Method for evaluating the stiffness-toughness balance performance of impact copolymer polypropylene

Abstract

The present invention relates to the technical field of polyolefin performance evaluation, and discloses a method for evaluating the stiffness and toughness balance performance of impact copolymer polypropylene. The method includes: (1) measuring the melt flow rate of the evaluation sample of copolymer polypropylene and selecting a reference sample; (2) measuring the melt flow rate, flexural modulus and impact strength of the reference sample; (3) measuring the isotactic polypropylene content, xylene soluble content and glossiness of the reference sample and the evaluation sample, as well as the ethylene content in the xylene soluble; (4) evaluating the flexural modulus of the evaluation sample according to the isotactic polypropylene content of the evaluation sample and the reference sample; (5) evaluating the impact strength of the evaluation sample according to the xylene soluble content of the reference sample and the evaluation sample, combined with the ethylene content / xylene soluble content and glossiness. This method can quickly determine the stiffness and toughness of copolymer polypropylene during the production process.

Description

Technical Field

[0001] The present invention relates to the technical field of polyolefin performance evaluation, and particularly relates to a method for evaluating the stiffness and toughness balance performance of impact copolymer polypropylene. Background Art

[0002] Due to the rigidity of homopolypropylene and the impact resistance of the ethylene-propylene rubber component in impact copolymer polypropylene, it exhibits excellent stiffness and toughness balance performance and is widely used in fields such as household appliances, injection molded containers, automobiles, and packaging materials. Impact copolymer polypropylene is a complex mixture with short-range and long-range structures formed by components such as polypropylene, ethylene-propylene rubber, ethylene-propylene block copolymer, and a small amount of polyethylene.

[0003] There is often a balance relationship between the flexural property and impact strength of impact copolymer polypropylene: when the flexural property decreases, the impact strength increases; vice versa. There are corresponding international standards for the testing of properties such as flexural property and impact strength. GB / T 1043.1-2008 Plastics - Determination of Charpy impact properties - Part 1: Non-instrumented impact test is a commonly used standard for testing the impact properties of plastics (equivalent to ISO 179-1:2000). GB / T 9341-2000 Plastics - Methods of test for flexural properties is a commonly used standard for testing the flexural properties of plastics (equivalent to ISO 178:1993).

[0004] GB / T 2918-2018 Plastics - Standard atmospheres for conditioning and testing (equivalent to ISO 291:2008) stipulates the specifications for conditioning and testing plastics and all types of specimens under constant environmental conditions. In non-tropical regions, the standard environmental temperature is 23 ± 1 °C and the humidity is 50 ± 5%. Without special requirements, the conditioning time is not less than 88 hours. Generally, the domestic industry uniformly sets the conditioning time to 40 - 48 hours. That is to say, from receiving the product to obtaining the test data, at least 40 - 48 hours are required.

[0005] Therefore, it is of great significance to research and develop a method for quickly evaluating the stiffness and toughness balance performance of impact copolymer polypropylene. Summary of the Invention

[0006] The object of the present invention is to overcome the defect that in the production process of copolymerized polypropylene, the rigidity and toughness (flexural modulus and impact strength) of copolymerized polypropylene cannot be monitored in real time, and to provide a method for evaluating the rigid-tough balance performance of impact copolymerized polypropylene. This method can quickly determine the rigidity and toughness of copolymerized polypropylene during the production process of copolymerized polypropylene, and thus can avoid or reduce products that do not meet the quality indicators. In addition, this method can quickly evaluate the flexural modulus and impact strength of impact copolymerized polypropylene, greatly shortening the detection time.

[0007] To achieve the above object, the present invention provides a method for evaluating the rigid-tough balance performance of impact copolymerized polypropylene, wherein the method includes:

[0008] (1) Measuring the melt flow rate of the evaluation sample of impact copolymerized polypropylene and selecting a reference sample;

[0009] (2) Measuring the melt flow rate, flexural modulus and impact strength of the reference sample;

[0010] (3) Measuring the isotactic polypropylene content, xylene soluble content and glossiness of the reference sample and the evaluation sample, and measuring the ethylene content in the xylene soluble;

[0011] (4) Evaluating the flexural modulus of the evaluation sample according to the isotactic polypropylene content of the evaluation sample and the reference sample;

[0012] (5) Evaluating the impact strength of the evaluation sample according to the xylene soluble content of the reference sample and the evaluation sample, combined with the ethylene content / xylene soluble content and glossiness;

[0013] (6) Combining steps (4) and (5) to evaluate the rigid-tough balance performance of impact copolymerized polypropylene.

[0014] Through the above technical solution, the method of the present invention can quickly evaluate the flexural modulus and impact strength of impact copolymerized polypropylene, greatly shortening the detection time; and, the method of the present invention can quickly evaluate the difference in the rigid-tough balance performance between two different impact copolymerized polypropylenes, and can provide ideas for improving the impact strength and flexural modulus of products; in addition, with the expansion of the production capacity of the polypropylene device, the hourly output will increase, and timely grasping of the product performance can avoid losses caused by the production of off-grade materials in the polypropylene device. Description of the Drawings

[0015] Figure 1 is a graph showing the relationship between the isotactic polypropylene content and the flexural modulus under the condition of not containing a nucleating agent;

[0016] Figure 2It is a graph showing the relationship between the isotactic polypropylene content and the flexural modulus under the condition of containing a nucleating agent;

[0017] Figure 3 It is a graph showing the relationship between the isotactic polypropylene content and the flexural modulus under the condition of containing a nucleating agent, with a crystallinity higher than 40% and a melt flow rate ≥ 47 g / 10 min;

[0018] Figure 4 It is a graph showing the relationship between the xylene-soluble content and the impact strength at room temperature under the condition that the xylene-soluble content is 11 - 23% and the crystallinity is higher than 40%, and the melt flow rate ≥ 47 g / 10 min;

[0019] Figure 5 It is a graph showing the relationship between the xylene-soluble content and the impact strength at room temperature under the condition that the xylene-soluble content is 5 - 23%, high-crystalline products are removed, and the ethylene content / xylene-soluble content is less than 43;

[0020] Figure 6 It is a graph showing the relationship between the xylene-soluble content and the impact strength at room temperature under the condition that the xylene-soluble content is 15 - 23%, high-crystalline products are removed, and the ethylene content / xylene-soluble content is greater than or equal to 43. Detailed implementation manners

[0021] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0022] The present invention provides a method for evaluating the stiffness and toughness balance performance of impact copolymer polypropylene, wherein the method includes:

[0023] (1) Measuring the melt flow rate of the impact copolymer polypropylene of the evaluation sample and selecting a reference sample;

[0024] (2) Measuring the melt flow rate, flexural modulus and impact strength of the reference sample;

[0025] (3) Measuring the isotactic polypropylene content, xylene-soluble content and glossiness of the reference sample and the evaluation sample, and measuring the ethylene content in the xylene-soluble;

[0026] (4) Evaluating the flexural modulus of the evaluation sample according to the isotactic polypropylene content of the evaluation sample and the reference sample;

[0027] (5) Evaluate the impact strength of the evaluation sample based on the xylene-soluble content of the reference sample and the evaluation sample, the combined ethylene content / xylene-soluble content, and the glossiness.

[0028] (6) Evaluate the stiffness-toughness balance performance of the impact copolymer polypropylene by combining steps (4) and (5).

[0029] The inventors of the present invention have found that: the disadvantages of national or international detection standards for bending properties, impact strength, etc. in the prior art are that the measurement period is relatively long, the state adjustment time is not less than 88 hours, or it is uniformly stipulated in China to be 40 - 48 hours, which is difficult to meet the need for quickly obtaining the bending properties and impact strength properties of impact copolymer polypropylene. On the other hand, when it is desired to improve the bending properties or impact strength of the product, no good ideas can be given. Based on this, the inventors of the present invention unexpectedly found that the detection time of detection technologies such as nuclear magnetic, infrared spectroscopy, calorimeter, Raman spectroscopy, etc. is very short, even less than 1 hour; for example, the time for infrared spectroscopy to detect the ethylene content in impact copolymer polypropylene is less than 30 minutes. Therefore, by means of rapid detection, the inventors of the present invention can quickly evaluate the bending modulus and impact strength of unknown impact copolymer polypropylene by comparing the differences in the components and structures of different products, greatly shortening the detection time.

[0030] According to the present invention, the reference sample is selected according to the principle that the melt flow rate of the reference sample is close to that of the evaluation sample, that is, a sample with a melt flow rate close to that of the evaluation sample is selected as the reference sample; preferably, the absolute value of the difference between the melt flow rate of the reference sample and the melt flow rate of the evaluation sample is 0 - 8 g / 10 min, more preferably 0 - 6 g / 10 min. In the present invention, the closer the melt flow rate of the evaluation sample is to the melt flow rate of the reference sample, the more beneficial it is to evaluate the stiffness-toughness balance performance of the evaluation sample. Therefore, the reference sample is selected accordingly.

