Anti-impact co-polypropylene and preparation method thereof

Abstract

The invention relates to the field of co-polypropylene and preparation thereof, and discloses an anti-impact co-polypropylene and a preparation method thereof, and the method comprises the following steps: (1) measuring MFR and EPR of a competitive control and a common product; (2) through a continuous self-nucleation method, measuring and establishing a relationship diagram of the melting temperature and the heat flow of the competitive control and the common product, and respectively calculating the melting peak area and the peak temperature of the main peak of the competitive control and the common product; and (3) respectively calculating the slurry concentration, electron donor concentration and hydrogen concentration of the customized product according to the MFR, EPR, melting peak area and peak temperature of the main peak of the competitive reference substance and the common product in combination with the slurry concentration, electron donor concentration and hydrogen concentration of the common product, and carrying out extrusion granulation and drying on the powder obtained by polymerization to obtain the finished product. And preparing to obtain a customized product anti-impact co-polypropylene. The method can be used for preparing the impact-resistant co-polypropylene with specific mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of copolymer polypropylene and its preparation, specifically to an impact-resistant copolymer polypropylene and its preparation method. Background Technology

[0002] Impact copolymer polypropylene (IPC) is a close blend of polypropylene (IPP) and α-olefin-propylene copolymers (such as ethylene propylene rubber "EPR"), or with a very small amount of linear low-density polyethylene. Its microstructure exhibits a multi-layered core-shell structure and it is widely used in commercial products such as automotive parts and appliances.

[0003] Typically, IPC contains 65-93% polypropylene (IPP) and 6-34% ethylene propylene rubber (EPR). EPR is dispersed in IPP, which acts as a binder (or continuous phase).

[0004] Recent studies have shown that the presence of atactic polypropylene or low molecular weight IPP in the base material weakens the binding effect of polymer chain segments, affects the melt viscosity of the base material, and ultimately leads to a loss of the rigidity-toughness balance of IPC. Isotactic polypropylene (IPP) is a key indicator affecting the rigidity of IPC.

[0005] Therefore, it is of great significance to research and develop an IPC product that improves both rigidity and toughness balance. Summary of the Invention

[0006] The purpose of this invention is to overcome the defect of poor mechanical properties of impact copolymer polypropylene (IPC) prepared by existing technology, and to provide an impact copolymer polypropylene and its preparation method, which can prepare impact copolymer polypropylene (custom products) with specific mechanical properties.

[0007] To achieve the above objectives, a first aspect of the present invention provides a method for preparing impact-resistant copolymer polypropylene, wherein the preparation method includes:

[0008] (1) Measure the MFR and EPR of the competing control and the ordinary product;

[0009] (2) By using a continuous self-nucleation method, the melting temperature and heat flow relationship diagrams of the competing control and the ordinary product are measured and established, and the melting peak area and peak temperature of the main peak of the competing control and the ordinary product are calculated respectively.

[0010] (3) Based on the MFR, EPR, melt peak area and peak temperature of the main peak of the competitive control and the ordinary product, and combined with the preparation parameters of the ordinary product, slurry concentration, electron donor concentration and hydrogen concentration, the preparation parameters of the customized product impact copolymer polypropylene, slurry concentration, electron donor concentration and hydrogen concentration, are calculated respectively. The powder obtained by polymerization is extruded, granulated and dried to prepare the customized product impact copolymer polypropylene.

[0011] A second aspect of the present invention provides an impact-resistant copolymer polypropylene prepared by the aforementioned preparation method.

[0012] The beneficial effects of the present invention through the above technical solution are as follows:

[0013] (1) A significant feature of the present invention is that a new type of impact copolymer polypropylene (custom product) is prepared by changing the preparation parameters of polypropylene (ordinary product) in impact copolymer polypropylene;

[0014] (2) Another significant feature of the present invention is that when preparing the polypropylene in the new impact copolymer polypropylene (customized product), the polypropylene polymerization process route of the ordinary product is followed, and the slurry concentration, electron donor concentration and hydrogen concentration in the key preparation (manufacturing) parameters are recalculated.

[0015] (3) Another significant feature of the present invention is that continuous self-nucleating annealing (SSA) is used to compare the microstructure of IPP base material in different IPCs. Based on the EPR, melting peak area and melting temperature of the main peak of the competing control and ordinary products, the slurry concentration, electron donor concentration and hydrogen concentration and other parameters in the known key preparation (manufacturing) parameters of ordinary products are used to calculate the slurry concentration, electron donor concentration and hydrogen concentration and other parameters in the key preparation (manufacturing) parameters of new impact copolymer polypropylene (custom products). Attached Figure Description

[0016] Figure 1 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 1 and the ordinary product 1 in Example 1;

[0017] Figure 2 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 2 and the ordinary product 2 in Example 2;

[0018] Figure 3 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 3 and the ordinary product 3 in Example 3; Figure 4 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 5 and the ordinary product 5 in Example 3. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] As mentioned above, the first aspect of the present invention provides a method for preparing impact-resistant copolymer polypropylene, wherein the preparation method includes:

[0021] (1) Measure the MFR and EPR of the competing control and the ordinary product;

[0022] (2) By using a continuous self-nucleation method, the melting temperature and heat flow relationship diagrams of the competing control and the ordinary product are measured and established, and the melting peak area and peak temperature of the main peak of the competing control and the ordinary product are calculated respectively.

[0023] (3) Based on the MFR, EPR, melt peak area and main peak melting temperature of the competitive control and the ordinary product, and combined with the slurry concentration, electron donor concentration and hydrogen concentration in the key preparation (manufacturing) parameters of the ordinary product, the slurry concentration, electron donor concentration and hydrogen concentration of the impact copolymer polypropylene (custom product) are calculated respectively. The impact copolymer polypropylene (custom product) is prepared by adding the following steps during the preparation process: extrusion granulation and drying of the powder obtained by polymerization.

