PP composite material and preparation method and application thereof

Abstract

The invention 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 invention is prepared from the following components in parts by mass: 58 to 82 parts of PP, 8 to 32 parts of HDPE (High-Density Polyethylene), 1 to 10 parts of polypropylene grafted maleic anhydride, 1 to 10 parts of polypropylene grafted styrene, 3 to 12 parts of flaky nano filler, 0.5 to 2.5 parts of ultraviolet light absorber and 0.5 to 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 present invention belongs to the technical field of polymer materials, and particularly relates to a PP composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Weather-resistant PP materials are widely used in industries such as automobiles, household appliances, and home decoration. However, at present, PP extruded sheets still have problems of low performance retention rate and poor color stability in the fields of outdoor equipment and outdoor buildings. The main reason is that in ordinary weather-resistant PP, the non-polar PP has low compatibility with polar weather-resistant agents, fillers, and additives. During outdoor use, colorants and additives precipitate and escape, resulting in a decrease in the mechanical properties of the material and large changes in color differences. Summary of the Invention

[0003] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a PP composite material, a preparation method thereof, and an application thereof, which have excellent mechanical property retention rate and color stability after long-term outdoor use, that is, excellent weather resistance.

[0004] To achieve the above purpose, in the first aspect of the present invention, the present invention provides a PP composite material, which comprises the following components in parts by mass:

[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 flaky nano-fillers, 0.5 - 2.5 parts of ultraviolet absorber, 0.5 - 2.5 parts of light stabilizer;

[0006] The grafting rate of the polypropylene grafted styrene is ≥10%, and the grafting rate of the polypropylene grafted maleic anhydride is ≥1.2%.

[0007] A PP composite material provided by the present invention is prepared by compounding components with appropriate mass parts, and the components have excellent comprehensive effects. Specifically, in the first aspect, the present invention selects sheet-like nano-fillers, polypropylene grafted maleic anhydride and polypropylene grafted styrene with a specific grafting rate range as compatibilizers. The bonding force between the sheet-like nano-fillers and PP can be significantly improved. At a specified stretching speed, the sheet-like nano-fillers rotate into an orientation conformation along the stretching direction, further improving the absorption and reflection of ultraviolet rays by the sheet-like nano-fillers, thereby enhancing the ultraviolet resistance of the product and maintaining a high mechanical property retention rate under ultraviolet irradiation. In the second aspect, by selecting PP resin and HDPE resin in combination, the present invention can avoid the Brownian motion of the sheet-like nano-fillers, thereby preventing the reduction of the orientation conformation of the sheet-like nano-fillers, improving the stability of the product, and ensuring the weather resistance of the product. In the third aspect, the present invention selects PP resin and HDPE resin for compounding, and at the same time cooperates with polypropylene grafted maleic anhydride and polypropylene grafted styrene with a specific grafting rate range as compatibilizers, which can effectively improve the dispersion effect of ultraviolet absorbers and light stabilizers in the resin matrix, avoid the precipitation and escape of ultraviolet absorbers and light stabilizers, and further enhance 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 and 82 parts, such as 60 - 80 parts, or it can be 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 and 32 parts, such as 10 - 30 parts, or it can be 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 and 10 parts, such as 2 - 8 parts, or it can be 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 and 10 parts, such as 2 - 8 parts, or it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.; the flaky nano filler can be any point value or any two-point range value between 3 and 12 parts, such as 5 - 10 parts, or it can be 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 and 2.5, such as 0.7 - 2.2 parts, or it can be 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 and 2.5, such as 0.7 - 2.2 parts, or it can be 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, in the PP composite material, the mass percentage of the PP resin ≥ 45%.

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

[0011] It should be noted that the grafting rate of the polypropylene grafted styrene is obtained by testing with an infrared spectrometer method; the grafting rate of the polypropylene grafted maleic anhydride is obtained by testing with an 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 it can be 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%, for example, it can be 1.2-1.8%, 1.2-2.0%, 1.4-1.8%, etc., or it 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 research of the present invention finds that the grafting rates of polypropylene grafted styrene and polypropylene grafted maleic anhydride not only affect the compatibility between PP and HDPE, but also affect the dispersibility and stability of the sheet-like nano-fillers, ultraviolet absorbers and light stabilizers in the resin matrix, thus affecting the weather resistance of the product; when the grafting rates of polypropylene grafted styrene and polypropylene grafted maleic anhydride are further selected within the above ranges respectively, the weather resistance of the obtained product is better.

[0017] It should be noted that the polypropylene grafted styrene can be obtained through commercial purchase or self-preparation. Exemplarily, the polypropylene grafted styrene can be prepared by the melt grafting method.