[0031] According to the present invention, in step (4), when the content of isotactic polypropylene in the evaluation sample is higher than the content of isotactic polypropylene in the reference sample, the bending modulus of the evaluation sample is also higher than the bending modulus of the reference sample; preferably, when the content of isotactic polypropylene in the evaluation sample is 0 - 25 wt% higher or lower than the content of isotactic polypropylene in the reference sample, the bending modulus of the evaluation sample is also 0 - 0.6 GPa higher or lower than the bending modulus of the reference sample.

[0032] According to the present invention, in step (5), when the absolute value of the difference between the ethylene content / xylene solubles content of the reference sample and that of the evaluation sample is 0 - 30, and the absolute value of the difference between the gloss of the reference sample and that of the evaluation sample is 0 - 40%, if the xylene solubles content of the evaluation sample is higher than that of the reference sample, then the impact strength of the evaluation sample is also higher than that of the reference sample.

[0033] According to the present invention, preferably, when the absolute value of the difference between the ethylene content / xylene solubles content of the reference sample and that of the evaluation sample is 0 - 15, and the absolute value of the difference between the gloss of the reference sample and that of the evaluation sample is 0 - 20%, if the xylene solubles content of the evaluation sample is 0 - 10% by weight higher than that of the reference sample, then the impact strength of the evaluation sample is 0 - 5.5 kJ / m higher than that of the reference sample. 2 。

[0034] According to the present invention, the impact copolymer polypropylene contains isotactic polypropylene, xylene solubles and an optional nucleating agent. Based on the total weight of the impact copolymer polypropylene, the content of isotactic polypropylene is 35 - 95% by weight, the content of xylene solubles is 1.5 - 45% by weight, and the content of the nucleating agent is 0 - 0.5% by weight; preferably, based on the total weight of the impact copolymer polypropylene, the content of isotactic polypropylene is 40 - 90% by weight, the content of xylene solubles is 6 - 35% by weight, and the content of the nucleating agent is 0 - 0.2% by weight.

[0035] According to the present invention, the xylene solubles contain ethylene. Based on the total weight of the xylene solubles, the content of ethylene is 1 - 25% by weight; preferably, the content of ethylene is 1 - 15% by weight.

[0036] In addition, it should be noted that the xylene solubles also contain propylene. In the present invention, the content of the xylene solubles can reflect the content of ethylene - propylene rubber.

[0037] According to the present invention, the melt flow rate of the impact copolymer polypropylene is 0.1 - 200 g / 10 min, and the crystallinity is 18 - 50%.

[0038] According to the present invention, further, the inventors of the present invention have found that the content of isotactic polypropylene is the basis for reflecting a higher flexural modulus of the product.

[0039] The first case: When the impact copolymerized polypropylene does not contain a nucleating agent and the isotactic polypropylene content is 40 - 75% by weight, the flexural modulus of the impact copolymerized polypropylene has the formula shown in Equation (1):

[0040] M1 = isotactic polypropylene content × 0.02085 - 0.22565, Equation (1);

[0041] Figure 1 is a schematic diagram showing the relationship between the isotactic polypropylene content and the flexural modulus under the condition of not containing a nucleating agent. It can be seen from Figure 1 that there is a linear relationship between the isotactic polypropylene content and the flexural modulus. In the range of 40 - 75% of the isotactic polypropylene content, flexural modulus = isotactic polypropylene content × 0.02085 - 0.22565.

[0042] The second case: When the impact copolymerized polypropylene contains a nucleating agent, more crystalline polypropylene will be formed, which is beneficial to improving the flexural modulus. When the isotactic polypropylene content is 45 - 90% by weight, the flexural modulus of the impact copolymerized polypropylene has the formula shown in Equation (2):

[0043] M2 = isotactic polypropylene content × 0.0133 + 0.41681, Equation (2);

[0044] Figure 2 is a diagram showing the relationship between the isotactic polypropylene content and the flexural modulus under the condition of containing a nucleating agent. It can be seen from Figure 2 that there is a linear relationship between the isotactic polypropylene content and the flexural modulus. Flexural modulus = isotactic polypropylene content × 0.0133 + 0.41681, where the range is 45 - 90%.

[0045] The third case: When the impact copolymerized polypropylene contains a nucleating agent and the crystallinity ≥ 40%, in the case of high crystallinity (crystallinity higher than 40%, mainly melt flow rate ≥ 47 g / 10 min), and when the isotactic polypropylene content is 60 - 85% by weight, the flexural modulus of the impact copolymerized polypropylene has the formula shown in Equation (3):

[0046] M3 = isotactic polypropylene content × 0.02325 - 0.07713, Equation (3);

[0047] Figure 3 is a diagram showing the relationship between the isotactic polypropylene content and the flexural modulus in the case of containing a nucleating agent and crystallinity higher than 40% with a melt flow rate ≥ 47 g / 10 min. It can be seen from Figure 3It can be seen that there is a linear relationship between the isotactic polypropylene content and the flexural modulus. In the range where the isotactic polypropylene content is 60 - 85%, flexural modulus = isotactic polypropylene content × 0.02325 - 0.07713.

[0048] Generally speaking, with the preferred increase in the isotactic polypropylene content, the flexural modulus of the product shows an upward trend.

[0049] According to the present invention, further, the inventors of the present invention found that the xylene soluble content is the basis for reflecting the higher impact strength of the product.

[0050] The first case: When the xylene soluble content of the impact copolymer polypropylene > 23% by weight, the impact strength at room temperature is in the brittle - ductile transition stage, preferably measured according to ISO 179 - 1:2010, and the impact strength Q1 of the impact copolymer polypropylene ≥ 30 kJ / m 2 ; It cannot be accurately estimated, and only based on the xylene soluble content, compare the impact strength at room temperature of the reference sample.

[0051] The second case: When the xylene soluble content of the impact copolymer polypropylene is 11 - 23% by weight, and the crystallinity ≥ 40%, and the melt flow rate ≥ 47 g / 10 min, the impact strength of the impact copolymer polypropylene has the formula shown in formula (4):

[0052] Q2 = xylene soluble content × 0.45411 - 1.15745, formula (4);

[0053] Figure 4 In the case where the xylene soluble content is less than 23% and the crystallinity is higher than 40%, and the melt flow rate ≥ 47 g / 10 min, the relationship diagram between the xylene soluble content and the impact strength at room temperature, from Figure 4 It can be seen that there is a linear relationship between the xylene soluble content and the impact strength at room temperature. In the range where the content of xylene soluble is 11 - 23%, impact strength at room temperature = xylene soluble content × 0.45411 - 1.15745.

[0054] The third case: When the xylene soluble content of the impact copolymer polypropylene is 5 - 23% by weight and high - crystalline products are excluded, and the ethylene content / xylene soluble content < 43, the impact strength of the impact copolymer polypropylene has the formula shown in formula (5):

[0055] Q3 = xylene soluble content × 0.29826 + 4.22918, formula (5);

[0056] In the present invention, it should be noted that high - crystalline products refer to products with a crystallinity higher than 40%.

[0057] Figure 5 It is a relationship graph of the xylene-soluble content and the impact strength at room temperature under the condition that the xylene-soluble content is 5-23% and high-crystalline products are removed, and the ethylene content / xylene-soluble content is less than 43; from Figure 5 it can be seen that: the xylene-soluble content and the impact strength at room temperature show a linear relationship, and the impact strength = xylene-soluble content × 0.29826 + 4.22918.

[0058] The fourth case: when the xylene-soluble content of the impact copolymer polypropylene is 5-23% by weight and high-crystalline products are removed, and the ethylene content / xylene-soluble content is greater than or equal to 43, the impact strength of the impact copolymer polypropylene has the formula shown in formula (6):

[0059] Q4 = xylene-soluble content × 0.5309 - 1.73675, formula (6);

[0060] Figure 6 It is a relationship graph of the xylene-soluble content and the impact strength at room temperature under the condition that the xylene-soluble content is 15-23% and high-crystalline products are removed, and the ethylene content / xylene-soluble content is greater than or equal to 43, from Figure 6 it can be seen that: the xylene-soluble content and the impact strength at room temperature show a linear relationship, and the impact strength = xylene-soluble content × 0.5309 - 1.73675.

[0061] According to the present invention, the melt flow rate of the reference sample at 230°C under a condition of 2.16 Kg is 0.1-200.0 g / 10 min, and the flexural modulus is 0.3-2.0 GPa; the impact strength at 23°C is 1.0-80.0 kJ / m 2 , and the glossiness at 60° is 20-100%; preferably, the melt flow rate of the reference sample at 230°C under a condition of 2.16 Kg is 0.2-105 g / 10 min, and the flexural modulus is 0.4-1.9 GPa; the impact strength at 23°C is 2.0-65.0 kJ / m 2 , and the glossiness at 60° is 30-80%.

