A polystyrene bead with high foaming ratio and a preparation method thereof

Abstract

The application relates to the polystyrene technical field and discloses high-foaming-ratio polystyrene beads and a preparation method thereof, wherein the high-foaming-ratio polystyrene beads are prepared from the following raw materials in parts by weight: 85-95 parts of polystyrene, 1-10 parts of organic allevardite, 2-4 parts of a foaming agent and 3-6 parts of a toughening agent; the preparation method of the organic allevardite comprises the following steps: A1, mixing sodium salt and allevardite slurry, aging and obtaining a suspension; A2, adding a cationic surfactant into the suspension, mixing and drying to obtain pretreated allevardite; and A3, mixing the pretreated allevardite with benzene sulfonyl hydroxamic acid, drying and obtaining the organic allevardite. Through the technical scheme, the problem of low compressive strength of polystyrene products prepared from the high-foaming-ratio polystyrene beads in the related art is solved.

Description

Technical Field

[0001] This invention relates to the field of polystyrene technology, specifically to a high foaming ratio polystyrene bead and its preparation method. Background Technology

[0002] High-expansion-ratio polystyrene beads have a wide range of applications, such as as thermal insulation materials. During the foaming process, gas is trapped inside the polystyrene beads, forming a large number of pores. Especially with high-expansion-ratio polystyrene beads, the resulting polystyrene products have a greater number of larger pores, resulting in a relative reduction in the solid portion of the product. Since the compressive strength of polystyrene products is closely related to the content and structure of the solid portion, a reduced solid portion naturally weakens the overall resistance to compression. Furthermore, as the expansion ratio increases, the cell wall thickness decreases accordingly. When polystyrene products are subjected to pressure, thinner cell walls are more prone to deformation and rupture. Some large and unevenly distributed pores become stress concentration points, leading to a decrease in the compressive strength of the polystyrene product.

[0003] Therefore, it is necessary to obtain a polystyrene bead with a high foaming ratio, which, when made into polystyrene products, has excellent compressive strength to meet the long-term application requirements of polystyrene products. Summary of the Invention

[0004] This invention proposes a high foaming ratio polystyrene bead and its preparation method, which solves the problem that polystyrene products made from high foaming ratio polystyrene beads have low compressive strength in related technologies.

[0005] The technical solution of the present invention is as follows: This invention proposes a high foaming ratio polystyrene bead, comprising the following raw materials in parts by weight: 85-95 parts polystyrene, 1-10 parts organo-attapulgite, 2-4 parts foaming agent, and 3-6 parts toughening agent; The preparation method of the organo-attapulgite includes the following steps: A1. Mix sodium salt and rettolith slurry, and age to obtain a suspension; A2. Add a cationic surfactant to the suspension, mix, and dry to obtain pretreated attapulgite; A3. The pretreated raptorite is mixed with benzenesulfonyl isohydroxamic acid and dried to obtain organoraptorite.

[0006] As a further technical solution, in step A1, the aging time is 20~25h.

[0007] As a further technical solution, in step A1, the mixing includes ball milling.

[0008] As a further technical solution, in step A3, the temperature during mixing is 122~125℃.

[0009] As a further technical solution, in steps A2 and A3, a washing process is performed before drying.

[0010] As a further technical solution, the mass-to-volume ratio of attapulgite to water in the attapulgite slurry is 1g:15~20mL, for example, it can be 1g:15mL, 1g:16mL, 1g:17mL, 1g:18mL, 1g:19mL, or 1g:20mL.

[0011] As a further technical solution, the mass ratio of the sodium salt to the attapulgite is 2~4:100, for example, it can be 2:100, 2.5:100, 3:100, 3.5:100, or 4:100.

[0012] As a further technical solution, the mass ratio of the cationic surfactant, benzenesulfonylhydroxamic acid and rettosite is 1.5~2.5:1:100, for example, it can be 1.5:1:100, 1.8:1:100, 2.0:1:100, 2.2:1:100, or 2.5:1:100.

[0013] As a further technical solution, the cationic surfactant includes one or two of hexadecyltrimethylammonium bromide and octadecyltrimethylammonium chloride.

[0014] As a further technical solution, the sodium salt includes one or more of sodium chloride, sodium carbonate, and sodium sulfate.

