Impact-resistant toughened polystyrene sheet and preparation method thereof
By introducing surface modified fibers into polystyrene materials and using polyphenol hydroxybenzophenanthrene to generate cross-linked polymer chains, the brittleness and compatibility problems of polystyrene materials are solved, its mechanical strength and impact resistance are improved, and its application range is expanded.
Patent Information
- Application Number
- CN202510657392.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-21
- Publication Date
- 2025-07-08
AI Technical Summary
The existing polystyrene materials have high brittleness and poor impact resistance, which limits their application in the engineering field. The existing modification methods have problems of poor compatibility and adhesion.
The surface-modified fiber is combined with polystyrene resin, and the cross-linking polymer chain with polyphenyl etherone as the crosslinking agent and modifier is formed in situ on the fiber surface with polyphenyl etherone as the main body, which enhances the compatibility and adhesion of the fiber with polystyrene, and utilizes the large planar configuration of benzophenyl and the compatibility of polyphenyl etherone to improve the mechanical strength and impact toughness of the material.
It effectively improves the mechanical strength and impact toughness of polystyrene materials, expands its application in the field of structural materials, reduces resource waste caused by brittle cracks, and improves product safety and economicality.
Smart Images
Figure BDA0005412828770000061
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polymer material preparation, and in particular to an impact-resistant toughened polystyrene sheet and a preparation method thereof. Background Art
[0002] Polystyrene (PS) is a widely used thermoplastic with advantages such as high transparency, easy processing and low cost. However, its brittleness and poor impact resistance severely limit its application in the engineering field. Unmodified polystyrene is prone to brittle fracture when subjected to external impact, resulting in a high breakage rate and short service life of the product. It is difficult to meet the requirements of scenes with high requirements for material toughness and durability as components (such as automotive components), housings (such as electronic device housings), and packaging materials (such as blister boxes). Impact-toughening modification can significantly improve the elongation at break and impact strength of the material, so that when it is subjected to mechanical stress, it can delay crack propagation by inducing silver streaks, shear yield, stress conduction and other energy dissipation mechanisms. Impact-toughening modification not only expands the application of polystyrene in the field of structural materials, but also reduces the waste of resources caused by material brittle fracture, improves product safety and economy, and is a key technical path to balance its performance shortcomings with market demand.
[0003] In addition to molecular structure modification, the existing technology mainly uses doping and blending methods to perform impact toughening modification, such as adding elastomers such as styrene-butadiene rubber and polybutadiene, or blending with acrylonitrile-butadiene-styrene copolymer ABS, or preparing composite materials with fiber materials. Although the above modification methods can improve its toughness and impact resistance to a certain extent, due to the low compatibility and adhesion between polystyrene and other materials, the pull-out effect is obvious, and the improvement of its toughness and impact resistance is relatively limited. Summary of the invention
[0004] In view of the above problems, the present invention provides an impact-resistant toughened polystyrene sheet and a preparation method thereof.
[0005] The purpose of the present invention is achieved by the following technical solutions:
[0006] An impact-resistant toughened polystyrene sheet comprises a polystyrene resin and a surface-modified fiber. The preparation method of the surface-modified fiber comprises the following steps:
[0007] (1) The fiber is sequentially alkali washed, acid washed and water washed, and then dried for later use;
[0008] (2) Weigh 2,3,6,7,10,11 - hexahydroxytriphenylene and disperse it in a reaction solvent. Under a protective atmosphere, add a salt - forming agent and the fiber prepared for washing. Heat the mixture to 150 - 170 °C, add 4,4'-difluorobenzophenone and hydroquinone, keep the temperature and stir for reflux reaction for 1 - 3 h. Seal the reaction system, heat it to 180 - 200 °C and continue to keep the temperature and stir for reaction for 1 - 3 h. After the reaction is completed, separate the fiber, wash and dry it to obtain the surface - modified fiber.
[0009] In some preferred embodiments, the melt index of the polystyrene resin is 4 - 8.5 g / 10 min (230 °C / 5 kg).
[0010] In some preferred embodiments, the mass ratio of the polystyrene resin to the surface - modified fiber is 100:(1 - 20).
