A polystyrene film material and a method for preparing the same
By preparing polystyrene microemulsions and subjecting them to thermal induction treatment, the problem of controlling the porosity of polystyrene materials was solved, and a high-porosity polystyrene through-network was realized, which is suitable for large-scale production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-09-04
- Publication Date
- 2026-06-09
Smart Images
Figure CN119552455B_ABST
Abstract
Description
Technical Field
[0001] This application relates to a polystyrene membrane material and its preparation method, belonging to the field of organic membrane materials. Background Technology
[0002] Polystyrene (PS) is a polymer made from styrene, with a main chain of saturated hydrocarbons and rigid benzene ring side chains. PS is characterized by high transparency, low price, low moisture absorption, good shrinkage, easy processing, strength, and electrical insulation. It is widely used in packaging, construction, and separation, and is the third largest resin plastic after polyethylene and polyvinyl chloride. Its main products can be divided into general-purpose polystyrene (GPPS), expanded polystyrene (EPS), high-impact polystyrene (HIPS), and syndiotactic polystyrene (SPS). Different types of PS have different properties and are used in different fields. PS has a relatively low heat distortion temperature (70~98℃), which is advantageous for plasticizing through melting in industrial production, but also limits its application range. High porosity PS is lightweight, has good cushioning and shock absorption properties, and is corrosion resistant, making it widely used in cushioning packaging, thermal insulation materials, and sports toys.
[0003] Methods for synthesizing high-porosity polymers can be divided into hard and soft template methods and non-templating methods. Template methods involve solidifying a two-phase mixture of a pore source template and a polymer precursor, followed by removing the template to leave pores. For example, CN103204965B discloses a method for preparing and applying ultra-low-density porous polystyrene blocks, using a W / O type gel emulsion obtained with a small-molecule gelling agent as a stabilizer as a template to initiate polymerization and obtain ultra-low-density porous polystyrene blocks. The preparation process is simple, requiring only room-temperature reaction stirring, simple washing, and room-temperature drying. However, porous polymers obtained using hard template methods generally have large pores in the micrometer range. Materials obtained using soft templates can have small pores, but the production cost is higher. CN108948236B discloses "A Macroscopic Molded Polystyrene Block and Its Preparation Method," which uses persulfate as an initiator, deionized water as a medium, an anionic surfactant as an emulsifier, and styrene as a monomer to perform emulsion polymerization to obtain a polystyrene microsphere emulsion. A water-soluble organic solvent is then added to the emulsion to cause demulsification and coagulation of the polystyrene microsphere emulsion. After drying, a polystyrene molded block is obtained. However, the block obtained by this method is dense and non-porous. CN103374143B discloses "A Macroporous Polymer Sphere and Its Preparation Method," which uses a two-step emulsification method to prepare a water-in-oil-in-water composite emulsion as a template for macroporous microspheres. Then, a solvent removal method is used to solidify the oil phase, forming macroporous microspheres with internal and external through-pores. This method can prepare microspheres with porosity as high as 10-90%. However, the emulsification operation involves a complex liquid flow process, which is not conducive to large-scale production, and the pores of the obtained samples are all macropores. Summary of the Invention
[0004] Based on the technical deficiencies existing in the background art, the purpose of this invention is to provide a polystyrene through-network with easily controllable pores. This method has a simple process, low production cost, strong controllability, high scalability, and is easy to achieve large-scale production.
[0005] According to one aspect of this application, a polystyrene film material is provided, the polystyrene film material having a through-network structure;
[0006] The porosity of the polystyrene membrane material is 12-75%.
[0007] According to another aspect of this application, a method for preparing the above-mentioned polystyrene film material is provided, comprising the following steps:
[0008] Raw materials containing styrene, surfactant, initiator and solvent are mixed and reacted under an inactive gas atmosphere to obtain a polystyrene microemulsion. After filtration / evaporation, a polystyrene array is obtained, and after thermal induction, the polystyrene membrane material is obtained.
