A high molecular weight propylene-based elastomer toughened polypropylene blend composite and a method for making the same

Abstract

The present application relates to polypropylene material and its preparation method, disclose a kind of high molecular weight propylene-based elastomer toughened polypropylene blend composite material and its preparation method;Its preparation method is, using high molecular weight propylene-based elastomer toughened polypropylene, the high molecular weight propylene-based elastomer is by propylene monomer and its comonomer (1-butene, styrene, 1-hexene, 1-octene, 1-decene and the like one or several) preparation by quinoline amine-based binuclear metal hafnium catalyst and cocatalyst (three five fluorophenyl boron, triphenyl carbonium tetrakis (five fluorophenyl) borate, aluminoxane, alkyl aluminum, alkyl aluminum chloride and the like one or several);While meeting the improvement PP toughness, keep its excellent strength and rigidity, and continue to give its excellent low temperature toughness, specifically, after toughening modification, the toughness of polypropylene-based blend composite material at room temperature (25 DEG C) and low temperature (-25 DEG C) are obviously improved, simultaneously, its tensile strength changes little.Therefore, the present application has originality innovation, provides new direction for the development of polyolefin material field.

Description

TECHNICAL FIELD

[0001] The present application relates to polypropylene material and preparation method, and particularly relates to a high molecular weight propylene-based elastomer toughened polypropylene blend composite material and a preparation method thereof. BACKGROUND

[0002] Polypropylene (PP) is widely used in the fields of automobile industry, household appliances, electronic products, building materials and packaging, etc. due to its low price, non-toxicity, easy processing and excellent comprehensive mechanical properties. In the past decade, the apparent consumption of PP in China has increased by 10% per year, and has become the second largest consumption synthetic resin after polyethylene. The rapid growth of PP production capacity and output has been driven by the booming market demand, and its output ranks the third after polyethylene and polyvinyl chloride. With the rapid development of science and technology, the requirements for the performance of PP materials are also increasing. Since the advent of PP, the modification of high performance has been the focus of researchers. At present, the modification of PP mainly focuses on high strength, high toughness, high transparency, low density, foaming and flame retardance, etc. Especially under the impetus of the trend of automobile lightweight, "plastic instead of steel" 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 notched impact strength. Therefore, the demand for high toughness PP is increasingly urgent, and the toughening modification of PP has become an important way to realize its high performance and plays 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-based elastomer (SBS, SEBS), etc. Although blending with elastomers can greatly improve the impact resistance of PP, due to the low intrinsic strength of elastomers, the toughness is improved, and the strength and stiffness are inevitably reduced, and the reduction amplitude of strength and stiffness often shows a positive correlation with the amount of elastomers. Therefore, the amount of elastomers should be reduced as much as possible while improving the toughness of PP, so as to reduce the adverse effects of elastomers on the strength and stiffness of PP. This puts forward higher requirements for the toughening efficiency of elastomers.

[0004] High molecular weight random polypropylene (HMW-aPP) elastomer has a more similar molecular structure with PP, and therefore, it is expected to be used as a high-efficiency toughening modifier of PP. For example, Byung-Kook et al. used HMW-aPP with a molecular weight of 30×10 4HMW-aPP with high molecular weight (HMW-aPP) around 100,000-200,000 g / mol as toughening modifier polymer of PP, research found that when the content of HMW-aPP was 20wt%, the notched impact strength of PP / HMW-aPP increased by 385% compared with pure PP (Macromolecular Research 2015, 23(9), 809-813). However, when the content of POE was about 20wt%, the notched impact strength of PP / HMW-aPP did not increase significantly compared with pure PP (Wuhan University of Technology, Master thesis, 2013). Although the use of HMW-aPP can improve the toughening efficiency of PP to some extent, due to the high glass transition temperature (usually ≥-10℃) of pure HMW-aPP, 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 would be significantly reduced. For example, when the content of HMW-aPP was 20wt%, the tensile yield of PP / HMW-aPP decreased by 37% compared with pure PP. Therefore, it is necessary to further improve the toughening efficiency of PP. In theory, HMW-aPP with higher molecular weight has higher toughening efficiency for PP, but there is almost no report on this aspect.

[0005] Therefore, it is necessary to provide a high molecular weight propylene-based elastomer toughened polypropylene blend composite and a preparation method thereof, which can improve the toughness of PP while maintaining its excellent strength and rigidity, and continue to endow it with excellent low temperature toughness, which is helpful to expand the application prospect of PP. SUMMARY

[0006] <Technical problems solved by the present application>

[0007] To solve the current problems (1) the glass transition temperature of pure HMW-aPP is too high (usually ≥-10℃), which is difficult to improve the low temperature toughness of PP; (2) the existing HMW-aPP will cause obvious loss of strength and rigidity while improving the toughness of PP, that is, the toughening efficiency of the existing HMW-aPP still needs to be further improved; (3) in theory, HMW-aPP with higher molecular weight has higher toughening efficiency for PP, but there is almost no report on this aspect.

