Modified plastic particles having impact resistance and method for making same

Abstract

This invention provides a modified plastic particle with impact resistance and its preparation method. The modified plastic particle comprises, by weight percentage: 82%-88% polypropylene, 8%-12% polyolefin elastomer-maleic anhydride copolymer, and 4%-6% functional composite modifier. This invention, by grafting maleic anhydride onto a polyolefin elastomer to form a polyolefin elastomer-maleic anhydride copolymer, effectively improves the interaction force between polypropylene and the polyolefin elastomer, thereby increasing the impact strength and elongation at break of the modified plastic particle.

Description

Technical Field

[0001] This invention relates to the field of plastic particle technology, and more specifically to a modified plastic particle with impact resistance and its preparation method. Background Technology

[0002] PP plastic has a very low density, making it one of the lightest types of plastics. PP plastic possesses excellent comprehensive properties, including good chemical resistance, heat resistance, electrical insulation, high wear resistance, high mechanical strength, and excellent flexural fatigue resistance, allowing it to withstand multiple folds and bends without damage. PP plastic has high application value in the manufacture of durable consumer goods and packaging materials, and is suitable for food packaging and medical devices.

[0003] However, PP plastic products have low brittleness and low impact strength. PP materials are prone to cracking or even breaking after being subjected to high pressure impact, blow or collision. For plastic products that require high impact resistance or impact performance, pure PP plastic is difficult to meet the usage requirements.

[0004] POE is a thermoplastic elastomer with good thermal stability, optical properties, and crack resistance. POE-modified copolymers can ensure product integrity in high-impact applications. Conventional POE-modified PP plastic particle processes only involve physical blending. While this method is simple and has low production costs, the resulting plastic particles are prone to low impact strength and low elongation at break. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a modified plastic particle with impact resistance and a method for preparing the same.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] This application discloses a modified plastic particle with impact resistance. The modified plastic particle is composed of the following components by weight percentage: 82%-88% polypropylene, 8%-12% polyolefin elastomer-maleic anhydride copolymer, and 4%-6% functional composite modifier.

[0008] By setting up the above technical solution, maleic anhydride is grafted onto polyolefin elastomer to form a polyolefin elastomer-maleic anhydride copolymer. When applied to polypropylene, it effectively improves the interaction force between polypropylene and polyolefin elastomer, and increases the impact strength and elongation at break of the modified plastic particles.

[0009] Preferably, by weight percentage, the composition of the polyolefin elastomer-maleic anhydride copolymer is as follows: 96% polyolefin elastomer and 4% maleic anhydride; the composition of the functional composite modifier is as follows: 5%-10% filler, 30%-40% solvent, 15%-25% initiator, 10%-14% isosorbide, and 20%-30% styrene.

[0010] By setting up the above technical solution, isosorbide can dissolve in PP melt and preferentially precipitate out to form nanofiber structure before PP begins to crystallize, inducing PP nucleation and crystallization, thereby increasing the crystallization rate of PP. The nanofiber structure formed by isosorbide enhances the structural strength of PP, which is beneficial to improving the structural strength and impact resistance of modified plastic particle products.

[0011] Preferably, the solvent is composed of xylene and epoxidized soybean oil in a mass ratio of 1:1.

[0012] By setting up the above technical solution, xylene and polyolefin elastomer have similar solubility parameters. Epoxidized soybean oil contains a large number of groups that can react with maleic anhydride. The combined effect of xylene and epoxidized soybean oil can improve the dispersion uniformity of maleic anhydride in polyolefin elastomer molecules, thereby fully improving the grafting rate and efficiency of maleic anhydride and polyolefin elastomer.

[0013] Preferably, the initiator is one of diisopropyl peroxide or benzoyl peroxide.

[0014] Preferably, the filler is modified wollastonite, and its preparation steps are as follows: wollastonite powder, acetone and water are weighed in a mass ratio of 7:2:5, 2% KH-560 is added dropwise under mechanical stirring, and the pH is adjusted to 5.5 with 0.2 mol HCl. The mixture is reacted at 85°C for 2 hours, and then filtered, washed and dried to obtain modified wollastonite.