[0011] In some preferred embodiments, the fiber in step (1) is one or more of glass fiber, basalt fiber, carbon fiber, and asbestos fiber.
[0012] In some preferred embodiments, the length of the fiber is 300 - 3000 μm; the diameter is 1 - 25 μm.
[0013] In some preferred embodiments, the protective atmosphere is carbon dioxide, nitrogen, or argon.
[0014] In some preferred embodiments, the salt - forming agent is a carbonate of an alkali metal, and the alkali metal is lithium, sodium, potassium, or rubidium. Further preferably, it is a mixture of potassium carbonate and sodium carbonate in an equimolar ratio.
[0015] In some preferred embodiments, the reaction solvent is one or more of dimethylformamide, dimethylacetamide, and diphenyl sulfone.
[0016] In some preferred embodiments, the mass ratio of 2,3,6,7,10,11 - hexahydroxytriphenylene to the salt - forming agent, the fiber, 4,4'-difluorobenzophenone, and hydroquinone is (3.5 - 4.5):(15 - 18):100:(9.5 - 11):(7 - 8).
[0017] In some preferred embodiments, the impact - toughened polystyrene sheet further includes an additive, and the mass fraction of the additive in the impact - toughened polystyrene sheet is 0.1 - 5%.
[0018] In some preferred embodiments, the auxiliary agent is one or several of a light stabilizer, an antioxidant, a plasticizer, a flame retardant, and a lubricant; the light stabilizer is an ultraviolet absorber, such as a benzophenone polymer, a benzotriazole polymer, or a salicylate polymer; the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 1035, antioxidant 2103, antioxidant 168, antioxidant 164, or antioxidant 626; the plasticizer is a phthalate, a citrate, or a chlorinated paraffin; the flame retardant is aluminum hydroxide, decabromodiphenyl ether, zinc borate, ammonium polyphosphate, or pentaerythritol; the lubricant is vinyl bisstearamide or polyethylene wax.
[0019] Another aspect of the present invention is to provide a method for preparing the impact-resistant and toughened polystyrene sheet, comprising the following steps:
[0020] Mix the polystyrene resin, the surface-modified fiber, and the auxiliary agent in a mixing device, then conduct mixing and kneading, and obtain a sheet after melt extrusion and calendering and cooling. The extrusion temperature is 180 - 240 °C; the sheet can be softened and then vacuum thermoformed on a mold and cooled to obtain a thermoformed box.
[0021] The beneficial effects of the present invention are as follows:
[0022] Aiming at the problem that the improvement of the impact-resistant and toughened morphology is limited due to poor compatibility and adhesion in the existing doping and blending modification methods, the present invention reduces the interfacial effect between the fiber and the polystyrene resin by adding a surface-modified fiber, thereby effectively improving the mechanical strength and impact toughness of the polystyrene material; specifically, the present invention uses polyphenolic hydroxyl benzophenanthrene as a cross-linking agent and a modifier, uses difluorobenzophenone and hydroquinone as monomers, and in-situ generates a cross-linked polymerization product with a polyphenylene ether ketone as the main polymer chain on the surface of the reinforcing fiber. By virtue of the symmetric large planar configuration of benzophenanthrene and the compatibility between polyphenylene ether ketone and polystyrene, benzophenanthrene can be inserted between the polystyrene molecular chains to form a conjugate and increase the molecular chain gap, reduce the attraction between the molecular chains, and at the same time, the interfacial layer between the polyphenylene ether ketone with a similar chain structure and polystyrene is blurred, increasing the compatibility and adhesion between the polystyrene resin and the fiber, and improving the mechanical strength and impact toughness of polystyrene. Specific Embodiments
[0023] The present invention will be further described in combination with the following examples.
[0024] Example 1
[0025] An impact-resistant and toughened polystyrene sheet, which is composed of polystyrene resin and surface-modified fibers. The preparation method is as follows: The polystyrene resin and the surface-modified fibers are placed in a mixing device for mixing, then kneaded, melt-extruded, and finally calendered and cooled to obtain the sheet. The extrusion temperature is 210°C. The sheet can be softened, then vacuum thermoformed on a mold and cooled to obtain a thermoformed box.
[0026] The melt index of the polystyrene resin is 5.5 g / 10 min (190°C / 5 kg).
