A composite grafting compatilizer, polypropylene composite material and its preparation method and application

Abstract

The application discloses a composite grafting type compatilizer, a polypropylene composite material and a preparation method and application thereof, and relates to the technical field of modified plastics. The composite grafting type compatilizer comprises a PE section, a POE section and a GMA section, and the mass ratio of the PE section, the POE section and the GMA section is (60-90):(10-40):(2-8). The composite grafting type compatilizer can significantly improve the compatibility between PP resin and PC resin, and is suitable for preparing a polypropylene composite material for an IML process.

Description

Technical Field

[0001] This invention relates to the field of modified plastics technology, and in particular to a composite grafted compatibilizer, a polypropylene composite material, its preparation method and application. Background Technology

[0002] IML (In-Mold Label) is a currently popular in-mold injection molding technology. Its most significant feature is that the surface is a hardened transparent film, the middle is a printed pattern layer, and the back is a plastic layer. Because the ink is sandwiched in the middle, it can prevent the product surface from being scratched and is resistant to abrasion, and can maintain the color vividly and not easily faded for a long time. This technology can make the molded parts highlight the visual and design aesthetics, and is widely used in the surface decoration of products such as mobile phones, MP3 players, home appliances, and instruments.

[0003] Because the product surface needs to be scratch-resistant and abrasion-resistant, wear-resistant polycarbonate resin (PC) or polyethylene terephthalate (PET) is often chosen as the film. However, these materials have high overall cost and heavy density. In the future, using polypropylene resin (PP) as the plastic layer to replace PC or PET is an important demand of customer value engineering (VAVE) and weight reduction.

[0004] Polypropylene is the lightest plastic, transparent in appearance, and resistant to corrosion from acids, alkalis, salt solutions and various organic solvents below 80°C. It is widely available, inexpensive, and has excellent mechanical properties and good modification design capabilities, making it one of the most commonly used general-purpose plastics.

[0005] Replacing engineering plastics with polyolefins such as PP or PE is a major future trend. For the IML process, it is necessary to ensure good interfacial adhesion between the PP plastic layer and the PC film (while maintaining a certain level of transparency and mechanical properties). However, the molecular structures, polarities, and solubility parameters of PP and PC or PET are vastly different. Direct physical blending results in a completely incompatible macroscopic phase separation with extremely poor interfacial adhesion. Therefore, PP materials need to be modified. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a composite grafted compatibilizer, a polypropylene composite material, its preparation method, and its application. The composite grafted compatibilizer can improve the compatibility between PP resin and PC resin, expanding the application range of polypropylene composite materials.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A composite grafted compatibilizer, comprising a PE segment, a POE segment, and a GMA segment, wherein the mass ratio of the PE segment, the POE segment, and the GMA segment is (60-90):(10-40):(2-8).

[0009] The aforementioned composite grafted compatibilizer contains a non-polar PE segment, which exhibits good compatibility with polypropylene and helps improve the light transmittance of the material, thus improving the compatibility between PP and PC. The POE segment can disrupt the crystalline state of polypropylene, helping to improve the transparency of the material and also enhancing its toughness. The GMA segment is highly polar, contributing to improved compatibility with PC materials. The composite grafted compatibilizer of this invention can significantly improve the compatibility between PP and PC, enabling PP to replace other engineering plastics in the IML process. Compared to directly adding PE, POE, and GMA during the preparation of polypropylene composites, this composite grafted compatibilizer can significantly improve the compatibility between PP and PC, enhancing the overall performance of the composite material.

[0010] Preferably, the mass ratio of PE, POE, and GMA is (70-80):(20-30):(4-6). When the above requirements are met, the polypropylene composite material using the composite grafted compatibilizer has superior mechanical properties.

[0011] In addition, the present invention also provides a method for preparing the composite grafted compatibilizer, wherein the preparation method comprises: mixing PE resin, POE resin and initiator evenly, and adding them into the extruder through the main feed port of a twin-screw extruder; then injecting GMA into the extruder through the third screw section for melt grafting, followed by cooling, granulation and drying to obtain the composite grafted compatibilizer; the parameters of the twin-screw extruder are: 80-120℃ in zone 1, 220-240℃ in zones 2 to 5, 250-260℃ in other zones, and a rotation speed of 300-400 rpm.

