A styrene resin composition and its preparation method and application

Abstract

The present invention discloses a styrene resin composition comprising the following components, by weight: 70 parts of a styrene resin; 5-15 parts of lamellar kaolin; 0.5-1.5 parts of a dispersant; and 2-5 parts of a compatibilizer. The dispersant is a compound of a silane coupling agent and a titanate coupling agent in a weight ratio of (1.5-3):1; and the compatibilizer is selected from a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer. By selecting lamellar kaolin with a specific specific surface area, a dispersant in a specific ratio, and a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer with a specific GMA content, the present invention can simultaneously improve scratch resistance and dimensional stability.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a preparation method and application of a styrene resin composition. Background Art

[0002] ABS (acrylonitrile-butadiene-styrene) is a terpolymer of acrylonitrile, butadiene, and styrene. By combining the superior properties of its three components, ABS resin offers excellent impact strength, good processing properties, and chemical stability. It is easy to mold, produces glossy products, and exhibits both toughness and flexibility, resulting in excellent overall performance. Due to its exceptional comprehensive properties, ABS resin is widely used in the automotive, electronics, light appliance, textile, and construction industries. In recent years, the automotive industry has become increasingly concerned about interior assembly gaps and scratches on components. Interior assembly gaps primarily arise from the thermal expansion and contraction of interlocking components. Large gaps can directly impact the driver and passenger experience, and can even affect driving safety. Scratches on interior components not only affect the driving experience, but excessive scratches can also negatively impact mood.

[0003] Not only in the automotive sector, but also in other fields such as home appliances and electronic appliances, products with both low CLTE and scratch resistance will undoubtedly provide consumers with a healthier and more comfortable experience. Styrene alloys are widely used in various national fields, so the development and design of materials with both low CLTE and scratch resistance is of great value and significance. Summary of the Invention

[0004] The object of the present invention is to provide a scratch-resistant, low-CLTE styrene resin composition, and a preparation method and application thereof.

[0005] The present invention is achieved through the following technical solutions:

[0006] A styrene resin composition comprising the following components in parts by weight:

[0007] 70 parts of styrene resin;

[0008] 5-15 parts of lamellar kaolin;

[0009] Dispersant 0.5-1.5 parts;

[0010] 2-5 parts of compatibilizer;

[0011] Wherein, the dispersant is a compound of a silane coupling agent and a titanate coupling agent, and the weight ratio of the silane coupling agent to the titanate coupling agent is (1.5-3):1;

[0012] The compatibilizer is selected from a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, the weight content of glycidyl methacrylate is in the range of 2.0-3.3wt%, and the weight content of styrene units is in the range of 65-75wt%;

[0013] The specific surface area of ​​the lamellar kaolin is 4-22m 2 / g, and the kaolin surface is coated with a dispersant.

[0014] Preferably, the weight ratio of the silane coupling agent to the titanate coupling agent is (1.9-2.6):1.

[0015] Preferably, the weight content of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate terpolymer is in the range of 2.6-2.9 wt %, and the weight content of the styrene unit is in the range of 68-72 wt %.

[0016] The GMA content test method is as follows: Weigh a certain amount of epoxy resin sample and dissolve it in a hydrochloric acid-acetone solution. After adding an indicator, titrate with a standard sodium hydroxide solution (ml / ml), and record the volume consumed. The epoxy value is calculated using the formula: Epoxy Value = (V0 - V1) × N / W, where V0 is the volume of NaOH consumed in the blank titration, V1 is the volume of NaOH consumed in the sample titration, N is the concentration of the NaOH solution, and W is the sample weight.

[0017] The styrene / acrylonitrile / glycidyl methacrylate ternary random copolymer can be a commercially available product or can be prepared in-house. The preparation method is as follows: styrene, acrylonitrile and glycidyl methacrylate are mixed according to the ratio of each unit, and a suspension polymerization method is used to cause glycidyl methacrylate, styrene and acrylonitrile to undergo free radical polymerization. The reaction temperature is 60-140° C. and the pressure in the reactor is 0.1-1.2 MPa. Thus, the styrene / acrylonitrile / glycidyl methacrylate ternary random copolymer is obtained.