[0015] As a further technical solution, the following raw materials are also included in parts by weight: 2 to 6 parts of metal oxide.

[0016] As a further technical solution, the metal oxide includes one or more of zinc oxide, aluminum oxide, zirconium oxide, and cerium oxide.

[0017] In this invention, in addition to adding organic tartaric acid, metal oxides are also added to the high foaming ratio polystyrene beads to synergistically improve the compressive strength of the polystyrene products made from the high foaming ratio polystyrene beads, while also improving the tensile properties of the polystyrene products.

[0018] As a further technical solution, the foaming agent includes low-boiling-point hydrocarbons.

[0019] In this invention, the foaming agent includes a low-boiling-point hydrocarbon, such as petroleum ether, butane, pentane, etc., preferably pentane.

[0020] As a further technical solution, the toughening agent includes one or two of styrene-butadiene-styrene block copolymer and ethylene-octene copolymer.

[0021] In this invention, the toughening agent is a styrene-butadiene-styrene block copolymer and / or an ethylene-octene copolymer, which can improve the processing fluidity of polystyrene beads, enhance the impact resistance of expanded polystyrene products, reduce cracking and damage caused by collisions during use, and improve the service life of polystyrene products.

[0022] This invention also proposes a method for preparing polystyrene beads with a high expansion ratio, which includes the following steps: The raw materials for polystyrene beads are mixed and then extruded and granulated to obtain the polystyrene beads.

[0023] As a further technical solution, the mixing time is 20-30 minutes.

[0024] The working principle and beneficial effects of this invention are as follows: In this invention, organic attapulgite is added to polystyrene beads with high foaming ratio. The attapulgite is then subjected to organic treatment with cationic surfactant and benzenesulfonyl hydroxamic acid in sequence to obtain organic attapulgite with good compatibility with the polystyrene bead matrix. This improves the compressive strength of polystyrene products made from polystyrene beads with high foaming ratio (more than 50 times). Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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.

[0026] In the following examples and comparative examples, the polystyrene is designated as PH88, the ethylene-octene copolymer as 8450G, the styrene-butadiene-styrene block copolymer as F875, the attapulgite particle size as 300 nm, the cerium oxide particle size as 50 nm, and the zirconium oxide particle size as 100 nm.

