PMMA composite material and preparation method thereof

Abstract

The invention provides a PMMA composite material and a preparation method thereof. The PMMA composite material is prepared from the following components in parts by weight: 45 to 85 parts of PMMA, 10 to 35 parts of styrene-acrylonitrile copolymer and 3 to 20 parts of amide polymer, the amide polymer comprises polyamide and / or polyether amide; the refractive indexes of the polyamide and the polyether amide are respectively and independently 1.51-1.56, and the mass percentage content of acrylonitrile in the styrene-acrylonitrile copolymer is less than or equal to 26%. The specific composition of the PMMA composite material is designed, and the styrene-acrylonitrile copolymer and the amide polymer with the specific refractive index are further introduced into the PMMA matrix, so that the PMMA composite material has relatively high ethanol tolerance and relatively good mechanical properties while the transparency of the PMMA composite material is ensured, and the PMMA composite material can be used for preparing medical equipment.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer composites, and particularly relates to a PMMA composite material and a preparation method thereof. Background Art

[0002] PMMA is an organic polymer material polymerized from "methyl methacrylate monomer Methyl Methacrylate (MMA)". It has excellent transparency, weather resistance, and coloring properties. Its surface has high hardness and good scratch resistance, and is widely used in various fields, especially the medical device industry, and has been increasingly used due to its excellent transparency.

[0003] Ethanol, as the main component of commonly used hospital disinfectants, has a wide application in medical devices; however, as a polyester material, PMMA has poor tolerance to ethanol. Especially under the action of stress, it is easy to cause cracks and cracking in the product, resulting in the failure of the product; at the same time, the PMMA material itself is relatively brittle, and it is inevitable to be broken due to collision during use, resulting in failure. Therefore, to solve the above problems, materials such as PET, PC, and MABS are currently used. These materials have their own pain points. For example, PET has limitations on the thickness of the parts, difficult molding, and easy scratching; PC and MABS have poor tolerance to alcohol and are prone to cracking, etc.; at the same time, the transparency is significantly different from that of PMMA.

[0004] Therefore, how to provide a PMMA composite material with high tolerance to ethanol and high mechanical properties has become an urgent technical problem to be solved at present. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a PMMA composite material and a preparation method thereof. The present invention designs the specific composition of the PMMA composite material, and further introduces styrene-acrylonitrile copolymer and amide polymer with a specific refractive index into the PMMA matrix. While ensuring the transparency of the PMMA composite material, the PMMA composite material has high ethanol tolerance and good mechanical properties, and can be used to prepare medical devices.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a PMMA composite material, and the PMMA composite material comprises the following components in parts by weight:

[0008] 45 - 85 parts of PMMA;

[0009] 10 - 35 parts of styrene-acrylonitrile copolymer;

[0010] 3 - 20 parts of amide polymers;

[0011] The amide polymers include polyamides and / or polyether amides;

[0012] The refractive indices of the polyamides and the polyether amides are independently 1.51 - 1.56;

[0013] The mass percentage of acrylonitrile in the styrene - acrylonitrile copolymer is ≤26%.

[0014] By designing the specific composition of the PMMA composite material, and further introducing a styrene - acrylonitrile copolymer and an amide polymer with a specific refractive index into the PMMA matrix, the present invention prepares a PMMA composite material with high ethanol tolerance and good mechanical properties, which can be used for preparing medical devices.

[0015] Furthermore, by designing the specific selection of the polyamide polymers, through the use of polyamides and / or polyether amides, the PMMA composite material has good ethanol tolerance; by using the styrene - acrylonitrile copolymer and controlling the refractive indices of the polyamides and polyether amides within a specific range, a PMMA composite material with high transparency is prepared. If the refractive indices of the polyamides and polyether amides are too small or too large, the haze of the PMMA composite material will be large.

[0016] In the present invention, by controlling the mass percentage of acrylonitrile in the styrene - acrylonitrile copolymer within a specific range, a PMMA composite material with excellent comprehensive properties is prepared. If the mass percentage of acrylonitrile in the styrene - acrylonitrile copolymer is too large, the transparency of the PMMA composite material will be poor.

[0017] In the present invention, the weight parts of PMMA in the PMMA composite material can be 45 parts, 47 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 84 parts or 85 parts, etc.

[0018] The weight parts of the styrene - acrylonitrile copolymer in the PMMA composite material can be 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 27 parts, 30 parts, 33 parts or 35 parts, etc.

[0019] The weight parts of the amide polymers in the PMMA composite material can be 3 parts, 5 parts, 7 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts, etc.