[0018] Preferably, the specific surface area of ​​the lamellar kaolin is 6-16m 2 / g. The specific surface area test method is as follows: the powder sample to be tested is placed in a U-shaped sample tube, and a mixed gas containing a certain proportion of adsorbate is passed through the sample. The adsorption amount of the adsorbate molecules (N2) by the sample to be tested is determined based on the change in gas concentration before and after adsorption, and the specific surface area of ​​the powder to be tested is calculated.

[0019] The styrene resin is selected from at least one of ABS, ASA, and AES. Preferably, the weight percentage of the styrene resin in the styrene resin composition of the present invention is not less than 65 wt%. Preferably, the melt index of the styrene resin is in the range of 15-25 g / 10 min (220 kg, 10°C).

[0020] The silane coupling agent is selected from at least one of an ethoxysilane coupling agent, an aminosilane coupling agent, and a methacrylate silane coupling agent; wherein the aminosilane coupling agent can be N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; optionally, the brand of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane can be: KH792 of Xiangfeng Weiye.

[0021] The titanate coupling agent may be diisopropyl bis(triethanolamine)titanate; optionally, the brand of diisopropyl bis(triethanolamine)titanate may be HY-1803 produced by Jessica Chemical.

[0022] It is optional to add 0-2 parts of auxiliary agents according to actual conditions. The auxiliary agents are selected from at least one of antioxidants, lubricants, and light stabilizers.

[0023] The method for preparing a styrene resin composition comprises the following steps: pre-mixing a dispersant with lamellar kaolin according to a specific ratio, then uniformly mixing the mixture with the other components, and extruding the mixture into pellets through a twin-screw extruder to obtain the styrene resin composition. The screw barrel temperature range is 220-250°C.

[0024] The styrene resin composition is used to prepare electrical appliance housings and vehicle-mounted parts.

[0025] The present invention has the following beneficial effects:

[0026] The present invention selects a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer with a specific GMA content as a compatibilizer and a specific dispersant, which can improve the dispersion effect of flaky kaolin. The higher the specific surface area of ​​the kaolin, the stronger the binding ability with the compatibilizer and the dispersant. However, the higher the specific surface area of ​​the kaolin, the more difficult it is to disperse. Therefore, when the specific surface area of ​​the kaolin is within a specific range, a portion of the kaolin forms a dispersed state of a flaky structure on the surface, achieving a scratch-resistant effect, and the other portion of the kaolin is better dispersed in the resin matrix, reducing the linear thermal expansion dilution of the system, resulting in a reduction in the influence of temperature changes on the size of the unit length of the material, thereby improving dimensional stability. DETAILED DESCRIPTION

[0027] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those skilled in the art, several variations and improvements can be made without departing from the scope of the present invention. These all fall within the scope of protection of the present invention.

[0028] The raw materials used in the present invention come from the following sources:

[0029] ABS resin: Shanghai Gaoqiao Petrochemical Company, brand ABS 8434;

[0030] AES resin: Japan TECHNO, AES 491;

[0031] The lamellar kaolin was purchased from the CMP series of Wanzhu Mining. Raw materials with different specific surface areas were obtained through screening and testing:

[0032] Lamellar structure kaolin A: specific surface area is 4m 2 / g,;

[0033] Lamellar kaolin B: specific surface area is 8m 2 / g,;

[0034] Lamellar kaolin C: Specific surface area is 16m 2 / g, Wanzhu Mining;

[0035] Lamellar kaolin D: Specific surface area is 20m 2 / g,;

[0036] Lamellar kaolin E: Specific surface area is 2m 2 / g,;

[0037] Lamellar kaolin F: specific surface area is 30m 2 / g,;

[0038] Silane coupling agent: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, Xiangfeng Weiye, KH792;

[0039] Titanate coupling agent: diisopropyl bis(triethanolamine) titanate, Jessica Chemical, HY-1803;

[0040] Antioxidant: a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, produced and provided by Ciba;

[0041] Lubricant: Pentaerythritol stearate, LOZA company, brand GLYCOLUBE-P.