[0024] The inventors of this invention prepared a new type of impact-resistant copolymer polypropylene (custom product) by modifying the preparation parameters of polypropylene (ordinary product) in impact-resistant copolymer polypropylene, namely slurry concentration, electron donor concentration, and hydrogen concentration. In preparing the new impact-resistant copolymer polypropylene (custom product), the polypropylene polymerization process route of the ordinary product was followed, and the slurry concentration, electron donor concentration, and hydrogen concentration in the key preparation (manufacturing) parameters were recalculated. Continuous self-nucleating annealing (SSA) was used to compare the microstructure of IPP matrix in different IPCs. Based on the MFR, EPR, melt peak area, and main peak melting temperature of the competing control and the ordinary raw material, combined with the known key preparation (manufacturing) parameters such as slurry concentration, electron donor concentration, and hydrogen concentration of the ordinary product, the key preparation (manufacturing) parameters of the impact-resistant copolymer polypropylene (custom product) were calculated. This allows for the preparation of impact-resistant copolymer polypropylene (custom product) with mechanical properties close to or greater than those of the competing control.

[0025] According to the present invention, the EPR content of the competing control and the ordinary product is 6-34%, preferably 11-29%, and more preferably 13-27%.

[0026] According to the present invention, the absolute value of the difference between the ethylene propylene rubber (EPR) of the competing control and the ordinary product is between 1% and 10%, preferably 3% to 6%, and more preferably 3.4% to 5.4%. If the absolute value of the difference between the competing control and the ordinary product is too high, it will result in the disadvantage that it is impossible to prepare an impact-resistant copolymer polypropylene (custom product) with mechanical properties close to or greater than that of the competing control; if the absolute value of the difference between the competing control and the ordinary product is too low, it will result in the disadvantage that it is impossible to prepare an impact-resistant copolymer polypropylene (custom product) with mechanical properties close to or greater than that of the competing control.

[0027] According to the present invention, the IPP content of the competing control and the ordinary product is 65-93%, preferably 72-86%.

[0028] In this invention, the calculation method for IPP content is shown in formula (a):

[0029] IPP IPC =100% - EPR IPC , (a).

[0030] Among them, IPP IPC For IPC, the IPP content, EPR IPC This refers to the EPR content of IPC.

[0031] According to the present invention, the polymerization process is a combination of liquid-phase bulk polymerization and gas-phase copolymerization. The liquid-phase bulk polymerization is a loop process, with 1-2 loops, preferably 2 loops. The gas-phase copolymerization process includes 1-2 gas-phase fluidized beds, preferably 1 fluidized bed. Examples include Sinopec's ST loop process, LyondellBasell's Spheripol-II process, and ExxonMobil's ExxonMobil process.

[0032] According to the present invention, the catalyst is a Ziegler-Natta (ZN) catalyst, such as Sinopec's DQ series and DQC series, Lyondell Basell's Avant ZN series, and Clariant (China)'s... The catalyst used is CS-2 catalyst from Liaoning Yingkou Xiangyang Catalyst Co., Ltd.; the internal electron donor is a phthalate ester, typically di-n-butyl phthalate and diisobutyl phthalate; the co-catalyst is triethylaluminum (TEAL); the external electron donor is one of the following: C-donor (cyclohexylmethyldimethoxysilane), D-donor (dicyclopentyldimethoxysilane), P-donor (diisopropyldimethoxysilane), or B-donor (diisobutyldimethoxysilane). Hydrogen is used as the relative molecular mass regulator; the amount of hydrogen added to the loop reactor is calculated as needed.

[0033] In this invention, while maintaining the original catalyst system of the ordinary product, the polymerization control parameters are calculated based on the difference in IPP segment distribution between the competing control and the ordinary product. The amount of IPP or the melt index in the ordinary product are changed to prepare IPC with mechanical properties similar to the competing control.

[0034] According to the present invention, the slurry concentration of the impact-resistant copolymer polypropylene (custom product) is calculated according to formula (I);

[0035]

[0036] The EPR of the competing control and the ordinary product was measured.

[0037] In this invention, the slurry concentration of the ordinary product, i.e., the initial original slurry concentration of the ordinary product before calculation and correction, is determined based on the polypropylene polymerization process route of the ordinary product. Furthermore, "before calculation and correction" can be understood as the polymerization process route of the ordinary product, and "after calculation and correction" can be understood as the polymerization process route of the customized product.

[0038] According to the present invention, the electron donor concentration of the impact copolymer polypropylene (custom product) is calculated according to formula (II);

[0039]

[0040] The EPR of the competing control and the ordinary product is measured; the melt peak area of ​​the competing control and the ordinary product is measured by a continuous self-nucleation method; the electron donor concentration of the ordinary product is determined according to the polypropylene polymerization process route of the ordinary product; in this invention, the initial electron donor concentration of the ordinary product, that is, the initial electron donor concentration of the ordinary product before calculation and correction, is determined according to the polypropylene polymerization process route of the ordinary product.

[0041] In fact, the method for calculating the electron donor concentration is to increase or decrease the electron donor concentration by decreasing or increasing the T / D while keeping the T (triethylaluminum) concentration constant; the T / D calculation method for customized products is shown in formula (2):

[0042]

[0043] In this invention, the melting peak area is determined by a continuous self-nucleation method (SSA).

[0044] According to the present invention, the hydrogen concentration of impact copolymer polypropylene (custom product) is calculated according to formula (III);

[0045]

[0046] The EPR of the competing control and the ordinary product is measured; the peak temperatures of the competing control and the ordinary product are measured by a continuous self-nucleation method; the hydrogen concentration of the ordinary product is determined according to the polypropylene polymerization process route of the ordinary product; in this invention, the initial hydrogen concentration of the ordinary product, i.e., the initial hydrogen concentration of the ordinary product before calculation and correction, is determined according to the polypropylene polymerization process route of the ordinary product.

[0047] In this invention, the peak temperature is determined by a continuous self-nucleation method (SSA).