[0062] According to the present invention, the reference sample contains isotactic polypropylene, xylene-soluble matter and an optional nucleating agent. Based on the total weight of the reference sample, the content of the isotactic polypropylene is 35-95% by weight, the content of the xylene-soluble matter is 1.5-45% by weight, and the content of the nucleating agent is 0-0.5% by weight; preferably, based on the total weight of the reference sample, the content of the isotactic polypropylene is 40-90% by weight, the content of the xylene-soluble matter is 6-35% by weight, and the content of the nucleating agent is 0-0.2% by weight.

[0063] According to the present invention, the xylene-soluble matter contains ethylene. Based on the total weight of the xylene-soluble matter, the content of the ethylene is 1-25% by weight; preferably, the content of the ethylene is 1-15% by weight.

[0064] According to the present invention, the melt flow rate of the impact copolymer polypropylene under the conditions of 230 °C and 2.16 Kg is 0.1-200.0 g / 10 min, and the flexural modulus is 0.3-2.0 GPa; the impact strength under the condition of 23 °C is 1.0-80.0 kJ / m 2 , and the glossiness under the condition of 60° is 20-100%; preferably, the melt flow rate of the reference sample under the conditions of 230 °C and 2.16 Kg is 0.2-105 g / 10 min, and the flexural modulus is 0.4-1.9 GPa; the impact strength under the condition of 23 °C is 2.0-65.0 kJ / m 2 , and the glossiness under the condition of 60° is 30-90%.

[0065] According to the present invention, the reference sample is selected from one or more of M30RH, M60RHC, PPB-M02, PPB-M09, AP03B, M50RH, M60RHC, and M100RHC.

[0066] According to the present invention, the impact copolymer polypropylene is selected from one or more of M30RJ, M2600R, M60RHI, K7726H, M30RI, K8003, SP179, M10RG, 7555KNE2, BM3900, BX3900, and BX3920.

[0067] According to the present invention, the melt flow rate is measured by GB / T 3682, ISO1133, ASTM D1238, preferably measured according to ISO1133 under the conditions of 230 °C and 2.16 Kg;

[0068] According to the present invention, the flexural modulus is measured according to the methods of GB / T 9341, ISO 178:2019, ASTM D747, ASTM D790, preferably ISO 178:2019.

[0069] According to the present invention, the impact strength is measured according to GB / T 1043.1, ISO 179-1:2010, ISO 180, ASTM D256, preferably ISO 179-1:2010 at 23 °C.

[0070] According to the present invention, the content of isotactic polypropylene and xylene-soluble matter is measured by instruments such as small nuclear magnetic resonance, Raman spectroscopy, near-infrared spectroscopy, X-ray diffraction, etc.; preferably measured by small nuclear magnetic resonance calibrated by 13C-NMR.

[0071] According to the present invention, the content of ethylene is measured by instruments such as Fourier transform infrared spectroscopy, small nuclear magnetic resonance, Raman spectroscopy, near-infrared spectroscopy, X-ray diffraction, etc., preferably Fourier transform infrared spectroscopy calibrated by 13C NMR.

[0072] According to the present invention, the glossiness is measured according to GB 8807-1988 under conditions such as 30°, 60°, 90°, etc., preferably measured under the condition of 60°.

[0073] According to a particularly preferred embodiment of the present invention, a method for evaluating the stiffness-toughness balance performance of impact copolymerized polypropylene includes:

[0074] (1) Measuring the standards for the performance indicators of the reference sample and the evaluation sample:

[0075] The melt flow rate is measured according to ISO 1133 (230 °C, 2.16 Kg); the isotactic polypropylene content is measured by small nuclear magnetic resonance calibrated by 13C NMR; the ethylene content is measured by Fourier transform infrared spectroscopy (FTIR) calibrated by 13C NMR; the xylene-soluble matter content is measured by small nuclear magnetic resonance calibrated by 13C NMR; the flexural modulus is measured according to ISO178:2019; the impact strength is measured according to ISO 179-1:2010; the glossiness (60°) is measured according to GB 8807-1988. The actual measurement time for the above measurement items is less than 1 hour;

[0076] (2) Measuring the performance indicators of the reference sample and the evaluation sample:

[0077] The content of isotactic polypropylene and xylene-soluble matter, glossiness (60°), impact strength and flexural modulus of the reference sample are sequentially detected, and the content of ethylene in the xylene-soluble matter is measured; and the ethylene content / xylene-soluble matter content is calculated, and

[0078] Successively detect the isotactic polypropylene content, xylene soluble content, glossiness (60°) of the unknown sample, and measure the ethylene content in the xylene soluble; and calculate the ethylene content / xylene soluble content;

[0079] (3) Evaluation:

[0080] Evaluate the evolution trend of the impact strength or flexural modulus of the unknown sample by comparing the isotactic polypropylene content, xylene soluble content, and ethylene content in the xylene soluble of the reference sample and the unknown sample.

[0081] In the present invention, the microstructure is the internal factor affecting the impact strength and flexural modulus of the unknown sample. Changing the isotactic polypropylene, xylene soluble content, ethylene content in the xylene soluble, and ethylene content / xylene soluble content of the unknown sample ultimately affects the impact strength and flexural modulus of the unknown sample.

[0082] Among them, the higher the glossiness (60°), the lower the content of long ethylene chain - ethylene - propylene block copolymer (long ethylene crystalline chain segment), and the higher the content of long propylene chain - ethylene - propylene block copolymer (long propylene crystalline chain segment). The lower the ethylene content / xylene soluble content, the higher the content of long propylene chain - ethylene - propylene block copolymer, and the better the compatibility between ethylene - propylene rubber and polypropylene.

[0083] Among them, the higher the isotactic polypropylene content, the more conducive to the formation of a high flexural modulus.

[0084] Among them, the ethylene content / xylene soluble content is the key factor affecting the impact strength of impact - copolymerized polypropylene. Generally speaking, with the increase of the ethylene content / xylene soluble content, the impact strength will be higher and higher, and the flexural modulus will be lower and lower.

[0085] The present invention will be described in detail below through examples.

[0086] Example 1

[0087] This example aims to illustrate the rapid evaluation of the flexural modulus and impact strength of M30RJ polypropylene using the method of the present invention.

[0088] (1) Select a reference sample:

[0089] The M30RJ polypropylene of Zhenhai Refining and Chemical Company, Sinopec is used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, the M30RH polypropylene of Zhenhai Refining and Chemical Company, Sinopec is selected as the reference sample.

[0090] (2) Experimental steps:

[0091] 1. Measure the melt flow rate, flexural modulus, and impact strength of the reference sample M30RH polypropylene according to ISO1133 (230 °C, 2.16 Kg), ISO178:2019, and ISO179-1:2010 respectively;

[0092] 2. Measure the melt flow rate of the evaluation sample M30RJ polypropylene according to ISO1133 (230 °C, 2.16 Kg);

[0093] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples of the reference sample and the evaluation sample according to the small nuclear magnetic resonance calibrated by 13C-NMR;

[0094] 4. Measure the ethylene content of the two samples of the reference sample and the evaluation sample according to the Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0095] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data are shown in Table 1;

[0096] 6. The above measurement items can be completed respectively within 1 hour, and the total time-consuming is 0.8 hours.

[0097] 7. The absolute value of the difference in the ethylene content / xylene-soluble content between the reference sample and the evaluation sample is 3. M30RJ has a lower ethylene content / xylene-soluble content, indicating that it has a better mixing form of polypropylene and ethylene-propylene rubber; the absolute value of the difference in the glossiness (60°) between the reference sample and the evaluation sample is 0, indicating that the two samples have similar long ethylene crystalline chain segment mass numbers.

[0098] 8. M30RJ has a higher isotactic polypropylene content, and it can be evaluated that M30RJ has a slightly higher flexural modulus; in addition, M30RJ has a higher xylene-soluble content, and it can be evaluated that M30RJ has a slightly higher impact strength at 23 °C.

[0099] (3) Verify according to the formula

[0100] According to the nucleating agent addition mode:

[0101] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.0133 + 0.41681;

[0102] M30RJ flexural modulus (according to ISO178:2019) = 69.5 × 0.0133 + 0.41681 = 1.34 GPa;

[0103] When the xylene soluble content is less than 25% and the high-crystallinity products are removed, and the ethylene content / xylene soluble content is greater than or equal to 43, the impact strength at room temperature (measured according to ISO179-1:2010, kJ / m 2 ) = xylene soluble content × 0.5309 - 1.73675, where the xylene soluble content ranges from 5% to 23%;

[0104] The impact strength at room temperature of M30RJ (according to ISO179-1:2010) = 17.7 × 0.5309 - 1.73675 = 7.7 kJ / m 2 ;

[0105] (4) Calibration:

[0106] After conditioning for 40 - 48 hours, measure the impact strength and flexural modulus of M30RJ polypropylene according to ISO179-1:2010 and ISO 178:2019 respectively. The measured data are: the impact strength at 23°C is 7.4 kJ / m 2 , and the flexural modulus is 1.36 GPa.