[0020] In the present invention, the refractive indices of the polyamide and the polyetheramide are each independently 1.510 - 1.560, and can be, for example, 1.510, 1.512, 1.516, 1.519, 1.520, 1.521, 1.524, 1.527, 1.530, 1.535, 1.540, 1.545, 1.550, 1.552, 1.555, 1.558 or 1.560, etc.

[0021] In the present invention, the mass percentage content of acrylonitrile in the styrene - acrylonitrile copolymer is ≤26%, and can be, for example, 20%, 21%, 22%, 23%, 24%, 25% or 26%, etc.

[0022] In the present invention, the mass percentage content of acrylonitrile in the styrene - acrylonitrile copolymer is determined by elemental analysis. The specific method is: by elemental analysis, measure the mass fraction X of N element, and the acrylonitrile content can be obtained by calculating according to the following formula: acrylonitrile mass percentage = 53X / 14.

[0023] It should be noted that in the present invention, there is no special limitation on the range of the weight - average molecular weight of the styrene - acrylonitrile copolymer. Commonly used styrene - acrylonitrile copolymers in the art are applicable, and its weight - average molecular weight includes, by way of example and not limitation, 40,000 - 150,000, and can be, for example, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 110,000, 120,000, 130,000, 140,000 or 150,000, etc.

[0024] In the present invention, the test method for the weight - average molecular weight of the styrene - acrylonitrile copolymer is to test by using GPC.

[0025] In the present invention, the test method for the refractive index of the polyamide is: injection - mold the polyamide into a square plate with dimensions of 10 cm × 10 cm × 4 mm (i.e., length and width are both 10 cm and thickness is 4 mm), and test according to the ASTM D542 - 2017 standard method.

[0026] The test method for the refractive index of the polyetheramide is: injection - mold the polyetheramide into a square plate with dimensions of 10 cm × 10 cm × 4 mm (i.e., length and width are both 10 cm and thickness is 4 mm), and test according to the ASTM D542 - 2017 standard method.

[0027] In the present invention, based on the mass percentage content of the PMMA composite material being 100%, the mass percentage content of the amide - type polymer is 2 - 20% (for example, it can be 2%, 3%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20%, etc.), and preferably 3 - 18%.

[0028] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved.

[0029] As a preferred technical solution of the present invention, the melt index of the PMMA under the conditions of 230°C and 3.8 kg is 1-17 g / 10 min, and can be, for example, 1 g / 10 min, 2 g / 10 min, 3 g / 10 min, 4 g / 10 min, 5 g / 10 min, 6 g / 10 min, 7 g / 10 min, 8 g / 10 min, 9 g / 10 min, 10 g / 10 min, 11 g / 10 min, 12 g / 10 min, 13 g / 10 min, 14 g / 10 min, 15 g / 10 min, 16 g / 10 min or 17 g / 10 min, etc.

[0030] In the present invention, the test method for the melt index of PMMA refers to ISO 1133-2022.

[0031] As a preferred technical solution of the present invention, the mass percentage content of acrylonitrile in the styrene-acrylonitrile copolymer is 21-26%, and can be, for example, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5% or 26%, etc.

[0032] If the mass percentage content of acrylonitrile in the styrene-acrylonitrile copolymer is too small, the ethanol tolerance of the PMMA composite material is poor; if the mass percentage content of acrylonitrile in the styrene-acrylonitrile copolymer is too large, the transparency of the PMMA composite material is poor.

[0033] As a preferred technical solution of the present invention, the polyamide includes transparent polyamide.

[0034] The refractive index of the transparent polyamide is 1.510-1.560 (for example, it can be 1.510, 1.512, 1.516, 1.519, 1.520, 1.521, 1.524, 1.527, 1.530, 1.535, 1.540, 1.545, 1.550, 1.552, 1.555, 1.558 or 1.560, etc.).

[0035] As a preferred technical solution of the present invention, the refractive index of the polyetheramide is 1.510-1.520, and can be, for example, 1.510, 1.511, 1.512, 1.513, 1.514, 1.515, 1.516, 1.517, 1.518, 1.519 or 1.520, etc.

[0036] In the present invention, the comprehensive properties of the PMMA composite material are further improved by using a transparent polyamide with a specific refractive index and / or a polyether amide with a specific refractive index.

[0037] It should be noted that the present invention has no special restrictions on the viscosity of the polyamide and the polyether amide, and the commonly used polyamides and polyether amides in the art are applicable.

[0038] As a preferred technical solution of the present invention, the amide polymer includes a combination of a polyamide and a polyether amide.

