Durable antibacterial polypropylene filament non-woven geotextile and preparation method thereof

Abstract

According to the long-lasting antibacterial polypropylene filament non-woven geotextile and the preparation method thereof, organosilicon quaternary ammonium salt containing double bonds serves as an antibacterial agent and is subjected to melt blending with polypropylene master batches at a certain temperature, a proper amount of initiator is added, graft copolymerization is promoted, the antibacterial agent and polypropylene form covalent bonds, and the long-lasting antibacterial polypropylene filament non-woven geotextile is prepared. The antibacterial components are uniformly distributed and are not lost. The geotextile prepared by the needling process has strong antibacterial property and durability, effectively inhibits the growth of microorganisms, prolongs the service life, and enhances the functional stability under various environmental conditions. The geotextile meets the market requirements of environmental protection and sustainable development, is suitable for projects needing to be exposed to high-humidity and complex microbial environments for a long time, and provides reliable guarantee for wider engineering application.

Description

Technical Field

[0001] The invention relates to a durable antibacterial polypropylene filament nonwoven geotextile and a preparation method thereof, belonging to the technical field of polymer materials. Background Art

[0002] In many fields such as civil engineering, environmental protection, agriculture and horticulture, polypropylene filament non-woven geotextiles are widely used for reinforcement, isolation, filtration and drainage. However, traditional polypropylene filament non-woven geotextiles often face the challenge of microbial erosion during use. Since the chemical structure of polypropylene itself does not have natural antibacterial properties, geotextiles can easily become a breeding ground for microorganisms such as bacteria and fungi in a humid, organic-rich environment. The reproduction of such microorganisms will not only lead to the biodegradation of the material, resulting in a decrease in its mechanical properties and toughness, but may also cause odor and pollution, seriously affecting the service life and functionality of the material. In addition, in some applications, such as landfills or sewage treatment facilities, the accumulation of microorganisms may pose a threat to the environment and human health. Therefore, giving polypropylene filament non-woven geotextiles antibacterial properties can effectively inhibit the growth of microorganisms, extend the service life of the material, and maintain its structural strength and functional characteristics.

[0003] While dealing with the above problems, the market demand for high-performance polypropylene geotextiles is growing, especially in projects that require long-term exposure to high humidity and complex microbial environments. By introducing antimicrobial agents into polypropylene materials, microbial erosion can be prevented at the source. However, the selection and addition method of antimicrobial agents directly affect the antimicrobial effect and physical properties of the material. Existing studies have attached inorganic antimicrobial agents such as nanometals or metal oxides, organic antimicrobial agents such as chitosan, surfactants, etc. to the surface of polypropylene filament fibers or geotextiles by spraying, cast coating, etc., so that they have antibacterial effects, but the above methods have the problem of easy detachment of antimicrobial agents, which affects the durability of antibacterial properties, and the types of antimicrobial agents are relatively single, which is difficult to meet the use needs of multiple industries. Therefore, it is necessary to develop a new type of antimicrobial agent and introduce it into polypropylene filaments by melt grafting copolymerization to prolong its antibacterial effect.

[0004] As a highly effective and long-lasting antibacterial agent, silicone quaternary ammonium salt is used in a variety of materials due to its chemical stability and safety. However, how to effectively incorporate it into polypropylene masterbatch to ensure that the antibacterial components are evenly distributed in the material and do not leak, and do not affect its spinning performance and the mechanical properties of the final product, is still a technical challenge. Summary of the invention

[0005] In view of the shortcomings of the prior art, especially the problems that the existing antibacterial polypropylene filament geotextile has unstable antibacterial performance, the antibacterial agent is easy to fall off, the antibacterial effect is not long-lasting, and the types of antibacterial agents are few, the present invention provides a durable antibacterial polypropylene filament non-woven geotextile and a preparation method thereof.

[0006] The present invention uses an organosilicon quaternary ammonium salt having antibacterial function and containing double bonds as an antibacterial agent, melt-blends it with a polypropylene masterbatch at a certain temperature, and adds an appropriate amount of initiator to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and polypropylene, so that the antibacterial agent is firmly combined with the polypropylene molecular chain. Then, the antibacterial polypropylene filament non-woven geotextile is prepared through a needle punching process, and the obtained geotextile has strong antibacterial performance and strong antibacterial persistence, prolongs its service life and enhances its functional stability under various environmental conditions.