[0012] Preferably, the melt flow rate of the PE resin measured at 190°C and 2.16 kg is 3-20 g / 10 min, and the melt flow rate is measured with reference to GB / T 3682.1-2018; the initiator is at least one of benzoyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0013] Meanwhile, the present invention also discloses a polypropylene composite material prepared using the above-mentioned composite grafted compatibilizer, wherein the polypropylene composite material comprises the following components in parts by weight: 70-95 parts of PP resin, 2-15 parts of composite grafted compatibilizer, 3-15 parts of PC resin, 0.2-2 parts of weathering agent, 0.2-2 parts of lubricant, and 0.2-2 parts of antioxidant.

[0014] More preferably, in the polypropylene composite material, the weight parts of PP resin are 70-90 parts, the weight parts of composite grafted compatibilizer are 3-15 parts, and the weight parts of PC resin are 5-15 parts.

[0015] The polypropylene composite material prepared using the above method can form a good bond with the PC film as a plastic layer, making it suitable for use in the IML process.

[0016] Preferably, the melt flow rate of the PP resin measured at 230℃ and 2.16kg is 10-25 g / 10min, and the melt flow rate of the PC resin measured at 300℃ and 1.2kg is 6-19 g / 10min. The melt flow rates are measured with reference to GB / T 3682.1-2018. The above-mentioned limitations on the melt flow rates of the PP and PC resins ensure that the materials have good processing performance and improve the overall performance of the polypropylene composite material.

[0017] Preferably, the weathering agent is a hindered amine light stabilizer, the lubricant is at least one of EBS and erucamide, and the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant DLTDP.

[0018] Meanwhile, this invention also discloses a method for preparing the polypropylene composite material. The method involves mixing the components evenly according to the specified ratio, adding them to a twin-screw extruder for melt blending, extrusion granulation, and obtaining the polypropylene composite material. The preparation conditions for the polypropylene composite material are: 80-120℃ in zone one, 180-200℃ in zones two to five, and 200-230℃ in other zones.

[0019] Furthermore, the present invention also discloses the application of the polypropylene composite material in the IML process.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention screens the components of the composite grafted compatibilizer and provides a composite grafted compatibilizer that can significantly improve the compatibility of PP resin and PC resin; in addition, by screening the components of the polypropylene composite material, the impact resistance and tensile strength of the polypropylene composite material are improved, and the polypropylene composite material also has good light transmittance. Detailed Implementation

[0021] 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.

[0022] Unless otherwise specified, the materials used in the examples and comparative examples are commercially available.

[0023] The materials used in the examples and comparative examples are as follows:

[0024] PE: Grade DMDA8008, Lanzhou Chemical Co., Ltd.

[0025] POE: Grade POE ENGAGE 7447, Dow Chemical;

[0026] GMA: Glycidyl methacrylate (GMA), Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0027] PP1: PP 150 powder, Yueyang Petrochemical, the melt mass flow rate measured at 230℃ and 2.16kg was 15g / 10min;

[0028] PP2: PP HP500N, CNOOC Shell, with a melt mass flow rate of 10 g / 10 min measured at 230℃ and 2.16 kg.

[0029] PP3: PP SZ30S, Sino-Korean (Wuhan) Petrochemical, the melt mass flow rate measured at 230℃ and 2.16kg was 25g / 10min;

[0030] PP4: PP 320 powder, Yueyang Petrochemical, the melt mass flow rate measured at 230℃ and 2.16kg was 32g / 10min;

[0031] PP5: PP ST30, Sinopec Wuhan, the melt mass flow rate measured at 230℃ and 2.16kg was 3g / 10min;

[0032] PC1: PC FN2200, a formaldehyde-based teflon, with a melt mass flow rate of 11 g / 10 min measured at 300℃ and 1.2 kg.

[0033] PC2: PC A2500, Formosa Plastics Idemitsu Taflon, the melt mass flow rate measured at 300℃ and 1.2kg was 7g / 10min;

[0034] PC3: PC A1900, Formosa Plastics Idemitsu Taflon, with a melt mass flow rate of 19 g / 10 min measured at 300℃ and 1.2 kg.

[0035] PC4: PC H-3000F, Haojing Industrial (Shanghai) Co., Ltd., with a melt mass flow rate of 30 g / 10 min measured at 300℃ and 1.2 kg.

[0036] PC5: PC 1300-03NP, LG Chem, the melt mass flow rate measured at 300℃ and 1.2kg was 3g / 10min;

[0037] Initiator: Organic peroxide initiator, DTBP;

[0038] Weather stabilizer: Hindered amine light stabilizer, commercially available;

[0039] Lubricant: EBS, commercially available;

[0040] Antioxidant: Antioxidant 1010, commercially available.

