A kind of flow pattern master batch and its preparation method and application

Abstract

The application discloses a kind of stream grain master batch and its preparation method and application, belong to high polymer material field.The stream grain master batch of the application uses PP as matrix resin, adds PPE to improve its melting point, and by adding PS, polypropylene grafting styrene and polypropylene grafting glycidyl methacrylate improves the compatibility of PPE and PP, and has higher melting point, not only compatible with plate matrix resin PP in the process of continuous extrusion of plate, but also not easy to melt, stream grain effect is good, line is uniform, and the color difference with plate matrix is high;Plate matrix is not dyed, and the color difference with standard color is low, suitable for being used to prepare decorative plate with stream grain pattern.

Description

Technical Field

[0001] This application relates to the field of polymer materials, specifically to a flow pattern masterbatch, its preparation method, and its application. Background Technology

[0002] Continuously extruded sheets are widely used in building walls, home roofing and flooring, and public facility floors, primarily serving to provide moisture and water insulation, weather resistance, heat insulation, and aesthetic enhancement. For flooring in home decoration and public facilities, the industry typically uses flow-textured masterbatch during the continuous extrusion process to achieve a wood-grain effect on the sheet surface. This requires the flow-textured masterbatch to be compatible with the sheet's matrix resin but not to completely melt during extrusion to avoid complete fusion with the matrix resin and the inability to achieve the desired texture. Since sheets often use PP or PE as the matrix material, the demand for a high-melting-point PP matrix material flow-textured masterbatch is increasingly prominent. However, currently available flow-textured masterbatch base materials are mainly high-melting-point engineering resins, such as PA and PBT, which have poor compatibility with the PP matrix, easily leading to problems such as peeling, uneven texture, and high cost. Summary of the Invention

[0003] Based on the deficiencies of the existing technology, the purpose of this application is to provide a flow pattern masterbatch, its preparation method and application. The obtained flow pattern masterbatch has a high melting point, and during the continuous extrusion process of the sheet, it not only has good compatibility with the sheet matrix resin PP, but is also not easily melted, resulting in a good flow pattern effect.

[0004] To achieve the above objectives, in a first aspect, this application provides a flow pattern masterbatch comprising the following components in parts by weight:

[0005]

[0006] PPE has a high melting point and good heat resistance. Adding a specific amount of PPE to PP can improve its melting point and heat resistance. However, PPE and PP have poor compatibility. Adding specific amounts of PS, polypropylene grafted with styrene, and polypropylene grafted with glycidyl methacrylate can improve the compatibility between PPE and PP. PS and PP are partially compatible; using polypropylene grafted with styrene can improve their compatibility, promoting better dispersion of PS in PP and forming a PS island phase. PS and PPE are completely compatible; good dispersion of PS in PP helps improve the dispersion of PPE in PP. Polypropylene grafted with glycidyl methacrylate can further improve the compatibility between PPE and PP.

[0007] The flow pattern masterbatch, under the combined action of the above-mentioned specific amounts of each component, has a high melting point. During the continuous extrusion process of the sheet, it not only has good compatibility with the sheet matrix resin PP, but is also not easily melted, resulting in a good flow pattern effect, uniform lines, and high color difference with the sheet matrix; the sheet matrix is ​​undyed and has a low color difference with the standard color.

[0008] Preferably, the melt flow rate of the PS at 200°C and 5 kg is 0.5–7 g / 10 min. More preferably, the melt flow rate of the PS at 200°C and 5 kg is 0.8–4.2 g / 10 min.

[0009] Controlling the melt flow rate of PS at 200℃ and 5kg within the range of 0.5 to 7 g / 10 min, especially within the range of 0.8 to 4.2 g / 10 min, is beneficial to increasing the size of the dispersed phase formed by PS, so that PPE can be better and easier to disperse in PS, thereby improving the dispersion of PPE in PS and the flow pattern effect.

[0010] The melt flow rate of the PS can be measured according to ISO 1133-2022.

[0011] Preferably, the intrinsic viscosity of the PPE is 33–55 mL / g. More preferably, the relative viscosity of the PPE is 35–38 mL / g.

