A san / pa6 alloy material and a preparation method and application thereof

Abstract

The application discloses a SAN / PA6 alloy material, which comprises the following components in parts by weight: SAN resin 25-58 parts, PA6 resin 24-50 parts, toughening agent 10-30 parts and compatilizer 2-5 parts. By introducing PA6 into SAN, the solvent resistance of SAN is improved. SAN and PA6 have partial compatibility, by adding the compatilizer and controlling the amount of the compatilizer, the compatibility between the two is improved, and the solvent resistance is not affected. By using high nitrile SAN with a specific content, the solvent swelling resistance of the material is improved, by selecting a specific toughening agent, the discoloration of the material is significantly reduced, and the comprehensive performance is excellent.

Description

Technical Field

[0001] This invention relates to the field of engineering plastics technology, specifically to a SAN / PA6 alloy material, its preparation method, and its applications. Background Technology

[0002] Styrene-acrylonitrile copolymer (SAN), also known as AS resin, is a colorless and transparent thermoplastic resin. It possesses high-temperature resistance, excellent gloss, and resistance to chemical media, as well as good hardness, rigidity, dimensional stability, and high load-bearing capacity. However, SAN resin itself is brittle, and its toughness can be improved using rubber toughening agents such as high-rubber powder.

[0003] Essential oils refer to the general term for volatile aromatic substances extracted from aromatic plants or scent-producing animals. In practice, we have found that when using current ABS resin to package essential oils, ABS easily swells and exhibits significant discoloration. Although ABS / PBT resin alloys have improved solvent resistance, they still swell and exhibit noticeable discoloration. Summary of the Invention

[0004] In order to overcome the shortcomings or defects of the prior art, the present invention proposes a SAN / PA6 alloy material, its preparation method and application.

[0005] This invention is achieved through the following technical solution:

[0006] A SAN / PA6 alloy material comprises the following components in parts by weight: 25-58 parts of SAN resin (e.g., 25 parts, 28 parts, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 ​​parts, 50 parts, 53 parts, 55 parts, 58 parts, etc.); 24-50 parts of PA6 resin (e.g., 24 parts, 27 parts, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 ​​parts, 50 parts, etc.); and 10-30 parts of toughening agent (e.g., 10 parts, 13 parts, 15 parts, 1...). 8 parts, 20 parts, 23 parts, 25 parts, 28 parts, 30 parts, etc.); 2-5 parts of compatibilizer (e.g., 2 parts, 3 parts, 4 parts, 5 parts, etc.); in the SAN resin, based on the total mass of the SAN resin, the mass content of acrylonitrile is greater than or equal to 30% (e.g., 30%, 31%, 32%, 33%, 34%, 35%, 36%, etc.); the relative viscosity of PA6 resin is 3.2-4.2 (e.g., 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2).

[0007] As a preferred embodiment, the SAN / PA6 alloy material of the present invention comprises the following components in parts by weight:

[0008]

[0009] The SAN / PA6 alloy material of the present invention contains both SAN resin and PA6 resin. By modifying PA6 resin with a specific amount of SAN resin, the resulting SAN / PA6 alloy has a firm color and significantly improves its discoloration phenomenon after moisture absorption.

[0010] As a preferred embodiment, the mass ratio of SAN resin to PA6 resin is (1-1.4):1.

[0011] As a preferred embodiment, the acrylonitrile content in the SAN resin is 30-35% based on the total mass of the SAN resin.

[0012] Currently, the acrylonitrile content of most commercial SAN resins is between 24-27 wt%. However, the SAN resin selected in this application is a high-acrylonitrile SAN resin with an acrylonitrile content of no less than 30%. Higher acrylonitrile content in the SAN resin increases its polarity, leading to a greater difference in solubility parameters with essential oils. This results in reduced compatibility between the SAN resin and essential oils, thus exhibiting better essential oil soaking swelling and discoloration properties. The synergistic effect of the components in this application effectively enhances the oil resistance, solvent resistance, and stability of the resulting PA6 resin, resulting in excellent overall performance.

[0013] As a preferred embodiment, the toughening agent is an organosilicon-acrylate rubber.

[0014] The inventors of this application have also discovered that selecting a suitable toughening agent can significantly reduce the yellowing problem after solvent immersion.

[0015] As a preferred embodiment, the compatibilizer is a styrene-N-phenylmaleimide-anhydrous maleic anhydride copolymer.

[0016] As a preferred embodiment, the SAN / PA6 alloy material further includes the following components in parts by weight:

[0017] 0.2-2 parts of auxiliary agent;

[0018] The additives include any one or more of antioxidants or lubricants.

[0019] As a preferred embodiment, the product also includes the following components in parts by weight:

[0020] Antioxidant 0.2-1 part;

[0021] Lubricant 0.5-1 part;

[0022] The antioxidant is at least one of copper salt-containing composite antioxidants, hindered phenolic antioxidants, and phosphite antioxidants;

[0023] The lubricant includes at least one of silicone lubricants, ester lubricants, amide lubricants, polyethylene lubricants, stearic acid lubricants, or fatty acid lubricants.

[0024] The mass percentage of SAN resin in the alloy material is not less than 18%.

