San / pa6 alloy material, and preparation method therefor and use thereof

Abstract

An SAN / PA6 alloy material, which comprises the following components in parts by weight: 25-58 parts of an SAN resin, 24-50 parts of a PA6 resin, 10-30 parts of a flexibilizer and 2-5 parts of a compatilizer. By introducing the PA6 into the SAN, the solvent resistance of the SAN is improved. The SAN and the PA6 have partial compatibility, and the solvent resistance is not affected when the compatibility of the two is improved by adding the compatilizer and controlling the usage amount of the compatilizer. The solvent expansion resistance of the material is improved by means of a specific content of high-nitrile SAN; the discoloration property of the material is significantly reduced by selecting the specific flexibilizer; and the comprehensive performance is excellent.

Description

A SAN / PA6 alloy material and its preparation method and application Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and in particular to a SAN / PA6 alloy material and a preparation method and application thereof. Background Art

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

[0003] Essential oils are a general term for volatile, aromatic substances extracted from aromatic plants or aromatic animals. We've found that when using current ABS resins to package essential oils, ABS easily swells and exhibits noticeable discoloration. While 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 above-mentioned deficiencies or defects of the prior art, the present invention proposes a SAN / PA6 alloy material and a preparation method and application thereof.

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

[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.); 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 (for example, 2 parts, 3 parts, 4 parts, 5 parts, etc.); in the SAN resin, the mass content of acrylonitrile is greater than or equal to 30% (for example, 30%, 31%, 32%, 33%, 34%, 35%, 36%, etc.) based on the total mass of the SAN resin; and the relative viscosity of the PA6 resin is 3.2-4.2 (for example, 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] The SAN / PA6 alloy material of the present invention is added with SAN resin and PA6 resin at the same time. By modifying the PA6 resin with a specific content of SAN resin, the obtained SAN / PA6 alloy has strong coloring and significantly improves its discoloration phenomenon after moisture absorption.

[0009] As a preferred solution, the mass ratio of the SAN resin to the PA6 resin is (1-1.4):1.

[0010] As a preferred solution, the mass content of acrylonitrile in the SAN resin is 30-35% based on the total mass of the SAN resin.

[0011] Currently, the acrylonitrile content of most commercial SAN resins is between 24-27% by weight. The SAN resin selected in this application is a high-nitrile SAN resin, with an acrylonitrile content of no less than 30% by weight. Higher acrylonitrile content in SAN resin increases its polarity, increasing the difference in solubility parameters with essential oils, reducing its compatibility with essential oils. This results in improved swelling and discoloration properties when soaked in essential oils. The synergistic effects of the various components in this application contribute to the resulting PA6 resin's enhanced oil resistance, solvent resistance, and stability, resulting in excellent overall performance.

[0012] As a preferred solution, the toughening agent is silicone-acrylate rubber.

[0013] The inventors of the present application have also discovered that selecting a suitable toughening agent can significantly reduce the yellowing problem after solvent immersion.

[0014] As a preferred embodiment, the compatibilizer is styrene-N-phenylmaleimide-anhydrous maleic anhydride copolymer.

[0015] As a preferred embodiment, the SAN / PA6 alloy material further comprises the following components in parts by weight:

[0016] 0.2-2 parts of additives;

[0017] The auxiliary agent includes any one or more of antioxidants or lubricants.

[0018] As a preferred embodiment, the following components in parts by weight are also included:

[0019] 0.2-1 part of antioxidant;

[0020] 0.5-1 part of lubricant;

[0021] The antioxidant is at least one of a copper salt composite antioxidant, a hindered phenol antioxidant, and a phosphite antioxidant;

[0022] The lubricant includes at least one of a silicone lubricant, an ester lubricant, an amide lubricant, a polyethylene lubricant, a stearic acid lubricant or a fatty acid lubricant.

[0023] The mass percentage of SAN resin in the alloy material is not less than 18%.

[0024] The present invention is achieved through the following technical solutions:

[0025] A method for preparing a SAN / PA6 alloy material comprises the following steps:

[0026] S1: Weigh and pre-mix the components according to the ratio to obtain a premix;

[0027] S2: The premix of step S1 is put into an extruder for melt blending and extrusion granulation to obtain the SAN / PA6 alloy material.