[0048] According to the present invention, the melt flow rate (MFR) of the competing control and the ordinary product is 1.8-120 g / 10 min, preferably 10-80 g / 10 min, more preferably 20-60 g / 10 min; preferably, the absolute value of the difference between the melt flow rate (MFR) of the competing control and the ordinary product is between 0.2 and 10, preferably 0.3-2, more preferably 0.4-1.5.

[0049] According to the present invention, the ethylene content of the competing control and the ordinary product is 0.5-13%, preferably 3.5-17%, more preferably 4-16.5%; preferably, the absolute value of the difference between the ethylene content of the competing control and the ordinary product is between 0.1-5%, preferably 0.2-2%, more preferably 0.3-1.6%.

[0050] According to the present invention, in step (2), the self-nucleation method includes the following steps:

[0051] (a) The competing control and the ordinary product are subjected to a heating-holding-cooling treatment to eliminate the thermal history of the competing control and the ordinary product;

[0052] (b) The competing control and the ordinary product are crystallized through multiple melt-cool cycles;

[0053] (c) The competitive control obtained in step (b) and the ordinary product are subjected to a heating-holding-cooling process to achieve thermodynamic phase separation.

[0054] According to the present invention, the process of step (a) includes: heating the competitive control and the ordinary product to 190-250°C, holding at that temperature for 0-60 min, and then cooling to 20-35°C to eliminate the thermal history of the competitive control and the ordinary product.

[0055] According to the present invention, the mass of the competing control and the ordinary product is 4-10 mg each.

[0056] According to the present invention, the heating rate is 5-60°C / min, preferably 10-30°C / min; preferably, the competing control and the ordinary product are heated to 200-230°C.

[0057] According to the present invention, the heat preservation time is 3-10 minutes.

[0058] According to the present invention, the cooling rate is 5-30℃ / min, preferably 10-20℃ / min; preferably, after heat preservation, the competing control and the ordinary product are cooled to 25-30℃.

[0059] In this invention, it should be noted that, in the process of processing the competing control and the ordinary product, the competing control and the ordinary product can be processed separately, or the competing control and the ordinary product can be processed together.

[0060] According to the present invention, the processing in step (b) includes: heating the competitive control and the ordinary product obtained in step (a) to 163-171°C, holding at that temperature for 0-60 min, and then cooling to 20-35°C; repeating the above process, with the final temperature decreasing by 2-15°C with each repetition, until the final temperature is 80-145°C.

[0061] According to the present invention, the competitive control or ordinary product obtained in step (a) is heated to 166-171°C; preferably, the heating rate is 2-30°C / min, more preferably 8-12°C / min.

[0062] According to the present invention, the heat preservation time is 3-5 minutes;

[0063] According to the present invention, the cooling rate is 0.5-50℃ / min, preferably 8-12℃ / min; preferably, after heat preservation, the competing control and the ordinary product are cooled to 25-30℃;

[0064] According to the present invention, the final temperature of the heating process decreases by 5-10°C with each repetition; preferably, the final temperature of the heating process is 80-140°C.

[0065] According to the present invention, the processing in step (c) includes: heating the competitive control and the ordinary product obtained in step (b) to 190-220°C, holding at that temperature for 0-60 min, and then cooling to 20-35°C to perform thermodynamic phase separation.

[0066] According to the present invention, the competitive control and the ordinary product obtained in step (b) are heated to 200-210°C; preferably, the heating rate is 2-30°C / min, more preferably 8-12°C / min.

[0067] According to the present invention, the heat preservation time is 3-5 minutes.

[0068] According to the present invention, the cooling rate is 0.5-50℃ / min, preferably 8-12℃ / min; preferably, after heat preservation, the competing control and the ordinary product are cooled to 25-30℃.

[0069] In this invention, the microstructural differences of the competing control and the ordinary product's IPP are compared using SSA test results. Preferably, the SSA test steps include:

[0070] (a) Measure the optimal self-nucleation temperature of the sample according to the Müller method, which is in the range of 166-171 °C; under nitrogen protection, heat 4-10 mg of sample to 190-250 °C at 10 °C / min, hold at that temperature for 0-60 min to eliminate thermal history, and then heat to the first optimal self-nucleation temperature T at 10 °C / min. S1 For example, 167℃, held at that temperature for 10 minutes, then cooled to 30℃ at a rate of 10℃ / min;

[0071] (b) Repeat the above step, with a temperature interval of 3-10℃ each time, and set the termination temperature T. S结束 Temperatures range from 80 to 140℃.

[0072] (c) Finally, raise the temperature to 200-230℃ at a rate of 10℃ / min, hold for 3 min, and then lower the temperature to 30℃ at a rate of 10℃ / min to complete the melting test. According to the sample normalization method, record the melting curve with melting temperature as the X-axis (in ℃) and heat flow as the Y-axis (in W / g) and export the data.

[0073] According to this invention, data is imported into Origin software from Origin Labs to establish a relationship curve between heat flux and melting temperature, with melting temperature as the X-axis (unit: °C) and heat flux as the Y-axis (unit: W / g). The heat flux versus melting temperature curves for both the competing control and the ordinary product are integrated to calculate the peak area and peak temperature (T). m主峰 and T m次峰 ).

[0074] According to the present invention, based on the Thomson-Gibbs equation, Among them, equilibrium melting point ΔH0=184×10 6 J·m -3 σ = 0.0496 J·m 2 L represents the lamellar thickness, which is related to the length of the isotactic segment in IPP. T m The melting peak temperature is positively correlated with the length of the isotactic segments of IPP; after processing by the self-nucleation method, the main peak and secondary peaks are arranged in descending order of temperature; preferably, the melting temperature of the main peak is 168-185℃, and the melting temperature of the secondary peak is 160-176℃; preferably, the melting temperature of the main peak is 170-183℃, and the preferred temperature of the secondary peak is 162-174℃; even more preferably, the melting temperature of the main peak is 172-180℃, and the preferred temperature of the secondary peak is 164-172℃.