[0025] This invention is achieved through the following technical solution:

[0026] A method for preparing a SAN / PA6 alloy material includes the following steps:

[0027] S1: Weigh out each component according to the ratio, premix them, and obtain the premix;

[0028] S2: The premix from step S1 is fed into an extruder for melt blending and extrusion granulation to obtain the SAN / PA6 alloy material.

[0029] As a preferred embodiment, the extruder is further described as a twin-screw extruder, wherein the screw length-to-diameter ratio of the twin-screw extruder is (40 48):1, the screw speed of the twin-screw extruder is 250 600 r / min, and the temperatures of each screw barrel from the feed port to the die head of the twin-screw extruder are 160℃ 180℃, 180℃ 220℃, 200℃ 240℃, 220℃ 240℃, 220℃ 250℃, 220℃ 250℃, 220℃ 240℃, 220℃ 240℃, 200℃ 240℃, and 200℃ 240℃, respectively. The feeding speed is 100-1000 kg / h, and the vacuum degree is (-0.1)-0 MPa.

[0030] The melt treatment is injection molding, blow molding, or pultrusion.

[0031] The present invention also provides the application of the above-mentioned SAN / PA6 alloy material in oil-resistant packaging materials, such as skin care product packaging, beauty oil packaging, essential oil packaging, etc.

[0032] The present invention has the following advantages and effects compared with the prior art:

[0033] This invention provides a SAN / PA6 alloy material. By introducing PA6 into SAN, the solvent resistance of SAN is improved. SAN and PA6 have partial compatibility. By adding a compatibilizer and controlling the amount of compatibilizer, the compatibility between the two is improved without affecting solvent immersion swelling and discoloration. Solvent swelling resistance is improved by using a specific content of high-nitrile SAN, and discoloration is significantly reduced by selecting specific toughening agents, resulting in excellent overall performance. This invention also provides a method for preparing the SAN / PA6 alloy material. This method has simple operation steps and can achieve large-scale industrial production. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. 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.

[0035] <Preparation of Examples and Comparative Examples>

[0036] The raw materials used in the embodiments and comparative examples of this invention are all commercially available, but are not limited to these materials:

[0037] PA6 resin A: PA6 1022B, with a relative viscosity of 3.37, purchased from Ube Rubber Equipment, Japan;

[0038] PA6 Resin B: PA6 1030B, relative viscosity 4.08, purchased from Ube Rubber Equipment, Japan;

[0039] PA6 resin C: relative viscosity 2.5, grade M2500I, purchased from Xinhui Meida;

[0040] SAN Resin A: Based on the total mass of SAN resin, acrylonitrile content 35%, grade SAN 350N HW, purchased from Kumho Petrochemical;

[0041] SAN Resin B: Acrylonitrile content 30%, grade SAN 350N, purchased from Kumho;

[0042] SAN Resin C: Acrylonitrile content 25%, grade SAN2200, purchased from Formosa Plastics.

[0043] Toughening agent: Organosilicon-acrylate rubber, brand name SX-006, purchased from Mitsubishi, Japan.

[0044] Compatibilizer A: Styrene-N-phenylmaleimide-anhydrous maleic anhydride copolymer, brand name MS-NB, purchased from Denki Kagaku, Japan;

[0045] Compatibilizer B: ABS grafted with maleic anhydride, brand name ABS KT-2, purchased from Shenyang Ketong;

[0046] Antioxidant: Antioxidant 1010 and Antioxidant 168 were mixed at a mass ratio of 1:2 and purchased from Beijing Jiyi Chemical.

[0047] Lubricant: Pentaerythritol stearate, brand name PETS, purchased from Guangzhou Jiadelai Biochemical Technology Co., Ltd.

[0048] PBT: Grade PBTGX121, purchased from Sinopec;

[0049] ABS high-adhesion powder: grade HR-181, purchased from Kumho, South Korea.

[0050] The preparation methods of the embodiments and comparative examples of the present invention are as follows:

[0051] S1: Weigh each component according to the proportions in Table 1 and Table 3, premix them, and obtain the premix;

[0052] S2: The premix from step S1 is fed into a twin-screw extruder for melt blending and extrusion granulation to obtain SAN / PA6 alloy material.

[0053] The twin-screw extruder has a screw length-to-diameter ratio of 40:1. The barrel temperatures from the feed port to the die head are 160℃, 180℃, 240℃, 240℃, 240℃, 240℃, 240℃, 240℃, 240℃, and 230℃, respectively. The feeding speed is 400-600 kg / h, the vacuum degree is -0.1 MPa, and the screw speed is 300-500 r / min.