[0009] The surfactant is selected from at least one of ionic surfactants, nonionic surfactants, and amphoteric surfactants;
[0010] Optionally, the surfactant is selected from at least one of polypyrrolidone, polyvinyl alcohol, and sodium dodecyl sulfate;
[0011] The initiator is selected from at least one of potassium persulfate, benzoyl peroxide, and azobisisobutyronitrile;
[0012] The solvent is selected from water and / or ethanol.
[0013] In the raw materials, the mass ratio of styrene to the solvent is 3 to 15;
[0014] Optionally, the mass ratio of styrene to solvent is 6 to 10;
[0015] The surfactant has a mass content of 0.1~3 wt%;
[0016] Optionally, the surfactant content is 0.15~1.5 wt%;
[0017] The initiator is present in an amount of 0.5 to 5 wt% of the styrene.
[0018] Optionally, the initiator is present in an amount of 0.65 to 2.5 wt% of the styrene mass.
[0019] Optionally, the raw material further contains a pore-forming agent;
[0020] The pore-forming agent is selected from at least one of silicon dioxide or alkanes;
[0021] The pore-forming agent in the raw materials has a mass content of 0.01~20wt%.
[0022] The inactive gas atmosphere is selected from at least one of nitrogen, argon, and helium.
[0023] The reaction temperature is 60~120℃;
[0024] The reaction time is 6 to 24 hours.
[0025] In the microemulsion containing polystyrene, the particle size of the polystyrene is 30 nm to 3 μm;
[0026] Optionally, in the polystyrene-containing microemulsion, the polystyrene particle size is 50~800nm.
[0027] The polystyrene can be swollen by chloroform.
[0028] The microemulsion may also contain at least one of polyvinylbenzene, phenolic resin and divinyl styrene copolymer;
[0029] The polystyrene-containing microemulsion has a solid content of 0.5-60 wt%.
[0030] Optionally, the polystyrene-containing microemulsion has a solid content of 1 to 30 wt%.
[0031] The thickness of the polystyrene array is 0.1 mm to 10 cm;
[0032] Optionally, the thickness of the polystyrene array is 1 mm to 5 cm.
[0033] The thermally induced atmosphere is an atmosphere containing nitrogen and / or hydrogen.
[0034] Optionally, the thermal induction is carried out in a vacuum;
[0035] The temperature for thermal induction is 60~230℃;
[0036] Optionally, the temperature for thermal induction is 80~200℃;
[0037] The thermally induced heating rate is 0.5~20℃ / min;
[0038] Optionally, the thermally induced heating rate is 1~15℃ / min;
[0039] The thermal induction time is 0.1~15h;
[0040] Optionally, the thermal induction time is 0.3 to 12 hours.
[0041] Specifically,
[0042] Includes the following steps:
[0043] Step 1: Dissolve the surfactant in deionized water or ethanol as the continuous phase, remove the air with nitrogen or argon, use styrene and / or other monomers as the dispersed phase, use silica or alkanes as pore-forming agents, add the initiator under a nitrogen or argon atmosphere, react at 60~120℃ for 6~24h, and cool to room temperature to obtain polystyrene microemulsions of different sizes.
[0044] Step 2: The polystyrene microemulsion is filtered or evaporated to obtain a polystyrene array;
[0045] Step 3: Heat the array obtained in Step 2 to 60-230°C under air, nitrogen, hydrogen or vacuum conditions at a rate of 0.5-20°C / min, and maintain for 0.1-15 hours.
[0046] The beneficial effects that this application can produce include:
[0047] This invention develops a new, simple, and effective method for preparing novel polystyrene through-networks. The preparation method is simple, yields high output, has a porosity of up to 75%, and exhibits good network uniformity.
[0048] The polystyrene through-network prepared by this invention has abundant pore volume. Unlike traditional top-down or bottom-up methods, this invention uses an intermediate transition array structure to induce deformation of the polymer through thermal induction, thereby obtaining the through-network structure.
