Modified polyphenyl ether resin and preparation method of extruded foamed sheet material of modified polyphenyl ether resin
By blending and modifying chloromethylated micro-cross-linked polystyrene with polyphenylene ether, the problem of polystyrene/polyphenylene ether resin being difficult to extrude into high modulus sheets at low temperatures was solved, the preparation of high modulus sheets was achieved, the mechanical properties were improved and energy consumption was reduced.
Patent Information
- Application Number
- CN202510874337.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-27
- Publication Date
- 2025-09-09
AI Technical Summary
In the prior art, polystyrene/polyphenylene ether resins cannot be extruded into high modulus sheets at relatively low temperatures, and there are problems of difficulty in processing and molding and excessive energy consumption.
By introducing chloromethylated micro-crosslinked polystyrene and polyphenylene ether for blending and modification, the cross-linking reaction between chloromethyl and the benzene ring of polyphenylene ether is utilized to form a covalent bond interface structure, thereby improving the resin compatibility. The modified polyphenylene ether resin extrusion foaming board is prepared using supercritical carbon dioxide foaming agent.
The extrusion of high modulus sheets at low temperatures improves the mechanical properties and compressive strength of the product while reducing energy consumption, and has good application prospects.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polymer materials, and in particular to a method for preparing a modified polyphenylene ether resin and an extruded foaming plate thereof. Background Art
[0002] As a new high-performance engineering plastic, polyphenylene ether (PPE) has been widely used in aerospace, electronics, transportation, and fuel cell fields due to its excellent flame retardancy, dimensional stability, electrical insulation, heat resistance, and mechanical properties. However, PPE suffers from poor solvent resistance, prone to stress cracking in finished products, low notched impact strength, and expensive raw materials. Its fatal weakness lies in its high melt viscosity, poor fluidity, and softening temperature above 300°C. Furthermore, it is prone to degradation during high-temperature processing at 330°C, making processing and molding difficult and consuming excessive energy.
[0003] To overcome these shortcomings and impart new properties to polyphenylene ether, it is often modified by blending it with polystyrene. Both polyphenylene ether and polystyrene are non-crystalline polymers with good compatibility, allowing them to form thermoplastic resins within a wide range of blending ratios. Polyphenylene ether / polystyrene resins of varying blending ratios exhibit a single glass transition temperature, while the addition of polystyrene can lower the softening temperature of pure polyphenylene ether. While these resins retain the excellent properties of pure polyphenylene ether and exhibit improved fluidity, they also suffer from reduced molecular chain rigidity and a lower Young's modulus.
[0004] To further improve the modulus of polyphenylene ether / polystyrene resins, the present invention introduces chloromethylated, slightly cross-linked polystyrene for blending and modification with polyphenylene ether. The chloromethyl groups react with the benzene rings of the polyphenylene ether during the co-extrusion process, forming a covalently bonded interface between the polystyrene and the polyphenylene ether. This helps improve the compatibility of the two resins and further enhances the product's modulus. By blending chloromethylated, cross-linked polystyrene with polyphenylene ether in varying proportions, thermoplastic resins with excellent thermal and mechanical properties can be produced. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to provide a modified polyphenylene ether resin and a method for preparing an extruded foamed board thereof, so as to solve the problem in the prior art that polystyrene / polyphenylene ether resin cannot be extruded into high modulus boards at relatively low temperatures.
[0006] In order to solve the above technical problems, the technical solutions of the present invention are as follows: A modified polyphenylene ether resin and a preparation method of an extruded foamed plate thereof are synthesized from styrene, divinylbenzene, a chloromethylation agent, a catalyst, polyphenylene ether, a flame retardant, an antioxidant, and a light stabilizer as raw materials. The foamed plate is produced by an extrusion method.
[0007] Preferably, the modified polyphenylene ether resin and the preparation method of the extruded foamed plate thereof are synthesized from the following raw materials in parts by weight: 40 parts by weight of styrene, 2 parts by weight of divinylbenzene, 0.04 parts by weight of benzoyl peroxide, 25 parts by weight of chloromethylation agent, 70 parts by weight of polyphenylene ether, 0.5 parts by weight of catalyst, 7 parts by weight of flame retardant, 0.4 parts by weight of antioxidant, and 4 parts by weight of foaming agent.
[0008] Preferably, the chloromethylation agent is 1,4-dichloromethoxybutane; Preferably, the catalyst is aluminum chloride; Preferably, the flame retardant is tetraphenyl (bisphenol-A) diphosphate; Preferably, the antioxidant is 3,5-di-tert-butyl-hydroxyphenyl propionate; Preferably, the light stabilizer is 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methyl-phenol; Preferably, the foaming agent is carbon dioxide.