[0028] As a preferred embodiment, further, the extruder is a twin-screw extruder, the screw aspect ratio of the twin-screw extruder is (40-48): 1, the screw speed of the twin-screw extruder is 250-600r / min, and the barrel temperatures of the twin-screw extruder from the feeding port to the die are 160℃-180℃, 180℃-220℃, 200℃-240℃, 220℃-240℃, 220℃-250℃, 220℃-250℃, 220℃-240℃, 220℃-240℃, 200℃-240℃, 200℃-240℃, the feeding rate is 100-1000kg / h, and the vacuum degree is (-0.1)-0MPa.

[0029] The melt processing is injection molding, blow molding or pultrusion.

[0030] The present invention also provides the use 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.

[0031] The present invention has the following advantages and effects compared to the prior art:

[0032] The present invention provides a SAN / PA6 alloy material that improves SAN's solvent resistance by introducing PA6 into the SAN. SAN and PA6 are partially compatible. By adding a compatibilizer and controlling the amount of the compatibilizer, the compatibility between the two is improved while maintaining solvent swelling and discoloration resistance. By using a specific content of high-nitrile SAN, the material's solvent swelling resistance is enhanced, while by selecting a specific toughening agent, discoloration is significantly reduced, resulting in excellent overall performance. The present invention also provides a method for preparing the SAN / PA6 alloy material, which has simple steps and can be industrialized and mass-produced. DETAILED DESCRIPTION

[0033] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0034] <Preparation of Examples and Comparative Examples>

[0035] The raw materials used in the examples and comparative examples of the present invention are all commercially available, but are not limited to these materials:

[0036] PA6 resin A: PA6 1022B, relative viscosity 3.37, purchased from UBE, Japan;

[0037] PA6 resin B: PA6 1030B, relative viscosity 4.08, purchased from UBE, Japan;

[0038] PA6 resin C: relative viscosity is 2.5, brand is M2500I, purchased from Xinhui Meida;

[0039] SAN resin A: Based on the total mass of SAN resin, the acrylonitrile content is 35%, the brand is SAN 350 N HW, purchased from Kumho Petrochemical;

[0040] SAN resin B: acrylonitrile content of 30%, brand SAN 350 N, purchased from Kumho;

[0041] SAN resin C: acrylonitrile content of 25%, brand SAN2200, purchased from Formosa Chemical Corporation;

[0042] Toughening agent: silicone-acrylate rubber, brand SX-006, purchased from Mitsubishi, Japan.

[0043] Compatibilizer A: styrene-N-phenylmaleimide-anhydrous maleic anhydride copolymer, brand MS-NB, purchased from Nippon Denki Kagaku;

[0044] Compatibilizer B: ABS grafted maleic anhydride, brand ABS KT-2, purchased from Shenyang Ketong;

[0045] Antioxidant: Antioxidant 1010 and antioxidant 168 were mixed in a mass ratio of 1:2 and purchased from Beijing Jiyi Chemical;

[0046] Lubricant: Pentaerythritol stearate, brand PETS, purchased from Guangzhou Jiadele Biochemical Technology Co., Ltd.

[0047] PBT: brand PBTGX121, purchased from Sinopec;

[0048] ABS high glue powder: brand HR-181, purchased from Kumho, South Korea.

[0049] The preparation methods of the embodiments of the present invention and the comparative examples are as follows:

[0050] S1: According to the ratios in Table 1 and Table 3, weigh and pre-mix the components to obtain a premix;

[0051] S2: The premix of step S1 is put into a twin-screw extruder for melt blending and extrusion granulation to obtain a SAN / PA6 alloy material.

[0052] The screw length-to-diameter ratio of the twin-screw extruder is 40:1, and the barrel temperatures of the twin-screw extruder from the feeding port to the die head are 160°C, 180°C, 240°C, 240°C, 240°C, 240°C, 240°C, 240°C, 230°C, respectively; the feeding rate is 400-600kg / h, the vacuum degree is -0.1MPa, and the screw speed of the twin-screw extruder is 300-500r / min.