[0107] Compare the measured data with the evaluation values in Table 1. The error is small and meets the expectations.

[0108] Table 1

[0109]

[0110]

[0111] In the present invention, it should be noted that: the "flexural modulus" and "impact strength at 23°C" of M30RJ in Table 1 are evaluated by using the reference sample M30RH on the one hand, which belong to the evaluation values; on the other hand, for the purpose of improving accuracy, they are calculated according to the parameters and formulas of M30RJ, and also belong to the evaluation values; finally, they are calibrated using the test standards. The same applies hereinafter.

[0112] Example 2

[0113] This example aims to illustrate the rapid evaluation of the flexural modulus and impact strength of M2600R polypropylene by using the method of the present invention.

[0114] (1) Selection of reference sample:

[0115] The M2600R polypropylene of Shanghai Petrochemical Company Limited, Sinopec is used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, the M30RH polypropylene of Zhenhai Refining & Chemical Company Limited, Sinopec is selected as the reference sample.

[0116] (2) Experimental steps:

[0117] 1. Measure the melt flow rate, flexural modulus, and impact strength of M30RH polypropylene according to ISO1133 (230 °C, 2.16 Kg), ISO178:2019, and ISO 179-1:2010 respectively;

[0118] 2. Measure the melt flow rate of M2600R polypropylene according to ISO1133 (230 °C, 2.16 Kg);

[0119] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples using a small nuclear magnetic resonance calibrated by 13C-NMR;

[0120] 4. Measure the ethylene content of the two samples using Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0121] 5. Measure the gloss (60°) according to GB 8807-1988; the measured data is shown in Table 2;

[0122] 6. The above measurement items can be completed within 1 hour, with a total time consumption of 0.8 hours.

[0123] 7. The absolute value of the difference in the ethylene content / xylene-soluble content between the reference sample and the evaluation sample is 1, indicating that the two samples have a similar mixing state of polypropylene and ethylene-propylene rubber; the absolute value of the difference in the gloss (60°) between the reference sample and the evaluation sample is 10, and M2600R polypropylene has a higher gloss (60°) value, indicating that it has a smaller mass number of long ethylene crystalline chain segments.

[0124] 8. M2600R polypropylene has a lower isotactic polypropylene content, and it can be evaluated that the flexural modulus of M2600R will be lower than that of M30RH; in addition, M2600R polypropylene has more xylene-soluble substances and ethylene content, and it can be evaluated that M2600R has a higher impact strength at 23 °C.

[0125] (3) Verify according to the formula

[0126] According to the nucleating agent addition mode:

[0127] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.0133 + 0.41681

[0128] Flexural modulus of M2600R (according to ISO178:2019) = 65.3 × 0.0133 + 0.41681 = 1.28 GPa;

[0129] When the xylene soluble content is less than 23% and the high-crystallinity products are removed, and when the ethylene content / xylene soluble content is greater than or equal to 43, the impact strength at room temperature (measured in accordance with ISO 179-1:2010, kJ / m 2 ) = xylene soluble content × 0.5309 - 1.73675, where the range of the xylene soluble content is 5 - 23%

[0130] The impact strength at room temperature of M2600R (measured in accordance with ISO 179-1:2010) = 19.0 × 0.5309 - 1.73675 = 8.3 kJ / m 2 ;

[0131] (4) Calibration:

[0132] After conditioning for 40 - 48 hours, the impact strength and flexural modulus of M2600R polypropylene were measured in accordance with ISO 179-1:2010 and ISO 178:2019 respectively. The measured data were: the impact strength at 23°C was 7.8 kJ / m 2 , and the flexural modulus was 1.22 GPa.

[0133] The measured data were compared with the evaluation data in Table 2, and the error was small, meeting the expectations.

[0134] Table 2

[0135]

[0136] Example 3

[0137] This example is to illustrate the rapid evaluation of the flexural modulus and impact strength of M60RHI polypropylene by using the method of the present invention.

[0138] (1) Selection of reference sample:

[0139] The M60RHI polypropylene of Zhenhai Refining and Chemical Company, Sinopec was used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, the M60RHC polypropylene of Zhenhai Refining and Chemical Company, Sinopec was selected as the reference sample.

[0140] (2) Experimental procedure:

[0141] 1. Measure the melt flow rate, flexural modulus and impact strength of M60RHC polypropylene in accordance with ISO1133 (230°C, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively;

[0142] 2. Measure the melt flow rate of M60RHI polypropylene in accordance with ISO1133 (230°C, 2.16 Kg);

[0143] 3. Calibrate the small nuclear magnetic resonance according to 13C-NMR and measure the isotactic polypropylene and xylene-soluble content of the two samples;

[0144] 4. Measure the ethylene content of the two samples by Fourier transform infrared spectroscopy (FTIR) calibrated according to 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0145] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data are shown in Table 3;

[0146] 6. The above measurement items can be completed respectively within 1 hour, and the total time consumption is 0.8 hours;

[0147] 7. M60RHI polypropylene has a lower ethylene content / xylene-soluble content value, indicating that it has a better mixing form of polypropylene and ethylene-propylene rubber; the two samples have the same glossiness (60°) value, indicating that they have similar long ethylene crystalline chain segment mass numbers.

[0148] 8. M60RHI has a lower isotactic polypropylene content, which can evaluate that M60RHI has a lower flexural modulus; M60RHI has a higher xylene-soluble content, which can evaluate that M60RHI has a higher impact strength at 23°C.

[0149] (3) Verify according to the formula

[0150] According to the high-crystallinity mode:

[0151] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.02325 - 0.07713;

[0152] Flexural modulus (according to ISO178:2019) = 70.2 × 0.02325 - 0.07713 = 1.56 GPa;

[0153] When the xylene-soluble content is less than 23% and the high crystallinity (crystallinity is higher than 40%, mainly melt flow rate ≥ 47): Charpy impact strength at room temperature (measured according to ISO179-1:2010, kJ / m 2 ) = xylene-soluble content × 0.45411 - 1.15745, where the xylene-soluble content ranges from 11 - 23%;

[0154] M60RHI Charpy impact strength at room temperature (measured according to ISO179-1:2010) = 17.1 × 0.45411 - 1.15745 = 6.6 kJ / m 2 ;

[0155] (4) Calibration

[0156] After 40 - 48 hours of conditioning, the impact strength and flexural modulus of M60RHI polypropylene were measured according to ISO 179-1:2010 and ISO 178:2019 respectively. The measured data were: impact strength at 23℃ was 6.9 kJ / m 2 , and flexural modulus was 1.51 GPa.

[0157] Comparing the measured data with the evaluation data in Table 3, the error was small and met the expectations.

[0158] Table 3

[0159]

[0160] Example 4

[0161] This example is to illustrate the rapid evaluation of the flexural modulus and impact strength of K7726H polypropylene by using the method of the present invention.

[0162] (1) Select reference samples:

[0163] K7726H polypropylene from Yanshan Petrochemical Company, Sinopec was used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, AP03B polypropylene from Exxon Mobil Corporation was selected as the reference sample.

[0164] (2) Experimental procedures:

[0165] 1. Measure the melt flow rate, flexural modulus and impact strength of AP03B polypropylene according to ISO1133 (230℃, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively;

[0166] 2. Measure the melt flow rate of K7726H polypropylene according to ISO1133 (230℃, 2.16 Kg);

[0167] 3. Measure the isotactic polypropylene and xylene soluble content of the two samples according to the small nuclear magnetic resonance calibrated by 13C-NMR;

[0168] 4. Measure the ethylene content of the two samples by Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene soluble content;

[0169] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data are shown in Table 4;

[0170] 6. The above measurement items can be completed separately within 1 hour, with a total time consumption of 0.8 hours.

[0171] 7. The absolute value of the difference in ethylene content / xylene solubles content between the reference sample and the evaluation sample is 3. AP03B polypropylene has a lower ethylene content / xylene solubles content, indicating better compatibility and mixing state between its polypropylene and ethylene-propylene rubber. The absolute value of the difference in gloss (60°) between the reference sample and the evaluation sample is 2, indicating that the two samples have similar long ethylene crystalline chain segment mass numbers.

[0172] 8. K7726H polypropylene contains a lower isotactic polypropylene content, enabling the evaluation that K7726H has a lower flexural modulus. K7726H polypropylene has more xylene solubles and ethylene content, enabling the evaluation that K7726H has a higher impact strength at 23°C.

