PP composite material, preparation method and application thereof

Abstract

The application discloses a PP composite material and a preparation method and application thereof, and belongs to the technical field of high polymer materials; the PP composite material provided by the application comprises the following components in parts by mass: 58-82 parts of PP, 8-32 parts of HDPE, 1-10 parts of polypropylene grafted maleic anhydride, 1-10 parts of polypropylene grafted styrene, 3-12 parts of sheet-shaped nano filler, 0.5-2.5 parts of ultraviolet absorber and 0.5-2.5 parts of light stabilizer; the grafting rate of the polypropylene grafted styrene is greater than or equal to 10%, and the grafting rate of the polypropylene grafted maleic anhydride is greater than or equal to 1.2%; the obtained PP composite material has excellent weather resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a PP composite material and a preparation method and application thereof. BACKGROUND

[0002] The weather-resistant PP material is widely used in the automobile, household appliance, home furnishing and decoration industries, but the PP extruded plate still has the problems of low performance retention rate and poor color stability in the outdoor equipment and outdoor building fields. The main reason is that the non-polar PP has low compatibility with the polar weather-resistant agent, filler and additive in the ordinary weather-resistant PP, and the color powder and additive escape during outdoor use, resulting in the decrease of the mechanical properties of the material and the large color difference. SUMMARY

[0003] The application aims to overcome the defects of the prior art and provide a PP composite material with excellent mechanical property retention rate and color stability after long outdoor use, i.e., the PP composite material with excellent weather resistance, and a preparation method and application thereof.

[0004] To achieve the above-mentioned purpose, in the first aspect of the application, the application provides a PP composite material, which comprises the following components by mass fraction:

[0005] 58-82 parts of PP, 8-32 parts of HDPE, 1-10 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 1-10 parts of polypropylene grafted styrene (PP-g-St), 3-12 parts of sheet-shaped nano filler, 0.5-2.5 parts of ultraviolet absorber and 0.5-2.5 parts of light stabilizer.

[0006] The grafting rate of the polypropylene grafted styrene is greater than or equal to 10%, and the grafting rate of the polypropylene grafted maleic anhydride is greater than or equal to 1.2%.

[0007] The PP composite provided by the application has excellent comprehensive effect between components by selecting appropriate mass fractions of components, specifically, in the first aspect, the application selects a sheet-shaped nano filler and polypropylene grafted maleic anhydride and polypropylene grafted styrene with a specific grafting rate range as a compatibilizer, the bonding force of the sheet-shaped nano filler and PP can be significantly improved, under a specified stretching speed, the sheet-shaped nano filler rotates to an oriented conformation along the stretching direction, further improving the absorption and reflection of the sheet-shaped nano filler to ultraviolet rays, thereby improving the ultraviolet resistance of the product, and the mechanical property retention rate is high under ultraviolet irradiation. In the second aspect, the application selects PP resin and HDPE resin for use, which can avoid Brownian motion of the sheet-shaped nano filler, thereby avoiding reduction of the oriented conformation of the sheet-shaped nano filler, thereby improving the stability of the product and ensuring the weather resistance of the product. In the third aspect, the application selects PP resin and HDPE resin for compounding, and simultaneously uses polypropylene grafted maleic anhydride and polypropylene grafted styrene with a specific grafting rate range as a compatibilizer, which can effectively improve the dispersion effect of the ultraviolet absorber and the light stabilizer in the resin matrix, avoid precipitation and escape of the ultraviolet absorber and the light stabilizer, thereby further improving the mechanical property retention rate and color stability of the product under ultraviolet irradiation.

[0008] Exemplarily, the PP can be any point value or any two-point range value between 58-82 parts, such as 60-80 parts, or 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, etc.; the HDPE can be any point value or any two-point range value between 8-32 parts, such as 10-30 parts, or 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, etc.; the polypropylene grafted maleic anhydride can be any point value or any two-point range value between 1-10 parts, such as 2-8 parts, or 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.; the polypropylene grafted styrene can be any point value or any two-point range value between 1-10 parts, such as 2-8 parts, or 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.; the sheet-shaped nano filler can be any point value or any two-point range value between 3-12 parts, such as 5-10 parts, or 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, etc.; the ultraviolet absorber can be any point value or any two-point range value between 0.5-2.5, such as 0.7-2.2 parts, or 0.5 parts, 0.7 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, etc.; the light stabilizer can be any point value or any two-point range value between 0.5-2.5, such as 0.7-2.2 parts, or 0.5 parts, 0.7 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, etc.