[0075] According to the present invention, based on the principle of similar MFR and mechanical properties of the competing control, a suitable ordinary product is selected. During the production process of impact copolymer polypropylene (custom product), the slurry concentration, electron donor concentration and hydrogen concentration of impact copolymer polypropylene (custom product) are calculated and converted respectively. The powder obtained by polymerization is subjected to extrusion granulation and drying steps to obtain impact copolymer polypropylene (custom product).

[0076] According to a preferred embodiment of the present invention, a method for preparing an impact-resistant copolymer polypropylene (custom product) includes:

[0077] (1) Determine the composition of the common product and the competing control: EPR and ethylene content;

[0078] (2) Determine the quality indicators for ordinary products and competitive controls: MFR;

[0079] (3) Calculate the slurry concentration of the customized product according to formula (I);

[0080] (4) Calculate the electron donor concentration T / D of the customized product according to formula (II);

[0081] (5) Calculate the hydrogen concentration during IPP polymerization in the customized product according to formula (III);

[0082] (6) Custom product preparation process:

[0083] In the process of preparing the custom product, the slurry concentration, electron donor concentration and hydrogen concentration of the impact copolymer polypropylene (custom product) are calculated according to the above formulas (I), (II) and (III), respectively, and the powder obtained by polymerization is subjected to extrusion granulation and drying steps to obtain the new impact copolymer polypropylene (custom product).

[0084] (7) Measure the MFR, flexural modulus and impact strength of IPC according to ISO1133-1:2022 (2.16Kg load, 230℃), ISO178:2019 and ISO179-1:2010 respectively; compare the mechanical properties of competing controls and new custom products.

[0085] A second aspect of the present invention provides an impact-resistant copolymer polypropylene (custom product) prepared by the aforementioned preparation method.

[0086] According to the present invention, the mechanical properties of the impact-resistant copolymer polypropylene (custom product) are close to or greater than the mechanical properties of the competing control.

[0087] According to the present invention, the flexural modulus of the competing control is 0.450-2.200 GPa, and the impact strength at +23°C is 1-80 KJ / m. 2 .

[0088] The present invention will be described in detail below through embodiments.

[0089] In the following examples and comparative examples:

[0090] MFR was measured according to ISO 1133-1:2022 (2.16 kg load, 230 °C);

[0091] Use 13 Ethylene content was measured using Fourier Exchange Infrared Spectroscopy (FTIR) calibrated by C-NMR.

[0092] Measure EPR content according to ISO 16152:2022;

[0093] Measure the flexural modulus according to ISO 178:2019;

[0094] Measure the impact strength at +23°C according to ISO 179-1:2010.

[0095] Example 1

[0096] The following components are used in this embodiment:

[0097] Competitive control 1: A commercial IPC with an MFR of 30.1 g / 10 min, an EPR of 20%, and an ethylene content of 8.9%;

[0098] Common Product 1: An IPC produced using Ziegler-Natta (ZN) catalyst, with an MFR of 30.5 g / 10 min, an EPR of 16.6%, and an ethylene content of 9.2%.

[0099] Implementation steps:

[0100] (1) Determine the physical properties of competition control 1 and ordinary product 1:

[0101] The MFR, flexural modulus, and +23°C impact strength of competing control 1 and ordinary product 1 were measured according to ISO 1133-1:2022 (2.16 kg load, 230°C), ISO 178:2019, and ISO 179-1:2010, respectively; the EPR content was measured according to ISO 16152:2022; 13 Ethylene content was measured by Fourier exchange infrared spectroscopy (FTIR) calibrated by C-NMR; the physical properties of competition control 1 and ordinary product 1 are shown in Table 1.

[0102] Table 1

[0103]

[0104] (2) Calculate the slurry concentration of customized product 1:

[0105]

[0106] The slurry concentration of ordinary product 1 was determined using the same polypropylene polymerization process as the ordinary product, and was 510 kg PP / m³. 3 Substitute into the following formula:

[0107]

[0108] (3) Complete the SSA experiment, export the data, and process the data:

[0109] (3-1) Sample preparation: Take 7 mg of competitive control 1 and place the sample into the sample position of the calorimetric scanning analyzer;

[0110] (3-2) Eliminate thermal history: Set parameters to heat from room temperature (25℃, the same below) to 210℃ at a heating rate of 50℃ / min, hold for 10min, and then cool down to room temperature at a cooling rate of 50℃ / min.

[0111] (3-3) Melting and cooling crystallization: The initial heating endpoint temperature was set at 167℃, the heating rate was 10℃ / min, the heating endpoint temperature was held for 3min, and then the temperature was cooled to 30℃ at a cooling rate of 10℃ / min; the heating endpoint temperature was reduced by 5℃ with each repetition, and the heating endpoint temperature was 137℃.

[0112] (3-4) Thermodynamic phase separation: The temperature is increased from room temperature to 210℃ at a rate of 10℃ / min, held for 3 min, and then decreased to 30℃ at a rate of 10℃ / min.

[0113] (3-5) Repeat steps (3-1) to (3-4) to complete the measurement of ordinary product 1, record the melt curve, and export the data;

[0114] (3-6) Import the data into Origin software from Origin Labs to establish a heat flux versus melting temperature curve, with melting temperature as the X-axis (°C) and heat flux as the Y-axis (W / g). Integrate the heat flux versus melting temperature curves for both the competitive control 1 and the ordinary product 1, and calculate the peak area and peak temperature (T). m主峰 and T m次峰 ).

[0115] The SSA test scores of competing control 1 and ordinary product 1 are shown in Table 2.

[0116] Table 2

[0117]

[0118]

[0119] in addition, Figure 1 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 1 and the ordinary product 1 in Example 1. Figure 1 It can be seen that the peak height of the main peak of the competing control 1 is significantly different from that of the main peak of the ordinary product 1. Furthermore, the peak heights of their secondary peaks are also significantly different.