[0042] Compatibilizer A: Styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, GMA content is 2.0wt%, the weight content of styrene units is 74wt%, homemade;

[0043] Compatibilizer B: Styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, GMA content is 2.6wt%, the weight content of styrene units is 71wt%, homemade;

[0044] Compatibilizer C: Styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, GMA content is 2.9wt%, the weight content of styrene units is 69wt%, homemade;

[0045] Compatibilizer D: Styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, GMA content is 3.3wt%, the weight content of styrene units is 66wt%, homemade;

[0046] Compatibilizer E: Styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, GMA content is 1.3wt%, the weight content of styrene units is 70wt%, homemade;

[0047] Compatibilizer F: Styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, GMA content is 4.0wt%, the weight content of styrene units is 70wt%, homemade;

[0048] The homemade method is as follows: according to the ratio of each unit, styrene, acrylonitrile and glycidyl methacrylate are subjected to free radical polymerization by suspension polymerization method, the reaction temperature is 60-140°C, and the pressure in the reactor is 0.1-1.2MPa; a styrene / acrylonitrile / glycidyl methacrylate ternary random copolymer is obtained.

[0049] The following examples and comparative examples describe a method for preparing a styrene resin composition: All components were mixed uniformly and then added to the main barrel of a twin-screw extruder (screw diameter: 35 mm, aspect ratio: L / D = 48). The main barrel section temperatures (from the feed port to the die exit) were controlled at 220°C, 235°C, 245°C, 250°C, and 245°C, respectively. The twin-screw speed was 300 rpm. The extruded strands were cooled in a water tank and then pelletized to obtain the styrene resin composition.

[0050] Various test methods:

[0051] (1) Scratch resistance: The test was conducted in accordance with Geely Q / JLY J7110536B-2016 standard. The electric scratch tester scraper speed was set to (1000±50) mm / min, the pressure was selected to be 10N, and the head was selected to be 1mm. Then, the scratch tester scraper was used to make parallel scratches of 40 mm in length every 2 mm in one direction on the surface of the plastic sample. At least 20 parallel lines were drawn. Then, the sample was rotated 90° and the above operation was repeated to form a grid. At least three parallel samples were scratched and the color difference △L of the scratched area before and after the test was measured.

[0052] (2) CLTE test, tested in accordance with ISO 11359-2:2011 standard.

[0053] Table 1: Content of each component of styrene resin in Examples 1-5 (parts by weight) and test results

[0054] Example 1 Example 2 Example 3 Example 4 Example 5 ABS resin 70 70 70 70 AES resin 70 Lamellar structure kaolin A 10 15 10 10 10 Silane coupling agent 0.6 0.9 0.66 0.72 0.75 Titanate coupling agent 0.4 0.6 0.34 0.28 0.25 Compatibilizer A 3 5 3 3 3 antioxidants 0.2 lubricant 0.2 △L 0.8 0.6 0.7 0.7 0.8 CLTE / (μm / (m*℃)) 62 64 58 59 62

[0055] It can be seen from Examples 1 / 3 / 4 / 5 that the preferred silane coupling agent / titanate coupling agent compounding ratio has better scratch resistance and lower CLTE.

[0056] Table 2: Content of each component of styrene resin in Examples 6-11 (parts by weight) and test results

[0057] Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 ABS resin 70 70 70 70 70 70 Lamellar structure kaolin A 10 10 10 Lamellar structure kaolin B 10 Lamellar structure kaolin C 10 Lamellar structure kaolin D 10 Silane coupling agent 0.6 0.6 0.6 0.6 0.6 0.6 Titanate coupling agent 0.4 0.4 0.4 0.4 0.4 0.4 Compatibilizer A 3 3 3 Compatibilizer B 3 Compatibilizer C 3 Compatibilizer D 3 △L 0.7 0.7 0.8 0.6 0.5 0.8 CLTE / (μm / (m*℃)) 56 59 63 54 52 62

[0058] It can be seen from Examples 1 / 6 / 7 / 8 that the preferred lamellar kaolin has better scratch resistance and dimensional stability than the surface area.

[0059] It can be seen from Examples 1 / 8 / 10 / 11 that when the compatibilizer with a higher GMA / st unit content is used, the scratch resistance and dimensional stability are better.

[0060] It can be seen from the above examples that the styrene-based resin of the present invention has a ΔL value of less than 0.9 and a CLTE value of less than μ65 m / (m*°C).