[0009] Preferably, the mass percentage of the PP resin in the PP composite material is ≥45%.

[0010] More preferably, the mass percentage of the PP resin in the PP composite material is 58-72%.

[0011] It should be noted that the grafting rate of the polypropylene grafted styrene is obtained by infrared spectrometer method; and the grafting rate of the polypropylene grafted maleic anhydride is obtained by acid-base titration method.

[0012] Exemplarily, the grafting rate of the polypropylene grafted styrene can be any point value or any two-point range value ≥10%, such as 10-15%, 10-18%, 10-12%, etc., or 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, etc.

[0013] Exemplarily, the grafting rate of the polypropylene grafted maleic anhydride can be any point value or any two-point range value between 1.2% and 2.0%, such as 1.2-1.8%, 1.2-2.0%, 1.4-1.8%, etc., or can be 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, etc.

[0014] Preferably, the grafting rate of the polypropylene grafted styrene is 12-15%.

[0015] Preferably, the grafting rate of the polypropylene grafted maleic anhydride is 1.4-1.8%.

[0016] The present application researches and finds that the grafting rate of the polypropylene grafted styrene and the polypropylene grafted maleic anhydride not only affects the compatibility between PP and HDPE, but also affects the dispersibility and stability of the sheet-shaped nano filler, the ultraviolet absorber and the light stabilizer in the resin matrix, thereby affecting the weather resistance of the product; when the grafting rate of the polypropylene grafted styrene and the polypropylene grafted maleic anhydride is further selected to be within the above range, the weather resistance of the obtained product is better.

[0017] It should be noted that the polypropylene grafted styrene can be obtained by market or self-made. Exemplarily, the polypropylene grafted styrene can be prepared by a melt grafting method.

[0018] As a preferred embodiment of the PP composite material of the present application, the PP composite material comprises the following components in parts by mass: 65-70 parts of PP, 18-23 parts of HDPE, 3-5 parts of polypropylene grafted maleic anhydride, 3-5 parts of polypropylene grafted styrene, 5-7 parts of sheet-shaped nano filler, 1-1.5 parts of ultraviolet absorber, and 1-1.5 parts of light stabilizer.

[0019] The present application researches and finds that the parts by mass of the components in the PP composite material will affect the comprehensive performance of the product; when the parts by mass of the components are further selected to be within the above range, the comprehensive performance of the obtained product is better.

[0020] As a preferred embodiment of the PP composite material of the present application, the average diameter of the sheet-shaped nano filler is 30-100 nm.

[0021] It should be noted that the average diameter of the sheet-shaped nano filler is obtained by scanning electron microscope test.

[0022] Exemplarily, the average diameter of the sheet-shaped nano filler can be any point value or any two-point range value between 30 nm and 100 nm, such as 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc.

[0023] As a preferred embodiment of the PP composite material according to the present application, the sheet-shaped nano filler comprises at least one of sheet-shaped nano zinc oxide and sheet-shaped nano titanium dioxide.

[0024] The present application finds that, under the action of polypropylene grafted styrene and polypropylene grafted maleic anhydride at a specific grafting rate range of the sheet-shaped nano filler, the bonding force of the sheet-shaped nano filler to the resin matrix is improved, and the sheet-shaped nano filler can also improve the absorption and reflection of ultraviolet rays, and especially when the sheet-shaped nano filler comprises at least one of sheet-shaped nano zinc oxide and sheet-shaped nano titanium dioxide, the comprehensive performance of the product is better.

[0025] As a preferred embodiment of the PP composite material according to the present application, the melt index of the PP at 230℃ / 2.16kg is 0.01-4g / 10min.

