High molecular weight propenyl elastomer toughened polypropylene blend composite material and preparation method thereof

Abstract

The invention relates to a polypropylene material and a preparation method thereof, and discloses a high molecular weight propenyl elastomer toughened polypropylene blend composite material and a preparation method thereof. The preparation method comprises the following steps: toughening polypropylene by using a high-molecular-weight propenyl elastomer; the high-molecular-weight propenyl elastomer is prepared from propylene monomers and comonomers (one or more of 1-butene, styrene, 1-hexene, 1-octylene, 1-decene and the like) through a quinoline amino binuclear metal hafnium catalyst and co-catalysts (tri-pentafluorophenyl boron, triphenylcarbonium tetra (pentafluorophenyl) borate, aluminoxane, aluminum alkyl and the like). And one or more of alkyl aluminum chloride and the like). According to the present invention, the polypropylene-based blend composite material has characteristics of PP toughness improving, excellent strength and excellent rigidity maintaining, and excellent low temperature toughness, specifically, after the toughening modification, the normal temperature (25 DEG C) toughness and the low temperature (-25 DEG C) toughness of the polypropylene-based blend composite material are significantly improved, and the tensile strength change is not significant. Therefore, the invention has original innovation, and provides a new direction for the development of the field of polyolefin materials.

Description

Technical Field

[0001] The invention relates to a polypropylene material and a preparation method thereof, in particular to a high molecular weight propylene-based elastomer toughened polypropylene blend composite material and a preparation method thereof. Background Art

[0002] Polypropylene (PP) is widely used in the automotive industry, household appliances, electronic products, building materials and packaging because of its low price, non-toxicity, easy processing and excellent comprehensive mechanical properties. In the past decade, the apparent consumption of PP in my country has increased by 10% annually, and has become the second largest consumption synthetic resin after polyethylene. The strong market demand has driven the rapid growth of PP production capacity and output. At present, its output ranks third after polyethylene and polyvinyl chloride. With the rapid development of science and technology, the requirements for the performance of PP materials are also constantly improving. Since the advent of PP, its high-performance modification has always been a key area of ​​concern for researchers. At present, PP modification is mainly focused on high strength, high toughness, high transparency, low density, foaming and flame retardancy. Especially driven by the trend of lightweight automobiles, "replacing steel with plastic" has gradually become the goal of the automobile manufacturing industry. However, PP has the disadvantages of poor toughness, especially poor low-temperature toughness and low notch impact strength. Therefore, the demand for high-toughness PP is becoming increasingly urgent. The toughening modification of PP has become an important way to achieve its high performance and has played a key role in expanding the application field of PP.

[0003] Rubber or thermoplastic elastomer toughening modification is considered to be the most effective method for PP toughening modification. Commonly used PP toughening elastomers include ethylene propylene rubber (EPDM), ethylene-octene copolymer (POE, OBC), styrene elastomer (SBS, SEBS), etc. Although blending with elastomers will greatly improve the impact resistance of PP, due to the low intrinsic strength of elastomers, the increase in toughness will inevitably cause a decrease in strength and stiffness, and the decrease in strength and stiffness often shows a positive correlation with the amount of elastomer used. Therefore, while improving the toughness of PP, the amount of elastomer should be reduced as much as possible to reduce its adverse effects on the strength and stiffness of PP. This puts higher requirements on the toughening efficiency of elastomers.