[0027] Example 1 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 85 parts polystyrene, 1 part organo-attapulgite, 2 parts n-pentane, and 3 parts ethylene-octene copolymer. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and raphe slurry were ball-milled for 40 min and aged for 20 h to obtain a suspension; the ball milling speed was 300 r / min. A2. First, add octadecyltrimethylammonium chloride to the suspension and mix, wash, dry, then mix with benzenesulfonylhydroxamic acid, react at 122℃ for 30 min, cool, wash, dry, and obtain organoprothiolane; In the patella slurry, the mass-to-volume ratio of patella to water is 100g:1500mL; The mass ratio of sodium carbonate to attapulgite is 2:100; The mass ratio of octadecyltrimethylammonium chloride, benzenesulfonylhydroxamic acid, and rettosite is 1.5:1:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 20 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0028] Example 2 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 90 parts polystyrene, 5 parts organo-attapulgite, 3 parts n-pentane, and 4 parts ethylene-octene copolymer. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and retrolite slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. First, add hexadecyltrimethylammonium bromide to the suspension and mix, wash, dry, then mix with benzenesulfonylhydroxamic acid, react at 125℃ for 25 min, cool, wash, dry, and obtain organoprothiolane; In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:1800mL; The mass ratio of sodium carbonate to attapulgite is 4:100; The mass ratio of hexadecyltrimethylammonium bromide, benzenesulfonylhydroxamic acid, and rettosite is 2:1:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 25 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0029] Example 3 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 95 parts polystyrene, 10 parts organo-attapulgite, 4 parts n-pentane, and 6 parts styrene-butadiene-styrene block copolymer. The preparation method of organo-attapulgite includes the following steps: A1. Sodium chloride, sodium carbonate, and retardant slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. First, add hexadecyltrimethylammonium bromide to the suspension and mix, wash, dry, then mix with benzenesulfonylhydroxamic acid, react at 125℃ for 25 min, cool, wash, dry, and obtain organoprothiolane; In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:2000mL; The mass ratio of sodium chloride, sodium carbonate, and attapulgite is 1:2:100; The mass ratio of hexadecyltrimethylammonium bromide, benzenesulfonylhydroxamic acid, and rettosite is 2.5:1:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 30 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0030] Example 4 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 90 parts polystyrene, 5 parts organo-attapulgite, 3 parts n-pentane, 4 parts ethylene-octene copolymer, and 4 parts cerium oxide. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and retrolite slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. First, add hexadecyltrimethylammonium bromide to the suspension and mix, wash, dry, then mix with benzenesulfonylhydroxamic acid, react at 125℃ for 25 min, cool, wash, dry, and obtain organoprothiolane; In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:1800mL; The mass ratio of sodium carbonate to attapulgite is 4:100; The mass ratio of hexadecyltrimethylammonium bromide, benzenesulfonylhydroxamic acid, and rettosite is 2:1:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 25 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0031] Example 5 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 90 parts polystyrene, 5 parts organo-attapulgite, 3 parts n-pentane, 4 parts ethylene-octene copolymer, 3 parts cerium oxide, and 3 parts zirconium oxide. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and retrolite slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. First, add hexadecyltrimethylammonium bromide to the suspension and mix, wash, dry, then mix with benzenesulfonylhydroxamic acid, react at 125℃ for 25 min, cool, wash, dry, and obtain organoprothiolane; In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:1800mL; The mass ratio of sodium carbonate to attapulgite is 4:100; The mass ratio of hexadecyltrimethylammonium bromide, benzenesulfonylhydroxamic acid, and rettosite is 2:1:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 25 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0032] Example 6 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 90 parts polystyrene, 5 parts organo-attapulgite, 3 parts n-pentane, 4 parts ethylene-octene copolymer, and 2 parts cerium oxide. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and retrolite slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. First, add hexadecyltrimethylammonium bromide to the suspension and mix, wash, dry, then mix with benzenesulfonylhydroxamic acid, react at 125℃ for 25 min, cool, wash, dry, and obtain organoprothiolane; In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:1800mL; The mass ratio of sodium carbonate to attapulgite is 4:100; The mass ratio of hexadecyltrimethylammonium bromide, benzenesulfonylhydroxamic acid, and rettosite is 2:1:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 25 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0033] Example 7 The only difference between this embodiment and Embodiment 2 is that, by weight, the polystyrene bead raw material with a high foaming ratio contains 9 parts of organo-attapulgite.

[0034] Comparative Example 1 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 90 parts polystyrene, 5 parts organo-attapulgite, 3 parts n-pentane, and 4 parts ethylene-octene copolymer. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and retrolite slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. Add hexadecyltrimethylammonium bromide to the suspension, mix, wash, and dry to obtain organoprothiolane; In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:1800mL; The mass ratio of sodium carbonate to attapulgite is 4:100; The mass ratio of hexadecyltrimethylammonium bromide to retrolite is 3:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 25 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0035] Comparative Example 2 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 90 parts polystyrene, 5 parts organo-attapulgite, 3 parts n-pentane, and 4 parts ethylene-octene copolymer. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and retrolite slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. Add benzenesulfonyl isohydroxamic acid to the suspension and mix. React at 125°C for 25 min. Cool, wash, and dry to obtain organoprothiolane. In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:1800mL; The mass ratio of sodium carbonate to attapulgite is 4:100; The mass ratio of benzenesulfonyl hydroxamic acid to rettosite is 3:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 25 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0036] Comparative Example 3 High foaming ratio polystyrene beads comprise the following raw materials in parts by weight: 90 parts polystyrene, 5 parts organo-attapulgite, 3 parts n-pentane, and 4 parts ethylene-octene copolymer. The preparation method of organo-attapulgite includes the following steps: A1. Sodium carbonate and retrolite slurry were ball-milled for 40 min and aged for 25 h to obtain a suspension; the ball milling speed was 300 r / min. A2. Mix benzenesulfonyl hydroxamic acid in a suspension and react at 125°C for 25 min. Cool, wash, dry, then add hexadecyltrimethylammonium bromide and mix. Wash and dry to obtain organoprothiolane. In the attapulgite slurry, the mass-to-volume ratio of attapulgite to water is 100g:1800mL; The mass ratio of sodium carbonate to attapulgite is 4:100; The mass ratio of hexadecyltrimethylammonium bromide, benzenesulfonylhydroxamic acid, and rettosite is 2:1:100; High-expansion-ratio polystyrene beads are produced by the following steps: After mixing the raw materials for polystyrene beads for 25 minutes, the mixture is extruded and granulated to obtain polystyrene beads.