[0026] It should be noted that the melt index of the PP at 230℃ / 2.16kg is tested according to ISO 1133-2011.

[0027] Exemplarily, the melt index of the PP at 230℃ / 2.16kg can be any point value or any two-point range value between 0.01-4g / 10min, such as 0.01g / 10min, 0.05g / 10min, 0.1g / 10min, 0.5g / 10min, 1g / 10min, 1.5g / 10min, 2g / 10min, 2.5g / 10min, 3g / 10min, 3.5g / 10min, 4g / 10min, etc.

[0028] As a preferred embodiment of the PP composite material according to the present application, the melt index of the HDPE at 190℃ / 2.16kg is 0.05-5g / 10min.

[0029] It should be noted that the melt index of the HDPE at 190℃ / 2.16kg is tested according to ISO 1183-2011.

[0030] Exemplarily, the melt index of the HDPE at 190℃ / 2.16kg can be any point value or any two-point range value between 0.05-6g / 10min, such as 0.05g / 10min, 0.1g / 10min, 0.5g / 10min, 1g / 10min, 1.5g / 10min, 2g / 10min, 2.5g / 10min, 3g / 10min, 3.5g / 10min, 4g / 10min, 4.5g / 10min, 5g / 10min, 5.5g / 10min, 6g / 10min, etc.

[0031] The application researches and finds that when the melt indexes of PP and HDPE are further selected in the above ranges, the comprehensive performance of the obtained product is better.

[0032] As a preferred embodiment of the PP composite material of the application, the ultraviolet absorber comprises at least one of benzotriazole substances and benzophenone substances.

[0033] Exemplarily, the benzotriazole substances can be 5411, and the benzophenone substances can be UV531.

[0034] As a preferred embodiment of the PP composite material of the application, the light stabilizer comprises hindered amine substances.

[0035] Exemplarily, the hindered amine substances can be V9900 and 3808PP5.

[0036] In the second aspect of the application, the application provides a preparation method of the PP composite material, and the preparation method comprises the following steps: uniformly mixing components and then melt extruding to obtain the PP composite material.

[0037] As a preferred embodiment of the preparation method of the application, the temperature of the melt extrusion is 180-230 DEG C, the rotation speed is 40-60 rpm, and the length-diameter ratio is (46-50):1.

[0038] In the third aspect of the application, the application provides an application of the PP composite material in preparing outdoor materials.

[0039] Exemplarily, the outdoor materials comprise automobile outer decoration, building materials, and electric appliance outer machines.

[0040] Compared with the prior art, the application has the following beneficial effects:

[0041] The PP composite material provided by the application can effectively improve the stability of the product by selecting appropriate mass fractions of components, limiting the polypropylene grafted styrene and polypropylene grafted maleic anhydride as the compatilizer in a specific grafting rate range, and selecting the nano filler as a sheet structure, and adding appropriate mass fractions of ultraviolet absorbers and light stabilizers under the above specific components and mass fractions, so that the product has excellent weather resistance. DETAILED DESCRIPTION

[0042] For better illustrating the purpose, technical scheme and advantages of the application, the application will be further described in combination with specific examples.

[0043] The reagents, methods and equipment used in the application are all conventional reagents, methods and equipment in the field unless otherwise specified, and the raw materials used in parallel experiments are the same batch of raw materials unless otherwise specified.

[0044] PP-1: 6600A, melt index 0.5 g / 10 min, Formosa Plastics;

[0045] PP-2: PPH GGN01, melt index 1 g / 10 min, Juren;

[0046] HDPE-1: 5502, melt index 0.2 g / 10 min, Sinopec;

[0047] HDPE-2: 2200J, melt index 5 g / 10 min, Yanshan Petrochemical;

[0048] PP-g-St-1: grafting rate 12%, self-made;

[0049] PP-g-St-2: grafting rate 15%, self-made;

[0050] PP-g-St-3: 1616FA, grafting rate 10%, BYK Chemical;

[0051] PP-g-St-4: grafting rate 18%, self-made;

[0052] PP-g-St-5: grafting rate 8%, self-made;