[0004] High molecular weight atactic polypropylene (HMW-aPP) elastomer has a molecular structure more similar to PP, so it is expected to be used as an efficient toughening modifier for PP. For example, Byung-Kook et al. 4High molecular weight random polypropylene (HMW-aPP) with a content of about 100 g / mol is used as a toughening and modifying polymer for PP. Studies have found that when the content of HMW-aPP is 20wt%, the notched impact strength of PP / HMW-aPP increases by 385% compared with pure PP (Macromolecular Research 2015, 23(9), 809-813). When the content of POE is about 20wt%, the notched impact strength of PP / HMW-aPP does not increase significantly compared with pure PP (Wuhan University of Technology, Master's thesis, 2013). Although the use of HMW-aPP can improve the toughening efficiency of PP to a certain extent, due to the high glass transition temperature of pure HMW-aPP (usually ≥-10°C), its contribution to the low-temperature toughness of PP is often very limited; in addition, Byung-Kook et al. also found that the strength and rigidity of PP / HMW-aPP will be significantly lost. For example, when the content of HMW-aPP is 20wt%, the tensile yield of PP / HMW-aPP is reduced by 37% compared with pure PP. Therefore, it is necessary to further improve the toughening efficiency of PP. In theory, HMW-aPP with a higher molecular weight has a higher toughening efficiency for PP, but there are almost no reports on this aspect.

[0005] Therefore, a high molecular weight propylene-based elastomer toughened polypropylene blend composite material and a preparation method thereof are provided, which can improve the toughness of PP while maintaining its excellent strength and rigidity and continue to give it excellent low-temperature toughness, which is very helpful for expanding the application prospects of PP. Summary of the invention

[0006] <Technical Problems Solved by the Invention>

[0007] It is used to solve the current problems that (1) the glass transition temperature of pure HMW-aPP (usually ≥-10℃) is too high, making it difficult to improve the low-temperature toughness of PP; (2) while the existing HMW-aPP improves the toughness of PP, it will bring about obvious losses in strength and rigidity, that is, the toughening efficiency of the existing HMW-aPP still needs to be further improved; (3) in theory, higher molecular weight HMW-aPP has a higher toughening efficiency for PP, but there are almost no related reports.

[0008] <Technical solution adopted by the present invention>

[0009] In view of the above technical problems, the object of the present invention is to provide a high molecular weight propylene-based elastomer toughened polypropylene blend composite material and a preparation method thereof.

[0010] The specific contents are as follows:

[0011] First, the present invention provides a high molecular weight propylene-based elastomer toughened polypropylene blend composite material, wherein the main toughening component is a high molecular weight propylene-based elastomer, and after toughening modification, the room temperature (25°C) toughness and low temperature (-25°C) toughness of the polypropylene-based blend composite material are significantly improved;

[0012] The high molecular weight propylene-based elastomer is prepared from propylene monomer and comonomer (one or more of 1-butene, styrene, 1-hexene, 1-octene, 1-decene, etc.) by quinoline amine binuclear metal hafnium catalyst and cocatalyst (one or more of trispentafluorophenyl boron, triphenylcarbonium tetrakis(pentafluorophenyl)borate, aluminoxane, alkyl aluminum, alkyl aluminum chloride, etc.);

[0013] Wherein, the structure of the quinolineamino binuclear metal hafnium catalyst is shown in formula (I):

[0014]

[0015] Second, the molecular weight range of the high molecular weight propylene-based elastomer is 50 to 500×10 4 g / mol; the isotacticity (measured as the percentage of the isotactic sequence pentad [mmmm] of the propylene unit in the propylene molecular chain) ranges from 5 to 50 mmmm%; and the glass transition temperature ranges from -50 to 0°C.

[0016] Third, in the above preparation method, the high molecular weight propylene-based elastomer toughened polypropylene blend composite material is mainly composed of the following components in the following weight ratios: 100 parts of polypropylene, 2 to 40 parts of high molecular weight propylene-based elastomer, 0 to 10 parts of disentanglement agent, and 0 to 10 parts of other additives (antioxidants, light stabilizers, etc.);

[0017] Fourth, in the above preparation method, in order to coordinate the contradiction between the processing viscosity of the high molecular weight propylene-based elastomer and its toughening efficiency, the disentanglement agent is one or more of white oil, stearic acid, PE wax, etc.;

[0018] Fifth, in the above preparation method, in order to improve the processing and use stability of the high molecular weight propylene-based elastomer toughened polypropylene blend composite material, the other additives are antioxidants, light stabilizers, etc.