[0015] By setting up the above technical solution, the surface polarity of wollastonite treated with coupling agent is reduced, and the active sites of wollastonite are increased. It can be uniformly dispersed in copolymers of polypropylene, polyolefin elastomers and maleic anhydride. Some maleic anhydride combines with modified wollastonite to form hydrogen bonds, which enhances the intermolecular interface effect and is beneficial to improving the structural strength and impact resistance of modified plastic ions.

[0016] Preferably, the preparation steps of the polyolefin elastomer-maleic anhydride copolymer are as follows: weigh the polyolefin elastomer and maleic anhydride according to the proportion, dissolve the maleic anhydride in acetone, disperse the polyolefin elastomer and the dissolved maleic anhydride solution in a high-speed disperser for 2 minutes, and after the acetone has completely evaporated, add it to a screw extruder for extrusion and granulation to obtain the polyolefin elastomer-maleic anhydride copolymer.

[0017] Preferably, in the preparation process of polyolefin elastomer-maleic anhydride copolymer, solvent is weighed in proportion and dispersed together with polyolefin elastomer and maleic anhydride at high speed.

[0018] Preferably, the extrusion conditions of the screw extruder are: screw speed: 150~300 rpm, screw temperature: 225~245℃, die head melt pressure: 50 bar, and reaction residence time: 150~200 s.

[0019] Preferably, the polypropylene is pretreated, and the specific steps are as follows: after weighing the polypropylene, it is placed in the sample chamber of the pressure-volume-temperature measuring instrument, heated until the polypropylene melts, and the air bubbles are completely removed. The polypropylene is then treated with pressures of 20MPa, 60MPa, 100MPa, and 140MPa in sequence, and non-isothermal crystallization is carried out at a cooling rate of 2K / min. After cooling to room temperature, isotactic polypropylene is selected by wide-angle X-ray diffraction and small-angle X-ray scattering experiments.

[0020] This application also discloses a method for preparing modified plastic particles with impact resistance. The preparation method includes the following steps: weighing polyolefin elastomer-maleic anhydride copolymer, isotactic polypropylene and functional composite modifier in proportion, mixing them evenly, and then adding them to a twin-screw extruder for extrusion and granulation to obtain modified plastic particles with impact resistance.

[0021] The extrusion conditions for the twin-screw extruder are as follows:

[0022] Screw speed: 150~300rpm, screw temperature: 225~245℃, die head melt pressure: 50bar, reaction residence time: 150~200s.

[0023] By setting up the above technical solution, polypropylene is melted and then subjected to high-pressure treatment to form polypropylene with α, β, and γ crystal forms. Among them, the γ crystal form of polypropylene is isotactic polypropylene, which can be selected by wide-angle X-ray diffraction and small-angle X-ray scattering experiments. The system composed of modified wollastonite, isotactic polypropylene, and polyolefin elastomer-maleic anhydride copolymer has good component compatibility and strong interfacial adhesion, which enhances the tensile strength and comprehensive mechanical properties of the prepared modified plastic particles. After styrene is grafted into the system composed of isotactic polypropylene and polyolefin elastomer-maleic anhydride copolymer, the melt flow rate of isotactic polypropylene is reduced and its melt strength is increased. Isotactic polypropylene with high melt strength can better maintain shape stability during processing and reduce flow deformation, thereby improving the dimensional accuracy and surface quality of the modified plastic particles.

[0024] The beneficial effects of this invention are as follows:

[0025] This invention grafts maleic anhydride onto a polyolefin elastomer to form a polyolefin elastomer-maleic anhydride copolymer, which, when applied to polypropylene, effectively improves the interaction force between polypropylene and the polyolefin elastomer, thereby increasing the impact strength and elongation at break of the modified plastic particles.

[0026] Xylene and polyolefin elastomers have similar solubility parameters. Epoxidized soybean oil contains a large number of groups that can react with maleic anhydride. The combined effect of xylene and epoxidized soybean oil can improve the dispersion uniformity of maleic anhydride in polyolefin elastomer molecules, thereby significantly improving the grafting rate and efficiency of maleic anhydride and polyolefin elastomers.