[0053] PP-g-MAH-1: 8112FA, grafting rate 1.4%, BYK Chemical;

[0054] PP-g-MAH-2: 9212FA, grafting rate 1.8%, BYK Chemical;

[0055] PP-g-MAH-3: 2112GA, grafting rate 1.2%, BYK Chemical;

[0056] PP-g-MAH-4: 10213, grafting rate 2.0%, BYK Chemical;

[0057] PP-g-MAH-5: 1001CN, grafting rate 1%, Polyram;

[0058] Flaky nano filler 1: flaky nano zinc oxide, average diameter 30 nm, model DK-ZnO-30, Beijing Dekedaojin Chemical;

[0059] Flaky nano filler 2: flaky nano zinc oxide, average diameter 100 nm, model DK-ZnO-100, Beijing Dekedaojin Chemical;

[0060] Flaky nano filler 3: flaky nano titanium dioxide, average diameter 60 nm, model DK405-1, Beijing Dekedaojin Chemical;

[0061] Zinc oxide: average diameter of 30 μm, Hebei Bao O;

[0062] UV absorber 1: Cyasorb UV5411, benzotriazole, Solvay Chemicals;

[0063] UV absorber 2: Cyasorb UV531, benzophenone, Solvay Chemicals;

[0064] Light stabilizer 1: Tinuvin® V9900, hindered amine, Solvay Chemicals;

[0065] Light stabilizer 2: Tinuvin® 3808PP5, hindered amine, Solvay Chemicals;

[0066] The self-made method of PP-g-St adopts a melt grafting method, including the following steps: using 0.5%wt of benzoyl peroxide, after a certain amount of styrene (such as 8%, 12%, 15%) is dissolved in acetone, adding polypropylene (PP 320, the melt mass-flow rate at 230℃ / 2.16kg is 30g / 10min), after stirring fully, adding a twin-screw extruder, temperature control 160-200℃, main machine rotation speed 120rpm, feeding screw rotation speed 20rpm; obtaining PP-g-St; PP-g-St with different grafting rates is realized by controlling the addition amount of styrene.

[0067] Examples 1-15 and Comparative Examples 1-7

[0068] The examples and comparative examples of the present application provide a PP composite material, the component content (weight parts) of the PP composite material is shown in Table 1-2;

[0069] Table 1

[0070]

[0071]

[0072] Table 2

[0073]

[0074]

[0075] The preparation method of the PP composite material provided by Example 1 is as follows:

[0076] After the components are uniformly mixed, melt extrusion is performed to obtain the PP composite material; wherein the temperature of each zone of the melt extrusion is 180℃, 190℃, 200℃, 230℃, 230℃, 230℃, 200℃ respectively, the screw rotation speed is 50r / min, and the screw length-diameter ratio is 48:1.

[0077] The preparation method of the PP composite provided in Examples 2-15 and Comparative Examples 1-7 is consistent with that of Example 1, and no relevant components are added.

[0078] Effect Example

[0079] The weather resistance of the PP composite prepared in the verification examples and the comparative examples of the present application is verified. It is tested according to Method A in ISO 4892-2:2013, and the parameters involved in Table in ISO 4892-2:2013 during the test process are as follows: 102 min of drying, 18 min of spraying, a radiant power per square meter of 60 W / m 2 , a radiant power density per nanometer of wavelength of 0.51 W / m 2 nm; a blackboard temperature of 65℃; a temperature of 38℃ and a humidity of 50%; and a test time of 10000 hours.

[0080] The impact performance retention rate and the tensile strength retention rate and the color difference ΔE after 10000 hours of xenon lamp irradiation are calculated.

[0081] Among them, the notch impact performance test is tested according to ISO 180-2023, the tensile strength is tested according to ISO 527-2-2012, and the color difference ΔE is tested according to GB / T 3979-2008, and the specific is spectral photometry test.

[0082] The test results are shown in Table 3.

[0083] Table 3

[0084]

[0085]

[0086] As can be seen from Table 3, when the technical solution provided by the present application is used, the product obtained has excellent weather resistance; specifically, after 10000 hours of xenon lamp irradiation, the impact performance retention rate is above 74.70%, the tensile strength retention rate is above 84.70%, and the color difference is below 2.92.