[0039] Preferably, the mass ratio of the polyamide to the polyether amide is 1:(0.5 - 2.0), and for example, it can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2.0, etc.

[0040] In the present invention, by using the polyamide and the polyether amide together and controlling the mass ratio of the two within a specific range, the comprehensive properties of the PMMA composite material are further improved.

[0041] As a preferred technical solution of the present invention, the PMMA composite material further includes 0.01 - 1 part by weight of an antioxidant, and for example, it can be 0.01 part by weight, 0.02 part by weight, 0.05 part by weight, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight or 1 part by weight.

[0042] Preferably, the antioxidant is selected from any one or a combination of at least two of hindered phenol antioxidants, phosphite antioxidants, metal alkyl thiophosphate antioxidants, carbamate antioxidants or organic sulfur antioxidants, and more preferably a phosphoric acid ester antioxidant.

[0043] It should be noted that the present invention has no special restrictions on the specific selection of hindered phenol antioxidants, phosphite antioxidants, metal alkyl thiophosphate antioxidants, carbamate antioxidants, and organic sulfur antioxidants, and the commonly used antioxidants of the above types in the art are applicable.

[0044] As a preferred technical solution of the present invention, the PMMA composite material further includes 0.01 - 1 part by weight of a lubricant, and for example, it can be 0.01 part by weight, 0.02 part by weight, 0.05 part by weight, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight or 1 part by weight.

[0045] Preferably, the lubricant is selected from any one or a combination of at least two of amide lubricants, polysiloxane lubricants, stearate lubricants, PE wax or PP wax.

[0046] It should be noted that the present invention has no special restrictions on the specific selection of amide lubricants, polysiloxane lubricants, and stearate lubricants, and the above-mentioned types of lubricants commonly used in the art are applicable.

[0047] In a second aspect, the present invention provides a method for preparing the PMMA composite material as described in the first aspect, and the preparation method includes the following steps:

[0048] Mix and melt granulate the components of the PMMA composite material to obtain the PMMA composite material.

[0049] The method of melt granulation includes extrusion and granulation using a twin-screw extruder.

[0050] Preferably, the temperature of the twin-screw extruder is divided into ten zones, the temperature of the first to second zones is 120°C to 170°C (for example, it can be 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C or 170°C, etc.), the temperature of the third to fifth zones is 200°C to 240°C (for example, it can be 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C or 240°C, etc.), and the temperature of the sixth to tenth zones is 170°C to 190°C (for example, it can be 170°C, 172°C, 174°C, 176°C, 178°C, 180°C, 182°C, 184°C, 186°C, 188°C or 190°C, etc.).

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] (1) By designing the specific composition of the PMMA composite material, and further introducing styrene-acrylonitrile copolymer and polyamide with a specific refractive index and / or polyether amide with a specific refractive index into the PMMA matrix, while ensuring the transparency of the PMMA composite material, the PMMA composite material has high ethanol tolerance and good mechanical properties, and can be used for preparing medical devices.

[0053] (2) By further selecting a combination of polyamide and polyether amide as the amide polymer, and controlling the mass ratio of polyamide and polyether amide and their refractive indices within specific ranges respectively, the comprehensive performance of the PMMA composite material is further improved. Specific Embodiments

[0054] To facilitate the understanding of the present invention, the following embodiments are listed. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0055] The sources of some components in the examples and comparative examples are shown in Table 1 below:

[0056] Table 1

[0057]

[0058]

[0059] Examples 1 - 16, Comparative Examples 1 - 5

[0060] Examples 1 - 16 and Comparative Examples 1 - 5 respectively provide a PMMA composite material. The specific composition of the PMMA composite material is shown in Tables 2 - 4 below. The dosages of each component in Tables 2 - 4 are all in parts by weight;

[0061] The preparation method of the PMMA composite material is as follows:

[0062] Mix the components of the PMMA composite material, and use a twin - screw extruder for extrusion and pelletizing to obtain the PMMA composite material;

[0063] Among them, the temperature of the twin - screw extruder is divided into ten zones, and the temperatures of the first zone to the tenth zone are 122°C, 150°C, 200°C, 220°C, 240°C, 240°C, 235°C, 230°C, 230°C, 230°C in sequence.

[0064] Comparative Example 6

[0065] This comparative example provides a PMMA material, and the PMMA material is PMMA - 2 in Table 1.