[0027] The preparation method of the surface-modified fibers includes the following steps:
[0028] (1) Wash the glass fibers successively with 0.1 mol / L sodium hydroxide solution, 0.1 mol / L hydrochloric acid solution, and deionized water, and dry them for later use. The length of the glass fibers is 800 μm, and the diameter is 2.5 μm.
[0029] (2) Weigh 2,3,6,7,10,11-hexahydroxytriphenylene (CAS No.: 4877-80-9) and disperse it in diphenyl sulfone solvent. Under a carbon dioxide or nitrogen atmosphere, add a salt-forming agent and the washed glass fibers for later use. Heat up to 150 - 170°C, add 4,4'-difluorobenzophenone and hydroquinone, keep stirring and refluxing for 2 h, seal the reaction system, heat up to 200°C and continue to keep stirring and reacting for 2 h. After the reaction is completed, separate the fibers, wash and dry them to obtain the surface-modified fibers. The mass ratio of 2,3,6,7,10,11-hexahydroxytriphenylene to the salt-forming agent, the glass fibers, 4,4'-difluorobenzophenone, and hydroquinone is 4.32:16.2:100:10.2:7.3.
[0030] The mass ratio of the polystyrene resin to the surface-modified fibers is 100:8.6.
[0031] The salt-forming agent is a mixture of potassium carbonate and sodium carbonate with an equimolar ratio.
[0032] Example 2
[0033] An impact-resistant and toughened polystyrene sheet, which is composed of polystyrene resin and surface-modified fibers. The preparation method is as follows: The polystyrene resin and the surface-modified fibers are placed in a mixing device for mixing, then kneaded, melt-extruded, and finally calendered and cooled to obtain the sheet. The extrusion temperature is 210°C. The sheet can be softened, then vacuum thermoformed on a mold and cooled to obtain a thermoformed box.
[0034] The melt index of the polystyrene resin is 5.5 g / 10 min (190°C / 5 kg).
[0035] The preparation method of the surface-modified fiber comprises the following steps:
[0036] (1) Wash the glass fiber successively with 0.1 mol / L sodium hydroxide solution, 0.1 mol / L hydrochloric acid solution and deionized water, and dry for later use; the length of the glass fiber is 800 μm; the diameter is 2.5 μm;
[0037] (2) Weigh phloroglucinol and disperse it in diphenyl sulfone solvent. Add a salt-forming agent and the glass fiber reserved after washing under a carbon dioxide or nitrogen atmosphere. Heat to 150 - 170 °C, add 4,4'-difluorobenzophenone and hydroquinone, keep warm and stir for reflux reaction for 2 h, seal the reaction system, heat to 200 °C and continue to keep warm and stir for reaction for 2 h. After the reaction is completed, separate the fiber, wash and dry to obtain the surface-modified fiber; the mass ratio of phloroglucinol to the salt-forming agent, the glass fiber, 4,4'-difluorobenzophenone and hydroquinone is 1.68:16.2:100:10.2:7.3;
[0038] The mass ratio of the polystyrene resin to the surface-modified fiber is 100:8.6;
[0039] The salt-forming agent is a mixture of potassium carbonate and sodium carbonate with an equimolar ratio.
[0040] Example 3
[0041] An impact-resistant and toughened polystyrene sheet is composed of a polystyrene resin and a surface-modified fiber. The preparation method is to mix the polystyrene resin and the surface-modified fiber in a mixing device and then carry out mixing and kneading, and then melt and extrude and finally calender and cool to obtain a sheet. The extrusion temperature is 210 °C; the sheet can be softened, vacuum thermoformed on a mold and then cooled to obtain a thermoformed box;
[0042] The melt index of the polystyrene resin is 5.5 g / 10 min (190 °C / 5 kg);
[0043] The preparation method of the surface-modified fiber comprises the following steps:
[0044] (1) Wash the glass fiber successively with 0.1 mol / L sodium hydroxide solution, 0.1 mol / L hydrochloric acid solution and deionized water, and dry for later use; the length of the glass fiber is 800 μm; the diameter is 2.5 μm;
[0045] (2) Weigh 2,3,6,7,10,11 - hexahydroxytriphenylene and disperse it in diphenyl sulfone solvent. Add a salt - forming agent under a carbon dioxide or nitrogen atmosphere, heat up to 150 - 170 °C, add 4,4'-difluorobenzophenone and hydroquinone, keep warm and stir for reflux reaction for 2 h, seal the reaction system, heat up to 200 °C and continue to keep warm and stir for reaction for 2 h. After the reaction is completed, add the glass fiber prepared for washing, let it stand overnight and then separate the fiber. After washing and drying, the surface - modified fiber is obtained; the mass ratio of 2,3,6,7,10,11 - hexahydroxytriphenylene to the salt - forming agent, the glass fiber, 4,4'-difluorobenzophenone and hydroquinone is 4.32:16.2:100:10.2:7.3;
[0046] The mass ratio of the polystyrene resin to the surface - modified fiber is 100:8.6;
[0047] The salt - forming agent is a mixture of potassium carbonate and sodium carbonate with an equimolar ratio.