[0009] Preferably, the modified polyphenylene ether resin has a structure as shown in formula (I). The introduction of chloromethyl groups can cause a cross-linking reaction with the benzene rings of the polyphenylene ether during the co-extrusion process, so that the polystyrene and the polyphenylene ether form a covalent bond interface structure, which helps to improve the compatibility of the two resins and further improve the modulus of the product.
[0010] (I) The present invention provides a method for preparing the modified polyphenylene ether resin and the extruded foamed plate thereof, comprising the following steps: (1) dissolving styrene and divinylbenzene in a solvent and mixing them evenly, adding benzoyl peroxide to initiate a polymerization reaction to obtain slightly cross-linked polystyrene; (2) dissolving the slightly cross-linked polystyrene obtained in step (1) with a chloromethylation agent and a catalyst in a solvent and reacting them to obtain chloromethylated slightly cross-linked polystyrene; (3) Melting and extruding the chloromethylated slightly cross-linked polystyrene obtained in step (2) with polyphenylene ether, flame retardant, antioxidant, and light stabilizer in proportion, using supercritical carbon dioxide as a foaming agent, and cooling and shaping to obtain a modified high modulus polyphenylene ether resin extruded foamed sheet; Preferably, in step (1), the reaction temperature is 80°C and the reaction time is 3h; Preferably, in step (2), the reaction temperature is 20°C and the reaction time is 2h; Preferably, in step (3), the extruder temperature is 270-290°C, and the mold temperature is 220-260°C; Preferably, step (2) specifically comprises: dissolving micro-crosslinked polystyrene, a chloromethylation agent and a catalyst in a solvent and reacting them fully to obtain a white crosslinked product; treating the product mixture with dilute hydrochloric acid after the reaction to fully wash away the attached catalyst; filtering the mixture, washing the product with an organic solvent to remove the residual solvent, and then washing the product with distilled water and ethanol, and vacuum drying to obtain chloromethylated micro-crosslinked high modulus polystyrene; Preferably, the organic solvent is 1,4-dioxane; Preferably, in step (2), the concentration of the dilute hydrochloric acid is 1 mol / L.
[0011] Preferably, step (3) specifically comprises: adding polyphenylene ether, flame retardant, antioxidant, light stabilizer, and foaming agent to the chloromethylated slightly cross-linked polystyrene obtained in step (2), and heating the mixture in an extruder to form a melt; Preferably, in step (3), the mass ratio of the chloromethylated slightly cross-linked polystyrene to the polyphenylene ether is controlled at 1:1.
[0012] The extruder temperature is 260-320℃, and the mold temperature is 200-280℃; The present invention also provides an application of the modified polyphenylene ether resin extruded foaming plate in the field of materials.
[0013] The above solution of the present invention includes at least the following beneficial effects: The modified polyphenylene ether resin of the present invention is synthesized from styrene, divinylbenzene, benzoyl peroxide, a chloromethylation agent, a catalyst, polyphenylene ether, a flame retardant, an antioxidant, a light stabilizer, and a foaming agent as raw materials. The modified polyphenylene ether resin extrusion foaming plate of the present invention is produced by an extrusion method. The modified polyphenylene ether resin of the present invention first undergoes chloromethylation modification on polystyrene. The introduction of the chloromethyl group not only improves the modulus of the polystyrene, but also introduces active sites on the polymer molecular chain. During the co-extrusion process of polystyrene and polyphenylene ether, a cross-linking reaction is generated with the polyphenylene ether, thereby helping to improve the compatibility of the two components. In addition, the addition of the chloromethylated cross-linked polystyrene of the present invention can reduce the extrusion temperature of the polyphenylene ether resin, thereby improving the modulus and compressive strength of the product, thereby enabling the extrusion of a high-modulus plate at relatively low temperatures, thereby reducing a large amount of energy consumption while improving the mechanical properties of the product, and achieving the effect of energy conservation and emission reduction. (2) The preparation method of modified polyphenylene ether resin and its extruded foamed board has a simple preparation process, which solves the problem in the prior art that polystyrene / polyphenylene ether resin cannot be extruded into high modulus boards at relatively low temperatures, and has good application prospects. DETAILED DESCRIPTION
[0014] The following describes exemplary embodiments of the present disclosure in more detail. Although exemplary embodiments of the present disclosure are shown, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. Instead, these embodiments are provided to enable a more thorough understanding of the present disclosure and to fully convey the scope of the present disclosure to those skilled in the art.