[0041] The weathering agents, lubricants, and antioxidants used in the examples and comparative examples were all commercially available products, and the melt flow rates mentioned above were measured with reference to GB / T 3682.1-2018.

[0042] Examples 1-5

[0043] Examples of the composite grafted compatibilizer of the present invention, the formulations of Examples 1 to 5 are shown in Table 1, and the preparation method is as follows: PE resin, POE resin and 0.5 parts of initiator are mixed evenly and added to the extruder through the main feed port of the twin-screw extruder. Then, GMA is injected into the extruder through the third section of the extruder barrel for melt grafting. Subsequently, the mixture is cooled, granulated, and dried to obtain the composite grafted compatibilizer. The temperature of the twin-screw extruder is set as follows: Zone 1 100℃, Zones 2 to 5 240℃, Zones 6 to 9 250℃, and the screw speed of the twin-screw extruder is 300 rpm.

[0044] Comparative Examples 1-2

[0045] Comparative Examples 1 and 2 are compatibilizers, and their preparation methods are the same as those in Example 1, except that the weight parts of each component are different, as shown in Table 1.

[0046] Comparative Example 3

[0047] Comparative Example 3 is a compatibilizer, and its only difference from Example 1 is that GMA was not added. The weight parts of each component are shown in Table 1.

[0048] Comparative Example 4

[0049] Comparative Example 4 is a compatibilizer. The only difference between it and Example 1 is that POE was not added. The weight parts of each component are shown in Table 1.

[0050] Comparative Example 5

[0051] Comparative Example 5 is a compatibilizer. The only difference between it and Example 1 is that no PE was added. The weight parts of each component are shown in Table 1.

[0052] Comparative Example 6

[0053] Comparative Example 6 is a compatibilizer, which differs from Example 1 only in that PP1 is used instead of PE.

[0054] Table 1 (parts by weight)

[0055]

[0056] Examples 6-10

[0057] Examples of the polypropylene composite material of the present invention: The formulation of the polypropylene composite material in Example 6 is shown in Table 2. The difference between Examples 7-10 and Example 6 is only that the types of composite grafted compatibilizers are different. The composite grafted compatibilizers used in Examples 6-10 are Examples 1-5, respectively. The preparation method of the polypropylene composite material is as follows: the components are mixed evenly according to the formula, added to a twin-screw extruder for melt blending, extrusion granulation, and the polypropylene composite material is obtained. The preparation conditions of the polypropylene composite material are: 100°C in Zone 1, 180°C in Zones 2 to 5, and 220°C in Zones 6 to 9.

[0058] Comparative Examples 7–12

[0059] Comparative Examples 7-12 are polypropylene composite materials. The only difference between the polypropylene composite materials in Comparative Examples 7-12 and Example 6 is that the composite grafted compatibilizers used are Comparative Examples 1-6, respectively.

[0060] Comparative Example 13

[0061] A polypropylene composite material differs from Example 6 only in that no composite grafted compatibilizer is prepared in advance. In the process of preparing the polypropylene composite material, PE, POE, GMA are mixed with other components and melt-extruded. The mass ratio of PE, POE, and GMA is 75:25:5, and the total weight of the three is the same as that of the composite grafted compatibilizer in Example 6.

[0062] Comparative Example 14

[0063] A polypropylene composite material, which differs from Example 6 only in that no composite grafted compatibilizer is added.

[0064] Examples 11-21

[0065] The formulations of the polypropylene composite materials described in this invention, specifically Examples 11 to 21, are shown in Table 2. The preparation methods are the same as in Example 1, and the composite grafted compatibilizer used is the same as that described in Example 1.

[0066] Table 2 (parts by weight)

[0067]

[0068]

[0069] The performance of the polypropylene composite materials described in the examples and comparative examples was tested using the following methods:

[0070] 1) Tensile strength was tested according to ISO527-2012, using type 1A spline, at a speed of 50 mm / min;

[0071] 2) Test impact performance according to ISO 180-2019, using type A spline;

[0072] 3) Test light transmittance according to GB / T 2410-2008, using a 2mm sample;

[0073] 4) Peel strength test: After in-mold injection molding of polypropylene composite material and PC film with inkjet printing, the peel strength is evaluated. The rating method is shown in Table 3.

[0074] The test results are shown in Table 4.