[0027] Coupling agent treatment reduces the surface polarity of wollastonite and increases its active sites, enabling it to be uniformly dispersed in copolymers of polypropylene, polyolefin elastomers, and maleic anhydride. Some maleic anhydride combines with modified wollastonite to form hydrogen bonds, enhancing the intermolecular interface and improving the structural strength and impact resistance of the modified plastic ions. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Example 1: This example discloses a modified plastic particle with impact resistance. The composition of the modified plastic particle by weight percentage is as follows: 82% polypropylene, 12% polyolefin elastomer-maleic anhydride copolymer and 6% functional composite modifier.

[0030] By weight percentage: The composition of the polyolefin elastomer-maleic anhydride copolymer is as follows: polyolefin elastomer 96%, maleic anhydride 4%; The composition of the functional composite modifier is as follows: modified wollastonite 5%, xylene 15%, epoxidized soybean oil 15%, diisopropyl peroxide 25%, isosorbide 10%, styrene 30%.

[0031] In this embodiment, the preparation steps of the polyolefin elastomer-maleic anhydride copolymer are as follows: weigh the polyolefin elastomer, maleic anhydride and diisophenylpropionyl peroxide according to the proportion, dissolve the maleic anhydride in acetone, disperse the dissolved maleic anhydride solution with the polyolefin elastomer and diisophenylpropionyl peroxide in a high-speed disperser for 2 minutes, and after the acetone has completely evaporated, add it to a screw extruder for extrusion and granulation to obtain the polyolefin elastomer-maleic anhydride copolymer.

[0032] The screw speed is 150 rpm, the screw temperature is 225°C, the melt pressure at the die head is 50 bar, and the reaction residence time is 150 s.

[0033] It is worth noting that the preparation steps of modified wollastonite are as follows: Weigh wollastonite powder, acetone and water in a mass ratio of 7:2:5, add 2% KH-560 by mass dropwise under mechanical stirring, adjust the pH to 5.5 with 0.2 mol HCl, react at 85℃ for 2 hours, and then filter, wash and dry to obtain modified wollastonite.

[0034] It is worth noting that the polypropylene pretreatment process involves the following steps: after weighing the polypropylene, it is placed in the sample chamber of the pressure-volume-temperature measuring instrument. After heating the polypropylene to melt, the air bubbles are completely removed. The polypropylene is then treated with pressures of 20 MPa, 60 MPa, 100 MPa, and 140 MPa in sequence, and non-isothermal crystallization is carried out at a cooling rate of 2 K / min. After cooling to room temperature, isotactic polypropylene is selected using wide-angle X-ray diffraction and small-angle X-ray scattering experiments.

[0035] This embodiment also discloses a method for preparing modified plastic particles with impact resistance, comprising the following steps:

[0036] Weigh out polyolefin elastomer-maleic anhydride copolymer, isotactic polypropylene and functional composite modifier in proportion, mix them evenly and then add them to a twin-screw extruder for extrusion and granulation to obtain modified plastic particles with impact resistance.

[0037] The extrusion conditions for the twin-screw extruder are as follows:

[0038] Screw speed: 150 rpm, screw temperature: 225℃, die head melt pressure: 50 bar, reaction residence time: 150 s.

[0039] Example 2: This example discloses a modified plastic particle with impact resistance. The composition of the modified plastic particle by weight percentage is as follows: 88% polypropylene, 8% polyolefin elastomer-maleic anhydride copolymer and 4% functional composite modifier.

[0040] By weight percentage: The composition of the polyolefin elastomer-maleic anhydride copolymer is as follows: polyolefin elastomer 96%, maleic anhydride 4%; The composition of the functional composite modifier is as follows: modified wollastonite 10%, xylene 20%, epoxidized soybean oil 20%, benzoyl peroxide 16%, isosorbide 14%, styrene 20%.

[0041] In this embodiment, the preparation steps of the polyolefin elastomer-maleic anhydride copolymer are as follows: weigh the polyolefin elastomer, maleic anhydride and benzoyl peroxide according to the proportion, dissolve the maleic anhydride in acetone, disperse the dissolved maleic anhydride solution with the polyolefin elastomer and benzoyl peroxide in a high-speed disperser for 2 minutes, and after the acetone has completely evaporated, add it to the screw extruder for extrusion and granulation to obtain the polyolefin elastomer-maleic anhydride copolymer.