[0008] <Technical solutions adopted by the present application>

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

[0010] The specific content is as follows:

[0011] First, the present application provides a high molecular weight propylene-based elastomer toughened polypropylene blend composite, the main toughening component is a high molecular weight propylene-based elastomer, after toughening modification, the toughness of the polypropylene-based blend composite at room temperature (25℃) and low temperature (-25℃) is significantly improved.

[0012] 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 amine-based dinuclear hafnium catalyst and cocatalyst (one or more of tri(pentafluorophenyl)boron, triphenylcarbenium tetrakis(pentafluorophenyl)borate, aluminoxane, alkyl aluminum, alkyl aluminum chloride, etc.).

[0013] The structure of the quinoline amine-based dinuclear hafnium catalyst is shown in formula (I):

[0014]

[0015] Second, the molecular weight of the above-mentioned high molecular weight propylene-based elastomer ranges from 50 to 500 x 10 4 g / mol; the isotacticity (calculated as the percentage of propylene unit isotactic sequence pentad [mmmm] in the propylene molecular chain) ranges from 5 to 50 mmmm%; the glass transition temperature ranges from -50 to 0℃.

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

[0017] Fourth, in the above-mentioned 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 detangling agent is one or more of white oil, stearic acid, PE wax, etc.

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

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

[0020] Step one: weigh the polypropylene, high molecular weight propylene-based elastomer, detangling agent and other additives according to the mass fraction, and mix them in a mixer for 3-5 minutes;

[0021] Step two: use an extruder to granulate, the temperature setting range is 170-250℃, and the screw rotation speed setting range is 100-500 rpm. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 DSC plot for a homopolypropylene-based elastomer having a molecular weight range of 8 x 10 5 g / mol and isotacticity of 8.2 mmmm %.

[0023] Figure 2 DSC plot for a propylene-1-octene copolymer elastomer having a molecular weight range of 12 x 10 5 g / mol.

[0024] Figure 3 DSC plot for a homopolypropylene-based elastomer having a molecular weight range of 4 x 10 5 g / mol and isotacticity of 15.4 mmmm %.

[0025] Figure 4 GPC plot for a homopolypropylene-based elastomer having a molecular weight range of 8 x 10 5 g / mol and isotacticity of 8.2 mmmm %.

[0026] Figure 5 GPC plot for a propylene-1-octene copolymer elastomer having a molecular weight range of 12 x 10 5 g / mol.

[0027] Figure 6 GPC plot for a homopolypropylene-based elastomer having a molecular weight range of 4 x 10 5 g / mol and isotacticity of 15.4 mmmm %.

[0028] Figure 7 NMR carbon spectrum plot for a homopolypropylene-based elastomer having a molecular weight range of 8 x 10 5 g / mol and isotacticity of 8.2 mmmm %.

[0029] Figure 8 NMR carbon spectrum plot for a homopolypropylene-based elastomer having a molecular weight range of 4 x 10 5 g / mol and isotacticity of 15.4 mmmm %. DETAILED DESCRIPTION

[0030] The present application is further illustrated by the following examples without limiting the present application thereto. The examples of the present application can make the skilled in the art more fully understand the present application.

[0031] The experimental methods used in the following examples are conventional methods unless otherwise specified.

[0032] The present application is described in detail by the following specific examples.

[0033] <Example>

[0034] Example 1

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

[0036] (2) The above mixture was mixed in a mixer for 3-5 minutes;

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

[0038] (4) Samples were prepared using an injection molding machine (Jiangsu Tianyuan Test Equipment Co., Ltd., TY-7003H), with the three-stage injection molding temperature set to 210°C, 235°C, and 220°C, respectively, and the mold temperature set to 40°C.

[0039] Example 2

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

[0041] (2) The above mixture was mixed in a mixer for 3-5 minutes;

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

[0043] (4) Samples were prepared using an injection molding machine (Jiangsu Tianyuan Test Equipment Co., Ltd., TY-7003H), with the three-stage injection molding temperature set to 210°C, 235°C, and 220°C, respectively, and the mold temperature set to 40°C.

[0044] Example 3

[0045] (1) Polypropylene, high molecular weight homopolypropylene-based elastomer, white oil, and antioxidant were weighed by mass fraction: polypropylene 100 parts, high molecular weight propylene-based elastomer 20 parts, white oil 5 parts, antioxidant 1 part;

[0046] (2) The above mixture was mixed in a mixer for 3-5 minutes;

[0047] (3) Granulation was performed using an extruder (Kobe Dosei Kikai Co., Ltd., CTE20) with a screw and a die temperature set in the range of 170 to 250°C and a screw rotation speed set in the range of 200 rpm.

[0048] (4) The sample was prepared using an injection molding machine (Jiangsu Tianyuan Experimental Equipment Co., Ltd., TY-7003H) with three-stage injection molding temperatures of 210°C, 235°C, and 220°C, and a mold temperature of 40°C.

[0049] <Comparative Example>

[0050] Comparative Example 1

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

[0052] (2) The above mixture was mixed in a mixer for 3 to 5 minutes.

