Polystyrene compatilizer and preparation method thereof

Abstract

The invention discloses a polystyrene compatilizer and a preparation method thereof, and belongs to the technical field of compatilizers. The preparation method is used for solving the technical problems that in the prior art, the mechanical property of a polystyrene material is comprehensively improved by compounding a compatilizer, and the fireproof and weather-resistant properties are poor. The preparation method of the polystyrene compatilizer comprises the following steps: uniformly mixing the polystyrene, the ACS resin, the epoxidized rubber and the copolymer, and internally mixing to obtain the prepared polystyrene compatilizer. The natural latex solution is subjected to acidification, oxidation and demulsification processes, and the epoxidized rubber is prepared. And enabling the trimellitic anhydride to sequentially react with 2-ethylhexanol and ethidene diamine to prepare the copolymer. The polystyrene compatilizer prepared by the preparation method disclosed by the invention has good compatibility with polystyrene and ACS (Acrylonitrile-Butadiene-Styrene) resin; wherein the epoxidized rubber plays a role in toughening, and the copolymer serves as a compatilizer base material and plays a role in enhancing the mechanical strength.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of compatilizer, in particular to a polystyrene compatilizer and a preparation method thereof. BACKGROUND

[0002] As a thermoplastic plastic, polystyrene is hard in texture, rigid, excellent in chemical performance and electrical insulation, and easy to be shaped into various transparent, bright-colored and glossy products, which are widely used in electrical, instrument packaging, decoration and daily life. The presence of benzene ring on the polystyrene macromolecular chain makes the steric hindrance effect larger, and the internal rotation of the molecule is limited, which shows hard and brittle properties in the stretching process. In addition, polystyrene has the problems of low mechanical strength and poor heat resistance, which to some extent limits its application. If polystyrene materials are used to make electrical housings, building decoration materials, automobile covers, lighting fixture housings, etc., there are still technical problems of poor fire resistance and weather resistance.

[0003] Patent application CN101230119A discloses a polystyrene / polyethylene alloy and a special compatilizer and preparation method thereof. The compatilizer used in the polystyrene / polyethylene alloy is PE-g-PS, which can increase the compatibility of polystyrene and polyethylene. The prepared blend has excellent performance of both polystyrene and polyethylene components, and has higher impact strength and better processing performance compared with ordinary polystyrene materials. However, the fire resistance and weather resistance of the polystyrene and polyethylene alloy doped with the compatilizer have not been significantly improved.

[0004] In view of the above technical defects, a solution is proposed. SUMMARY

[0005] The present application aims to provide a polystyrene compatilizer and a preparation method thereof, which solves the technical problem of how to improve the mechanical properties and poor fire resistance and weather resistance of polystyrene materials by compounding compatilizers.

[0006] The purpose of the present application can be achieved by the following technical solutions: According to weight parts, 5-10 parts of polystyrene, 5-10 parts of ACS resin, 10-20 parts of epoxidized rubber and 70-80 parts of copolymer are uniformly mixed and milled to obtain the prepared polystyrene compatilizer.

[0007] Further, the preparation method of the epoxidized rubber comprises the following steps: B1, the natural latex solution is diluted with deionized water, and a surfactant is added and mixed to obtain a mixture; the mixture is stirred and reacted at 50-60 DEG C for 10-20 min to obtain a reaction system; formic acid and 60-70 wt% hydrogen peroxide are continuously added to the reaction system, and the reaction is continuously carried out at 40-50 DEG C for 6-10 h, and then the reaction is stopped to obtain an epoxidized natural latex solution; B2, the epoxidized natural latex solution is added to anhydrous ethanol to cause it to be demulsified and flocculated to obtain a rubber block; the rubber block is washed with NaOH solution and deionized water in sequence, and then dried to constant weight to obtain the prepared epoxidized rubber.

[0008] Further, in step B1, the amount ratio of the natural latex solution, deionized water, surfactant, formic acid and hydrogen peroxide is 150-250 mL:100 mL:3-5 mL:5-10 mL:5-10 mL; in step B2, the mass ratio of the epoxidized natural latex solution and anhydrous ethanol is 1:2-3.