[0087] As can be seen from Example 1 and Comparative Examples 1-2, the PP and HDPE provided by the present application can interact to play the role of resin matrix stabilizing the product. When only PP is added in Comparative Example 1, the impact performance and tensile strength retention rate of the product obtained are significantly decreased, and the color difference before and after irradiation is large. When only HDPE is added in Comparative Example 2, the impact performance and tensile strength retention rate of the product obtained are significantly decreased, and the color difference before and after irradiation is large.

[0088] As can be seen from Example 1 and Comparative Examples 3-4, the polypropylene grafted styrene and the polypropylene grafted maleic anhydride are indispensable in the component of the present application; when only one of them is added in Comparative Examples 3-4 respectively, the weather resistance of the obtained product is significantly reduced; as can be seen from Example 1, Examples 6-11 and Comparative Examples 5-6, the grafting rate of the polypropylene grafted styrene and the polypropylene grafted maleic anhydride also affects the performance of the product; when the grafting rate of the polypropylene grafted styrene is too low in Comparative Example 5, the weather resistance of the obtained product is significantly reduced; when the grafting rate of the polypropylene grafted maleic anhydride is too low in Comparative Example 6, the weather resistance of the obtained product is also significantly reduced;

[0089] As can be seen from Example 1, Examples 12-13 and Comparative Example 7, the type of the sheet-shaped nano-filler affects the weather resistance of the product, but at the same time, its morphology also significantly affects the weather resistance of the product; when zinc oxide instead of sheet-shaped zinc oxide is used in Comparative Example 7, the impact performance and the tensile strength retention rate of the obtained product before and after irradiation are both significantly reduced, and the color difference also shows an increasing trend.

[0090] Finally, it should be noted that the above examples are used to illustrate the technical solutions of the present application, but not to limit the protection scope of the present application; although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A PP composite material, characterized in that, The PP composite material comprises the following components in parts by weight: 58-82 parts PP, 8-32 parts HDPE, 1-10 parts polypropylene grafted maleic anhydride, 1-10 parts polypropylene grafted styrene, 3-12 parts flake nanofiller, 0.5-2.5 parts UV absorber, 0.5-2.5 parts light stabilizer; The grafting rate of the polypropylene grafted with styrene is 10-18%, and the grafting rate of the polypropylene grafted with maleic anhydride is 1.2-2%.

2. The PP composite material according to claim 1, characterized in that, The PP composite material comprises the following components in parts by weight: 65-70 parts PP, 18-23 parts HDPE, 3-5 parts polypropylene grafted maleic anhydride, 3-5 parts polypropylene grafted styrene, 5-7 parts flake nanofiller, 1-1.5 parts ultraviolet absorber, and 1-1.5 parts light stabilizer.

3. The PP composite material according to claim 1, characterized in that, The grafting rate of the polypropylene grafted with styrene is 12-15%.

4. The PP composite material according to claim 1, characterized in that, The grafting rate of the polypropylene grafted with maleic anhydride is 1.4-1.8%.

5. The PP composite material according to claim 1, characterized in that, The average diameter of the sheet-like nanofiller is 30-100 nm.

6. The PP composite material according to claim 1, characterized in that, The sheet-like nanofiller includes at least one of sheet-like nano zinc oxide and sheet-like nano titanium dioxide.

7. The PP composite material according to claim 1, characterized in that, The melt flow index of the PP at 230℃ / 2.16kg is 0.01-4g / 10min; And / or, the melt index of the HDPE at 190℃ / 2.16kg is 0.05-6g / 10min.

8. The PP composite material according to claim 1, characterized in that, The ultraviolet absorber includes at least one of benzotriazole and benzophenone. And / or, the light stabilizer includes hindered amines.

9. The method for preparing the PP composite material according to any one of claims 1-8, characterized in that, The preparation method includes the following steps: mixing the components evenly and then melting and extruding to obtain PP composite material.

10. The application of the PP composite material as described in any one of claims 1-8 in the preparation of outdoor materials.

Images