[0061] Table 3: Content of each component (parts by weight) of styrene resin in Comparative Examples 1-6 and test results

[0062] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 ABS resin 70 70 70 70 70 70 Lamellar structure kaolin A 10 10 10 10 Lamellar structure kaolin E 10 Lamellar structure kaolin F 10 Silane coupling agent 0.5 0.8 0.6 0.6 0.6 0.6 Titanate coupling agent 0.5 0.2 0.4 0.4 0.4 0.4 Compatibilizer A 3 3 1 3 3 Compatibilizer D 7 △L 1.4 1.3 1.8 1.5 1.1 1.2 CLTE / (μm / (m*℃)) 67 68 72 74 68 69

[0063] Table 4: Content of each component of styrene resin in comparative examples 7-8 (parts by weight) and test results

[0064] Comparative Example 7 Comparative Example 8 ABS resin 70 70 Lamellar structure kaolin A 10 10 Silane coupling agent 0.6 0.6 Titanate coupling agent 0.4 0.4 Compatibilizer E 3 Compatibilizer F 3 △L 1.2 1.3 CLTE / (μm / (m*℃)) 71 72

[0065] It can be seen from Comparative Examples 1 / 2 that when the ratio of the silane coupling agent to the titanate coupling agent is not within the range of the present invention, the scratch resistance and dimensional stability are poor.

[0066] It can be seen from Comparative Examples 3 / 4 that when the content of the styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer is too high or too low, the scratch resistance and dimensional stability are poor.

[0067] It can be seen from Comparative Examples 5 / 6 that if the specific surface area of ​​the lamellar kaolin is too high or too low, the scratch resistance and dimensional stability are poor.

[0068] It can be seen from Comparative Examples 7 and 8 that when the GMA content in the compatibilizer is not within the range of the present invention, the scratch resistance and dimensional stability are poor.

Claims

1. A styrene resin composition, characterized in that Calculated by weight, it includes the following components: 70 parts of styrene resin; 5-15 parts of lamellar kaolin; Dispersant 0.5-1.5 parts; 2-5 parts of compatibilizer; Wherein, the dispersant is a compound of a silane coupling agent and a titanate coupling agent, and the weight ratio of the silane coupling agent to the titanate coupling agent is (1.5-3):1; The compatibilizer is selected from a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, wherein the weight content of the glycidyl methacrylate unit is in the range of 2.0-3.3wt%, and the weight content of the styrene unit is in the range of 65-75wt%; The specific surface area of ​​the lamellar kaolin is 4-22m 2 / g, and the kaolin surface is coated with a dispersant.

2. The styrene resin composition according to claim 1, wherein The weight ratio of the silane coupling agent to the titanate coupling agent is (1.9-2.6):

1.

3. The styrene resin composition according to claim 1, wherein The weight content of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate terpolymer is in the range of 2.6-2.9 wt %, and the weight content of the styrene unit is in the range of 68-72 wt %.

4. The styrene resin composition according to claim 1, wherein The specific surface area of ​​the lamellar kaolin is 6-16m 2 / g.

5. The styrene resin composition according to claim 1, wherein The styrene resin is selected from at least one of ABS, ASA and AES.

6. The styrene resin composition according to claim 1, wherein The silane coupling agent is selected from at least one of an ethoxysilane coupling agent, an aminosilane coupling agent, and a methacrylate silane coupling agent; and the titanate coupling agent is selected from diisopropyl bis(triethanolamine) titanate.

7. The styrene resin composition according to claim 1, wherein The invention further comprises 0-2 parts of auxiliary agents by weight, wherein the auxiliary agents are selected from at least one of antioxidants, lubricants and light stabilizers.

8. The method for preparing the styrene resin composition according to any one of claims 1 to 7, characterized in that: The following steps are involved: According to the ratio, the dispersant is pre-mixed with the lamellar structure kaolin, and then evenly mixed with other components, and then extruded and granulated by a twin-screw extruder to obtain a styrene resin composition.

9. Use of the styrene resin composition according to any one of claims 1 to 7, characterized in that: Used for the preparation of electrical housings and automotive parts.