[0012] Controlling the intrinsic viscosity of PPE within the range of 33–55 mL / g, especially within the range of 35–38 mL / g, is beneficial for smoother diffusion of PPE in the continuous PP phase and for faster and more uniform entry into the dispersed PS phase, thereby improving the dispersion of PPE in PS and enhancing the flow pattern effect.

[0013] The intrinsic viscosity of the PPE can be measured according to GB / T 41874-2022 Polyphenylene oxide (PPE) resin, using the Ubbelohde viscometer method.

[0014] Preferably, the melt flow rate of the PP at 230°C and 2.16 kg is 0.1–5 g / 10 min. More preferably, the melt flow rate of the PP at 230°C and 2.16 kg is 0.2–1.5 g / 10 min.

[0015] Controlling the melt flow rate of PP at 230℃ and 2.16kg to 0.1~3.5g / 10min, especially 0.2~1.5g / 10min, is beneficial to the diffusion of PS and PPE, resulting in better dispersion of PPE in PS and better flow pattern effect.

[0016] The melt flow rate of the PP can be measured according to ISO 1133-2022.

[0017] Preferably, the grafting rate of styrene in the polypropylene-grafted styrene is 0.5 wt.% to 12 wt.%. More preferably, the grafting rate of styrene in the polypropylene-grafted styrene is 10 wt.% to 12 wt.% to achieve a better flow pattern effect.

[0018] Preferably, the grafting rate of glycidyl methacrylate in the polypropylene grafted with glycidyl methacrylate is 0.5 wt.% to 3 wt.%. More preferably, the grafting rate of glycidyl methacrylate in the polypropylene grafted with glycidyl methacrylate is 2 wt.% to 3 wt.% to achieve a better flow pattern effect.

[0019] Preferably, the colorant includes at least one of carbon black, iron oxide black, a mixture of chrome yellow and titanium dioxide, and a mixture of iron oxide red and titanium dioxide, wherein the mass ratio of chrome yellow to titanium dioxide in the mixture of chrome yellow and titanium dioxide is (0.5-2):1, and the mass ratio of iron oxide red to titanium dioxide in the mixture of iron oxide red and titanium dioxide is at least one of (0.5-2):1.

[0020] Preferably, the flow pattern masterbatch further includes the following components in parts by weight:

[0021] Light stabilizer 0.1 to 1 part;

[0022] Antioxidant 0.2 to 1 part.

[0023] Adding light stabilizers and antioxidants to flow pattern masterbatches helps improve the weather resistance of materials and extend their service life.

[0024] Preferably, the antioxidant comprises a first antioxidant and a second antioxidant, wherein the weight ratio of the first antioxidant to the second antioxidant is (1-5):(1-3), the first antioxidant is a triazine antioxidant, and the second antioxidant is a thioester antioxidant. Combining the triazine antioxidant and the thioester antioxidant, and controlling their weight ratio within the range of (1-5):(1-3), can synergistically improve the antioxidant properties of the material, thereby synergistically improving the material's weather resistance. The weight ratio of the first antioxidant to the second antioxidant can be selected as 1:3, 1:2, 1:1, 3:1, 4:1, or 5:1, etc. As an example, the triazine antioxidant can be selected from at least one of antioxidant 1010 and antioxidant 1790; the thioester antioxidant can be selected from at least one of antioxidant 412SDSTDP.

[0025] Preferably, the light stabilizer includes hindered amine light stabilizers.

[0026] Preferably, the weight percentage of PP in the flow pattern masterbatch is 25% or more, such as 25%, 30%, 40%, 50%, 60%, 70%, or 75%.

[0027] Secondly, this application provides a method for preparing flow pattern masterbatch, comprising the following steps: mixing and dispersing all raw materials, melt extruding, granulating, and obtaining flow pattern masterbatch.

[0028] Preferably, the temperature of the melt extrusion is 230-260°C.

[0029] Thirdly, this application provides the application of the flow pattern masterbatch in the preparation of boards with flow patterns. The flow pattern masterbatch can be used to prepare flooring boards with flow patterns for home decoration, public facilities, and other places.

[0030] Fourthly, this application also provides a sheet material with a flow pattern, comprising the following components in parts by weight:

[0031] 100 PP sheets;

[0032] The flow pattern masterbatch is 0.3 to 3 parts.