[0019] Sixth, in the above preparation method, the material is prepared according to the following process:

[0020] Step 1: Weigh polypropylene, high molecular weight propylene-based elastomer, disentanglement agent and other additives according to mass fractions, and mix them in a mixer for 3 to 5 minutes;

[0021] Step 2: Granulate using an extruder, with the temperature setting range being 170-250°C and the screw speed setting range being 100-500rpm. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The molecular weight range is 8×10 5 g / mol, DSC curve of homopolypropylene-based elastomer with an isotacticity of 8.2mmmm%.

[0023] Figure 2 The molecular weight range is 12×10 5 g / mol DSC curve of propylene-1-octene copolymer elastomer.

[0024] Figure 3 The molecular weight range is 4×10 5 g / mol, DSC curve of homopolypropylene-based elastomer with an isotacticity of 15.4mmmm%.

[0025] Figure 4 The molecular weight range is 8×10 5 g / mol, GPC curve of homopolypropylene-based elastomer with an isotacticity of 8.2mmmm%.

[0026] Figure 5 The molecular weight range is 12×10 5 GPC curve of propylene-1-octene copolymer elastomer with a density of g / mol.

[0027] Figure 6 The molecular weight range is 4×10 5 g / mol, GPC curve of homopolypropylene-based elastomer with an isotacticity of 15.4mmmm%.

[0028] Figure 7 The molecular weight range is 8×10 5 g / mol, NMR carbon spectrum of homopolypropylene-based elastomer with an isotacticity of 8.2mmmm%.

[0029] Figure 8 The molecular weight range is 4×10 5 g / mol, NMR carbon spectrum of homopolypropylene-based elastomer with an isotacticity of 15.4mmmm%. DETAILED DESCRIPTION

[0030] The present invention is further described by way of examples, but the present invention is not limited thereto. The examples of the present invention can enable those skilled in the art to understand the present invention more comprehensively.

[0031] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0032] The present invention is described below with reference to specific embodiments.

[0033] <Example>

[0034] Example 1

[0035] (1) Polypropylene and high molecular weight homopolymer elastomer (molecular weight 8×10 5 g / mol; isotacticity is 8.2mmmm%; glass transition temperature is -9°C), white oil and antioxidant are weighed by mass: 100 parts of polypropylene, 20 parts of high molecular weight propylene-based elastomer, 5 parts of white oil, and 1 part of antioxidant;

[0036] (2) mixing the above mixture in a mixer for 3 to 5 minutes;

[0037] (3) Granulation was performed using an extruder (CTE20, Coperion Machinery Co., Ltd.), with the temperature of the screw and die set in the range of 170-250°C and the screw speed set in the range of 200 rpm.

[0038] (4) The samples were prepared using an injection molding machine (Jiangsu Tianyuan Testing Equipment Co., Ltd., TY-7003H). The three-stage injection molding temperatures were 210°C, 235°C, and 220°C, respectively, and the mold temperature was 40°C.

[0039] Example 2

[0040] (1) Polypropylene and high molecular weight propylene-1-octene copolymer elastomer (molecular weight 12×10 5 g / mol glass transition temperature is -16°C), white oil and antioxidant are weighed by mass: 100 parts of polypropylene, 20 parts of high molecular weight propylene-based elastomer, 5 parts of white oil, and 1 part of antioxidant;

[0041] (2) mixing the above mixture in a mixer for 3-5 minutes;

[0042] (3) Granulation was performed using an extruder (CTE20, Coperion Machinery Co., Ltd.), with the temperature of the screw and die set in the range of 170-250°C and the screw speed set in the range of 200 rpm.

[0043] (4) The samples were prepared using an injection molding machine (Jiangsu Tianyuan Testing Equipment Co., Ltd., TY-7003H). The three-stage injection molding temperatures were 210°C, 235°C, and 220°C, respectively, and the mold temperature was 40°C.