[0048] Example 4
[0049] An impact - resistant and toughened polystyrene sheet is composed of polystyrene resin and surface - modified fiber. Its preparation method is as follows: place the polystyrene resin and the surface - modified fiber in a mixing device for mixing, then carry out mixing and kneading, and after melt - extrusion, it is calendered and cooled to obtain a sheet. The extrusion temperature is 210 °C; the sheet can be softened, vacuum - thermoformed on a mold and then cooled to obtain a thermoformed box;
[0050] The melt index of the polystyrene resin is 5.5 g / 10 min (190 °C / 5 kg);
[0051] The preparation method of the surface - modified fiber includes the following steps:
[0052] (1) Wash the carbon fiber successively with 0.1 mol / L sodium hydroxide solution, 0.1 mol / L hydrochloric acid solution and deionized water, and dry it for later use; the length of the carbon fiber is 800 μm; the diameter is 5 μm;
[0053] (2) Weigh 2,3,6,7,10,11 - hexahydroxytriphenylene and disperse it in diphenyl sulfone solvent. Under a carbon dioxide or nitrogen atmosphere, add the salt - forming agent and the carbon fiber prepared for washing, heat up to 150 - 170 °C, add 4,4'-difluorobenzophenone and hydroquinone, keep warm and stir for reflux reaction for 2 h, seal the reaction system, heat up to 200 °C and continue to keep warm and stir for reaction for 2 h. After the reaction is completed, separate the fiber, wash and dry it to obtain the surface - modified fiber; the mass ratio of 2,3,6,7,10,11 - hexahydroxytriphenylene to the salt - forming agent, the carbon fiber, 4,4'-difluorobenzophenone and hydroquinone is 4.32:16.2:100:10.2:7.3;
[0054] The mass ratio of the polystyrene resin to the surface-modified fiber is 100:8.6;
[0055] The salt-forming agent is a mixture of potassium carbonate and sodium carbonate in an equimolar ratio.
[0056] Example 5
[0057] An impact-resistant and toughened polystyrene sheet is composed of a polystyrene resin, a surface-modified fiber, and an additive. The preparation method is as follows: the polystyrene resin, the surface-modified fiber, and the additive are placed in a mixing device for mixing, then kneaded, melt-extruded, and finally calendered and cooled to obtain the sheet. The extrusion temperature is 210°C; after the sheet is softened, it can be vacuum thermoformed on a mold and then cooled to obtain a thermoformed box;
[0058] The melt index of the polystyrene resin is 5.5 g / 10 min (190°C / 5 kg);
[0059] The preparation method of the surface-modified fiber includes the following steps:
[0060] (1) Wash the basalt fiber successively with a 0.1 mol / L sodium hydroxide solution, a 0.1 mol / L hydrochloric acid solution, and deionized water, and dry it for later use; the length of the basalt fiber is 800 μm; the diameter is 6 μm;
[0061] (2) Weigh 2,3,6,7,10,11-hexahydroxytriphenylene and disperse it in diphenyl sulfone solvent. Under a carbon dioxide or nitrogen atmosphere, add the salt-forming agent and the washed basalt fiber, heat up to 150 - 170°C, add 4,4'-difluorobenzophenone and hydroquinone, keep stirring and refluxing for 2 h, seal the reaction system, heat up to 200°C and continue to keep stirring and reacting for 2 h. After the reaction is completed, separate the fiber, wash and dry it to obtain the surface-modified fiber; the mass ratio of 2,3,6,7,10,11-hexahydroxytriphenylene to the salt-forming agent, the basalt fiber, 4,4'-difluorobenzophenone, and hydroquinone is 4.32:16.2:100:10.2:7.3;
[0062] The additive is antioxidant 1010 and phenyl salicylate;
[0063] The mass ratio of the polystyrene resin to the surface-modified fiber, antioxidant 1010, and phenyl salicylate is 100:8.6:0.5:0.3;
[0064] The salt-forming agent is a mixture of potassium carbonate and sodium carbonate in an equimolar ratio.