[0120] (4) Calculate the electron donor concentration of Customized Product 1:

[0121]

[0122] The electron donor concentration of ordinary product 1 is determined based on the polypropylene polymerization process route used for ordinary product 1, and the electron donor concentration of ordinary product 1 is 5; substituting into the following formula:

[0123]

[0124]

[0125] (5) Calculate the hydrogen concentration during IPP polymerization in Customized Product 1:

[0126]

[0127] The IPP hydrogen concentration of ordinary product 1 is determined based on the polypropylene polymerization process route adopted by the ordinary product, and the IPP hydrogen concentration of ordinary product 1 is 3300 ml / m³. 3 Substitute into the following formula:

[0128]

[0129] (6) During the production process of ordinary product 1, the slurry concentration, electron donor concentration and hydrogen concentration of customized product 1 are calculated as shown in Table 3:

[0130] Table 3

[0131]

[0132] The powder obtained from polymerization was subjected to extrusion granulation and drying steps to obtain the customized product 1; the MFR, flexural modulus and impact strength of customized product 1 were measured according to ISO 1133 (230℃, 2.16Kg), ISO 178:2019 and ISO 179-1:2010 respectively; the stiffness and toughness of customized product 1 are close to or reach or even exceed the mechanical properties of the competing control 1, as shown in Table 4.

[0133] Table 4

[0134]

[0135] The results in Tables 1-4 show that, while maintaining the original catalyst system, the polymerization control parameters of the customized product 1 were calculated based on the difference in IPP segment distribution between the competing control 1 and the ordinary product 1. By changing the amount of IPP or the melt index in the customized product 1, a customized product 1 with similar mechanical properties to the competing control 1 was prepared.

[0136] Example 2

[0137] The following components are used in this embodiment:

[0138] Competitive control 2: A commercial IPC with an MFR of 15.9 g / 10 min, an EPR of 25.1%, and an ethylene content of 9.9%;

[0139] Common Product 2: An IPC produced using Ziegler-Natta (ZN) catalyst, with an MFR of 17.4 g / 10 min, an EPR of 29.6%, and an ethylene content of 10.7%.

[0140] Implementation steps:

[0141] (1) Determine the physical properties of competition control 2 and ordinary product 2:

[0142] The MFR, flexural modulus, and +23°C impact strength of the competing control 2 and the ordinary product 2 were measured according to ISO 1133-1:2022 (2.16 kg load, 230°C), ISO 178:2019, and ISO 179-1:2010, respectively; the EPR content was measured according to ISO 16152:2022; 13 Ethylene content was measured by Fourier exchange infrared spectroscopy (FTIR) calibrated by C-NMR; parameters of competing control 2 and ordinary product 2 are shown in Table 5.

[0143] Table 5

[0144]

[0145] (2) Calculate the slurry concentration of customized product 2.

[0146]

[0147] The slurry concentration of ordinary product 2 is determined based on the polypropylene polymerization process route of ordinary product 2, and the slurry concentration of ordinary product 2 is 450 kgPP / m³. 3 Substitute into the following formula:

[0148]

[0149] (3) Complete the SSA experiment, export the data, and process the data:

[0150] (3-1) Sample preparation: Take 7 mg of competitive control 2 and place the sample into the sample position of the calorimetric scanning analyzer;

[0151] (3-2) Eliminate thermal history: Set parameters to heat from room temperature (30℃, the same below) to 210℃ at a heating rate of 50℃ / min, hold for 3 minutes, and then cool down to room temperature at a cooling rate of 50℃ / min.

[0152] (3-3) Melting and cooling crystallization: The initial heating endpoint temperature was set at 167℃, the heating rate was 10℃ / min, the heating endpoint temperature was held for 3min, and then the temperature was cooled to 30℃ at a cooling rate of 10℃ / min; the heating endpoint temperature was reduced by 5℃ with each repetition, and the heating endpoint temperature was 137℃.

[0153] (3-4) Thermodynamic phase separation: The temperature is increased from room temperature to 210℃ at a rate of 10℃ / min, held for 3 minutes, and then decreased to 30℃ at a rate of 10℃ / min.

[0154] (3-5) Repeat steps (3-1) to (3-4) to complete the measurement of ordinary product 2, record the melt curve, and export the data;

[0155] (3-6) Import the data into Origin software from Origin Labs to establish a heat flux versus melting temperature curve, with melting temperature as the X-axis (°C) and heat flux as the Y-axis (W / g). Integrate the heat flux versus melting temperature curves for both the competitive control 2 and the ordinary product 2, and calculate the peak area and peak temperature (T). m主峰 and T m次峰 ).

[0156] The SSA test scores of competing control 2 and ordinary product 2 are shown in Table 6.

[0157] Table 6

[0158]

[0159] in addition, Figure 2 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 2 and the ordinary product 2 in Example 2. Figure 2 It can be seen that the peak height of the main peak of the competing control 2 is significantly different from that of the main peak of the ordinary product 2. Furthermore, the peak heights of their secondary peaks are also significantly different.

[0160] (4) Calculate the electron donor concentration for the customized product:

[0161]

[0162] The electron donor concentration of ordinary product 2 is determined based on the polypropylene polymerization process route used for ordinary product 2, and the electron donor concentration of ordinary product 2 is 4; substituting into the following formula:

[0163]

[0164]

[0165] (5) Calculate the hydrogen concentration during IPP polymerization in Customized Product 2:

[0166]

[0167] The IPP hydrogen concentration of ordinary product 2 is determined based on the polypropylene polymerization process route of ordinary product 2, and the IPP hydrogen concentration of ordinary product 2 is 6400 ml / m³. 3 Substitute into the following formula:

[0168]

[0169] (6) During the production process of customized product 2, the slurry concentration, electron donor concentration and hydrogen concentration of customized product 2 were calculated as shown in Table 7:

[0170] Table 7

[0171]

[0172] The powder obtained from polymerization was subjected to extrusion granulation and drying steps to obtain the customized product 2; the MFR, flexural modulus and impact strength of customized product 2 were measured according to ISO 1133 (230℃, 2.16Kg), ISO 178:2019 and ISO 179-1:2010 respectively; the stiffness and toughness of customized product 2 are close to or reach or even exceed the mechanical properties of the competing control 2, as shown in Table 8.