[0042] The screw speed is 300 rpm, the screw temperature is 245℃, the die head melt pressure is 50 bar, and the reaction residence time is 200 s.

[0043] It is worth noting that the preparation steps of modified wollastonite are as follows: Weigh wollastonite powder, acetone and water in a mass ratio of 7:2:5, add 2% KH-560 by mass dropwise under mechanical stirring, adjust the pH to 5.5 with 0.2 mol HCl, react at 85℃ for 2 hours, and then filter, wash and dry to obtain modified wollastonite.

[0044] It is worth noting that the polypropylene pretreatment process involves the following steps: after weighing the polypropylene, it is placed in the sample chamber of the pressure-volume-temperature measuring instrument. After heating the polypropylene to melt, the air bubbles are completely removed. The polypropylene is then treated with pressures of 20 MPa, 60 MPa, 100 MPa, and 140 MPa in sequence, and non-isothermal crystallization is carried out at a cooling rate of 2 K / min. After cooling to room temperature, isotactic polypropylene is selected using wide-angle X-ray diffraction and small-angle X-ray scattering experiments.

[0045] This embodiment also discloses a method for preparing modified plastic particles with impact resistance, comprising the following steps:

[0046] Weigh out polyolefin elastomer-maleic anhydride copolymer, isotactic polypropylene and functional composite modifier in proportion, mix them evenly and then add them to a twin-screw extruder for extrusion and granulation to obtain modified plastic particles with impact resistance.

[0047] The extrusion conditions for the twin-screw extruder are as follows:

[0048] Screw speed: 300 rpm, screw temperature: 245℃, die head melt pressure: 50 bar, reaction residence time: 200 s.

[0049] Example 3: This example discloses a modified plastic particle with impact resistance. The composition of the modified plastic particle by weight percentage is as follows: 88% polypropylene, 8% polyolefin elastomer-maleic anhydride copolymer and 4% functional composite modifier.

[0050] By weight percentage: The composition of the polyolefin elastomer-maleic anhydride copolymer is as follows: polyolefin elastomer 96%, maleic anhydride 4%; The composition of the functional composite modifier is as follows: modified wollastonite 10%, xylene 20%, epoxidized soybean oil 20%, benzoyl peroxide 15%, isosorbide 10%, styrene 25%.

[0051] In this embodiment, the preparation steps of the polyolefin elastomer-maleic anhydride copolymer are as follows: weigh the polyolefin elastomer, maleic anhydride and benzoyl peroxide according to the proportion, dissolve the maleic anhydride in acetone, disperse the dissolved maleic anhydride solution with the polyolefin elastomer and benzoyl peroxide in a high-speed disperser for 2 minutes, and after the acetone has completely evaporated, add it to the screw extruder for extrusion and granulation to obtain the polyolefin elastomer-maleic anhydride copolymer.

[0052] The screw speed is 300 rpm, the screw temperature is 245℃, the die head melt pressure is 50 bar, and the reaction residence time is 200 s.

[0053] It is worth noting that the preparation steps of modified wollastonite are as follows: Weigh wollastonite powder, acetone and water in a mass ratio of 7:2:5, add 2% KH-560 by mass dropwise under mechanical stirring, adjust the pH to 5.5 with 0.2 mol HCl, react at 85℃ for 2 hours, and then filter, wash and dry to obtain modified wollastonite.

[0054] It is worth noting that the polypropylene pretreatment process involves the following steps: after weighing the polypropylene, it is placed in the sample chamber of the pressure-volume-temperature measuring instrument. After heating the polypropylene to melt, the air bubbles are completely removed. The polypropylene is then treated with pressures of 20 MPa, 60 MPa, 100 MPa, and 140 MPa in sequence, and non-isothermal crystallization is carried out at a cooling rate of 2 K / min. After cooling to room temperature, isotactic polypropylene is selected using wide-angle X-ray diffraction and small-angle X-ray scattering experiments.