[0033] Preferably, the PP weight percentage in the sheet material with the flow pattern is above 97%, such as 97%, 98%, 99%, or 99.7%.

[0034] Fifthly, this application also provides the application of the aforementioned textured panels in building flooring or exterior wall decoration.

[0035] Compared with the prior art, the beneficial effects of this application are as follows:

[0036] (1) The flow pattern masterbatch of this application uses PP as the base resin, adds a specific amount of PPE to improve its melting point, and improves the compatibility between PPE and PP by adding a specific amount of PS, polypropylene grafted styrene and polypropylene grafted glycidyl methacrylate.

[0037] (2) The flow pattern masterbatch of this application has a high melting point under the combined action of the above-mentioned specific content of each component. During the continuous extrusion process of the board, it not only has good compatibility with the board matrix resin PP, but also does not melt easily, has a good flow pattern effect, uniform lines, and high color difference with the board matrix; the board matrix is ​​not dyed and has a low color difference with the standard color, making it suitable for preparing decorative boards with flow pattern. Detailed Implementation

[0038] To better illustrate the purpose, technical solutions, and advantages of this application, the following description, in conjunction with specific embodiments and comparative examples, aims to provide a detailed understanding of the content of this application, rather than limiting it. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this application. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this application are commonly used reagents and instruments. In this application, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0039] The raw materials used in the following embodiments and comparative examples are shown in Table 1, and unless otherwise specified, all raw materials are commercially available. Furthermore, the same raw materials were used in each parallel experiment.

[0040] PP 1: Melt flow rate of 0.5 g / 10 min at 230℃ and 2.16 kg, grade: 6600A, supplier: Taiwan Plastics.

[0041] PP 2: Melt flow rate of 0.3 g / 10 min at 230℃ and 2.16 kg, grade: PP B8101, supplier: Yanshan Petrochemical;

[0042] PP 3: Melt flow rate of 1 g / 10 min at 230℃ and 2.16 kg, grade: EPS30R, supplier: Dushanzi Petrochemical;

[0043] PP 4: Melt flow rate of 3 g / 10 min at 230℃ and 2.16 kg, grade: PP L5E89, supplier: Sichuan Petrochemical;

[0044] PS1: Melt flow rate of 3.1 g / 10 min at 200℃ and 5 kg, grade: 8265, supplier: INEOSSTYROLUTION;

[0045] PS2: Melt flow rate of 1g / 10min at 200℃ and 5kg, grade: EA3300, supplier: Yashide;

[0046] PS 3: Melt flow rate of 4g / 10min at 200℃ and 5kg, grade: PS 350K, supplier: Guoqiao;

[0047] PS 4: Melt flow rate of 5 g / 10 min at 200℃ and 5 kg, grade: HP8250, supplier: Taiwan Chemicals;

[0048] PPE 1: Intrinsic viscosity IV1 meets the requirement of 37 mL / g, grade: LXN035, supplier: Nantong Xingchen;

[0049] PPE 2: Intrinsic viscosity IV2 meets the requirement of 50 mL / g, grade: LXN050, supplier: Nantong Xingchen;

[0050] Polypropylene grafted with styrene 1: Styrene grafting rate 10 wt.%, Grade: 1616FA, Supplier: BYK Chemicals;

[0051] Polypropylene grafted styrene 2: Styrene and initiator DBTH were dispersed in methanol until no precipitate was found. The mixture was then poured into PP powder and stirred until the powder was no longer wettable. The powder was spread on a watch glass and allowed to stand and air dry for 24 hours to obtain an intermediate product. 0.5 g of the intermediate product was added to 1000 mL of toluene (toluene in excess). The mixture was refluxed and stirred until the intermediate product was completely dissolved. Then, 1500 mL of methanol (methanol in excess) was added to flocculate and precipitate the product. The precipitate was filtered and dried to obtain polypropylene grafted styrene 2 with a grafting rate of 8 wt.%. The styrene weight was 12% based on the weight of PP, the initiator DBTH weight was 4%, and the amount of methanol used was the minimum amount required to completely dissolve the styrene. The styrene was purchased from Denka, Japan, and the polypropylene used was PP 320 from Maoming Shihua.