[0173] Table 8

[0174]

[0175] The results in Tables 5-8 show that, while maintaining the original catalyst system of ordinary product 2, the polymerization control parameters of customized product 2 were calculated based on the difference in IPP segment distribution between the competing control and ordinary product 2. By changing the amount of IPP or the melt index in customized product 2, customized product 2 with mechanical properties similar to the competing control was prepared.

[0176] Example 3

[0177] The following components are used in this embodiment:

[0178] Competitive control 3: A commercial IPC with an MFR of 30.0 g / 10 min, an EPR of 27.1%, and an ethylene content of 10.1%;

[0179] Common Product 3: An IPC produced using Ziegler-Natta (ZN) catalyst, with an MFR of 29.0 g / 10 min, an EPR of 32.5%, and an ethylene content of 11.7%.

[0180] Implementation steps:

[0181] (1) Determine the physical properties of the competing control 3 and the ordinary product 3:

[0182] The MFR, flexural modulus, and +23°C impact strength of the competing control 3 and the ordinary product 3 were measured according to ISO 1133-1:2022 (2.16 kg load, 230°C), ISO 178:2019, and ISO 179-1:2010, respectively; the EPR content was measured according to ISO 16152:2022; 13Ethylene content was measured by Fourier exchange infrared spectroscopy (FTIR) calibrated by C-NMR; parameters of competing control 3 and ordinary product 3 are shown in Table 9.

[0183] Table 9

[0184]

[0185] (2) Calculate the slurry concentration of customized product 3:

[0186]

[0187] The slurry concentration of ordinary product 3 is determined based on the polypropylene polymerization process route of ordinary product 3, and the slurry concentration of ordinary product 3 is 430 kgPP / m³. 3 Substitute into the following formula:

[0188]

[0189] (3) Complete the SSA experiment, export the data, and process the data:

[0190] (3-1) Sample preparation: Take 7 mg of competitive control 3 and place the sample into the sample position of the calorimetric scanning analyzer;

[0191] (3-2) Eliminate thermal history: Set parameters to heat from room temperature (28℃, the same below) to 210℃ at a heating rate of 50℃ / min, hold for 7 minutes, and then cool down to room temperature at a cooling rate of 50℃ / min.

[0192] (3-3) Melting and cooling crystallization: The initial heating endpoint temperature was set at 167℃, the heating rate was 10℃ / min, the heating endpoint temperature was held for 3min, and then the temperature was cooled to 30℃ at a cooling rate of 10℃ / min; the heating endpoint temperature was reduced by 5℃ with each repetition, and the heating endpoint temperature was 137℃.

[0193] (3-4) Thermodynamic phase separation: The temperature is increased from room temperature to 210℃ at a rate of 10℃ / min, held for 3 minutes, and then decreased to 30℃ at a rate of 10℃ / min.

[0194] (3-5) Repeat steps (3-1) to (3-4) to complete the measurement of ordinary product 3, record the melt curve, and export the data.

[0195] (3-6) Import the data into Origin software from Origin Labs to establish a heat flux versus melting temperature curve, with melting temperature as the X-axis (°C) and heat flux as the Y-axis (W / g). Integrate the heat flux versus melting temperature curves for both the competitive control 3 and the raw material ordinary product 3, and calculate the peak area and peak temperature (T). m主峰 and Tm次峰 ).

[0196] The SSA test scores of competing control 3 and ordinary product 3 are shown in Table 10.

[0197] Table 10

[0198] in addition, Figure 3 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 3 and the ordinary product 3 in Example 3. Figure 3 It can be seen that the peak height of the main peak of the competing control 3 is significantly different from that of the ordinary product 3. Secondly, the peak heights of their secondary peaks are also significantly different. (4) Calculate the electron donor concentration of the customized product 3: The electron donor concentration of ordinary product 3 was determined using the same polypropylene polymerization process as ordinary product 3, and the electron donor for ordinary product 3 was 3; substituting into the following formula: (5) Calculate the hydrogen concentration during IPP polymerization in customized product 3: The IPP hydrogen concentration of ordinary product 3 was determined using the same polypropylene polymerization process as ordinary product 3, and the IPP hydrogen concentration of ordinary product 3 was 6100 ml / m³. 3 Substitute into the following formula:

[0199]

[0200] (6) During the production process of customized product 3, the slurry concentration, electron donor concentration and hydrogen concentration of customized product 3 were calculated as shown in Table 11:

[0201] Table 11

[0202]

[0203] The powder obtained from polymerization was subjected to extrusion granulation and drying steps to obtain the customized product 3; the MFR, flexural modulus and impact strength of the customized product 3 were measured according to ISO 1133 (230℃, 2.16Kg), ISO 178:2019 and ISO 179-1:2010 respectively; the mechanical properties of the customized product 3 are close to or reach or even exceed those of the competing control 3, as shown in Table 12.

[0204] Table 12

[0205]

[0206] The results in Table 9-12 show that, while maintaining the original catalyst system of ordinary product 3, the polymerization control parameters of customized product 3 were calculated based on the difference in IPP segment distribution between the competing control 3 and ordinary product 3. By changing the amount of IPP or the melt index in customized product 3, customized product 3 with similar mechanical properties to the competing control 3 was prepared.

[0207] Comparative Example 1

[0208] The following components were used in this comparative example:

[0209] Competitive control 4: A commercial IPC with an MFR of 29.5 g / 10 min, an EPR of 16.3%, and an ethylene content of 7.3%;

[0210] Common Product 4: An IPC produced using Ziegler-Natta (ZN) catalyst, with an MFR of 30.5 g / 10 min, an EPR of 16.6%, and an ethylene content of 9.2%.