[0055] This embodiment also discloses a method for preparing modified plastic particles with impact resistance, comprising the following steps:

[0056] Weigh out polyolefin elastomer-maleic anhydride copolymer, isotactic polypropylene and functional composite modifier in proportion, mix them evenly and then add them to a twin-screw extruder for extrusion and granulation to obtain modified plastic particles with impact resistance.

[0057] The extrusion conditions for the twin-screw extruder are as follows:

[0058] Screw speed: 300 rpm, screw temperature: 245℃, die head melt pressure: 50 bar, reaction residence time: 200 s.

[0059] Comparative Example 1:

[0060] A modified plastic particle with impact resistance, which differs from Example 3 only in that a polyolefin elastomer is used instead of a polyolefin elastomer-maleic anhydride copolymer.

[0061] Comparative Example 2:

[0062] A modified plastic particle with impact resistance, which differs from Example 3 only in that no functional composite modifier is added.

[0063] Comparative Example 3:

[0064] A modified plastic particle with impact resistance, which differs from Example 3 only in that: the polypropylene is not pretreated, and ordinary polypropylene is used instead of isotactic polypropylene in the preparation step of the modified plastic particle.

[0065] Comparative Example 4:

[0066] A modified plastic particle with impact resistance, which differs from Example 3 only in that xylene and epoxidized soybean oil are not added.

[0067] Comparative Example 5:

[0068] A modified plastic particle with impact resistance, which differs from Example 3 only in that the solvent is entirely composed of xylene.

[0069] Comparative Example 6:

[0070] A modified plastic particle with impact resistance, which differs from Example 3 only in that the solvent is entirely composed of epoxidized soybean oil.

[0071] Comparative Example 7:

[0072] A modified plastic particle with impact resistance, which differs from Example 3 only in that benzoyl peroxide is not added.

[0073] Comparative Example 8:

[0074] A modified plastic particle with impact resistance, which differs from Example 3 only in that ordinary wollastonite is used instead of modified wollastonite.

[0075] Comparative Example 9:

[0076] A modified plastic particle with impact resistance, which differs from Comparative Example 8 only in that it does not contain wollastonite.

[0077] Mechanical property testing of polypropylene plastic:

[0078] 1. Take the modified plastic particles obtained in Examples 1-3 and Comparative Examples 1-9, prepare the test strips required for mechanical property testing, and uniformly make them into sheets of 100mm×100mm×1mm.

[0079] 2. Tensile properties: Tensile properties were tested on an INSTRON material mechanics testing machine according to GB / T1040-2006. The tensile rate was 60 mm / min and the test temperature was room temperature. Five samples were taken from each group for testing and the average value was taken as the final result. The results are shown in Table 1.

[0080] 3. Bending performance: Bending tests were conducted on the INSTRON material mechanics testing machine according to GB / T9341-2008. The test rate was 3 mm / min and the test temperature was room temperature. Five samples were taken from each group for testing and the average value was taken as the final result. The results are shown in Table 1.

[0081] 4. Impact Performance: The notched impact strength of the samples was tested on a cantilever beam impact testing machine according to GB / T1842-2008. Specific method: The injection-molded sample was machined into a V-shaped notch on a notch-making machine, with a bottom radius of 0.25 mm. The sample was placed at room temperature for 24 hours before testing. Five samples were taken from each group for testing, and the average value was taken as the final result. The results are shown in Table 1.

[0082] Table 1 Performance parameters of the modified plastic particles obtained in Examples 1-3 and Comparative Examples 1-9

[0083]

[0084] As shown in Table 1:

[0085] The tensile strength, flexural strength, and impact strength of the modified plastic particles in Examples 1-3 are all greater than those of the modified plastic particles in Comparative Examples 1-9. The functional composite modifier can complement polypropylene and polyolefin elastomer-maleic anhydride copolymer and improve the tensile strength, flexural strength, and impact strength of the modified plastic particles.

[0086] The main differences between Examples 1-3 are the specific content of each component and the slight differences in the parameters of the preparation method. The impact on the tensile strength, flexural strength and impact strength of the modified plastic particles is relatively small.