[0009] Further, the preparation method of the copolymer comprises the following steps: A1, the isophthalic acid anhydride and 2-ethylhexanol are added to a vacuum reaction kettle, heated to 200-210 DEG C, and then titanium tetraisobutoxide is added and mixed; the reaction is continuously carried out at this temperature for 3.5-5.5 h, and the esterification reaction is considered to be completed to obtain an intermediate; A2, the ethylenediamine is added dropwise to the intermediate, and after the addition is completed, the reaction is carried out at 0-5 DEG C for 20-30 min, and then filtered, and the solid is collected, washed with water and dried to obtain the prepared copolymer.

[0010] The isophthalic acid anhydride and 2-ethylhexanol are esterified to obtain an intermediate. The intermediate and the ethylenediamine are continuously reacted to finally prepare the copolymer.

[0011] Further, in step A1, the amount ratio of the isophthalic acid anhydride, 2-ethylhexanol and titanium tetraisobutoxide is 20-40 g:20-40 mL:1-3 g.

[0012] Further, the temperature of the internal mixer is 200-210 DEG C, and the mixing time is 3-5 min.

[0013] As another aspect of the present application, a polystyrene compatibilizer is prepared by the preparation method of the polystyrene compatibilizer.

[0014] The present application has the following advantages: 1. The polystyrene compatibilizer prepared by this invention is mainly used in composite materials of polystyrene and ACS resin. The polystyrene compatibilizer prepared by this invention has a polystyrene structure and acrylonitrile-styrene-chlorinated polyethylene structural units; therefore, the above-mentioned polystyrene compatibilizer has good compatibility with both polystyrene and ACS resin. After activating the natural latex solution with a surfactant, formic acid and hydrogen peroxide are added, followed by acidification and epoxidation reactions to prepare an epoxidized natural latex solution. The epoxidized natural latex solution undergoes a series of processing operations to form solid epoxidized rubber. The solid epoxidized rubber, as part of the polystyrene compatibilizer, plays a toughening role. Furthermore, the above-mentioned polystyrene compatibilizer has an epoxy structure, which can capture hydrogen chloride gas.

[0015] 2. ACS resin is a graft copolymer formed by grafting acrylonitrile and styrene onto the main chain of chlorinated polyethylene. The introduction of chlorine atoms enhances the flame retardancy of ACS resin. Replacing butadiene with chlorinated polyethylene, which has a double bond structure, in ACS resin further enhances its weather resistance. Esterification with trimellitic anhydride and 2-ethylhexanol, by controlling the amount of trimellitic anhydride, allows excess anhydride groups to continue reacting with ethylenediamine, thus preparing the copolymer. Blending and melting the above copolymer with other components of the compatibilizer improves mechanical strength and toughens the resin. Furthermore, during the mixing process, epoxidized rubber and the copolymer can chemically react to act as an intermediate bridge connecting polystyrene and ACS resin. Detailed Implementation

[0016] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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. Example 1

[0017] This embodiment provides a method for preparing a copolymer for a polystyrene compatibilizer, comprising the following steps: A1. Select a 500mL laboratory vacuum reactor. Connect the vacuum reactor to a thermometer, stirrer, condenser, and alcohol-water separator. Add 20g of trimellitic anhydride and 20mL of 2-ethylhexanol to the vacuum reactor and mix well. Heat the vacuum reactor to 200℃. Then add 1g of tetraisobutyl titanate to the vacuum reactor and mix well. React at this temperature for 3.5h, which is considered the end of the esterification reaction, and the intermediate is obtained.

[0018] A2. Select a 250mL laboratory three-necked flask, add 20g of the intermediate, and then add 10mL of 28 dropwise to the flask. After the addition is complete, maintain the temperature of the three-necked flask at 0℃ using a water bath and react at this temperature for 20min. Then filter and collect the solid. Wash the solid with water and dry it to obtain the prepared copolymer. Example 2

[0019] This embodiment provides a method for preparing a copolymer for a polystyrene compatibilizer, comprising the following steps: A1. Select a 500mL laboratory vacuum reactor. Connect the vacuum reactor to a thermometer, stirrer, condenser, and alcohol-water separator. Add 30g of trimellitic anhydride and 30mL of 2-ethylhexanol to the vacuum reactor and mix well. Heat the vacuum reactor to 2050℃. Then add 2g of tetraisobutyl titanate and mix well. React at this temperature for 4.5h, which is considered the end of the esterification reaction, and the intermediate is obtained.