[0173] (3) Verification according to the formula

[0174] According to the nucleating agent addition mode:

[0175] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.0133 + 0.41681

[0176] Flexural modulus of K7726H (according to ISO178:2019) = 67.0 × 0.0133 + 0.41681 = 1.31 GPa;

[0177] When the xylene solubles content is less than 23% and high-crystalline products are removed, and the ethylene content / xylene solubles content is greater than or equal to 43, the impact strength at room temperature (measured according to ISO179-1:2010, kJ / m 2 ) = xylene solubles content × 0.5309 - 1.73675, where the xylene solubles content ranges from 5 - 23%

[0178] Impact strength of K7726H at room temperature (according to ISO179-1:2010) = 17.5 × 0.5309 - 1.73675 = 7.6 kJ / m 2 ;

[0179] (4) Calibration:

[0180] After 40 - 48 hours of conditioning, the impact strength and flexural modulus of K7726H polypropylene are measured according to ISO 179-1:2010 and ISO 178:2019 respectively. The measurement data are: impact strength at 23°C 7.8 kJ / m 2 , flexural modulus 1.30 GPa.

[0181] Compare the measured data with the evaluation data in Table 4. The error is small and meets the expectations.

[0182] Table 4

[0183]

[0184] Example 5

[0185] This example aims to illustrate the rapid evaluation of the flexural modulus and impact strength of M30RI polypropylene using the method of the present invention.

[0186] (1) Select the reference sample:

[0187] The M30RI polypropylene of Zhenhai Refining & Chemical Company, Sinopec is used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, the M30RH polypropylene of Zhenhai Refining & Chemical Company, Sinopec is selected as the reference sample.

[0188] (2) Experimental steps:

[0189] 1. Measure the melt flow rate, flexural modulus and impact strength of M30RH polypropylene according to ISO1133 (230 °C, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively.

[0190] 2. Measure the melt flow rate of M30RI polypropylene according to ISO1133 (230 °C, 2.16 Kg);

[0191] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples according to the small nuclear magnetic resonance calibrated by 13C-NMR;

[0192] 4. Measure the ethylene content of the two samples according to the Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0193] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data are shown in Table 5;

[0194] 6. The above measurement items can be completed respectively within 1 hour, and the total time-consuming is 0.8 hours.

[0195] 7. The absolute value of the difference in ethylene content / xylene solubles content between the reference sample and the evaluation sample is 3. The ethylene content / xylene solubles content of M30RI polypropylene is slightly lower, indicating that it has a better mixing state of polypropylene and ethylene-propylene rubber. The absolute value of the difference in gloss (60°) between the reference sample and the evaluation sample is 4. The gloss (60°) of M30RI polypropylene is slightly higher, indicating that it has a lower mass number of long ethylene crystalline segments.

[0196] 8. M30RI has a lower isotactic polypropylene content, and it can be evaluated that the flexural modulus of M30RI is lower than that of M30RH. M30RI has higher xylene solubles and ethylene content, and it is evaluated that M30RI has a higher impact strength at 23 °C.

[0197] (3) Verification is carried out according to the formula

[0198] According to the mode of adding nucleating agent:

[0199] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.0133 + 0.41681.

[0200] Flexural modulus (according to ISO178:2019) = 59.5 × 0.0133 + 0.41681 = 1.21 GPa;

[0201] When the xylene solubles content is less than 23% and high-crystalline products are removed, and the ethylene content / xylene solubles content is greater than or equal to 43, the impact strength at room temperature (measured according to ISO179-1:2010, kJ / m 2 ) = xylene solubles content × 0.5309 - 1.73675, where the range of xylene solubles content is 5 - 23%;

[0202] The impact strength of M30RI at room temperature (according to ISO179-1:2010) = 21.7 × 0.5309 - 1.73675 = 9.8 kJ / m 2 ;

[0203] (4) Calibration:

[0204] After 40 - 48 hours of conditioning, the impact strength and flexural modulus of M30RI polypropylene are measured according to ISO 179-1:2010 and ISO 178:2019 respectively. The measured data are: the impact strength at 23 °C is 9.9 kJ / m 2 , and the flexural modulus is 1.22 GPa.

[0205] The measured data are compared with the evaluation data in Table 5, and the error is small, meeting the expectations.

[0206] Table 5

[0207]

[0208] Example 6

[0209] This example aims to illustrate the rapid evaluation of the flexural modulus and impact strength of K8003 polypropylene using the method of the present invention.

[0210] (1) Select a reference sample:

[0211] The K8003 polypropylene of SINOPEC ZhongHan (Wuhan) Petrochemical Co., Ltd. is used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, the PPB-M02 polypropylene of SINOPEC Zhenhai Refining & Chemical Company is selected as the reference sample.

[0212] (2) Experimental steps:

[0213] 1. Measure the melt flow rate, flexural modulus and impact strength of PPB-M02 polypropylene according to ISO1133 (230 °C, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively.

[0214] 2. Measure the melt flow rate of K8003 polypropylene according to ISO1133 (230 °C, 2.16 Kg);

[0215] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples according to the small nuclear magnetic resonance calibrated by 13C-NMR;

[0216] 4. Measure the ethylene content of the two samples according to the Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0217] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data are shown in Table 6;

[0218] 6. The above measurement items can be completed respectively within 1 hour, and the total time consumption is 0.8 hours.

[0219] 7. The absolute value of the difference in the ethylene content / xylene-soluble content between the reference sample and the evaluation sample is 19, and the ethylene content / xylene-soluble content of K8003 polypropylene is lower, indicating that it has a better mixing state of polypropylene and ethylene-propylene rubber; the absolute value of the difference in the glossiness between the reference sample and the evaluation sample is 4, and the glossiness (60°) of K8003 polypropylene is slightly higher, indicating that it has a lower mass number of long ethylene crystalline chain segments.

[0220] 8. The isotactic polypropylene content of K8003 polypropylene is relatively lower than that of PPB-M02 polypropylene, and the flexural modulus of K8003 polypropylene is inferior to that of PPB-M02 polypropylene; the xylene-soluble content of K8003 polypropylene is greater than or equal to 20-23%, and the ethylene content / xylene-soluble content is 33. It is evaluated that the room-temperature impact strength of K8003 polypropylene is in the brittle-ductile transition stage, and the room-temperature impact strength (preferably measured in accordance with ISO179-1:2010) is greater than 30 kJ / m 2 Above, it cannot be accurately estimated;

[0221] (3) Verify according to the formula

[0222] According to the mode without adding nucleating agent:

[0223] Flexural modulus (measured in accordance with ISO178:2019, GPa) = isotactic polypropylene content × 0.02085 - 0.22565

[0224] Flexural modulus (in accordance with ISO178:2019) = 60.9 × 0.02085 - 0.22565 = 1.04 GPa;

[0225] (4) Calibration:

[0226] After conditioning for 40-48 hours, the impact strength and flexural modulus of K8003 polypropylene are measured respectively in accordance with ISO 179-1:2010 and ISO 178:2019. The measured data are: impact strength at 23°C is 65 kJ / m 2 , and the flexural modulus is 0.9 GPa.

[0227] Compare the measured flexural modulus data with the evaluation data in Table 6. The difference is not significant, the error is small, and it meets the expectation; the measured impact strength at 23°C is 65 kJ / m 2 is quite different from the evaluated value of 30 kJ / m 2 because there is an upward transition period for this data and it is difficult to predict; when this value is greater than 30 kJ / m 2 , it is already high enough and meets the expectation.

[0228] Table 6

[0229]

[0230] Example 7

[0231] This example is to illustrate the rapid evaluation of the flexural modulus and impact strength of SP179 polypropylene by using the method of the present invention.

[0232] (1) Select a reference sample:

[0233] Taking the SP179 polypropylene of North Huajin Chemical Industry Group Co., Ltd. as the evaluation sample, according to the melt flow rate of the evaluation sample and the reference sample, the PPB-M09 polypropylene of Zhenhai Refining & Chemical Company, Sinopec was selected as the reference sample.

[0234] (2) Experimental steps:

[0235] 1. Measure the melt flow rate, flexural modulus and impact strength of PPB-M09 polypropylene according to ISO1133 (230 °C, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively.

[0236] 2. Measure the melt flow rate of SP179 polypropylene according to ISO1133 (230 °C, 2.16 Kg);

[0237] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples by small nuclear magnetic resonance calibrated by 13C-NMR;

[0238] 4. Measure the ethylene content of the two samples by Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0239] 5. Measure the gloss (60°) according to GB 8807-1988; the measured data are shown in Table 7;

[0240] 6. The above measurement items can be completed respectively within 1 hour, and the total time-consuming is 0.8 hours.

[0241] 7. The absolute value of the difference in the ethylene content / xylene-soluble content of the reference sample and the evaluation sample is 1, and the values of the ethylene content / xylene-soluble content of the two samples are close, indicating that the two samples have a similar mixing state of polypropylene and ethylene-propylene rubber; the absolute value of the difference in the gloss (60°) of the reference sample and the evaluation sample is 14, and the gloss (60°) of SP179 polypropylene is lower, indicating that it has a higher mass number of long ethylene crystalline chain segments.