[0015] In the examples of the present invention, if specific conditions are not specified, the experiments were carried out under conventional conditions or the conditions recommended by the manufacturer. Reagents or instruments used without manufacturer specified are all commercially available conventional products. The following only provides some of the reagents used in the examples of the present invention. Raw materials of different manufacturers and types do not affect the implementation of the technical solutions of the present invention and the achievement of the technical effects.
[0016]
[0017] Example 1 The modified polyphenylene ether resin and the extruded foamed plate of this embodiment are synthesized from the following raw materials in parts by weight: 40 parts by weight of styrene, 2 parts by weight of divinylbenzene, 0.04 parts by weight of benzoyl peroxide, 20 parts by weight of chloromethylation agent, 0.5 parts by weight of catalyst, 60 parts by weight of polyphenylene ether, 7 parts by weight of flame retardant, 0.4 parts by weight of antioxidant, 0.4 parts by weight of light stabilizer, and 4 parts by weight of foaming agent.
[0018] The chloromethylation agent is 1,4-dichloromethoxybutane; the catalyst is tin chloride; the flame retardant is tetraphenyl (bisphenol-A) diphosphate; the antioxidant is 3,5-di-tert-butyl-hydroxyphenyl propionate octadecyl ester; the light stabilizer is 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methyl-phenol; and the foaming agent is carbon dioxide.
[0019] The modified polyphenylene ether resin has a structure as shown in formula (I):
[0020] (I) The method for preparing the modified polyphenylene ether resin and the extruded foamed plate thereof described in this embodiment comprises the following steps: (1) dissolving styrene and divinylbenzene in a solvent and mixing them evenly, adding benzoyl peroxide to initiate styrene polymerization, and reacting to obtain slightly cross-linked polystyrene; (2) The slightly cross-linked polystyrene obtained in step (1), the chloromethylation reagent and the catalyst are dissolved in a solvent and fully reacted to obtain a white cross-linked product. After the reaction, the product mixture is treated with dilute hydrochloric acid to fully wash away the attached catalyst, filtered, and washed with an organic solvent to remove the residual solvent. The product is then washed with distilled water and ethanol, and vacuum dried to obtain chloromethylated slightly cross-linked polystyrene. The reaction formula is as follows:
[0021] (3) Add polyphenylene ether resin from the first feeder port, add the chloromethylated slightly cross-linked polystyrene obtained in step (2) from the second feeder port, add antioxidant and light stabilizer from the third feeder port, add flame retardant from the liquid feeder port, heat and melt the melt in an extruder, and simultaneously introduce supercritical carbon dioxide foaming agent. After cooling and shaping, a modified polyphenylene ether resin extruded foamed sheet is obtained. The reaction formula is as follows:
[0022] Example 2 The modified polyphenylene ether resin and the extruded foamed plate of this embodiment are synthesized from the following raw materials in parts by weight: 40 parts by weight of styrene, 2 parts by weight of divinylbenzene, 0.04 parts by weight of benzoyl peroxide, 25 parts by weight of chloromethylation agent, 0.5 parts by weight of catalyst, 60 parts by weight of polyphenylene ether, 7 parts by weight of flame retardant, 0.4 parts by weight of antioxidant, 0.4 parts by weight of light stabilizer, and 4 parts by weight of foaming agent.
[0023] The chloromethylation agent is 1,4-dichloromethoxybutane; the catalyst is tin chloride; the flame retardant is tetraphenyl (bisphenol-A) diphosphate; the antioxidant is 3,5-di-tert-butyl-hydroxyphenyl propionate octadecyl ester; the light stabilizer is 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methyl-phenol; and the foaming agent is carbon dioxide.
[0024] The preparation method of the modified polyphenylene ether resin extrusion foamed board described in this embodiment is the same as that in Example 1.
[0025] Example 3 The modified polyphenylene ether resin and the extruded foamed plate of this embodiment are synthesized from the following raw materials in parts by weight: 40 parts by weight of styrene, 2 parts by weight of divinylbenzene, 0.04 parts by weight of benzoyl peroxide, 30 parts by weight of chloromethylation agent, 0.5 parts by weight of catalyst, 60 parts by weight of polyphenylene ether, 7 parts by weight of flame retardant, 0.4 parts by weight of antioxidant, 0.4 parts by weight of light stabilizer, and 4 parts by weight of foaming agent.
[0026] The chloromethylation agent is 1,4-dichloromethoxybutane; the catalyst is tin chloride; the flame retardant is tetraphenyl (bisphenol-A) diphosphate; the antioxidant is 3,5-di-tert-butyl-hydroxyphenyl propionate octadecyl ester; the light stabilizer is 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methyl-phenol; and the foaming agent is carbon dioxide.