[0049] The preparation method of the present invention has good scalability and controllability. The method is applicable to materials such as styrene, styrene-diethylenebenzene copolymer, and low cross-linking phenolic resin. Furthermore, the porosity of the obtained through-network can be changed by adjusting conditions such as microemulsion particle size, particle porosity, thermal induction temperature, thermal induction time, and microemulsion solid content. Attached Figure Description
[0050] Figure 1 This is a cross-section of the polystyrene through-network prepared in Example 1. Figure 1 The scale is 1 μm;
[0051] Figure 2 This is a high-magnification scanning electron micrograph (SEM) of the cross-section of the polystyrene through-network prepared in Example 1. Figure 2 The scale is 100 nm;
[0052] Figure 3These are photographs of the planar and cross-sectional layered structure of the polystyrene array prepared in Example 1. Figure 3 The size is 400 nm;
[0053] Figure 4 These are SEM images of the planar and cross-sectional layered structure of the polystyrene array prepared in Example 1. Figure 4 The size is 400 nm;
[0054] Figure 5 This is a photograph of a polystyrene through-network prepared by thermal induction from the polystyrene array prepared in Example 1. Figure 5 The scale is 1 μm.
[0055] Figure 6 This is a SEM image of the polystyrene through-network fabrication prepared by thermal induction from the polystyrene array in Example 1. Figure 6 The size is 100nm. Detailed Implementation
[0056] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0057] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.
[0058] Example 1
[0059] (1) Preparation of microemulsions or suspensions
[0060] First, thoroughly wash 50 mL of styrene sequentially with 10 mL of 10 wt.% NaOH solution and deionized water to remove the stabilizer. Add the washed styrene to a three-necked round-bottom flask containing 1.2 g of polypyrrolidone in 250 mL of deionized water. Bubble with nitrogen for 15 minutes, then preheat at 75°C for 30 minutes.
[0061] Subsequently, 20 mL of an aqueous solution of 0.4 g of K₂S₂O₈ was rapidly added to the flask to initiate the polymerization reaction of styrene. After stirring at 70 °C for 24 hours, the mixture was cooled to obtain a monodisperse polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. Polystyrene or other microemulsions / suspensions with particle sizes of 30 nm to 3 μm were obtained through other synthetic methods.
[0062] (2) Array fabrication
[0063] The microemulsion was filtered to obtain a 0.5 cm thick intermediate transition polystyrene array.
[0064] (3) The dried polystyrene array was heated to 130°C at 5°C / min under air conditions and maintained for 8 hours to obtain a polystyrene through-network with a porosity of 67%.
[0065] Figure 1 , 2 The image shows a cross-section of the polystyrene through-network prepared in Example 1 and its high-magnification scanning electron micrograph (SEM). Figure 1 The scale is 1 μm. Figure 2 The scale is 100 nm; this indicates that the sample has a network structure with through-holes, which is connected by 10 nm filaments, thus creating a large number of pores.
[0066] Figure 3 , 4 These are SEM images of the planar and cross-sectional layered structure of the polystyrene array prepared in Example 1. Figure 3 The size is 400nm. Figure 4 Its size is 400 nm; it is its intermediate transition state structure.
[0067] Figure 5 , 6 The polystyrene array prepared in Example 1 ( Figure 2 SEM images of polystyrene through-networks prepared by thermal induction. Figure 5 The scale is 1 μm. Figure 6 The size is 100 nm. The sample has a distinct layered structure.
[0068] The characterization results of other embodiments are similar to those of Embodiment 1.
[0069] Example 2
[0070] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 50 nm. The polystyrene through-network with a porosity of 25% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0071] Example 3
[0072] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 100 nm. The polystyrene through-network with a porosity of 27% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0073] Example 4
[0074] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 340 nm. The polystyrene through-network with a porosity of 54% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0075] Example 5
[0076] A 0.7 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 40% and a particle size of 50 nm. The polystyrene through-network with a porosity of 20% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0077] Example 6
[0078] A 0.7 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 40% and a particle size of 100 nm. The polystyrene through-network with a porosity of 25% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0079] Example 7
[0080] A 1.0 cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 60% and a particle size of 320 nm. The polystyrene through-network with a porosity of 45% was obtained by heating the microemulsion to 120 °C at a rate of 5 °C / min and maintaining the temperature for 12 hours.
[0081] Example 8
[0082] A 0.5 mm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 1% and a particle size of 50 nm. The polystyrene through-network with a porosity of 53% was obtained by heating the microemulsion to 125 °C at a rate of 5 °C / min and maintaining the temperature for 9 hours.