[0044] Example 3

[0045] (1) Weigh polypropylene, high molecular weight homopolymer elastomer, white oil and antioxidant according to their weight: 100 parts of polypropylene, 20 parts of high molecular weight homopolymer elastomer, 5 parts of white oil and 1 part of antioxidant;

[0046] (2) mixing the above mixture in a mixer for 3-5 minutes;

[0047] (3) Granulation was performed using an extruder (CTE20, Coperion Machinery Co., Ltd.), with the temperature of the screw and die set in the range of 170-250°C and the screw speed set in the range of 200 rpm.

[0048] (4) The samples were prepared using an injection molding machine (Jiangsu Tianyuan Testing Equipment Co., Ltd., TY-7003H). The three-stage injection molding temperatures were 210°C, 235°C, and 220°C, respectively, and the mold temperature was 40°C.

[0049] <Comparative Example>

[0050] Comparative Example 1

[0051] (1) Polypropylene and high molecular weight homopolymer elastomer (molecular weight 4×10 5 g / mol; isotacticity is 15.4mmmm%; glass transition temperature is -8°C), white oil and antioxidant are weighed by mass: 100 parts of polypropylene, 20 parts of high molecular weight propylene-based elastomer, 0 parts of white oil, and 1 part of antioxidant;

[0052] (2) mixing the above mixture in a mixer for 3-5 minutes;

[0053] (3) Granulation was performed using an extruder (CTE20, Coperion Machinery Co., Ltd.), with the temperature of the screw and die set in the range of 170-250°C and the screw speed set in the range of 200 rpm.

[0054] (4) The samples were prepared using an injection molding machine (Jiangsu Tianyuan Testing Equipment Co., Ltd., TY-7003H). The three-stage injection molding temperatures were 210°C, 235°C, and 220°C, respectively, and the mold temperature was 40°C.

[0055] Comparative Example 2

[0056] (1) Weigh polypropylene and antioxidant by weight: 100 parts of polypropylene and 1 part of antioxidant;

[0057] (2) mixing the above mixture in a mixer for 3-5 minutes;

[0058] (3) Granulation was performed using an extruder (CTE20, Coperion Machinery Co., Ltd.), with the temperature of the screw and die set in the range of 170-250°C and the screw speed set in the range of 200 rpm.

[0059] (4) The samples were prepared using an injection molding machine (Jiangsu Tianyuan Testing Equipment Co., Ltd., TY-7003H). The three-stage injection molding temperatures were 210°C, 235°C, and 220°C, respectively, and the mold temperature was 40°C.

[0060] <Test example>

[0061] The samples prepared in Example 1 (E1) and Comparative Examples 1-2 (C1-C2) were tested for notched impact (GB / T1843-2008) and tensile properties (GB / T1040.1-2006). The results are shown in Table 1-1.

[0062] Table 1-1 Comparison of performance test results of E1, C1 and C2

[0063]

[0064] It can be seen from Table 1-1 that compared with pure PP (C2), 4×10 5 The room temperature (25°C) notched impact strength of PP (C1) modified with a high molecular weight homopolypropylene-based elastomer of 3.6 kJ / m 2 Increased to 16.2 kJ / m 2 , increased by 350.0%, which is a significant increase; low temperature (-25℃) notched impact strength increased from 1.1kJ / m 2 Increase to 1.5 kJ / m 2 , there is little change; the tensile strength decreases from 33.7MPa to 26.1MPa, a decrease of 29.1%.

[0065] 8×10 5 The room temperature (25°C) notched impact strength and low temperature (-25°C) notched impact strength of PP (E1) modified with high molecular weight homopolypropylene elastomer increased to 18.9 kJ / m 2 and 1.7 kJ / m 2 , increased by 16.7% and 13.3% respectively compared with C1, and the increase in low temperature (-25℃) notched impact strength was not very obvious; the tensile strength decreased to 27.4MPa, which was 23.0% lower than C1.

[0066] The samples prepared in Example 2 (E2) and Comparative Examples 1-2 (C1-C2) were tested for notched impact (GB / T1843-2008) and tensile properties (GB / T1040.1-2006). The results are shown in Table 1-2.