[0007] To achieve the above object, the present invention is implemented by the following technical solutions:

[0008] The first object of the present invention is to provide a durable antibacterial polypropylene filament nonwoven geotextile.

[0009] A durable antibacterial polypropylene filament nonwoven geotextile is prepared by melt blending a double-bond organic silicon quaternary ammonium salt and a polypropylene masterbatch in a mass ratio of (1-3): (200-1500), graft copolymerizing the mixture under an initiator, and subjecting the obtained graft copolymer to a needle punching process;

[0010] The double-bond-containing organosilicon quaternary ammonium salt has a structure shown in Formula I:

[0011]

[0012] Preferably according to the present invention, the number average molecular weight Mn of the double bond-containing organosilicon quaternary ammonium salt is 4000-30000.

[0013] According to the preferred embodiment of the present invention, the double bond-containing organosilicon quaternary ammonium salt is prepared by reacting terminal chloromethyl epoxy silicone oil II with dimethylaminoethyl methacrylate III under certain temperature and solvent conditions through a nucleophilic substitution reaction;

[0014]

[0015] Preferably, according to the present invention, the solvent for the preparation reaction of the double-bond organosilicon quaternary ammonium salt is one or a mixture of two or more of 1,4-dioxane, toluene, xylene, 1,2-dichloroethane, tetrahydrofuran and water.

[0016] Preferably according to the present invention, the temperature of the preparation reaction of the double-bond organosilicon quaternary ammonium salt is 50-150°C.

[0017] Most preferably, the temperature for the preparation reaction of the double-bond organosilicon quaternary ammonium salt is 80-120°C.

[0018] Preferably according to the present invention, the nucleophilic substitution reaction time is 10-20 hours.

[0019] Preferably according to the present invention, the mass ratio of the terminal chloromethyl epoxy silicone oil II to the dimethylaminoethyl methacrylate III is (50-1000):1.

[0020] Most preferably, the mass ratio of the terminal chloromethyl epoxy silicone oil II to dimethylaminoethyl methacrylate III is (100-800):1.

[0021] Preferably, according to the present invention, the mass ratio of the total mass of the chloromethyl-terminated epoxy silicone oil II and dimethylaminoethyl methacrylate III to the solvent is 1:(1-9).

[0022] Most preferably, the total mass ratio of the chloromethyl-terminated epoxy silicone oil II and dimethylaminoethyl methacrylate III to the solvent mass is 1:(2-6).

[0023] The second object of the present invention is to provide a method for preparing the above-mentioned durable antibacterial polypropylene filament non-woven geotextile.

[0024] According to a preferred embodiment of the present invention, a method for preparing a durable antibacterial polypropylene filament nonwoven geotextile comprises the following steps:

[0025] 1) melt blending the above-mentioned double-bond organosilicon quaternary ammonium salt and polypropylene masterbatch in a screw extruder, wherein the blending temperature is controlled between the melting point of polypropylene and the thermal decomposition temperature of the organosilicon quaternary ammonium salt to ensure that the two are uniformly mixed;

[0026] 2) During the melt blending process, an initiator is added to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and the polypropylene molecular chain to form a stable graft copolymer;

[0027] 3) spinning the graft copolymer obtained in step 2) into filaments to obtain a uniform filament structure;

[0028] 4) Lay the filaments to form the initial structure of the geotextile, and then reinforce the structure of the geotextile through a needle punching process to improve its strength and stability;

[0029] 5) The geotextile after needle punching is subjected to heat setting treatment to obtain a durable antibacterial polypropylene filament non-woven geotextile.

[0030] Preferably according to the present invention, in step 1), the mass ratio of the double-bond-containing organosilicon quaternary ammonium salt to the polypropylene masterbatch is (1-3): (200-1500).

[0031] Preferably, in step 2), the amount of the initiator is 1-10% of the mass of the double-bond organosilicon quaternary ammonium salt;

[0032] Preferably according to the present invention, in step 2), the initiator is one or two of dibenzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, Ziegler-Natta catalyst, and metallocene catalyst.

[0033] The spinning process to produce filaments, web laying, needle punching and heat setting treatment are carried out according to the existing technology.