[0083] Example 9
[0084] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 50 nm. The polystyrene through-network with a porosity of 17% was obtained by heating the microemulsion to 115 °C at a rate of 20 °C / min and maintaining the temperature for 14 hours.
[0085] Example 10
[0086] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 50 nm. The polystyrene through-network with a porosity of 12% was obtained by heating the microemulsion to 120 °C at a rate of 1 °C / min and maintaining the temperature for 14 hours.
[0087] Example 11
[0088] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. The polystyrene through-network with a porosity of 45% was obtained by heating the microemulsion to 135 °C at a rate of 10 °C / min and maintaining the temperature for 1 hour.
[0089] Example 12
[0090] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. The array was then immersed in silicone oil and heated to 130 °C at a rate of 10 °C / min and maintained for 3 hours to obtain a polystyrene through-network with a porosity of 67%.
[0091] Example 13
[0092] A 0.5 cm thick array was prepared by filtering a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. Water vapor at 130 °C was introduced and maintained for 3 hours to obtain a polystyrene through-network with a porosity of 43%.
[0093] Example 14
[0094] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. Under a nitrogen atmosphere, the temperature was increased to 130 °C at 5 °C / min and maintained for 8 hours to obtain a polystyrene through-network with a porosity of 70%.
[0095] Example 15
[0096] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. Under vacuum conditions, the temperature was increased to 130 °C at a rate of 5 °C / min and maintained for 3 hours to obtain a polystyrene through-network with a porosity of 65%.
[0097] Example 16
[0098] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. Under hydrogen conditions, the temperature was increased to 130 °C at 5 °C / min and maintained for 3 hours to obtain a polystyrene through-network with a porosity of 43%.
[0099] Example 17
[0100] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. Under argon atmosphere, the temperature was increased to 130 °C at 5 °C / min and maintained for 3 hours to obtain a polystyrene through-network with a porosity of 57%.
[0101] Example 18
[0102] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 350 nm. Hexane was added to the microemulsion as a pore-forming agent. Under argon conditions, the temperature was increased to 120 °C at 5 °C / min and maintained for 4 hours to obtain a polystyrene through-network with a porosity of 75%.
[0103] Example 19
[0104] A 0.5 cm thick array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. After swelling with chloroform at room temperature for 2 h, the swollen polystyrene array was obtained by vacuum filtration. Under vacuum conditions, the temperature was increased to 120 °C at 5 °C / min and maintained for 4 h to obtain a polystyrene through-network with a porosity of 58%.
[0105] Example 20
[0106] A 0.5 cm thick array of styrene-diethylenebenzene polymer with a solid content of 5% and a particle size of 170 nm and a crosslinking degree of 20% was obtained by filtration. The polystyrene through-network with a porosity of 45% was obtained by heating to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0107] Example 21
[0108] A 0.5 cm thick array was obtained by filtering a phenolic resin dispersion with a solid content of 21% and a particle size of 150 nm. The polystyrene through-network with a porosity of 34% was obtained by heating the dispersion to 230 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0109] Example 22
[0110] A 0.3 cm thick array was obtained by filtration of a polyvinyl acetate microemulsion with a solid content of 5% and a particle size of 550 nm. The polystyrene through-network with a porosity of 45% was obtained by heating the microemulsion to 180 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0111] Example 23
[0112] A 1.0 cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 40% and a particle size of 800 nm. The polystyrene through-network with a porosity of 58% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0113] Example 24
[0114] A 1.0 cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 40% and a particle size of 1.2 μm. The polystyrene through-network with a porosity of 61% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0115] Example 25
[0116] A 1.0 cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 40% and a particle size of 3.0 μm. The polystyrene through-network with a porosity of 64% was obtained by heating the microemulsion to 130 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0117] Comparative Example 1
[0118] A 0.5 cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. The polystyrene through-network with a porosity of 4% was obtained by heating the microemulsion to 180 °C at a rate of 5 °C / min and maintaining the temperature for 8 hours.
[0119] Excessive temperature caused the polystyrene to melt rapidly, which, upon testing, led to the structural collapse.