[0211] Implementation steps:

[0212] Determine the physical properties of competition control 4 and ordinary product 4:

[0213] The MFR, flexural modulus, and +23°C impact strength of competing control 4 and ordinary product 4 were measured according to ISO 1133-1:2022 (2.16 kg load, 230°C), ISO 178:2019, and ISO 179-1:2010, respectively; the EPR content was measured according to ISO 16152:2022; 13 Ethylene content was measured by Fourier exchange infrared spectroscopy (FTIR) calibrated by C-NMR; the physical properties of competition control 4 and ordinary product 4 are shown in Table 13.

[0214] Table 13

[0215]

[0216] The results showed that the mechanical properties of ordinary product 4 were inferior to those of the competing control product 4.

[0217] Comparative Example 2

[0218] The following components were used in this comparative example:

[0219] Competitive control 5: A commercial IPC with an MFR of 30.0 g / 10 min, an EPR of 27.1%, and an ethylene content of 10.1%;

[0220] Common Product 5: An IPC produced using Ziegler-Natta (ZN) catalyst, with an MFR of 30.5 g / 10 min, an EPR of 16.6%, and an ethylene content of 9.2%.

[0221] Implementation steps:

[0222] (1) Determine the physical properties of the competing control 5 and the ordinary product 5:

[0223] The MFR, flexural modulus, and +23°C impact strength of the competing control 5 and the ordinary product 5 were measured according to ISO 1133-1:2022 (2.16 kg load, 230°C), ISO 178:2019, and ISO 179-1:2010, respectively; the EPR content was measured according to ISO 16152:2022; 13 Ethylene content was measured by Fourier exchange infrared spectroscopy (FTIR) calibrated by C-NMR; parameters of competing control 5 and ordinary product 5 are shown in Table 14.

[0224] Table 14

[0225]

[0226] (2) Calculate the slurry concentration of customized product 5:

[0227]

[0228] The slurry concentration of ordinary product 5 is determined based on the polypropylene polymerization process route used for ordinary product 5, and the slurry concentration of ordinary product 5 is 510 kgPP / m³. 3 Substitute into the following formula:

[0229]

[0230] (3) Complete the SSA experiment, export the data, and process the data:

[0231] (3-1) Sample preparation: Take 7 mg of competitive control 5 and place the sample into the sample position of the calorimetric scanning analyzer;

[0232] (3-2) Eliminate thermal history: Set parameters to heat from room temperature (28℃, the same below) to 210℃ at a heating rate of 50℃ / min, hold for 7 minutes, and then cool down to room temperature at a cooling rate of 50℃ / min.

[0233] (3-3) Melting and cooling crystallization: The initial heating endpoint temperature was set at 167℃, the heating rate was 10℃ / min, the heating endpoint temperature was held for 3min, and then the temperature was cooled to 30℃ at a cooling rate of 10℃ / min; the heating endpoint temperature was reduced by 5℃ with each repetition, and the heating endpoint temperature was 137℃.

[0234] (3-4) Thermodynamic phase separation: The temperature is increased from room temperature to 210℃ at a rate of 10℃ / min, held for 3 minutes, and then decreased to 30℃ at a rate of 10℃ / min.

[0235] (3-5) Repeat steps (3-1) to (3-4) to complete the measurement of ordinary product 5, record the melt curve, and export the data.

[0236] (3-6) Import the data into Origin software from Origin Labs to establish a heat flux versus melting temperature curve, with melting temperature on the X-axis (°C) and heat flux on the Y-axis (W / g). Integrate the heat flux versus melting temperature curves for both the competitive control 5 and the raw material ordinary product 5, and calculate the peak area and peak temperature (T). m主峰 and T m次峰 ).

[0237] The SSA test scores of competing control 5 and ordinary product 5 are shown in Table 15.

[0238] Table 15

[0239]

[0240]

[0241] in addition, Figure 4 This is a graph showing the relationship between the melting temperature and heat flow of the competing control 5 and the ordinary product 5 in Example 3. Figure 4 It can be seen that the peak height of the main peak of the competing control 5 is significantly different from that of the main peak of the ordinary product 5. Furthermore, the peak heights of their secondary peaks are also significantly different.

[0242] (4) Calculate the electron donor concentration of customized product 5:

[0243]

[0244] The electron donor concentration of ordinary product 5 is determined based on the polypropylene polymerization process route that follows ordinary product 5, and the electron donor concentration of ordinary product 5 is 5.0; substituting into the following formula:

[0245]

[0246]

[0247] (5) Calculate the hydrogen concentration during IPP polymerization in customized product 5:

[0248]

[0249] The IPP hydrogen concentration of ordinary product 5 is determined based on the polypropylene polymerization process route used in ordinary product 5, and the IPP hydrogen concentration of ordinary product 5 is 3300 ml / m³. 3 Substitute into the following formula:

[0250]

[0251] (6) During the production process of customized product 5, the slurry concentration, electron donor concentration and hydrogen concentration of customized product 5 were calculated as shown in Table 16:

[0252] Table 16

[0253]

[0254] The powder obtained from polymerization was subjected to extrusion granulation and drying steps to obtain the customized product 5; the MFR, flexural modulus and impact strength of the customized product 5 were measured according to ISO 1133 (230℃, 2.16Kg), ISO 178:2019 and ISO 179-1:2010 respectively; whether the stiffness and toughness of the customized product 5 can reach the mechanical properties of the competing control 5 is shown in Table 17.

[0255] Table 17

[0256]

[0257] The results, as shown in Tables 14-17, indicate that when the EPR content of ordinary product 5 differs significantly from that of the competing control product 5, the polymerization control parameters of customized product 5 are calculated based on the difference in IPP segment distribution between the competing control product 5 and ordinary product 5, while maintaining the original catalyst system. By changing the amount of IPP or the melt index in customized product 5, the mechanical properties of the prepared customized product 5 differ significantly from those of the competing control product 5 and fail to meet the expected requirements.

