy material. DETAILED DESCRIPTION

[0028] In order to make the technical problems, technical solutions and intentions to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0029] The embodiments and comparative examples of the present invention use the following materials, but are not limited to the following materials:

[0030] The bulk flame retardant PPE resin is commercially available;

[0031] PPE, trade name LXN040, produced by Nantong Xingchen Synthetic Materials Co., Ltd.;

[0032] HIPS, the Taiwanese trade name is HP9450, produced by Formosa Chemical Corporation;

[0033] Flame retardant glass fiber, homemade;

[0034] Glass fiber, trade name ECS306HR, produced by Chongqing International Composite Materials Co., Ltd.;

[0035] Flame retardant BDP, produced by Zhejiang Wansheng Co., Ltd.;

[0036] Synergistic flame retardant, homemade;

[0037] Hydroxyapatite, commercially available;

[0038] Processing aid. Product name LYSI-100E, produced by Chengdu Silike Technology Co., Ltd.

[0039] Antioxidant 1010, hindered phenol antioxidant, commercially available;

[0040] Antioxidant 9228, phosphite antioxidant, commercially available;

[0041] Masterbatch, trade name XP6581A, produced by Cabot;

[0042] Preparation methods of Examples 1-6 and Comparative Examples 1-6:

[0043] Preparation method of PPE / PS alloy material

[0044] (1) Weigh various dried raw materials according to the formula ratio; mix the functionalized MPPE resin, polystyrene resin, compatibilizer, flame retardant, and other additives uniformly by a high-speed mixer, and set aside; weigh the reinforcement according to the ratio, and set aside;

[0045] (2) The resin and additive mixture is added through the main feed port of a twin-screw extruder, and the filler is added through the side feed port of the twin-screw extruder. After melt extrusion, granulation, drying and other processes, the PPE / PS alloy material is obtained. Preparation of PPE / PS alloy material test specimens:

[0046] The above materials were dried in a forced air drying oven at 120° C. for 4 hours and then injection molded into standard specimens at an injection molding temperature of 280-330° C. The prepared mechanical properties specimens were conditioned in a standard laboratory environment (23° C., 50% RH) for 24 hours before testing.

[0047] Test methods for each performance index:

[0048] Tensile properties: According to ISO 527 method, sample size: 170*10*4mm, test speed 5mm / min.

[0049] Bending properties: According to ISO 178 method, sample size: 80*10*4mm, test speed 2mm / min.

[0050] Notched impact performance: According to ISO 179 method, sample size: 80*10*4mm.

[0051] Heat deformation temperature: according to ISO 75 method, sample size: 80*10*4, test condition: 1.8MPa.

[0052] Flame retardant performance: According to UL94 method, sample size: 127*12.7*1.6mm.

[0053] Table 1: Composition and properties of PPE / PS alloy materials in Examples 1-6 and Comparative Examples 1-6

[0054]

[0055]

[0056] It can be seen from the results of the embodiments and comparative examples in Table 1 that the introduction of flame-retardant glass fiber and synergistic flame retardant in the formulation design can reduce the amount of flame retardant added, and achieving the same flame retardant effect can improve the mechanical properties of PPE / PS alloy materials. By Example 2 and Comparative Example 6, the flame-retardant PPE resin and flame-retardant glass fiber of Comparative Example 6 achieve the same flame retardant effect compared with conventional PPE resin and glass fiber. This is because the terminal functional groups of the PPE resin and the surface coating of the glass fiber have flame retardant properties. The amount of flame retardant added in the formulation design is small, and the PPE resin is functionalized and the glass fiber is surface coated to increase the compatibility of MPPE with glass fiber and flame retardant, thereby increasing the mechanical properties of the alloy material, and the strength, rigidity and toughness of the alloy material are higher. It can be seen from Examples 1-4 that the synergistic flame retardant coated with phenyl phosphate has a higher carbonization efficiency, because the synergistic flame retardant can promote carbonization reaction and increase the flame retardant properties of the material. Compared with simple physical blending, the coating of epoxy phosphate increases the flame retardant efficiency of the synergistic flame retardant and the compatibility of the resin is better. It can be seen from Examples 1, 5 and 6 that the technical advantages of the present invention are well demonstrated in different grades of PPE / PS alloys. The PPE / PS alloy material prepared by the present invention has excellent mechanical properties, processing properties and flame retardant properties, and can be used in electronic and electrical, household appliances, automobiles and other products.