[0067] Table 1-2 Comparison of performance test results between E2, C1 and C2

[0068]

[0069] From Table 1-2, we can see that 12×10 5 The room temperature (25°C) notched impact strength and low temperature (-25°C) notched impact strength of PP (E2) modified with high molecular weight propylene-1-octene copolymer elastomer increased to 19.1 kJ / m 2and 4.5 kJ / m 2 , increased by 17.9% and 200.0% respectively compared with C1, and the low temperature (-25℃) notched impact strength increased significantly; the tensile strength increased to 28.4MPa, an increase of 8.8% compared with C1.

[0070] The samples prepared in Example 3 (E3) and Comparative Examples 1-2 (C1-C2) were tested for notched impact (GB / T1843-2008) and tensile properties (GB / T1040.1-2006). The results are shown in Tables 1-3.

[0071] Table 1-3 Comparison of performance test results of E3, C1 and C2

[0072]

[0073] From Table 1-3, we can see that 11×10 5 The room temperature (25°C) notched impact strength and low temperature (-25°C) notched impact strength of PP (E3) modified with high molecular weight homopolypropylene-based elastomer (high regularity) of 1.5 g / mol were changed to 15.4 kJ / m 2 and 1.6 kJ / m 2 ; The tensile strength increased to 31.5MPa.

[0074] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high molecular weight propylene-based elastomer toughened polypropylene blend composite material, characterized in that: The toughening component of polypropylene is a high molecular weight propylene-based elastomer. After toughening modification, the toughness of the polypropylene-based blend composite material at room temperature (25°C) and low temperature (-25°C) are significantly improved; the high molecular weight propylene-based elastomer is prepared from propylene monomer and its comonomer (one or more of 1-butene, styrene, 1-hexene, 1-octene, 1-decene, etc.) by quinoline amino binuclear metal hafnium catalyst and co-catalyst (one or more of trispentafluorophenyl boron, triphenylcarbonium tetrakis(pentafluorophenyl)borate, aluminoxane, alkyl aluminum, alkyl aluminum chloride, etc.).

2. The high molecular weight propylene-based elastomer toughened polypropylene blend composite material according to claim 1, characterized in that: The molecular weight range of the high molecular weight propylene-based elastomer is 50 to 500×10 4 g / mol.

3. The high molecular weight propylene-based elastomer toughened polypropylene blend composite material according to claim 1, characterized in that: The isotacticity of the high molecular weight propylene-based elastomer (calculated as the percentage of the isotactic sequence pentad [mmmm] of propylene units in the propylene molecular chain) is in the range of 5 to 50 mmmm%.

4. The high molecular weight propylene-based elastomer toughened polypropylene blend composite material according to claim 1, characterized in that: The glass transition temperature of the high molecular weight propylene-based elastomer is in the range of -50 to 0°C.

5. The high molecular weight propylene-based elastomer toughened polypropylene blend composite material according to claim 1, characterized in that: The invention is composed of the following components in the following mass proportions: 100 parts of polypropylene, 2-40 parts of high molecular weight propylene-based elastomer, 0-10 parts of untangling agent, and 0-10 parts of other auxiliary agents (antioxidant, light stabilizer, etc.).

6. The high molecular weight propylene-based elastomer toughened polypropylene blend composite material according to claim 5, characterized in that The detangling agent is one or more of white oil, stearic acid, PE wax and the like.

7. The high molecular weight propylene-based elastomer toughened polypropylene blend composite material according to claim 5, characterized in that The other additives are antioxidants, light stabilizers and the like.

8. The high molecular weight propylene-based elastomer toughened polypropylene blend composite material according to any one of claims 1 to 7, characterized in that: The material is prepared according to the following process: Step 1: polypropylene, high molecular weight propylene-based elastomer, disentanglement agent and other additives are weighed according to mass fractions and mixed in a mixer for 3 to 5 minutes; Step 2: granulation is carried out using an extruder, the temperature setting range is 170 to 250°C, and the screw speed setting range is 100 to 500rpm.

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