[0075] Table 3

[0076] grade describe Level 1 Unable to bond Level 2 Poor adhesion, peels off easily, and the peeled-off film is smooth. Level 3 With less force, the membrane peeled off is smooth. Level 4 With less force, the peeled membrane becomes blurry. Level 5 It was peeled off with considerable force, the cross-section was blurred, and a small amount of resin residue remained on the diaphragm. Level 6 It was almost impossible to peel off; the cross-section was blurry; and there was resin residue on the membrane. Level 7 It was difficult to peel off; the cross-section was blurred; and large pieces of the membrane remained.

[0077] Table 4

[0078]

[0079]

[0080] As shown in Table 4, the polypropylene composite material of the present invention exhibits good adhesion to the PC film, with peel strength reaching grade 4 and light transmittance exceeding 60%, and also possesses good mechanical properties. The composite compatibilizers used in Comparative Examples 7-8 contain PE and POE segments that do not conform to the composite compatibilizer described in the present invention, resulting in polypropylene composite materials that cannot simultaneously satisfy the requirements of good adhesion to the PC film and good light transmittance. The composite compatibilizers used in Comparative Examples 9-11 each contain only two segments, and their light transmittance cannot reach 50%. In Comparative Example 12, PP is used instead of PE in the composite compatibilizer, reducing compatibility and consequently worsening the overall performance of the polypropylene composite material. Comparative Example 13 did not pre-prepare a composite grafting agent but directly used PE, POE, and GMA as compatibilizers, mixing and melting them with PP resin; the polypropylene composite material prepared using this method has poor light transmittance. Comparative Example 14 did not add a compatibilizer and therefore could not bond.

[0081] Comparing the performance test results of Examples 6-10, it can be found that the preferred mass ratio of PE, POE and GMA in the composite compatibilizer is (70-80):(20-30):(4-6).

[0082] Comparing the test results of Examples 6 and 12-15, it can be found that the melt flow rate of PP resin in polypropylene composite materials is preferably 10-25 g / 10 min. Comparing the test results of Examples 6 and 16-19, it can be found that the melt flow rate of PC resin is preferably 6-19 g / 10 min.

[0083] Comparing the test results of Examples 6, 11, and 20-21, it can be found that the preferred composition of the polypropylene composite material is: 70-90 parts of PP resin, 3-15 parts of composite grafted compatibilizer, and 5-15 parts of PC resin.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention 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 the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polypropylene composite material, characterized in that, It contains the following components in parts by weight: 70 parts PP resin 90 parts, composite grafted compatibilizer 3 15 parts, PC resin 5 15 parts; the composite grafted compatibilizer comprises PE segment, POE segment, and GMA segment, wherein the mass ratio of the PE segment, POE segment, and GMA segment is (70-80):(20-30):(4-6); the melt flow rate of the PP resin measured at 230℃ and 2.16kg is 10-32g / 10min, and the melt flow rate of the PC resin measured at 300℃ and 1.2kg is 6-30g / 10min, wherein the melt flow rate is measured with reference to GB / T 3682.1-2018.

2. A polypropylene composite material as described in claim 1, characterized in that, The method for preparing the composite grafted compatibilizer is as follows: PE resin, POE resin and initiator are mixed evenly, then GMA is added for melt grafting, and the mixture is extruded and granulated to obtain the composite grafted compatibilizer.

3. The polypropylene composite material as described in claim 2, characterized in that, The initiator is at least one of benzoyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

4. The polypropylene composite material as described in claim 1, characterized in that, The melt flow rate of the PP resin measured at 230℃ and 2.16kg was 10-25g / 10min, and the melt flow rate of the PC resin measured at 300℃ and 1.2kg was 6-19g / 10min. The melt flow rates were measured with reference to GB / T 3682.1-2018.

5. The polypropylene composite material as described in claim 1, characterized in that, The polypropylene composite material further comprises 0.2-2 parts of weathering agent, 0.2-2 parts of lubricant, and 0.2-2 parts of antioxidant; the weathering agent is a hindered amine light stabilizer, the lubricant is at least one of EBS and erucamide, and the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant DLTDP.

6. A method for preparing a polypropylene composite material as described in any one of claims 1-5, characterized in that, The preparation method is as follows: the components are mixed evenly according to the formula, added to a twin-screw extruder for melt blending, extrusion granulation, and the polypropylene composite material is obtained.

7. The application of a polypropylene composite material as described in any one of claims 1-5 in the IML process.

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