[0052] Polypropylene grafted with glycidyl methacrylate 1: Glycidyl methacrylate grafting rate 2.5 wt.%, grade: 8104FA, supplier: BYK Chemicals;

[0053] Polypropylene grafted with glycidyl methacrylate 2: Prepared according to CN116003914B, with a glycidyl methacrylate grafting rate of 0.5 wt.%, wherein the polypropylene used is PP 320 from Maoming Shihua, and the glycidyl methacrylate used is from Sigma-Aldrich.

[0054] Polypropylene grafted with maleic anhydride: grafting rate 1 wt.%, grade: 1001CN, supplier: Bondyram;

[0055] Carbon black: Carbon black masterbatch 2772, supplier: Cabot, containing 40 wt.% pure carbon black. The carbon black dosage in Tables 1 and 2 has been converted to pure carbon black dosage.

[0056] Light stabilizer: UV-3808PP5, commercially available;

[0057] First antioxidant: Antioxidant 1790, commercially available;

[0058] Second antioxidant: Antioxidant 412S, commercially available.

[0059] The following embodiments and comparative examples all provide a flow pattern masterbatch, including the following steps: after mixing and dispersing all raw materials, they are fed into a twin-screw extruder and granulated to obtain the flow pattern masterbatch, wherein the melt mixing temperature is 230-260℃.

[0060] The formulations of these examples and comparative flow pattern masterbatches are shown in Tables 1 and 2. The performance of these flow pattern masterbatches was tested as follows, and the test results are shown in Tables 1 and 2:

[0061] 1. Determine the melting point of the flow masterbatch according to ASTM D3418-2015 method. A melting point above 175℃ is acceptable; otherwise, it is unacceptable.

[0062] 2. The flow pattern masterbatch was mixed with PP (PP8101, grade: PPB8101, supplier: Yanshan Petrochemical) at a mass ratio of 2%:1, dispersed, and extruded at 200℃, screw speed 50rpm, and vacuum degree -0.1MPa to obtain a sheet with a length of 1.2m, a width of 15cm, and a thickness of 5cm. The following performance tests were performed on the sheet:

[0063] According to ASTM E1347-06(2020), the color difference ΔE1 between the flow pattern and the substrate of the sheet and the color difference ΔE2 between the substrate of the sheet and the standard color (i.e., the sheet obtained by extruding only PP B8101 from Yanshan Petrochemical using the same process as described above) were measured using a colorimeter. Five values ​​were randomly measured and the average value was calculated. If the average value of ΔE1 is greater than 3 and the average value of ΔE2 is less than 2, the flow pattern effect is good; otherwise, the flow pattern effect is not good.

[0064] Table 1

[0065]

[0066] Table 2

[0067]

[0068]

[0069] As can be seen from the above data, the flow pattern masterbatch in each embodiment has a high melting point and a good flow pattern effect in the PP substrate. For example, the melting point of the flow pattern masterbatch is above 172℃, the average color difference ΔE1 between the flow pattern and the substrate is greater than 3, and the average color difference ΔE2 between the substrate and the standard color is less than 2.

[0070] Comparative Examples 1 and 2 did not contain PPE, and the melting point of the flow pattern masterbatch was too low. During the continuous extrusion of the sheet, the flow pattern masterbatch completely melted, resulting in the inability to form a pattern.

[0071] Comparative Examples 3-7 did not contain PS, or did not contain polypropylene grafted with styrene, or used other compatibilizers instead of polypropylene grafted with styrene, or did not contain polypropylene grafted with glycidyl methacrylate, or used other compatibilizers instead of polypropylene grafted with glycidyl methacrylate, resulting in poor compatibility between PPE and PP, thus causing deviations in the flow pattern effect.

[0072] As can be seen from the comparison of Examples 5, 6-8, the melt flow rate of PP affects the flow pattern effect. To obtain a better flow pattern effect, the melt flow rate of PP at 230℃ and 2.16kg is preferably 0.2-1.5g / 10min.

[0073] As can be seen from the comparison of Examples 5 and 9-11, the melt flow rate of PS affects the flow pattern effect. To obtain a better flow pattern effect, the melt flow rate of PS at 200℃ and 5kg is preferably 0.8-4.2g / 10min.