[0120] Comparative Example 2
[0121] A 0.5 cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. The polystyrene through-network with a porosity of 0.5% was obtained by heating the microemulsion to 250 °C at a rate of 20 °C / min and maintaining the temperature for 8 hours.
[0122] Excessive temperature and rapid heating rate caused the polystyrene to melt quickly, leading to structural collapse, as revealed by testing.
[0123] Comparative Example 3
[0124] A 0.5 cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 16% and a particle size of 500 nm. The polystyrene through-network with a porosity of 3% was obtained by heating the microemulsion from 140 °C / min to 130 °C and maintaining the temperature for 36 hours.
[0125] Excessive heat treatment time led to complete crystallization of polystyrene, which, upon testing, resulted in structural collapse.
[0126] Comparative Example 4
[0127] A 12cm array was prepared by filtration of a polystyrene microemulsion with a solid content of 70% and a particle size of 500nm. The microemulsion was heated to 130℃ at a rate of 30℃ / min and maintained for 8 hours. The microemulsion was loose and did not clump together.
[0128] Uneven heating of the thick array was found to cause structural inhomogeneity after testing.
[0129] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing a polystyrene film material, characterized in that, Includes the following steps: Raw materials containing styrene, surfactant, initiator and solvent are mixed and reacted under an inactive gas atmosphere to obtain a microemulsion containing polystyrene, resulting in a polystyrene array. Thermal induction is then performed to obtain the polystyrene film material. The thickness of the polystyrene array is 0.1 mm to 1 cm; The thermal induction temperature is 115~135℃; The thermally induced heating rate is 1~20℃ / min; The thermal induction time is 1~15h; The polystyrene film material has a through-network structure; The porosity of the polystyrene membrane material is 12-75%.
2. The preparation method according to claim 1, characterized in that, The surfactant is selected from at least one of ionic surfactants, nonionic surfactants, and amphoteric surfactants; The initiator is selected from at least one of potassium persulfate, benzoyl peroxide, and azobisisobutyronitrile; The solvent is selected from water and / or ethanol.
3. The preparation method according to claim 2, characterized in that, The surfactant is selected from at least one of polypyrrolidone, polyvinyl alcohol, and sodium dodecyl sulfate.
4. The preparation method according to claim 1, characterized in that, In the raw materials, the mass ratio of styrene to solvent is 3-15; The surfactant has a mass content of 0.1~3 wt%; The initiator has a mass of 0.5 to 5 wt% of the styrene mass.
5. The preparation method according to claim 4, characterized in that, The mass ratio of styrene to solvent is 6-10; The surfactant has a mass content of 0.15~1.5wt%; The initiator has a mass of 0.65 to 2.5 wt% of the styrene mass.
6. The preparation method according to claim 1, characterized in that, The raw material also contains a pore-forming agent; The pore-forming agent is selected from at least one of silicon dioxide or alkanes; The pore-forming agent in the raw materials has a mass content of 0.01~20wt%.
7. The preparation method according to claim 1, characterized in that, The inactive gas atmosphere is selected from at least one of nitrogen, argon, and helium.
8. The preparation method according to claim 1, characterized in that, The reaction temperature is 60~120℃; The reaction time is 6 to 24 hours.
9. The preparation method according to claim 1, characterized in that, In the microemulsion containing polystyrene, the particle size of the polystyrene is 30 nm to 3 μm.
10. The preparation method according to claim 9, characterized in that, In the microemulsion containing polystyrene, the particle size of the polystyrene is 50~800nm.
11. The preparation method according to claim 1, characterized in that, The polystyrene-containing microemulsion has a solid content of 0.5 to 60 wt%.
12. The preparation method according to claim 11, characterized in that, The polystyrene-containing microemulsion has a solid content of 1-30 wt%.
13. The preparation method according to claim 1, characterized in that, The thickness of the polystyrene array is 1 mm to 1 cm.
14. The preparation method according to claim 1, characterized in that, The thermally induced atmosphere is an atmosphere containing nitrogen and / or hydrogen, or it is carried out in a vacuum.
15. The preparation method according to claim 1, characterized in that, The thermally induced heating rate is 1~15℃ / min; The thermal induction time is 1~12h.
16. A polystyrene film material, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 15.