[0242] 8. The isotactic polypropylene content of SP179 polypropylene is much lower than that of PPB-M09 polypropylene, and the flexural modulus of SP179 polypropylene is not as good as that of PPB-M09 polypropylene; although the ethylene content of SP179 polypropylene is lower, the xylene-soluble content is significantly higher than that of PPB-M09 polypropylene, and the xylene-soluble content of SP179 polypropylene is greater than or equal to 20-23%; the room temperature impact strength of SP179 polypropylene is in the brittle-ductile transition stage, and the room temperature impact strength (preferably measured according to ISO179-1:2010) is greater than 30 kJ / m 2 Above, it cannot be accurately estimated;

[0243] (3) Verify according to the formula

[0244] According to the mode without adding nucleating agent:

[0245] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.02085 - 0.22565

[0246] Flexural modulus (according to ISO178:2019) = 52.4 × 0.02085 - 0.22565 = 1.04 GPa;

[0247] (4) Calibrate

[0248] After conditioning for 40 - 48 hours, measure the impact strength and flexural modulus of SP179 polypropylene according to ISO 179-1:2010 and ISO 178:2019 respectively. The measured data are: impact strength at 23°C is 51 kJ / m 2 , flexural modulus is 0.97 Gpa.

[0249] Compare the measured flexural modulus data with the evaluation data in Table 7, the difference is not significant, and the error meets the expectation; the measured impact strength at 23°C is 51 kJ / m 2 and the evaluated value is 30 kJ / m 2 The difference is large because there is an upward transition period in this data, which is difficult to predict; when this value is greater than 30 kJ / m 2 , it is high enough and meets the expectation.

[0250] Table 7

[0251]

[0252] Example 8

[0253] This example is to illustrate the rapid evaluation of the flexural modulus and impact strength of M10RG polypropylene by using the method of the present invention.

[0254] (1) Select reference samples:

[0255] The M10RG polypropylene of Zhenhai Refining and Chemical Company, Sinopec is used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, PPB-M09 polypropylene of Zhenhai Refining and Chemical Company, Sinopec is selected as the reference sample.

[0256] (2) Experimental steps:

[0257] 1. Measure the melt flow rate, flexural modulus, and impact strength of M10RG polypropylene according to ISO 1133 (230 °C, 2.16 Kg), ISO 178:2019, and ISO 179-1:2010 respectively.

[0258] 2. Measure the melt flow rate of M10RG polypropylene according to ISO 1133 (230 °C, 2.16 Kg);

[0259] 3. Measure the isotactic polypropylene and xylene-soluble content of two samples using a small nuclear magnetic resonance calibrated by 13C-NMR;

[0260] 4. Measure the ethylene content of two samples using Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0261] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data is shown in Table 8;

[0262] 6. The above measurement items can be completed within 1 hour, with a total time consumption of 0.8 hours.

[0263] 7. The absolute value of the difference in the ethylene content / xylene-soluble content between the reference sample and the evaluation sample is 26. The ethylene content / xylene-soluble content value of M10RG polypropylene is significantly lower, indicating that it has a better mixing state of polypropylene and ethylene-propylene rubber; the absolute value of the difference in glossiness between the reference sample and the evaluation sample is 47. The glossiness (60°) of M10RG polypropylene is significantly higher, indicating that it has a very small mass number of long ethylene crystalline chain segments.

[0264] 8. The isotactic polypropylene content of M10RG polypropylene is much higher than that of PPB-M09 polypropylene, and the flexural modulus of M10RG polypropylene is higher than that of PPB-M09 polypropylene; the ethylene and xylene-soluble content of M10RG polypropylene is much lower than that of PPB-M09 polypropylene, and it will have a lower impact strength at 23 °C.

[0265] (3) Verify according to the formula

[0266] According to the nucleating agent addition mode:

[0267] Flexural modulus (measured according to ISO 178:2019, GPa) = isotactic polypropylene content × 0.0133 + 0.41681

[0268] Flexural modulus (according to ISO 178:2019) = 89.6 × 0.0133 + 0.41681 = 1.61 GPa;

[0269] When the xylene-soluble content is less than 23% and the high-crystalline products are removed, and when the ethylene content / xylene-soluble content is less than 43, the impact strength at room temperature (preferably measured in accordance with ISO 179-1:2010, kJ / m 2 ) = xylene-soluble content × 0.29826 + 4.22918, where the range of the xylene-soluble content is 5-23%; the impact strength at room temperature (in accordance with ISO 179-1:2010) = 8.5 × 0.29826 + 4.22918 = 6.8 kJ / m 2

[0270] (4) Calibration

[0271] After conditioning for 40-48 hours, the impact strength and flexural modulus of M10RG polypropylene were measured in accordance with ISO 179-1:2010 and ISO 178:2019 respectively. The measured data were: the impact strength at 23°C was 6.5 kJ / m 2 , and the flexural modulus was 1.58 GPa.

[0272] The measured data were compared with the evaluation data in Table 8, and the error was small, meeting the expectations.

[0273] Table 8

[0274]

[0275] Example 9

[0276] This example is to illustrate the rapid evaluation of the flexural modulus and impact strength of 7555KNE2 polypropylene using the method of the present invention.

[0277] (1) Selection of reference sample:

[0278] 7555KNE2 polypropylene from Exxon Mobil Corporation was used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, M50RH polypropylene from Zhenhai Refining & Chemical Company, Sinopec was selected as the reference sample.

[0279] (2) Experimental procedure:

[0280] 1. Measure the melt flow rate, flexural modulus and impact strength of 7555KNE2 polypropylene in accordance with ISO1133 (230°C, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively.

[0281] 2. Measure the melt flow rate of 7555KNE2 polypropylene in accordance with ISO1133 (230°C, 2.16 Kg);

[0282] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples using a small nuclear magnetic resonance calibrated by 13C-NMR;

[0283] 4. Measure the ethylene content of the two samples using Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0284] 5. Measure the glossiness (60°) in accordance with GB 8807-1988; the measured data are shown in Table 9;

[0285] 6. The above measurement items can be completed respectively within 1 hour, with a total time consumption of 0.8 hours.

[0286] 7. The absolute value of the difference in the ethylene content / xylene-soluble content between the reference sample and the evaluation sample is 10. The ethylene content / xylene-soluble content value of 7555KNE2 polypropylene is low, indicating that it has better compatibility and mixing morphology between polypropylene and ethylene-propylene rubber; the absolute value of the difference in glossiness between the reference sample and the evaluation sample is 11. The glossiness (60°) of 7555KNE2 polypropylene is higher, indicating that it has a lower mass number of long ethylene crystalline chain segments.

[0287] 8. The isotactic polypropylene content of 7555KNE2 polypropylene is higher than that of M50RH polypropylene, and the flexural modulus of 7555KNE2 polypropylene is higher than that of M50RH polypropylene; the ethylene content of 7555KNE2 polypropylene is lower than that of M50RH polypropylene, and it will have a lower impact strength at 23°C.

[0288] (3) Verify according to the formula

[0289] According to the high crystallization mode:

[0290] Flexural modulus (measured in accordance with ISO178:2019, GPa) = isotactic polypropylene content × 0.02325 - 0.07713;

[0291] Flexural modulus (in accordance with ISO178:2019) = 62.9 × 0.02325 - 0.07713 = 1.39 GPa;

[0292] In the case where the xylene-soluble content is less than 23% and the high crystallinity (crystallinity is higher than 40%, mainly the melt flow rate ≥ 47 g / 10 min): the room temperature impact strength (preferably measured in accordance with ISO179-1:2010, kJ / m 2 ) = xylene-soluble content × 0.45411 - 1.15745, where the xylene-soluble content ranges from 11 - 23%;

[0293] Charpy impact strength at ambient temperature (measured according to ISO179-1:2010) = 20.4×0.45411 - 1.15745 = 8.1 kJ / m 2 ;

[0294] (4) Calibration

[0295] After 40 - 48 hours of conditioning, the impact strength and flexural modulus of 7555KNE2 polypropylene were measured according to ISO 179-1:2010 and ISO 178:2019 respectively. The measured data are: Charpy impact strength at 23°C is 8.1 kJ / m 2 , and the flexural modulus is 1.38 GPa.

[0296] Comparing the measured data with the evaluation data in Table 9, the error is small and meets the expectations.

[0297] Table 9

[0298]

[0299] Example 10

[0300] This example is to illustrate the rapid evaluation of the flexural modulus and impact strength of BM3900 polypropylene using the method of the present invention.

[0301] (1) Selection of reference sample:

[0302] BM3900 polypropylene from SK Chemical Co., Ltd. is used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, M50RH polypropylene from Zhenhai Refining & Chemical Company, Sinopec is selected as the reference sample.

[0303] (2) Experimental procedures:

[0304] 1. Measure the melt flow rate, flexural modulus and impact strength of M50RH polypropylene according to ISO1133 (230°C, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively.