[0018] As a preferred embodiment of the PP composite material of the present invention, 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-like nano-fillers, 1-1.5 parts of ultraviolet absorber, 1-1.5 parts of light stabilizer.

[0019] The research of the present invention 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 within the above ranges, the comprehensive performance of the obtained product is better.

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

[0021] It should be noted that the average diameter of the sheet-like nano-fillers is obtained by testing with a scanning electron microscope.

[0022] Exemplarily, the average diameter of the sheet-like nano-fillers can be any point value or any two-point range value between 30-100 nm, for example, it can be 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 of the present invention, the sheet-like nano filler includes at least one of sheet-like nano zinc oxide and sheet-like nano titanium dioxide.

[0024] The present invention has found through research that under the action of polypropylene grafted styrene and polypropylene grafted maleic anhydride with a specific grafting rate range, the bonding force between the sheet-like nano filler and the resin matrix is improved, and at the same time, the absorption and reflection of ultraviolet rays by the sheet-like nano filler can also be improved. Especially when further selecting that the sheet-like nano filler includes at least one of sheet-like nano zinc oxide and sheet-like nano titanium dioxide, the comprehensive performance of the obtained product is better.

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

[0026] It should be noted that the melt index of the PP at 230 °C / 2.16 kg is obtained by referring to ISO 1133 - 2011 for testing.

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

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

[0029] It should be noted that the melt index of the HDPE at 190 °C / 2.16 kg is obtained by referring to ISO 1183 - 2011 for testing.

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

[0031] The research of the present invention finds that when the melt indices of PP and HDPE are further selected within the above ranges respectively, the comprehensive performance of the obtained product is better.

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

[0033] Exemplarily, the benzotriazole substance may be 5411, and the benzophenone substance may be UV531.

[0034] As a preferred embodiment of the PP composite material of the present invention, the light stabilizer includes hindered amine substances.

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

[0036] In the second aspect of the present invention, the present invention provides a preparation method of the PP composite material, and the preparation method includes the following steps: mixing the components evenly and then melt-extruding to obtain the PP composite material.

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

[0038] In the third aspect of the present invention, the present invention provides the application of the PP composite material in the preparation of outdoor materials.

[0039] Exemplarily, the outdoor materials include automotive exterior trims, building materials, electrical appliance exteriors, etc.

[0040] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0041] A PP composite material provided by the present invention selects appropriate mass parts of components, and simultaneously defines polypropylene grafted styrene and polypropylene grafted maleic anhydride with a specific grafting rate range as compatibilizers, and simultaneously selects nano-fillers with a flaky structure; adding appropriate mass parts of ultraviolet absorbers and light stabilizers under the above specific components and mass parts, and the components cooperate with each other, which can effectively improve the stability of the product and make the obtained product have excellent weather resistance. Specific Embodiments

[0042] To better illustrate the purpose, technical solution and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0043] The reagents, methods and equipment used in the present invention are all conventional reagents, methods and equipment in the art without special instructions; and without special instructions, the raw materials used in parallel experiments are of the same batch.

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

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

[0046] HDPE-1: 5502, melt index of 0.2 g / 10 min, Sino-Korea Petrochemical;

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

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

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

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

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

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

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

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

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

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

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

[0058] Flaky nano filler 1: flaky nano zinc oxide, average diameter of 30 nm, grade DK-ZnO-30, Beijing Deke Daojin Chemical;

[0059] Flaky nano filler 2: flaky nano zinc oxide, average diameter of 100 nm, grade DK-ZnO-100, Beijing Deke Daojin Chemical;

[0060] Flaky nano filler 3: flaky nano titanium dioxide, average diameter of 60 nm, grade DK405-1, Beijing Deke Daojin Chemical;

[0061] Zinc oxide: with an average diameter of 30 μm, from Hebei Boao;

[0062] Ultraviolet absorber 1: 5411, benzotriazole type, from Solvay Chemicals;

[0063] Ultraviolet absorber 2: UV531, benzophenone type substance, from Solvay Chemicals;

[0064] Light stabilizer 1: V9900, hindered amine type substance, from Solvay Chemicals;

[0065] Light stabilizer 2: 3808PP5, hindered amine type substance, from Solvay Chemicals;

[0066] Among them, the self-made method of PP-g-St adopts the melt grafting method, including the following steps: Using 0.5% wt of benzoyl peroxide, after dissolving it with a certain amount of styrene (such as 8%, 12%, 15%) in acetone, polypropylene (PP 320, with a melt mass flow rate of 30 g / 10 min at 230 °C / 2.16 kg) is added. After sufficient stirring, it is added to a twin-screw extruder, with the temperature controlled at 160 - 200 °C, the main machine speed at 120 rpm, and the feeding screw speed at 20 rpm; obtaining PP-g-St; Different grafting ratios of PP-g-St are achieved 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 invention provide a PP composite material, and the component contents (parts by weight) of the PP composite material are 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 mixing the components evenly, melt extrusion is carried out to obtain the PP composite material; among them, the temperatures of each zone for melt extrusion are 180 °C, 190 °C, 200 °C, 230 °C, 230 °C, 230 °C, 200 °C respectively, the screw speed is 50 r / min, and the screw length-diameter ratio is 48:1.