[0027] The preparation method of the modified polyphenylene ether resin extrusion foamed board described in this embodiment is the same as that in Example 1.
[0028] Example 4 The modified polyphenylene ether resin and the extruded foamed plate of this embodiment are synthesized from the following raw materials in parts by weight: 40 parts by weight of styrene, 2 parts by weight of divinylbenzene, 0.04 parts by weight of benzoyl peroxide, 35 parts by weight of chloromethylation agent, 0.5 parts by weight of catalyst, 60 parts by weight of polyphenylene ether, 7 parts by weight of flame retardant, 0.4 parts by weight of antioxidant, 0.4 parts by weight of light stabilizer, and 4 parts by weight of foaming agent.
[0029] The chloromethylation agent is 1,4-dichloromethoxybutane; the catalyst is tin chloride; the flame retardant is tetraphenyl (bisphenol-A) diphosphate; the antioxidant is 3,5-di-tert-butyl-hydroxyphenyl propionate octadecyl ester; the light stabilizer is 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methyl-phenol; and the foaming agent is carbon dioxide.
[0030] The preparation method of the modified polyphenylene ether resin extrusion foamed board described in this embodiment is the same as that in Example 1.
[0031] Example 5 This embodiment has the same raw materials and preparation method as that of embodiment 1, with the only difference being that in step (2), the chloromethylation reagent is chloromethyl ether.
[0032] Example 6 This embodiment has the same raw materials and preparation method as that of embodiment 1, with the only difference being that in step (2), the chloromethylation reagent is methyl chloride.
[0033] Example 7 This embodiment has the same raw materials and preparation method as that of embodiment 1, with the only difference being that in step (2), the chloromethylation reagent is trioxymethylene-hydrogen chloride.
[0034] Example 8 This embodiment has the same raw materials and preparation method as that of embodiment 1, with the only difference being that in step (2), the chloromethylation reagent is paraformaldehyde-hydrogen chloride.
[0035] Effect comparison ratio In order to verify the technical effect of the chloromethylated cross-linked high modulus polystyrene / polyphenylene ether resin extruded foamed board of the present invention, the following experiments were conducted: The modified polyphenylene ether resin extruded foamed sheets prepared in Comparative Example 1 and Examples 1-8 were taken as test samples, and their density, tensile strength, compressive strength and flame retardancy were tested respectively. The specific steps are as follows: Determine the sample density using the water displacement method. Perform a tensile strength test on the sample using a universal testing machine. Set the universal testing machine to a test speed of 50 mm / min and use a flat plate fixture to ensure the sample is securely clamped. Perform a static tensile test at a low strain rate and record the tensile strength. Take three measurements per group and average the results. Perform a compressive strength test on the sample using the universal testing machine. Perform a vertical combustion test on the sample using a vertical combustion apparatus.
[0036] After experimentation, the results are as follows:
[0037] The above experimental results show that the tensile strength of the polystyrene / polyphenylene ether resin extruded foam sheet without chloromethylated cross-linked high modulus polystyrene is only 9.4 MPa, and the compressive strength is only 1.9 MPa. In contrast, the modified polyphenylene ether resin extruded foam sheet in Comparative Examples 1-8 has stronger tensile and compressive properties.
[0038] As can be seen from the experimental results of Examples 1, 2, 3, and 4, the density of the modified polyphenylene ether resin extruded foamed plate first decreases and then increases as the degree of crosslinking increases, and its tensile strength and compressive strength can increase as the amount of chloromethylation increases, but the increase decreases. In particular, Example 1 is compared with Example 2, and the density of Example 2 is lower than that of Example 1, but its compressive strength is significantly higher than that of Example 1. As can be seen from the experimental results of Examples 1, 5, 6, and 7, the tensile strength and compressive strength of the modified polyphenylene ether resin extruded foamed plate decrease as the polarity of the chloromethylation agent decreases. This explanation shows that as the polarity of the chloromethylation agent increases, slightly cross-linked polystyrene is more likely to become methylated, thereby having a higher degree of crosslinking when mixed with polyphenylene ether for extrusion, and having a higher tensile strength and compressive strength.
[0039] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.
Claims
1. A method for preparing a modified polyphenylene ether resin and an extruded foaming plate thereof, characterized in that A modified polyphenylene ether resin is synthesized from styrene, divinylbenzene, benzoyl peroxide, a chloromethylation agent, a catalyst, polyphenylene ether, a flame retardant, an antioxidant, and a light stabilizer as raw materials. The resin is then melt-extruded through a twin-screw extruder while a physical foaming agent is introduced. After cooling and shaping, a high-modulus extruded foamed board is obtained.