[0305] 2. Measure the melt flow rate of BM3900 polypropylene according to ISO1133 (230°C, 2.16 Kg);

[0306] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples using a small NMR calibrated by 13C-NMR;

[0307] 4. Measure the ethylene content of the two samples using Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0308] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data are shown in Table 10;

[0309] 6. The above-mentioned measurement items can be completed respectively within 1 hour, and the total time-consuming is 0.8 hours.

[0310] 7. The absolute value of the difference in ethylene content / xylene soluble content between the reference sample and the evaluation sample is 4. BM3900 polypropylene has a relatively low ethylene content / xylene soluble content, indicating that it has better compatibility and mixing morphology between polypropylene and ethylene-propylene rubber; the absolute value of the difference in glossiness between the reference sample and the evaluation sample is 19. BM3900 polypropylene has a relatively high glossiness (60°), indicating that it has fewer long ethylene crystalline chain segment mass numbers.

[0311] 8. The isotactic polypropylene content of BM3900 polypropylene is much higher than that of M50RH polypropylene, and the flexural modulus of BM3900 polypropylene is higher than that of M50RH polypropylene; the ethylene and xylene soluble contents of BM3900 polypropylene are lower than those of M50RH polypropylene, and it will have a lower impact strength at 23°C.

[0312] (3) Verify according to the formula

[0313] According to the high crystallization mode:

[0314] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.02325 - 0.07713

[0315] Flexural modulus (according to ISO178:2019) = 68.2 × 0.02325 - 0.07713 = 1.51 GPa;

[0316] When the xylene soluble content is less than 23% and the crystallinity is high (crystallinity is higher than 40%, mainly melt flow rate ≥ 47 g / 10 min): Charpy impact strength at room temperature (measured according to ISO179-1:2010, kJ / m 2 ) = xylene soluble content × 0.45411 - 1.15745, where the xylene soluble content ranges from 11 - 23%;

[0317] Charpy impact strength at room temperature (measured according to ISO179-1:2010) = 17.6 × 0.45411 - 1.15745 = 6.8 kJ / m 2 ;

[0318] (4) Calibrate

[0319] After 40 - 48 hours of conditioning, the impact strength and flexural modulus of BM3900 polypropylene were measured according to ISO 179 - 1:2010 and ISO 178:2019 respectively. The measured data were: the impact strength at 23℃ was 6.1 kJ / m 2 , and the flexural modulus was 1.53 GPa.

[0320] Comparing the measured data with the evaluation data in Table 10, the error was small and met the expectations.

[0321] Table 10

[0322]

[0323] Example 11

[0324] This example is to illustrate the rapid evaluation of the flexural modulus and impact strength of BX3900 polypropylene using the method of the present invention.

[0325] (1) Select a reference sample:

[0326] BX3900 polypropylene from SK Chemical Co., Ltd. was used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, M60RHC polypropylene from Zhenhai Refining & Chemical Company, Sinopec was selected as the reference sample.

[0327] (2) Experimental procedures:

[0328] 1. Measure the melt flow rate, flexural modulus and impact strength of M60RHC polypropylene according to ISO1133 (230℃, 2.16 Kg), ISO178:2019 and ISO 179 - 1:2010 respectively.

[0329] 2. Measure the melt flow rate of BX3900 polypropylene according to ISO1133 (230℃, 2.16 Kg);

[0330] 3. Measure the isotactic polypropylene and xylene soluble content of the two samples using a small NMR calibrated by 13C - NMR;

[0331] 4. Measure the ethylene content of the two samples using Fourier transform infrared spectroscopy (FTIR) calibrated by 13C - NMR; calculate the ethylene content / xylene soluble content;

[0332] 5. Measure the glossiness (60°) according to GB 8807 - 1988; the measured data are shown in Table 11;

[0333] 6. The above - mentioned measurement items can be completed within 1 hour, and the total time consumption is 0.8 hours.

[0334] 7. The absolute value of the difference in ethylene content / xylene solubles content between the reference sample and the evaluation sample is 12. BX3900 polypropylene has a relatively low ethylene content / xylene solubles content, indicating better compatibility and mixing morphology between polypropylene and ethylene-propylene rubber; the absolute value of the difference in gloss between the reference sample and the evaluation sample is 22. BX3900 polypropylene has a relatively high gloss (60°), indicating a lower mass number of long ethylene crystalline chain segments.

[0335] 8. The isotactic polypropylene content of BX3900 polypropylene is much higher than that of M60RHC polypropylene, and the flexural modulus of BX3900 polypropylene is higher than that of M60RHC polypropylene; the ethylene and xylene solubles content of BX3900 polypropylene is lower than that of M60RHC polypropylene, and it will have a lower impact strength at 23°C.

[0336] (3) Verification according to the formula

[0337] According to the high-crystallinity mode:

[0338] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.02325 - 0.07713

[0339] Flexural modulus (according to ISO178:2019) = 79.9 × 0.02325 - 0.07713 = 1.78 GPa;

[0340] When the xylene solubles content is less than 23% and the crystallinity is high (crystallinity higher than 40%, mainly melt flow rate ≥ 47 g / 10 min): Charpy impact strength at room temperature (measured according to ISO179-1:2010, kJ / m 2 ) = xylene solubles content × 0.45411 - 1.15745, where the xylene solubles content ranges from 11 - 23%;

[0341] Charpy impact strength at room temperature (measured according to ISO179-1:2010) = 13.2 × 0.45411 - 1.15745 = 4.8 kJ / m 2

[0342] (4) Calibration

[0343] After conditioning for 40 - 48 hours, the impact strength and flexural modulus of BX3900 polypropylene are measured according to ISO 179-1:2010 and ISO 178:2019 respectively. The measured data are: Charpy impact strength at 23°C 5.4 kJ / m 2 , flexural modulus 1.72 GPa.

[0344] Compare the measured data with the evaluation data in Table 11. The error is small and meets the expectation.

[0345] Table 11

[0346]

[0347] Example 12

[0348] This example aims to illustrate the rapid evaluation of the flexural modulus and impact strength of BX3920 polypropylene using the method of the present invention.

[0349] (1) Select the reference sample:

[0350] The BX3920 polypropylene of SK Integrated Chemical Co., Ltd. is used as the evaluation sample. According to the melt flow rate of the evaluation sample and the reference sample, the M100RHC polypropylene of Zhenhai Refining & Chemical Company, Sinopec is selected as the reference sample.

[0351] (2) Experimental procedures:

[0352] 1. Measure the melt flow rate, flexural modulus and impact strength of M100RHC polypropylene according to ISO1133 (230 °C, 2.16 Kg), ISO178:2019 and ISO 179-1:2010 respectively.

[0353] 2. Measure the melt flow rate of BX3920 polypropylene according to ISO1133 (230 °C, 2.16 Kg);

[0354] 3. Measure the isotactic polypropylene and xylene-soluble content of the two samples using a small nuclear magnetic resonance calibrated by 13C-NMR;

[0355] 4. Measure the ethylene content of the two samples using Fourier transform infrared spectroscopy (FTIR) calibrated by 13C-NMR; calculate the ethylene content / xylene-soluble content;

[0356] 5. Measure the glossiness (60°) according to GB 8807-1988; the measured data are shown in Table 12;

[0357] 6. The above measurement items can be completed within 1 hour respectively, and the total time consumption is 0.8 hours.

[0358] 7. The absolute value of the difference in ethylene content / xylene solubles content between the reference sample and the evaluation sample is 5. BX3920 polypropylene has a relatively high ethylene content / xylene solubles content, indicating that it has worse compatibility and mixing morphology between polypropylene and ethylene-propylene rubber than M100RHC polypropylene; the absolute value of the difference in gloss between the reference sample and the evaluation sample is 20. BX3920 polypropylene has a relatively high gloss (60°), indicating that it has a lower mass number of long ethylene crystalline chain segments.

[0359] 8. The isotactic polypropylene content of BX3920 polypropylene is much higher than that of M100RHC polypropylene, and the flexural modulus of BX3920 polypropylene is higher than that of M100RHC polypropylene; the ethylene and xylene solubles content of BX3920 polypropylene is lower than that of M100RHC polypropylene, and it will have a lower impact strength at 23°C.

[0360] (3) Verification according to the formula

[0361] According to the high crystallization mode:

[0362] Flexural modulus (measured according to ISO178:2019, GPa) = isotactic polypropylene content × 0.02325 - 0.07713

[0363] Flexural modulus (according to ISO178:2019) = 82.1 × 0.02325 - 0.07713 = 1.83 GPa;

[0364] When the xylene solubles content is less than 23% and the crystallinity is high (crystallinity higher than 40%, mainly melt flow rate ≥ 47 g / 10 min): Charpy impact strength at room temperature (measured according to ISO179-1:2010, kJ / m 2 ) = xylene solubles content × 0.45411 - 1.15745, where the xylene solubles content ranges from 11 - 23%;

[0365] Charpy impact strength at room temperature (measured according to ISO179-1:2010) = 11.9 × 0.45411 - 1.15745 = 4.2 kJ / m 2

[0366] (4) Calibration

[0367] After conditioning for 40 - 48 hours, the impact strength and flexural modulus of BX3920 polypropylene are measured according to ISO 179-1:2010 and ISO 178:2019 respectively. The measured data are: Charpy impact strength at 23°C 4.4 kJ / m 2 , flexural modulus 1.87 Gpa.