[0037] Comparative Example 4 The only difference between this comparative example and Example 2 is that the organo-attapulgite in the high foaming ratio polystyrene bead raw material is replaced with cerium oxide, and the cerium oxide content in the raw material is 9 parts by weight.

[0038] Experimental Example 1 After the polystyrene beads obtained in Examples 1-7 and Comparative Examples 1-4 were molded into boards (polystyrene foam boards), the compressive strength (relative deformation <10%) was tested according to GB / T 8813-2020 "Determination of compressive properties of rigid foam plastics". The results are shown in Table 1 below.

[0039] Table 1 Compressive strength test results

[0040] Compared with Comparative Examples 1-4, the polystyrene beads obtained in Examples 1-7 have higher compressive strength after being molded into boards. This indicates that the organic attapulgite prepared by the present invention, and the synergistic effect of organic attapulgite and metal oxide, improve the compressive strength of polystyrene products made from polystyrene beads with high foaming ratio.

[0041] Experiment Example 2 The polystyrene beads obtained in Examples 2, 4-7, and Comparative Example 4 were molded into boards (polystyrene foam boards), and the tensile stress at break was tested according to the standard GB / T 9641-1988 "Tension Properties Test Method for Rigid Foamed Plastics". The results are shown in Table 2 below.

[0042] Table 2 Tensile property test results

[0043] The polystyrene beads prepared in Examples 4-6 exhibited higher tensile stress after being molded into boards, indicating that the synergistic effect of the organo-attapulgite prepared in this invention with metal oxides improves the tensile properties of polystyrene products made from polystyrene beads with high foaming ratio.

[0044] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A type of polystyrene beads with a high expansion ratio, characterized in that, The raw materials include the following parts by weight: 85-95 parts polystyrene, 1-10 parts organo-attapulgite, 2-4 parts foaming agent, and 3-6 parts toughening agent; The preparation method of the organo-attapulgite includes the following steps: A1. Mix sodium salt and rettolith slurry, and age to obtain a suspension; A2. Add a cationic surfactant to the suspension, mix, and dry to obtain pretreated attapulgite; A3. The pretreated raptorite is mixed with benzenesulfonyl isohydroxamic acid and dried to obtain organoraptorite.

2. The high foaming ratio polystyrene beads according to claim 1, characterized in that, In the rapa stone slurry, the mass-to-volume ratio of rapa stone to water is 1g:15~20mL; The mass ratio of the sodium salt to the attapulgite is 2-4:100; The mass ratio of the cationic surfactant, benzenesulfonyl hydroxamic acid, and attapulgite is 1.5~2.5:1:

100.

3. The high foaming ratio polystyrene beads according to claim 1, characterized in that, In step A1, the aging time is 20-25 hours.

4. The high foaming ratio polystyrene beads according to claim 1, characterized in that, In step A1, the mixing includes ball milling.

5. The high foaming ratio polystyrene beads according to claim 1, characterized in that, The cationic surfactant includes one or both of hexadecyltrimethylammonium bromide and octadecyltrimethylammonium chloride.

6. The high foaming ratio polystyrene beads according to claim 1, characterized in that, The sodium salt includes one or more of sodium chloride, sodium carbonate, and sodium sulfate.

7. The high foaming ratio polystyrene beads according to claim 1, characterized in that, It also includes the following raw materials in parts by weight: 2 to 6 parts of metal oxide.

8. The high foaming ratio polystyrene beads according to claim 7, characterized in that, The metal oxide includes one or more of zinc oxide, aluminum oxide, zirconium oxide, and cerium oxide.

9. A method for preparing high-expansion-ratio polystyrene beads, used to prepare the high-expansion-ratio polystyrene beads according to any one of claims 1 to 8, characterized in that, Includes the following steps: The raw materials for polystyrene beads are mixed and then extruded and granulated to obtain the polystyrene beads.

10. The method for preparing high-expansion-ratio polystyrene beads according to claim 9, characterized in that, The mixing time is 20-30 minutes.

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