[0054] <Test Standards>

[0055] The performance testing standards for the various embodiments and comparative examples of this invention are as follows:

[0056] Performance testing

[0057] 1. Mass swelling degree: The test samples prepared in the above examples and comparative examples were recorded with an initial mass m0. They were then soaked in essential oil for 15 days. After soaking, the test samples were removed, the essential oil on the surface of the test samples was wiped dry, and then weighed and recorded as m. t Then calculate the mass swelling degree W(g / g) = (m t -m0) / m0;

[0058] 2. Color Difference Test: A spectrophotometer (X-Rite CI7000A) was used to measure the L, A, and B values ​​of each color plate of the test samples. The measurement aperture was 20mm, and the CIELABD 65 10° reflection mode was used. The initial sample was used as the colorimetric reference standard, and the sample after soaking in the essential oil for 15 days was used as the colorimetric sample. The colorimetric results were measured using the fluctuation range of ΔL / Δa / Δb / ΔE as the evaluation index. The total color difference value ΔE = (ΔL / Δa / Δb / ΔE) / Δb ... 2 +Δa 2 +Δb 2 ) 1 / 2 ΔL = L value of test sample - L value of standard sample, Δa = a value of test sample - a value of standard sample, Δb = b value of test sample - b value of standard sample.

[0059] Table 1. Formulations (parts by weight) for Examples 1-10

[0060]

[0061] Table 2. Performance test results of Examples 1-10

[0062]

[0063] Table 3. Comparative Examples 1-7 Formulations (parts by weight)

[0064] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 PA6 Resin A 25 25 25 25 15 PA6 resin C 25 PBT 25 ABS 10 ABS high-polymer powder 10 SAN resin A 35 35 35 35 35 45 SAN resin C 35 toughening agent 10 10 10 10 20 Compatibilizer A 5 5 5 5 5 5 Compatibilizer B 5 antioxidants 0.3 0.3 0.3 0.3 0.3 0.3 0.3 lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5

[0065] Table 4. Performance test results of Comparative Examples 1-7

[0066] project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Mass swelling degree 2.6％ 1.5％ 2.1％ 1.6％ 0.5％ 0.1％ 2.2％ Color difference ΔE 5.2 8.5 3.2 2.8 1.1 1.6 4.5

[0067] Compared with Example 1, Comparative Example 1 uses PBT instead of PA6 resin, which results in an increase in the mass swelling degree and color difference of Comparative Example 1.

[0068] Compared with Example 1, Comparative Example 2 used ABS high-adhesion powder instead of SAN resin, which resulted in an increase in the mass swelling degree and a greater color difference.

[0069] Compared with Example 1, Comparative Example 3 has an acrylonitrile content of less than 30% in the SAN resin, which leads to an increase in the mass swelling degree and color difference.

[0070] Compared with Example 1, Comparative Example 4, which uses PA6+ABS+SAN, also showed increased mass swelling and color difference, indicating that the combination of PA6+ABS+SAN cannot solve the problems of high mass swelling and color difference after essential oil soaking.

[0071] Compared with Example 1, Comparative Example 5 used PA6 resin with a viscosity of less than 3.4, which resulted in greater mass swelling and color difference.

[0072] Compared with Example 1, Comparative Example 6 uses ABS grafted with maleic anhydride compatibilizer, resulting in a large color difference.

[0073] Compared with Example 5, Comparative Example 7 had an excess of SAN resin, resulting in increased mass swelling and greater color difference.

[0074] The SAN / PA6 alloy material obtained by this invention can be widely used in oil-resistant packaging materials, especially suitable for skin care product packaging, beauty oil packaging, essential oil packaging, etc., and has broad market prospects and market benefits.

[0075] The above description is only a preferred embodiment of the present invention and is 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 SAN / PA6 alloy material, characterized in that, The components include the following parts by weight: SAN resin 25-58 parts; 24-50 parts of PA6 resin; 10-30 parts toughening agent; 2-5 parts compatibilizer; In the SAN resin, based on the total mass of the SAN resin, the mass content of acrylonitrile is 30-35%; the relative viscosity of PA6 resin is 3.2-4.

2. The compatibilizer is a styrene-N-phenylmaleimide-anhydrous maleic anhydride copolymer; The mass ratio of SAN resin to PA6 resin is (1-1.4):

1.

2. The SAN / PA6 alloy material according to claim 1, characterized in that, The components include the following parts by weight: 28-36 parts of SAN resin; 24-32 parts of PA6 resin; 10-30 parts toughening agent; 2-5 parts compatibilizer.

3. The SAN / PA6 alloy material according to claim 1, characterized in that, The toughening agent is an organosilicon-acrylate rubber.

4. The SAN / PA6 alloy material according to claim 1, characterized in that, It also includes the following components in parts by weight: 0.2-2 parts of auxiliary agent; The additives include any one or more of antioxidants or lubricants.

5. The SAN / PA6 alloy material according to claim 4, characterized in that, The antioxidant is at least one of copper salt-containing composite antioxidants, hindered phenolic antioxidants, and phosphite antioxidants; The lubricant is at least one of silicone lubricants, ester lubricants, amide lubricants, polyethylene lubricants, stearic acid lubricants, or fatty acid lubricants.

6. A method for preparing the SAN / PA6 alloy material according to any one of claims 1-5, characterized in that, Includes the following steps: S1: Weigh out each component according to the ratio, premix them, and obtain the premix; S2: The premix from step S1 is fed into an extruder for melt blending and extrusion granulation to obtain the SAN / PA6 alloy material.

7. The application of the SAN / PA6 alloy material according to any one of claims 1-5 in oil-resistant packaging materials.

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