[0087] Comparing the mechanical property parameters of the modified plastic particles in Examples 1-9 with those in Example 3, it is evident that replacing the polyolefin elastomer-maleic anhydride copolymer with a polyolefin elastomer, not pretreating the polypropylene and using ordinary polypropylene instead of isotactic polypropylene, replacing the modified wollastonite with ordinary wollastonite, and not adding wollastonite all significantly reduce the tensile strength, flexural strength, and impact strength of the modified plastic particles. Changing the solvent type has a relatively small impact on the tensile strength, flexural strength, and impact strength of the modified plastic particles.

[0088] In summary, grafting maleic anhydride onto polyolefin elastomers to form polyolefin elastomer-maleic anhydride copolymers, when applied to polypropylene, effectively improves the interaction between polypropylene and polyolefin elastomers, thereby increasing the impact strength and elongation at break of the modified plastic particles.

[0089] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A modified plastic particle with impact resistance, characterized in that, The modified plastic particles are composed of the following components by weight percentage: 82%-88% polypropylene, 8%-12% polyolefin elastomer-maleic anhydride copolymer, and 4%-6% functional composite modifier. By weight percentage: The composition of the polyolefin elastomer-maleic anhydride copolymer is as follows: 96% polyolefin elastomer and 4% maleic anhydride; The functional composite modified material is composed of the following components: filler 5%-10%, solvent 30%-40%, initiator 15%-25%, isosorbide 10%-14%, and styrene 20%-30%. The solvent is composed of xylene and epoxidized soybean oil in a mass ratio of 1:1; The initiator is one of diisopropyl peroxide or benzoyl peroxide; The filler is modified wollastonite, and its preparation steps are as follows: Weigh wollastonite powder, acetone and water in a mass ratio of 7:2:5, add 2% KH-560 by mass dropwise under mechanical stirring, adjust the pH to 5.5 with 0.2 mol HCl, react at 85℃ for 2 hours, and then filter, wash and dry to obtain modified wollastonite. Polypropylene undergoes pretreatment, and the specific steps are as follows: After weighing polypropylene, it was placed in the sample chamber of a pressure-volume-temperature measuring instrument. The temperature was raised until the polypropylene melted, and the air bubbles were completely removed. The sample was then treated with pressures of 20 MPa, 60 MPa, 100 MPa, and 140 MPa in sequence. Non-isothermal crystallization was carried out at a cooling rate of 2 K / min. After cooling to room temperature, isotactic polypropylene was selected using wide-angle X-ray diffraction and small-angle X-ray scattering experiments.

2. The modified plastic particles having impact resistance according to claim 1, wherein, The preparation steps of the polyolefin elastomer-maleic anhydride copolymer are as follows: Weigh the polyolefin elastomer and maleic anhydride according to the proportion, dissolve the maleic anhydride in acetone, disperse the polyolefin elastomer and the dissolved maleic anhydride solution in a high-speed disperser for 2 minutes, and after the acetone has completely evaporated, add it to a screw extruder for extrusion and granulation to obtain the polyolefin elastomer-maleic anhydride copolymer.

3. The modified plastic particles having impact resistance according to claim 2, wherein, In the preparation of polyolefin elastomer-maleic anhydride copolymer, solvent is weighed according to the proportion and dispersed together with polyolefin elastomer and maleic anhydride at high speed.

4. The modified plastic particles having impact resistance according to claim 3, wherein The extrusion conditions for the screw extruder are: Screw speed: 150~300rpm, screw temperature: 225~245℃, die head melt pressure: 50bar, reaction residence time: 150~200s.

5. A method for producing the modified plastic particles having impact resistance according to claim 1, characterized by, The preparation method involves the following steps: weighing polyolefin elastomer-maleic anhydride copolymer, isotactic polypropylene and functional composite modifier in proportion, mixing them evenly, and then adding them to a twin-screw extruder for extrusion and granulation to obtain modified plastic particles with impact resistance. The extrusion conditions for the twin-screw extruder are as follows: Screw speed: 150~300rpm, screw temperature: 225~245℃, die head melt pressure: 50bar, reaction residence time: 150~200s.

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