[0258] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A process for the preparation of an impact copolymer polypropylene, characterized in that, The preparation method comprises: (1) measuring the MFR and EPR of the competitive control and the common product; (2) measuring and establishing the melting temperature and heat flow relationship of the competitive control and the common product by a continuous self-nucleation method, and calculating the melting peak area and the peak temperature of the main peak of the competitive control and the common product respectively; (3) according to the MFR, EPR, melting peak area and peak temperature of the main peak of the competitive control and the common product, and combining the preparation parameters of the common product, i.e. slurry concentration, electron donor concentration and hydrogen concentration, the preparation parameters of the customized product, i.e. slurry concentration, electron donor concentration and hydrogen concentration of the impact copolymerized polypropylene are calculated respectively, and the powder obtained by polymerization is subjected to extrusion granulation and drying treatment to prepare the customized product impact copolymerized polypropylene.

2. The production method according to claim 1, wherein The EPR content of the competitive control and the common product is 6-34%, preferably 11-29%, more preferably 13-27%. Preferably, the absolute value of the difference of the ethylene-propylene rubber EPR of the competitive control and the common product is between 1-10%, preferably 3-6%, more preferably 3.4-5.4%.

3. The production method according to claim 1 or 2, wherein The slurry concentration of the customized product impact copolymerized polypropylene is calculated according to formula (I); Wherein, the EPR of the competitive control and the common product is measured, and the slurry concentration of the common product is determined according to the polypropylene polymerization process route of the common product.

4. The production method according to any one of claims 1 to 3, wherein The electron donor concentration of the customized product impact copolymerized polypropylene is calculated according to formula (II); Wherein, the EPR of the competitive control and the common product is measured; the melting peak area of the competitive control and the common product is measured by a continuous self-nucleation method; and the electron donor concentration of the common product is determined according to the polypropylene polymerization process route of the common product.

5. The production process according to any one of claims 1 to 4, wherein The hydrogen concentration of the customized product impact copolymerized polypropylene is calculated according to formula (III); Wherein, the EPR of the competitive control and the common product is measured; the peak temperature of the competitive control and the common product is measured by a continuous self-nucleation method; and the hydrogen concentration of the common product is determined according to the polypropylene polymerization process route of the common product.

6. The production method according to claim 1, wherein The absolute value of the difference of the melt flow rate MFR of the competitive control and the common product is between 0.2-10, preferably 0.3-2, more preferably 0.4-1.

5.

7. The production method according to claim 1, wherein The absolute value of the difference of the ethylene content of the competitive control and the common product is between 0.1-5%, preferably 0.2-2%, more preferably 0.3-1.6%.

8. The production process according to any one of claims 1 to 7, wherein In step (2), the self-nucleation method comprises the following steps: (a) subjecting the competitive control and the common product to temperature rising-temperature holding-temperature falling treatment to eliminate the thermal history of the competitive control and the common product; (b) crystallizing the competitive control and the common product through multiple melting-cooling cycles; (c) subjecting the competitive control and the common product obtained in step (b) to temperature rising-temperature holding-temperature falling treatment for thermodynamic phase separation.

9. The production method according to claim 8, wherein The treatment of step (a) comprises: heating the competitive control and the common product to 190-250℃, holding for 0-60 min, and then cooling to 20-35℃ to eliminate the thermal history of the competitive control and the common product; Preferably, the mass of the competitive control and the common product is 4-10 mg respectively; Preferably, the heating rate is 5-60℃ / min, preferably 10-30℃ / min; Preferably, the competitive control and the common product are heated to 200-230℃; Preferably, the holding time is 3-10 min; Preferably, the cooling rate is 5-30℃ / min, preferably 10-20℃ / min; Preferably, the competitive control and the common product are cooled to 25-30℃ after holding.

10. The production method according to claim 8, wherein The treatment of step (b) comprises: heating the competitive control and the common product obtained in step (a) to 163-171℃, holding for 0-60 min, and then cooling to 20-35℃; repeating the above process, with the terminal heating temperature being lowered by 2-15℃ with each repetition, until the terminal heating temperature is 80-145℃; Preferably, the competitive control and the common product obtained in step (a) are heated to 166-171℃; Preferably, the heating rate is 2-30℃ / min, preferably 8-12℃ / min; Preferably, the holding time is 3-5 min; Preferably, the cooling rate is 0.5-50℃ / min, preferably 8-12℃ / min; Preferably, the competitive control and the common product are cooled to 25-30℃ after holding. Preferably, the terminal heating temperature is lowered by 5-10℃ with each repetition; Preferably, the terminal heating temperature is 80-140℃ after repeating.

11. The production method according to claim 8, wherein The treatment of step (c) comprises: heating the competitive control and the common product obtained in step (b) to 190-220℃, holding for 0-60 min, and then cooling to 20-35℃ to perform thermodynamic phase separation; Preferably, the competitive control and the common product obtained in step (b) are heated to 200-210℃; Preferably, the heating rate is 2-30℃ / min, preferably 8-12℃ / min; Preferably, the holding time is 3-5 min; Preferably, the cooling rate is 0.5-50℃ / min, preferably 8-12℃ / min; Preferably, the competitive control and the common product are cooled to 25-30℃ after holding.

12. The method of making according to claim 1 or 8, wherein, After the treatment by the self-nucleation method, the main peak and the secondary peak are in order of temperature from high to low; Preferably, the melting temperature of the main peak is 168-185℃, and the melting temperature of the secondary peak is 160-176℃; More preferably, the melting temperature of the main peak is 170-183℃, and the melting temperature of the secondary peak is 162-174℃; More preferably, the melting temperature of the main peak is 172-180℃, and the melting temperature of the secondary peak is 164-172℃.

13. An impact copolymer polypropylene prepared by the preparation method of any one of claims 1-12.

14. The impact copolymer polypropylene of claim 13, wherein, The mechanical properties of the impact copolymer polypropylene are close to or greater than or equal to the mechanical properties of the competitive control.

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