[0053] <Test Standard>

[0054] The performance test standards of the embodiments and comparative examples of the present invention are as follows:

[0055] Performance Testing

[0056] 1. Mass swelling degree: The test samples prepared in the above examples and comparative examples were taken, and the initial mass m0 was recorded. Then, the test samples were soaked in essential oil for 15 days. The soaked test samples were taken out, the essential oil on the surface of the test samples was wiped dry, and the weight was recorded as m0. t , then calculate the mass swelling degree W (g / g) = (m t -m0) / m0;

[0057] 2. Color difference test: Use a spectrophotometer (X-Rite CI-7000A) to measure the L, A, and B values ​​of each color plate of the test sample. The measurement observation aperture is 20mm, and the CIEL ABD65 10° reflection mode is used. The test sample at the beginning of sampling is used as the colorimetric reference standard, and the test sample after soaking in essential oil for 15 days is used as the colorimetric sample. The colorimetric results are measured by the fluctuation range of ΔL / Δa / Δb / ΔE. The total color difference value ΔE = (ΔL 2 +Δa 2 +Δb 2 ) 1 / 2 , ΔL = test sample L value - standard sample L value, Δa = test sample a value - standard sample a value, Δb = test sample b value - standard sample b value.

[0058] Table 1. Formula of Examples 1-10 (parts by weight)

[0059] Table 2. Performance test results of Examples 1-10

[0060] Table 3. Comparative Examples 1-7 formulations (parts by weight)

[0061] Table 4. Performance test results of comparative examples 1-7

[0062] Compared with Example 1, Comparative Example 1 uses PBT instead of PA6 resin, which results in an increase in the mass swelling degree and a larger color difference of Comparative Example 1.

[0063] Compared with Example 1, Comparative Example 2 uses ABS high-rubber powder instead of SAN resin, which results in an increase in the mass swelling degree and a larger color difference of Comparative Example 2.

[0064] Compared with Example 1, in Comparative Example 3, the mass content of acrylonitrile in the SAN resin is lower than 30%, resulting in an increase in the mass swelling degree and a larger color difference in Comparative Example 3.

[0065] Compared with Example 1, Comparative Example 4 uses PA6+ABS+SAN, and its mass swelling degree and color difference are also increased, indicating that the combination of PA6+ABS+SAN cannot solve the problems of high mass swelling degree and color difference after essential oil immersion.

[0066] Compared with Example 1, Comparative Example 5 uses PA6 resin with a viscosity lower than 3.4, which leads to greater mass swelling and color difference.

[0067] Compared with Example 1, Comparative Example 6 uses ABS grafted maleic anhydride compatibilizer, which leads to a large color difference.

[0068] Compared with Example 5, in Comparative Example 7, the amount of SAN resin was excessive, the mass swelling degree increased, and the color difference became larger.

[0069] The SAN / PA6 alloy material prepared by the present 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.

[0070] 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 in the scope of protection of the present invention.

Claims

1. A SAN / PA6 alloy material, characterized in that, Comprising the following components in parts by weight: 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%; the relative viscosity of the PA6 resin is 3.2 - 4.

2.

2. The SAN / PA6 alloy material according to claim 1, wherein Comprising the following components in parts by weight:

3. The SAN / PA6 alloy material according to claim 1, wherein the mass ratio of the SAN resin to the PA6 resin is (1 - 1.4):

1.

4. The SAN / PA6 alloy material according to claim 1, wherein in the SAN resin, based on the total mass of the SAN resin, the mass content of acrylonitrile is 30 - 35%.

5. The SAN / PA6 alloy material according to claim 1, wherein the toughening agent is a silicone-acrylate rubber.

6. The SAN / PA6 alloy material according to claim 1, wherein the compatibilizer is a styrene-N-phenylmaleimide-maleic anhydride copolymer.

7. The SAN / PA6 alloy material according to claim 1, wherein It further includes the following components in parts by weight: 0.2 - 2 parts of an auxiliary agent; the auxiliary agent includes any one or several of an antioxidant or a lubricant.

8. The SAN / PA6 alloy material according to claim 7, wherein the antioxidant is at least one of a copper salt-based compound antioxidant, a hindered phenol antioxidant, and a phosphite antioxidant; the lubricant is at least one of a silicone lubricant, an ester lubricant, an amide lubricant, a polyethylene lubricant, a stearic acid lubricant, or a fatty acid lubricant.

9. A method for preparing the SAN / PA6 alloy material according to any one of claims 1-8, characterized in that, It includes the following steps: S1: Weigh each component according to the ratio, pre-mix them to obtain a premix; S2: Put the premix of step S1 into an extruder, carry out melt blending and extrusion granulation to obtain the SAN / PA6 alloy material.

10. The application of the SAN / PA6 alloy material according to any one of claims 1 - 8 in an oil-resistant packaging material.

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