[0368] Compare the measured data with the evaluation data in Table 12, and the error is small, meeting the expectations.

[0369] Table 12

[0370]

[0371] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for evaluating the stiffness-toughness balance performance of impact copolymer polypropylene, characterized in that, The described method includes: (1) Measuring the melt flow rate of the evaluated impact copolymer polypropylene and selecting a reference sample; (2) Measuring the melt flow rate, flexural modulus, and impact strength of the reference sample; (3) Measuring the isotactic polypropylene content, xylene-soluble content, and gloss of the reference sample and the evaluated sample, and measuring the ethylene content in the xylene-soluble; (4) Evaluating the flexural modulus of the evaluated sample based on the isotactic polypropylene content of the evaluated sample and the reference sample; when the isotactic polypropylene content of the evaluated sample is higher than that of the reference sample, the flexural modulus of the evaluated sample is also higher than that of the reference sample; (5) Evaluating the impact strength of the evaluated sample based on the xylene-soluble content of the reference sample and the evaluated sample, in combination with the ratio of ethylene content / xylene-soluble content and gloss; under the condition that the absolute value of the difference between the ratio of ethylene content / xylene-soluble content of the reference sample and that of the evaluated sample is 0 - 30, and the absolute value of the difference between the gloss of the reference sample and that of the evaluated sample is 0 - 40%, when the xylene-soluble content of the evaluated sample is higher than that of the reference sample, the impact strength of the evaluated sample is also higher than that of the reference sample; (6) Evaluating the stiffness-toughness balance performance of the impact copolymer polypropylene by combining steps (4) and (5).

2. The method according to claim 1, wherein, Selecting the reference sample according to the principle that the melt flow rates of the reference sample and the evaluated sample are close; wherein, the principle that the melt flow rates are close is that the absolute value of the difference between the melt flow rates of the reference sample and the evaluated sample is 0 - 8 g / 10 min.

3. The method according to claim 2, wherein The absolute value of the difference between the melt flow rates of the reference sample and the evaluated sample is 0 - 6 g / 10 min.

4. The method according to claim 1, wherein In step (4), when the isotactic polypropylene content of the evaluated sample is 0 - 25 wt% higher or lower than that of the reference sample, the flexural modulus of the evaluated sample is 0 - 0.6 GPa higher or lower than that of the reference sample.

5. The method according to claim 1, wherein, In step (5), under the conditions that the absolute value of the difference between the ratio of ethylene content to xylene solubles content of the reference sample and the ratio of ethylene content to xylene solubles content of the evaluation sample is 0 - 15, and the absolute value of the difference between the gloss of the reference sample and the gloss of the evaluation sample is 0 - 20%, when the xylene solubles content of the evaluation sample is 0 - 10 wt% higher than the xylene solubles content of the reference sample, the impact strength of the evaluation sample is 0 - 5.5 kJ / m higher than the impact strength of the reference sample 2 .

6. The method according to claim 1, wherein The impact copolymer polypropylene contains isotactic polypropylene, xylene-soluble, and an optional nucleating agent, and based on the total weight of the impact copolymer polypropylene, the content of the isotactic polypropylene is 35 - 95 wt%, the content of the xylene-soluble is 1.5 - 45 wt%, and the content of the nucleating agent is 0 - 0.5 wt%; and / or, the xylene-soluble contains ethylene, and based on the total weight of the xylene-soluble, the content of the ethylene is 1 - 25 wt%; and / or, the melt flow rate of the impact copolymer polypropylene is 0.1 - 200 g / 10 min, and the crystallinity is 18 - 50%.

7. The method according to claim 6, wherein Based on the total weight of the impact copolymer polypropylene, the content of the isotactic polypropylene is 40 - 90 wt%, the content of the xylene-soluble is 6 - 35 wt%, and the content of the nucleating agent is 0 - 0.2 wt%.

8. The method according to claim 6, wherein, Based on the total weight of the xylene-soluble, the content of the ethylene is 1 - 15 wt%.

9. The method according to claim 7 or 8, wherein, When the impact copolymerized polypropylene does not contain a nucleating agent and the isotactic polypropylene content is 40 - 75% by weight, the flexural modulus of the impact copolymerized polypropylene has the formula shown in Equation (1): M1 = content of isotactic polypropylene × 0.02085 - 0.22565, Equation (1); and / or, when the impact copolymerized polypropylene contains a nucleating agent and the isotactic polypropylene content is 45 - 90% by weight, the flexural modulus of the impact copolymerized polypropylene has the formula shown in Equation (2): M2 = isotactic polypropylene content × 0.0133 + 0.41681, Equation (2); and / or, when the impact copolymerized polypropylene contains a nucleating agent and the crystallinity ≥ 40%, and the isotactic polypropylene content is 60 - 85% by weight, the flexural modulus of the impact copolymerized polypropylene has the formula shown in Equation (3): M3 = isotactic polypropylene content × 0.02325 - 0.07713, Equation (3).

10. The method according to claim 7 or 8, wherein When the xylene-soluble content of the impact copolymerized polypropylene > 23% by weight, the impact strength Q1 of the impact copolymerized polypropylene ≥ 30 kJ / m 2 ; and / or, when the xylene-soluble content of the impact copolymerized polypropylene is 11 - 23% by weight, the crystallinity ≥ 40%, and the melt flow rate ≥ 47 g / 10 min, the impact strength of the impact copolymerized polypropylene has the formula shown in Equation (4): Q2 = xylene-soluble content × 0.45411 - 1.15745, Equation (4); and / or, when the xylene-soluble content of the impact copolymerized polypropylene is 5 - 23% by weight and high-crystalline products are excluded, and the ratio of ethylene content / xylene-soluble content is less than 43, the impact strength of the impact copolymerized polypropylene has the formula shown in Equation (5): Q3 = xylene-soluble content × 0.29826 + 4.22918, Equation (5); and / or, when the xylene-soluble content of the impact copolymerized polypropylene is 5 - 23% by weight and high-crystalline products are excluded, and the ratio of ethylene content / xylene-soluble content ≥ 43, the impact strength of the impact copolymerized polypropylene has the formula shown in Equation (6): Q4 = xylene-soluble content × 0.5309 - 1.73675, Equation (6).

11. The method according to claim 1, wherein The reference sample contains isotactic polypropylene, xylene-soluble matter, and an optional nucleating agent. Based on the total weight of the reference sample, the content of isotactic polypropylene is 35 - 95% by weight, the content of xylene-soluble matter is 1.5 - 45% by weight, and the content of nucleating agent is 0 - 0.5% by weight; and / or, the xylene-soluble matter contains ethylene. Based on the total weight of the xylene-soluble matter, the content of ethylene is 1 - 25% by weight.

12. The method according to claim 11, wherein, Based on the total weight of the reference sample, the content of isotactic polypropylene is 40 - 90% by weight, the content of xylene-soluble matter is 6 - 35% by weight, and the content of nucleating agent is 0 - 0.2% by weight.

13. The method according to claim 11, wherein, Based on the total weight of the xylene-soluble matter, the content of ethylene is 1 - 15% by weight.

14. The method according to claim 7 or 8, wherein The melt flow rate of the reference sample at 230 °C under a condition of 2.16 Kg is 0.1 - 200 g / 10 min, and the flexural modulus is 0.3 - 2 GPa; the impact strength at 23 °C is 1 - 80 kJ / m 2 , and the glossiness at 60° is 20 - 100%.

15. The method according to claim 14, wherein, The melt flow rate of the reference sample under the conditions of 230 °C and 2.16 Kg is 0.2 - 105 g / 10 min, and the flexural modulus is 0.4 - 1.9 GPa; the impact strength under the condition of 23 °C is 2 - 65 kJ / m 2 , and the glossiness under the condition of 60° is 30 - 90%.

16. The method according to claim 7 or 8, wherein, The melt flow rate of the impact copolymer polypropylene under the conditions of 230 °C and 2.16 Kg is 0.1 - 200 g / 10 min, and the flexural modulus is 0.3 - 2 GPa; the impact strength under the condition of 23 °C is 1 - 80 kJ / m 2 , and the glossiness under the condition of 60° is 20 - 100%.

17. The method according to claim 16, wherein The melt flow rate of the reference sample under the conditions of 230 °C and 2.16 Kg is 0.2 - 105 g / 10 min, and the flexural modulus is 0.4 - 1.9 GPa; the impact strength under the condition of 23 °C is 2 - 65 kJ / m 2 , and the glossiness under the condition of 60° is 30 - 90%.

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