Claims

1. A high-performance PPE / PS alloy material, characterized in that: According to the following raw material composition by weight:

2. A high performance PPE / PS alloy material according to claim 1, characterized in that: The bulk flame-retardant MPPE resin is a functionally modified PPE resin, the weight average molecular weight of the PPE resin is 20000-60000, and the melt flow rate is 0.5-30g / 10min.

3. A high performance PPE / PS alloy material according to claim 2, characterized in that: The functional modification of PPE is divided into three steps: first, the carboxyl modified PPE resin is prepared by reacting butyl lithium and carbon dioxide in anhydrous toluene solvent; secondly, the carboxyl epoxy phosphate is further esterified to prepare the bulk flame retardant PPE resin, the structural formula of which is as follows:

4. A high performance PPE / PS alloy material according to claim 1, characterized in that: The polystyrene resin is selected from one or more of high impact polystyrene, general-purpose polystyrene, and SBS resin, with a density of 1.04-1.06 g / cm 3 , refractive index: 1.5-1.7, weight average molecular mass: 50000-200000.

5. A high performance PPE / PS alloy material according to claim 1, characterized in that: The polystyrene resin is high impact polystyrene.

6. A high performance PPE / PS alloy material according to claim 1, characterized in that: The flame retardant glass fiber has an alkali content of less than 0.8% and a volume density of 0.6-0.8 g / cm 3 , monofilament fiber diameter: 7-13μm, short cut length: 2-5mm, moisture content ≤0.05%, the glass fiber surface is sprayed with flame retardant solution for sizing treatment, and the mass fraction of sizing agent is greater than 0.3%.

7. A high performance PPE / PS alloy material according to claim 6, characterized in that: The mass fraction of the flame retardant in the flame retardant solution is 1%-10%. The flame retardant is a compound with a phosphate group, and the structural formula is as follows:

8. A high performance PPE / PS alloy material according to claim 6, characterized in that: The preparation of the flame retardant glass fiber comprises the following steps: (1) soaking the glass fiber in a mixed solution consisting of a silane coupling agent and an aqueous solution of ethylene glycol, wherein the silane coupling agent may be aminosilane, epoxysilane, etc., and the mass fraction of the silane coupling agent in the mixed solution is 15-20%, adjusting the pH of the solution, and performing a silane coupling agent modification treatment to obtain a silane coupling agent modified glass fiber; (2) The silane coupling agent modified glass fiber is immersed in a flame retardant solution for modification, wherein the mass fraction of the flame retardant is 0.8-1.2%, the solvent can be any one of ether and tetrahydrofuran, the temperature is 40-100°C, the time is 8-18h, and the flame retardant glass fiber is obtained.

9. A high performance PPE / PS alloy material according to claim 1, characterized in that: The synergistic flame retardant is prepared by coating the surface of hydroxyapatite with epoxyphenyl phosphate. The chemical formula of hydroxyapatite is Ca 10 (PO4)6(OH)2 is a white powdery solid; the structural formula of epoxyphenyl phosphate is as follows:

10. A high performance PPE / PS alloy material according to claim 9, characterized in that , the steps of epoxyphenyl phosphate coating the hydroxyapatite surface are as follows: (1) dissolving epoxy phenyl phosphate in anhydrous ethanol to obtain an epoxy phenyl phosphate-ethanol solution, then adding hydroxyapatite to the epoxy phenyl phosphate-ethanol solution under stirring conditions, heating to 60-90° C. for reaction for 0.5-3 h, and then cooling to room temperature to obtain a hydroxyapatite / epoxy phosphate composite flame retardant solution; (2) Filter, wash and dry the above solution to obtain a hydroxyapatite / epoxy phosphate composite synergistic flame retardant.

11. A high-performance PPE / PS alloy material and a preparation method and application thereof according to claim 1, characterized in that: The other auxiliary agents may be one or more of antioxidants, lubricants, and colorants.

12. The method for preparing a high-performance PPE / PS alloy material according to any one of claims 1 to 11, characterized in that: The following steps are involved: (1) Weigh various dried raw materials according to the formula ratio; mix the flame retardant MPPE resin, polystyrene resin, flame retardant, synergistic flame retardant and other additives uniformly by high-speed mixer, and set aside; weigh the flame retardant glass fiber according to the ratio, and set aside; (2) The resin and additive mixture is added through the main feed port of a twin-screw extruder, and flame-retardant glass fiber is added from the side feed port of the twin-screw extruder. After melt extrusion, granulation, drying and other processes, the PPE / PS alloy material is obtained.

Images