[0053] (3) Granulation was performed using an extruder (Kobe Dosei Kikai Co., Ltd., CTE20) with a screw and a die temperature set in the range of 170 to 250°C and a screw rotation speed set in the range of 200 rpm.

[0054] (4) The sample was prepared using an injection molding machine (Jiangsu Tianyuan Experimental Equipment Co., Ltd., TY-7003H) with three-stage injection molding temperatures of 210°C, 235°C, and 220°C, and a mold temperature of 40°C.

[0055] Comparative Example 2

[0056] (1) Polypropylene and antioxidant were weighed in parts by mass: polypropylene 100 parts and antioxidant 1 part.

[0057] (2) The above mixture was mixed in a mixer for 3 to 5 minutes.

[0058] (3) Granulation was performed using an extruder (Kobe Dosei Kikai Co., Ltd., CTE20) with a screw and a die temperature set in the range of 170 to 250°C and a screw rotation speed set in the range of 200 rpm.

[0059] (4) The sample was prepared using an injection molding machine (Jiangsu Tianyuan Experimental Equipment Co., Ltd., TY-7003H) with three-stage injection molding temperatures of 210°C, 235°C, and 220°C, and a mold temperature of 40°C.

[0060] <Experimental Example>

[0061] The samples prepared by 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), and the results are shown in Table 1-1.

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

[0063]

[0064] As can be seen from Table 1-1, compared with pure PP (C2), the notched impact strength at room temperature (25℃) of the 4×10 5 g / mol high molecular weight homopolypropylene-based elastomer modified PP (C1) is increased from 3.6kJ / m 2 to 16.2kJ / m 2 , an increase of 350.0%, which is obvious; the notched impact strength at low temperature (-25℃) is increased from 1.1kJ / m 2 to 1.5kJ / m 2 , which is not obvious; the tensile strength is reduced from 33.7MPa to 26.1MPa, a decrease of 29.1%.

[0065] The notched impact strength at room temperature (25℃) and low temperature (-25℃) of the 8×10 5 g / mol high molecular weight homopolypropylene-based elastomer modified PP (E1) is increased to 18.9kJ / m 2 and 1.7kJ / m 2 , respectively, an increase of 16.7% and 13.3% compared with C1, respectively, and the increase in notched impact strength at low temperature (-25℃) is not obvious; the tensile strength is reduced to 27.4MPa, a decrease of 23.0% compared with C1.

[0066] The samples prepared by 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), and the results are shown in Table 1-2.

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

[0068]

[0069] As can be seen from Table 1-2, the notched impact strength at room temperature (25℃) and low temperature (-25℃) of the 12×10 5 g / mol high molecular weight propylene-1-octene copolymer elastomer modified PP (E2) is increased to 19.1kJ / m 2and 4.5 kJ / m 2 , increased by 17.9% and 200.0% respectively, the low temperature (-25℃) notched impact strength increased significantly; the tensile strength increased to 28.4 MPa, increased by 8.8% compared with C1.

[0070] The samples prepared by 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), and the results are shown in Tables 1-3.

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

[0072]

[0073] As shown in Table 1-3, the 11×10 5 g / mol high molecular weight homopolypropylene-based elastomer (high regularity) modified PP (E3) had the notched impact strength at room temperature (25℃) and low temperature (-25℃) changed to 15.4 kJ / m 2 and 1.6 kJ / m 2 , respectively; the tensile strength increased to 31.5 MPa.

[0074] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

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 room temperature toughness and low temperature toughness of the polypropylene-based blend composite material are significantly improved. The high molecular weight propylene-based elastomer is prepared from propylene monomers and their comonomers. The comonomers are selected from one or more of 1-butene, styrene, 1-hexene, 1-octene, and 1-decene, using a quinolineamine-based binuclear metal hafnium catalyst and a cocatalyst. The catalyst structure is shown in Formula I. (I) The co-catalyst is selected from one or more of triphenylphenylborane, triphenylcarbazide tetra(pentafluorophenyl)borate, aluminoxane, alkylaluminum, and alkylaluminum chloride.

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 50~500×10⁻⁶. 4 g / mol.

3. The high molecular weight propylene-based elastomer-toughened polypropylene blend composite material according to claim 1, characterized in that, The isotactic range of the high molecular weight propylene-based elastomer is 5~50. mmmm% The isotacticity is expressed as the percentage content of the isotactic pentatonic group [mmmm] of propylene units in the propylene molecular chain.

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, It is composed of the following components in the indicated mass ratios: 100 parts polypropylene, 2-40 parts high molecular weight propylene-based elastomer, 0-10 parts unwinding agent, and 0-10 parts other additives, wherein the other additives are selected from antioxidants and light stabilizers.

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

7. The high molecular weight propylene-based elastomer-toughened polypropylene blend composite material according to any one of claims 1-6, characterized in that, The material is prepared according to the following process: Step 1: Weigh polypropylene, high molecular weight propylene-based elastomer, unwinding agent, antioxidant, and light stabilizer according to the mass fractions, and mix them in a mixer for 3-5 minutes; Step 2: Granulate using an extruder, with the temperature set in the range of 170-250 ℃ and the screw speed set in the range of 100-500 rpm.

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