[0066] Test the properties of the PMMA composite materials or PMMA materials provided in the above examples and comparative examples. The specific test methods are as follows:

[0067] Transparency test: For a 2.0 - mm - thick high - gloss square plate (when the light incident angle is 80°, the glossiness of the square plate is not less than 90%), test the light transmittance and haze of the material according to the GB / T 2410 - 2008 standard;

[0068] Notched impact strength: According to the requirements of ISO 180 - 2019, injection - mold a standard A - type notched impact specimen and test the notched impact strength of the material;

[0069] Ethanol tolerance: For injection-molded ISO standard mechanical splines, referring to the ISO 22088-1:2006 standard, using the bent strip method, fix the spline on a standard fixture with a curvature of 1%, then soak the bent and fixed spline in absolute ethanol, and observe whether the spline breaks. If the sample does not break after observing for 0.5 h, adjust to observe whether the spline breaks every 24 h.

[0070] Table 2

[0071]

[0072] Table 3

[0073]

[0074]

[0075] Table 4

[0076]

[0077]

[0078] As can be seen from the above, the present invention designs the specific composition of the PMMA composite material, and further introduces styrene-acrylonitrile copolymer and amide polymer with a specific refractive index into the PMMA matrix. While ensuring the transparency of the PMMA composite material, the PMMA composite material has high ethanol tolerance and good mechanical properties, and can be used for preparing medical devices. The light transmittance of the PMMA composite material is ≥78%, specifically 78 - 88.8%, the haze is ≤32.1%, specifically 10.5 - 32.1%, the notched impact strength is 3.0 - 5.1 MPa, and no breakage is found after 48 h of ethanol tolerance test.

[0079] From Example 1 and Examples 5 - 10 and Comparative Example 3, it can be seen that the present invention further improves the comprehensive performance of the PMMA composite material by controlling the mass percentage content of acrylonitrile in the styrene-acrylonitrile copolymer within a specific range and controlling the refractive index of the polyether amide to be 1.510 - 1.520. Its light transmittance is ≥85.3%, specifically 85.3 - 88.8%, and the haze is ≤17.3%, specifically 10.5 - 17.3%.

[0080] From Example 1 and Examples 11 - 16, it can be seen that the present invention further optimizes and improves the comprehensive performance of the PMMA composite material by controlling the synergy of the polyamide and the polyether amide and controlling their mass ratio within a specific range.

[0081] It can be seen from Examples 1-16, Comparative Examples 1-2, and Comparative Examples 3-7 that the present invention prepares a PMMA composite material with excellent comprehensive properties by controlling the amount of styrene-acrylonitrile copolymer within a specific range and combining it with an amide polymer having a specific refractive index.

[0082] In summary, by designing the specific composition of the PMMA composite material and further introducing a styrene-acrylonitrile copolymer and an amide polymer with a specific refractive index into the PMMA matrix, the present invention ensures the transparency of the PMMA composite material while endowing it with high ethanol tolerance and good mechanical properties, and it can be used for preparing medical devices.

[0083] The applicant declares that the present invention uses the above examples to illustrate the detailed process flow of the present invention, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A PMMA composite material, characterized in that: The PMMA composite material comprises the following components in parts by weight: PMMA 45-85 parts; 10-35 parts of styrene-acrylonitrile copolymer; 3-20 parts of amide polymer; The amide polymer includes polyamide and / or polyetheramide; The refractive index of the polyamide and the polyetheramide is independently 1.510-1.560; The mass percentage of acrylonitrile in the styrene-acrylonitrile copolymer is ≤26%.

2. The PMMA composite material according to claim 1, characterized in that: The PMMA has a melting index of 1-17 g / 10 min at 230° C. and 3.8 kg.

3. The PMMA composite material according to claim 1, characterized in that: The mass percentage of acrylonitrile in the styrene-acrylonitrile copolymer is 21-26%.

4. The PMMA composite material according to claim 1, characterized in that: The polyamide includes transparent polyamide.

5. The PMMA composite material according to claim 1, characterized in that: The refractive index of the polyetheramide is 1.510-1.

520.

6. The PMMA composite material according to claim 1, characterized in that: The amide polymer includes a combination of polyamide and polyetheramide.

7. The PMMA composite material according to claim 6, characterized in that: The mass ratio of the polyamide to the polyether amide is 1:(0.5-2.0).

8. The PMMA composite material according to claim 1, characterized in that: The PMMA composite material also includes 0.01-1 parts by weight of an antioxidant.

9. The PMMA composite material according to claim 1, characterized in that: The PMMA composite material also includes 0.01-1 parts by weight of lubricant.

10. A method for preparing a PMMA composite material according to any one of claims 1 to 9, characterized in that: The preparation method comprises the following steps: The components of the PMMA composite material are mixed and melt-granulated to obtain the PMMA composite material.

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