[0065] Taking the unmodified polystyrene resin as a control, the mechanical properties of the impact-resistant and toughened polystyrene materials prepared in Examples 1-5 were measured. Among them, the tensile strength was measured with reference to Standard ISO 527-1-2019; the flexural strength and flexural modulus were measured with reference to Standard ISO 178-2019; the notched impact strength was measured with reference to Standard ISO 179-1-2023; and the measurement was carried out with reference to Standard ISO1133-1-2022. The measurement results are shown in the following table:
[0066]
[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. An impact-resistant and toughened polystyrene sheet, characterized in that, It includes polystyrene resin and surface-modified fibers. The preparation method of the surface-modified fibers comprises the following steps: (1) Sequentially subject the fibers to alkali washing, acid washing and water washing, and reserve them after drying; (2) Weigh 2,3,6,7,10,11-hexahydroxy triphenylene and disperse it in a reaction solvent. Under a protective atmosphere, add a salt-forming agent and the fibers reserved after washing. Heat up to 150-170 °C, add 4,4'-difluorobenzophenone and hydroquinone, keep the temperature and stir for reflux reaction for 1-3 h. Seal the reaction system, heat up to 180-200 °C and continue to keep the temperature and stir for reaction for 1-3 h. After the reaction is completed, separate the fibers, wash and dry them to obtain the surface-modified fibers.
2. The impact-resistant and toughened polystyrene sheet according to claim 1, wherein The mass ratio of the polystyrene resin to the surface-modified fibers is 100:(1-20).
3. An impact-resistant and toughened polystyrene sheet according to claim 1, characterized in that, The fibers in step (1) are one or more of glass fiber, basalt fiber, carbon fiber, and asbestos fiber; the length of the fibers is 300-3000 μm; the diameter is 1-25 μm.
4. The impact-resistant and toughened polystyrene sheet according to claim 1, wherein, The protective atmosphere is carbon dioxide, nitrogen or argon.
5. The impact-resistant and toughened polystyrene sheet according to claim 1, characterized in that, The salt-forming agent is a carbonate of an alkali metal, and the alkali metal is lithium, sodium, potassium or rubidium.
6. The impact-resistant and toughened polystyrene sheet according to claim 1, wherein The reaction solvent is one or more of dimethylformamide, dimethylacetamide, and diphenyl sulfone.
7. The impact-resistant and toughened polystyrene sheet according to claim 1, wherein The mass ratio of 2,3,6,7,10,11-hexahydroxy triphenylene to the salt-forming agent, the fibers, 4,4'-difluorobenzophenone and hydroquinone is (3.5-4.5):(15-18):100:(9.5-11):(7-8).
8. The impact-resistant and toughened polystyrene sheet according to claim 1, wherein It also includes an auxiliary agent, and the mass fraction of the auxiliary agent in the impact-resistant and toughened polystyrene sheet is 0.1-5%.
9. The impact-resistant and toughened polystyrene sheet according to claim 8, wherein The auxiliary agent is one or more of a light stabilizer, an antioxidant, a plasticizer, a flame retardant, and a lubricant.
10. The preparation method of an impact-resistant and toughened polystyrene sheet according to claim 8 or 9, characterized in that, It comprises the following steps: Place the polystyrene resin, the surface-modified fibers and the auxiliary agent in a mixing device, mix them and then carry out mixing and kneading. After melt extrusion, calender and cool to obtain a sheet, and the extrusion temperature is 180-240 °C.