[0074] As can be seen from the comparison of Examples 5 and 12, the relative viscosity of PPE affects the flow pattern effect. To obtain a better flow pattern effect, the relative viscosity of PPE is preferably 35-38 mL / g.

[0075] The flow pattern masterbatch obtained in Example 5 was mixed with PP (melt flow rate of 0.5 g / 10 min at 230℃ and 2.16 kg, grade: PP B8101, supplier: Yanshan Petrochemical) at a mass ratio of 0.5%:1, dispersed, and extruded and injection molded at 200℃ to obtain sheet A.

[0076] The flow pattern masterbatch obtained in Example 5 was mixed with PP (melt flow rate of 0.5 g / 10 min at 230°C and 2.16 kg, grade: PP B8101, supplier: Yanshan Petrochemical) at a mass ratio of 2.5%:1, dispersed, and extruded and injection molded at 200°C to obtain sheet B.

[0077] The ΔE1 and ΔE2 of plates A and B were measured using the aforementioned method, and the results are shown in Table 3.

[0078] Table 3

[0079] Board A Board B <![CDATA[Color difference △E1 from the sheet body]]> 5.9 12.2 <![CDATA[Color difference △E2 between the extrusion board color and the standard color]]> 0.4 0.9

[0080] It is evident that both sheet materials A and B exhibit excellent flow pattern effects.

[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit the scope of protection of this application. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the substance and scope of the technical solutions of this application.

Claims

1. A flow pattern masterbatch, characterized in that, It includes the following components by weight: PP 25~77 parts, PS 10~30 parts, PPE 10~30 parts, colorant 0.3~0.5 parts, polypropylene grafted with styrene 2~10 parts, and polypropylene grafted with glycidyl methacrylate 2~10 parts. The PS has a melt flow rate of 0.5~7g / 10min at 200℃ and 5kg, the PPE has an intrinsic viscosity of 33~55mL / g, and the PP has a melt flow rate of 0.1~3.5g / 10min at 230℃ and 2.16kg.

2. The flow pattern masterbatch as described in claim 1, characterized in that, The PS has a melt flow rate of 0.8~4.2 g / 10 min at 200℃ and 5 kg.

3. The flow pattern masterbatch as described in claim 1, characterized in that, The intrinsic viscosity of the PPE is 35~38 mL / g.

4. The flow pattern masterbatch as described in claim 1, characterized in that, The melt flow rate of the PP at 230℃ and 2.16kg is 0.2~1.5g / 10min.

5. The flow pattern masterbatch as described in claim 1, characterized in that, It also includes the following components in parts by weight: 0.1 to 1 part of light stabilizer and 0.2 to 1 part of antioxidant.

6. The flow pattern masterbatch as described in claim 5, characterized in that, At least one of the following conditions must be met: S1. The colorant includes at least one of carbon black, iron oxide black, a mixture of chrome yellow and titanium dioxide, and a mixture of iron oxide red and titanium dioxide, wherein the mass ratio of chrome yellow to titanium dioxide in the mixture of chrome yellow and titanium dioxide is (0.5~2):1, and the mass ratio of iron oxide red to titanium dioxide in the mixture of iron oxide red and titanium dioxide is (0.5~2):

1. S2. The light stabilizer includes hindered amine light stabilizers; S3. The antioxidant includes a first antioxidant and a second antioxidant, wherein the weight ratio of the first antioxidant to the second antioxidant is (1~5):(1~3), the first antioxidant is a triazine antioxidant, and the second antioxidant is a thioester antioxidant.

7. The method for preparing flow pattern masterbatch according to any one of claims 1 to 6, characterized in that, Includes the following steps: All raw materials are mixed and dispersed, melt-extruded, and granulated to obtain flow pattern masterbatch.

8. The application of the flow pattern masterbatch as described in claim 1 in the preparation of sheets with flow patterns.

9. A sheet material with a flow pattern, characterized in that, It comprises the following components in parts by weight: 100 parts of PP, and 0.3 to 3 parts of the flow pattern masterbatch as described in any one of claims 1 to 6.

10. The application of the sheet material with the flow pattern as described in claim 9 in the decoration of building floors or exterior walls.

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