[0077] The preparation methods of the PP composites provided in Examples 2-15 and Comparative Examples 1-7 are the same as those in Example 1. If there are no relevant components, they can be omitted.

[0078] Effect Example

[0079] The weather resistance of the PP composites prepared in the verification examples and comparative examples of the present invention was verified; it was tested according to Method A in ISO4892-2:2013. During the test, the parameters involved in the table in ISO4892-2:2013 were: drying for 102 min, spraying for 18 min, the radiation power per square meter was 60 W / m 2 , and the radiation power density per nanometer wavelength was 0.51 W / m 2 nm; the blackboard temperature was 65 °C; the temperature was 38 °C and the humidity was 50%;

[0080] Calculate the retention rate of impact performance, the retention rate of tensile strength, and the color difference ΔE after 10,000 hours of xenon lamp irradiation;

[0081] Among them, the notched impact performance test was carried out with reference to ISO 180-2023, the tensile strength was tested with reference to ISO 527-2-2012, and the color difference ΔE was tested with reference to GB / T3979-2008, specifically for spectrophotometric testing;

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

[0083] Table 3

[0084]

[0085]

[0086] It can be seen from Table 3 that when the technical solution provided by the present invention is adopted, the obtained product has excellent weather resistance; specifically, after 10,000 hours of xenon lamp irradiation, the retention rate of impact performance is above 74.70%, the retention rate of tensile strength is above 84.70%, and the color difference is below 2.92;

[0087] It can be seen from Example 1 and Comparative Examples 1-2 that the PP and HDPE provided by the present invention can interact with each other to play a role in stabilizing the product of the resin matrix. When only PP is added in Comparative Example 1, the retention rates of the impact performance and tensile strength of the obtained product both decrease significantly, and the color difference before and after irradiation becomes larger; when only HDPE is added in Comparative Example 2, the retention rates of the impact performance and tensile strength of the obtained product both decrease significantly, and the color difference before and after irradiation becomes larger;

[0088] It can be seen from Example 1 and Comparative Examples 3-4 that polypropylene grafted styrene and polypropylene grafted maleic anhydride in the components of the present invention are both indispensable; when only one of them is added separately in Comparative Examples 3-4, the weather resistance of the obtained product significantly decreases; it can be seen from Example 1, Examples 6-11 and Comparative Examples 5-6 that the grafting rates of polypropylene grafted styrene and polypropylene grafted maleic anhydride also affect the performance of the product. When the grafting rate of polypropylene grafted styrene in Comparative Example 5 is too low, the weather resistance of the obtained product significantly decreases; when the grafting rate of polypropylene grafted maleic anhydride in Comparative Example 6 is too low, the weather resistance of the obtained product also significantly decreases.

[0089] It can be seen from Example 1, Examples 12-13 and Comparative Example 7 that the type of flaky nano-filler will affect the weather resistance of the product, but at the same time its morphology will also significantly affect the weather resistance of the product. When zinc oxide rather than flaky zinc oxide is used in Comparative Example 7, the impact performance and the retention rate of tensile strength of the obtained product before and after irradiation both significantly decrease, and the color difference also shows an increasing trend.

[0090] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A PP composite material, characterized in that: The PP composite material comprises the following components in parts by weight: 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 flaky nanofiller, 0.5-2.5 parts of ultraviolet absorber, 0.5-2.5 parts of light stabilizer; The grafting rate of the polypropylene grafted with styrene is ≥10%, and the grafting rate of the polypropylene grafted with maleic anhydride is ≥1.2%.

2. The PP composite material according to claim 1, characterized in that: 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 flaky nanofillers, 1-1.5 parts of ultraviolet absorbers, and 1-1.5 parts of light stabilizers.

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

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

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

6. The PP composite material according to claim 1, characterized in that: The flaky nano filler includes at least one of flaky nano zinc oxide and flaky nano titanium dioxide.

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

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

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

10. Use of the PP composite material according to any one of claims 1 to 8 in the preparation of outdoor materials.

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