2. The method for preparing a modified polyphenylene ether resin and an extruded foamed plate thereof according to claim 1, wherein: It is synthesized from the following raw materials in parts by weight: 20-50 parts by weight of styrene, 0.5-4 parts by weight of divinylbenzene, 0.02-0.05 parts by weight of benzoyl peroxide, 18-44 parts by weight of chloromethylation agent, 50-80 parts by weight of polyphenylene ether, 0.5-1 parts by weight of catalyst, 3-16 parts by weight of flame retardant, 0.2-0.6 parts by weight of antioxidant, and 0.5-5 parts by weight of foaming agent.
3. The method for preparing a modified polyphenylene ether resin and an extruded foamed plate thereof according to claim 1, wherein: The chloromethylation agent is one of 1,4-dichloromethoxybutane, trioxymethylene-hydrogen chloride, paraformaldehyde-hydrogen chloride, formaldehyde dimethyl acetal-hydrogen chloride, methyl chloride, and chloromethyl ether; Optionally, the catalyst is one of protonic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, or Lewis acids such as aluminum chloride and tin chloride; Optionally, the flame retardant is one or more of tetraphenyl (bisphenol-A) diphosphate and tetraphenyl resorcinol diphosphate; Optionally, the antioxidant is one of 3,5-di-tert-butyl-hydroxyphenylpropionate or 2,2-methylenebis(4-methyl-6-tert-butylphenol); Optionally, the light stabilizer is 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methyl-phenol; Optionally, blowing agents are organic liquids and gases which are gaseous under the process conditions, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases with inorganic gases, whereby mixtures of these substances are also possible; examples of suitable hydrocarbons are halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons; preferred organic blowing agents are saturated aliphatic hydrocarbons, such as butane or pentane; suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide, or mixtures of the aforementioned gases.
4. A method for preparing a modified polyphenylene ether resin and an extruded foamed sheet thereof according to any one of claims 1 to 3, characterized in that: The steps include: (1) dissolving styrene and divinylbenzene in a solvent and mixing them evenly, adding benzoyl peroxide to initiate a polymerization reaction to obtain slightly cross-linked polystyrene; (2) dissolving the slightly cross-linked polystyrene obtained in step (1) with a chloromethylation agent and a catalyst in a solvent and reacting them to obtain chloromethylated slightly cross-linked polystyrene; (3) The chloromethylated slightly cross-linked polystyrene obtained in step (2) is melt-mixed with polyphenylene ether, flame retardant, antioxidant, and light stabilizer in proportion and extruded, and a physical foaming agent is used to perform extrusion foaming, and after cooling and shaping, a modified high modulus polyphenylene ether resin extruded foamed sheet is obtained.
5. The method for preparing a modified polyphenylene ether resin and an extruded foamed plate thereof according to claim 4, wherein: In step (1), the reaction temperature is 70-90°C and the reaction time is 3-4h; Optionally, in step (2), the reaction temperature is 20-30°C and the reaction time is 1-2h; Optionally, in step (3), the extruder temperature is 260-320°C and the mold temperature is 200-280°C.
6. The method for preparing a modified polyphenylene ether resin and an extruded foamed plate thereof according to claim 4, characterized in that: Step (1) specifically comprises: dissolving styrene and divinylbenzene in a solvent and mixing them evenly, adding benzoyl peroxide to initiate a polymerization reaction, and cooling and drying the mixture after a period of reaction to obtain slightly cross-linked polystyrene.
7. The method for preparing a modified polyphenylene ether resin and an extruded foamed plate thereof according to claim 4, characterized in that: Step (2) specifically comprises: dissolving the slightly cross-linked polystyrene obtained in step (1), a chloromethylation agent and a catalyst in a solvent and fully reacting them to obtain a white cross-linked product; treating the product mixture with dilute hydrochloric acid after the reaction to fully wash away the attached catalyst; filtering the mixture; washing the product with an organic solvent to remove the residual solvent; then washing the product with distilled water and ethanol; and vacuum drying to obtain the chloromethylated slightly cross-linked polystyrene.
8. The method for preparing a modified polyphenylene ether resin and an extruded foamed plate thereof according to claim 4, characterized in that: In step (3), the mass ratio of the chloromethylated slightly cross-linked polystyrene to the polyphenylene ether is controlled at 1:1 to 1:
2.
9. Use of the modified polyphenylene ether resin according to any one of claims 1 to 3 and the method for preparing the same in the field of materials.