[0020] A2. Select a 250mL laboratory three-necked flask, add 30g of the intermediate, and then add 12mL of ethylenediamine dropwise to the flask. After the addition is complete, maintain the temperature of the three-necked flask in a water bath at 3℃ and react at this temperature for 22min. Then filter and collect the solid. Wash the solid with water and dry it to obtain the prepared copolymer. Example 3

[0021] This embodiment provides a method for preparing a copolymer for a polystyrene compatibilizer, comprising the following steps: A1. Select a 500mL laboratory vacuum reactor. Connect the vacuum reactor to a thermometer, stirrer, condenser, and alcohol-water separator. Add 40g of trimellitic anhydride and 40mL of 2-ethylhexanol to the vacuum reactor and mix well. Heat the vacuum reactor to 210℃, then add 3g of tetraisobutyl titanate and mix well. React at this temperature for 5.5h, which is considered the end of the esterification reaction, and the intermediate is obtained.

[0022] A2. Select a 250mL laboratory three-necked flask, add 40g of the intermediate, and then add 15mL of ethylenediamine dropwise to the flask. After the addition is complete, maintain the temperature of the three-necked flask in a water bath at 5℃ and react for 30min. Then filter and collect the solid. Wash the solid with water and dry it to obtain the prepared copolymer. Example 4

[0023] This embodiment provides a method for preparing epoxidized rubber for polystyrene compatibilizers, including the following steps: B1. Select a 500mL glass reactor. Add 150mL of natural latex solution to the reactor, then add 100mL of deionized water to dilute the natural latex solution. Add 3mL of surfactant to obtain a mixture. Transfer the glass reactor to a water bath and stir at 50℃ for 10 minutes to obtain the reaction system. Continue to add 5mL of formic acid and 5mL of 60wt% hydrogen peroxide to the glass reactor, and continue the reaction at 40℃ for 6 hours. Then stop the reaction to obtain an epoxidized natural latex solution.

[0024] B2. The epoxidized natural latex solution was added to anhydrous ethanol at a mass ratio of 1:2 to cause demulsification and flocculation, resulting in a rubber block. The rubber block was then washed sequentially with a 10wt% NaOH solution and deionized water, and then transferred to an oven at 60℃ to dry until constant weight, yielding the prepared epoxidized rubber. Example 5

[0025] This embodiment provides a method for preparing epoxidized rubber for polystyrene compatibilizers, including the following steps: B1. Select a 500mL glass reactor. Add 200mL of natural latex solution to the reactor, then add 100mL of deionized water to dilute the natural latex solution. Next, add 4mL of surfactant to obtain a mixture. Transfer the glass reactor to a water bath and stir at 55℃ for 15 minutes to obtain the reaction system. Continue adding 6mL of formic acid and 8mL of 65wt% hydrogen peroxide to the glass reactor, and continue the reaction at 45℃ for 8 hours. Then stop the reaction to obtain an epoxidized natural latex solution.

[0026] B2. The epoxidized natural latex solution was added to anhydrous ethanol at a mass ratio of 1:2 to cause demulsification and flocculation, resulting in a rubber block. The rubber block was then washed sequentially with a 12wt% NaOH solution and deionized water, and then transferred to an oven at 66℃ to dry until constant weight, yielding the prepared epoxidized rubber. Example 6

[0027] This embodiment provides a method for preparing epoxidized rubber for polystyrene compatibilizers, including the following steps: B1. Select a 500mL glass reactor. Add 250mL of natural latex solution to the reactor, then add 100mL of deionized water to dilute the natural latex solution. Next, add 5mL of surfactant to obtain a mixture. Transfer the glass reactor to a water bath and stir at 60℃ for 20 minutes to obtain the reaction system. Continue adding 10mL of formic acid and 10mL of 70wt% hydrogen peroxide to the glass reactor, and continue the reaction at 50℃ for 10 hours. Then stop the reaction to obtain an epoxidized natural latex solution.

[0028] B2. The epoxidized natural latex solution was added to anhydrous ethanol at a mass ratio of 1:2 to cause demulsification and flocculation, resulting in a rubber block. The rubber block was then washed sequentially with a 15wt% NaOH solution and deionized water, and then transferred to an oven at 70℃ to dry until constant weight, yielding the prepared epoxidized rubber. Example 7

[0029] This embodiment provides a method for preparing a polystyrene compatibilizer, including the following steps: According to the weight parts, 5 parts of polystyrene, 5 parts of ACS resin, 10 parts of the epoxidized rubber prepared in Example 4, and 70 parts of the copolymer prepared in Example 1 were mixed and added to a mixer and mixed at 200°C for 3 minutes to obtain the polystyrene compatibilizer. Example 8

[0030] This embodiment provides a method for preparing a polystyrene compatibilizer, including the following steps: According to the weight parts, 8 parts of polystyrene, 8 parts of ACS resin, 15 parts of the epoxidized rubber prepared in Example 5, and 75 parts of the copolymer prepared in Example 2 were mixed and added to a mixer and mixed at 205°C for 5 minutes to obtain the polystyrene compatibilizer. Example 9

[0031] This embodiment provides a method for preparing a polystyrene compatibilizer, including the following steps: According to the weight parts, 10 parts of polystyrene, 10 parts of ACS resin, 20 parts of epoxidized rubber prepared in Example 6, and 80 parts of copolymer prepared in Example 3 were mixed and added to a mixer and mixed at 210°C for 5 minutes to obtain the polystyrene compatibilizer. Example 10

[0032] This embodiment provides a method for preparing a polystyrene / ACS resin alloy, including the following steps: By weight, 40 parts of polystyrene, 40 parts of ACS resin and 5 parts of the polystyrene compatibilizer prepared in Example 7 were added to a twin-screw extruder for melt extrusion. The melt extrusion temperature was 200°C and the melt extrusion time was 3 minutes to obtain the product polystyrene / ACS resin alloy. Example 11

[0033] This embodiment provides a method for preparing a polystyrene / ACS resin alloy, including the following steps: By weight, 45 parts of polystyrene, 45 parts of ACS resin and 8 parts of the polystyrene compatibilizer prepared in Example 8 were added to a twin-screw extruder for melt extrusion. The melt extrusion temperature was 205°C and the melt extrusion time was 4 min, resulting in a polystyrene / ACS resin alloy. Example 12

[0034] This embodiment provides a method for preparing a polystyrene / ACS resin alloy, including the following steps: By weight, 50 parts of polystyrene, 50 parts of ACS resin and 10 parts of the polystyrene compatibilizer prepared in Example 9 were added to a twin-screw extruder for melt extrusion. The melt extrusion temperature was 210°C and the melt extrusion time was 5 min to obtain the product polystyrene / ACS resin alloy. Comparative Example 1

[0035] Compared to Example 9, step A2 is omitted, and the prepared copolymer is replaced with an equivalent mass of intermediate. Comparative Example 2

[0036] Compared to Example 9, the preparation of epoxidized rubber is carried out by replacing the same mass of rubber solids, specifically including the following steps: Natural latex was added to anhydrous ethanol at a mass ratio of 1:2 to cause demulsification and flocculation, resulting in a rubber block. The rubber block was then washed successively with 10wt% NaOH solution and deionized water, and then transferred to an oven at 70℃ to dry until constant weight, which is the prepared rubber solid. Comparative Example 3

[0037] Compared to Example 9, 20 parts by weight of polystyrene were used instead of 10 parts of polystyrene and 10 parts of ACS resin.

[0038] Performance testing: 1. In accordance with GB / T1040-2006, the polystyrene / ACS resin alloys prepared in Examples 10-12 were sequentially prepared into 150mm×10mm×4mm specimens with a stretching rate of 5mm / min.

[0039] 2. In accordance with GB / T1043.1-2008, the polystyrene / ACS resin alloys prepared in Examples 10-12 were sequentially prepared into 80mm×10mm×4mm specimens with type A notches. The notched impact strength of these specimens was then measured.

[0040] 3. The limiting oxygen index values ​​of the polystyrene / ACS resin alloys prepared in Examples 10-12 were tested sequentially using the limiting oxygen index method.

[0041] 4. The thermal stability of the polystyrene / ACS resin alloys prepared in Examples 10-12 was tested sequentially using a thermogravimetric analyzer. 5 mg of each polystyrene / ACS resin alloy prepared in Examples 10-12 was measured, and the maximum thermal decomposition temperature was measured at a heating rate of 10 °C / min. Specific test results are shown in Table 1.

[0042] Table 1. Sample Performance Test Data

[0043] Data Analysis: According to the data in Table 1, the polystyrene / ACS resin alloys prepared in Examples 10-12 of this invention exhibit excellent mechanical properties, particularly high tensile strength and notched impact strength. In Comparative Example 1, an intermediate was used instead of the prepared copolymer; the copolymer has stronger polarity, and the prepared compatibilizer has better compatibility with the polystyrene / ACS resin alloy. Therefore, the tensile strength and notched impact strength of the polystyrene / ACS resin alloy prepared in Comparative Example 1 deteriorated. In Comparative Example 2, solid rubber was used instead of the prepared epoxidized rubber. The epoxidized rubber can chemically crosslink with the ACS resin and copolymer during the mixing process; therefore, the tensile strength and notched impact strength of the polystyrene compatibilizer prepared in Comparative Example 2 decreased.

[0044] The polystyrene / ACS resin alloys prepared in Examples 10-12 of this invention exhibit both excellent flame retardancy and weather resistance. However, in Comparative Example 3, polystyrene and ACS resin were substituted with equal masses; the addition of ACS resin can further improve the flame retardancy and weather resistance of the prepared polystyrene / ACS resin alloys.

[0045] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0046] In the description of this specification, references to terms such as "an embodiment," "example," and "specific example" indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0047] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a polystyrene compatibilizer, characterized in that, It is prepared by the following steps: The polystyrene compatibilizer is prepared by mixing 5-10 parts of polystyrene, 5-10 parts of ACS resin, 10-20 parts of epoxidized rubber, and 70-80 parts of copolymer by weight and then mixing them thoroughly.

2. The method for preparing the polystyrene compatibilizer according to claim 1, characterized in that, The method for preparing the epoxidized rubber includes the following steps: B1. The natural latex solution is diluted with deionized water, and then a surfactant is added and mixed to obtain a mixture. The mixture is stirred and reacted at 50-60℃ for 10-20 min to obtain a reaction system. Formic acid and 60-70wt% hydrogen peroxide are added to the reaction system, and the reaction is continued at 40-50℃ for 6-10 h. Then the reaction is stopped to obtain an epoxidized natural latex solution. B2. Add the epoxidized natural latex solution to anhydrous ethanol to cause demulsification and flocculation, and obtain a rubber block; wash the rubber block with NaOH solution and deionized water in sequence, and then dry it to constant weight, which is the prepared epoxidized rubber.

3. The method for preparing the polystyrene compatibilizer according to claim 2, characterized in that, In step B1, the ratio of natural latex solution, deionized water, surfactant, formic acid and hydrogen peroxide is 150-250mL:100mL:3-5mL:5-10mL:5-10mL; in step B2, the mass ratio of epoxidized natural latex solution and anhydrous ethanol is 1:2-3.

4. The method for preparing the polystyrene compatibilizer according to claim 1, characterized in that, The method for preparing the copolymer includes the following steps: A1, trimellitic anhydride and 2-ethylhexanol are added to a vacuum reactor, heated to 200-210℃, and then tetraisobutyl titanate is added and mixed well; the reaction is continued at this temperature for 3.5-5.5 hours, which is considered the end of the esterification reaction, and the intermediate is obtained; A2. Ethylenediamine is added dropwise to the intermediate. After the addition is complete, the reaction is carried out at 0-5℃ for 20-30 minutes. The mixture is then filtered, the solid is collected, washed with water, and dried to obtain the copolymer.

5. The method for preparing the polystyrene compatibilizer according to claim 4, characterized in that, In step A1, the ratio of trimellitic anhydride, 2-ethylhexanol and tetraisobutyl titanate is 20-40g:20-40mL:1-3g.

6. The method for preparing the polystyrene compatibilizer according to claim 4, characterized in that, In step A2, the ratio of intermediate to ethylenediamine is 20-40g:10-15mL.

7. The method for preparing the polystyrene compatibilizer according to claim 1, characterized in that, The mixing temperature is 200-210℃ and the mixing time is 3-5 minutes.

8. A polystyrene compatibilizer, characterized in that, It is prepared using the method for preparing polystyrene compatibilizer as described in any one of claims 1-7.

Images