[0034] The organosilicon quaternary ammonium salt containing double bonds of the invention has the characteristics of high efficiency and lasting antibacterial properties. The double bonds of the organosilicon quaternary ammonium salt undergo graft copolymerization reaction with polypropylene to form a strong covalent bond, so that the antibacterial agent is firmly combined with the polypropylene molecular chain, effectively improving the loss or failure problem of the antibacterial polypropylene filament geotextile during long-term use. In addition, the long-chain silicon-oxygen bond of the organosilicon quaternary ammonium salt containing double bonds has the characteristics of low thermal conductivity and high temperature resistance of 300°C, and the heat transfer can be delayed by the low thermal conductivity. At the same time, the silicon-oxygen bond of the organosilicon is stable, and the creep of the polymer bond is partially locked, so that the temperature resistance of the geotextile is further improved, thereby synergistically improving the antibacterial and high temperature resistance of the polypropylene filament geotextile as a whole.

[0035] The technical features and excellent effects of the present invention are as follows:

[0036] 1. Highly effective antibacterial performance: The present invention adopts a double-bonded organosilicon quaternary ammonium salt as an antibacterial agent, which has a broad-spectrum antibacterial effect and can effectively inhibit the growth of a variety of microorganisms, including bacteria, molds and fungi. The present invention forms a strong covalent bond by grafting the double bonds of the organosilicon quaternary ammonium salt with polypropylene, so that the antibacterial agent is firmly combined with the polypropylene molecular chain, ensuring that the antibacterial component is evenly distributed in the material and does not leak, and does not affect its spinning performance and the mechanical properties of the final product.

[0037] 2. Enhanced durability: The present invention uses melt blending and graft copolymerization technology to evenly disperse the antibacterial agent in the polypropylene matrix to form a stable antibacterial layer. This structure not only improves the antibacterial performance of the geotextile, but also enhances its durability under harsh environmental conditions, prolongs its service life, ensures the long-term stability of the antibacterial performance of the geotextile, and avoids the problem of easy shedding of the antibacterial agent and short-term antibacterial effect.

[0038] 3. Excellent environmental adaptability: The chemical stability and thermal stability of the organosilicon quaternary ammonium salt of the present invention are high, which ensures that the antibacterial polypropylene filament nonwoven geotextile can maintain its function under various environmental conditions, including high humidity, high temperature and acid-base environment. This makes the geotextile more widely applicable in various engineering applications.

[0039] 4. Environmental protection and safety: The organosilicon quaternary ammonium salt antibacterial agent of the present invention has low toxicity and biodegradability and is environmentally friendly. In addition, due to its efficient antibacterial performance, the use of chemical disinfectants can be reduced, reducing the potential risks to the environment and human health.

[0040] 5. Maintaining physical properties: While imparting antibacterial properties to the geotextile, the method of the present invention will not affect the original physical properties of the polypropylene filament non-woven geotextile, such as strength, aging resistance and chemical resistance, thereby ensuring the reliability of the geotextile in various engineering applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a diagram showing the antibacterial effects of the antibacterial polypropylene filament geotextiles obtained in Examples 1-9 and Comparative Example 1. DETAILED DESCRIPTION

[0042] The present invention is further described in detail below with reference to the embodiments, but the contents of the present invention are not limited thereto.

[0043] Example 1

[0044] The preparation method of the organosilicon quaternary ammonium salt containing double bonds comprises the following steps:

[0045] 1 part of dimethylaminoethyl methacrylate, 200 parts of terminal chloromethyl epoxy silicone oil (Mn=10000) and 469 parts of toluene were mixed evenly, heated to 80°C, stirred for reaction for 12 hours, and toluene was removed under reduced pressure to obtain a double-bond organic silicon quaternary ammonium salt.

[0046] Preparation of antibacterial polypropylene filament non-woven geotextile:

[0047] 1) melt blending 1 part of double-bond organosilicon quaternary ammonium salt and 500 parts of polypropylene masterbatch in a screw extruder, wherein the blending temperature is controlled between the melting point of polypropylene and the thermal decomposition temperature of the organosilicon quaternary ammonium salt to ensure that the two are uniformly mixed;

[0048] 2) adding 0.05 parts of benzoyl peroxide for 1 hour during the melt blending process to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and the polypropylene molecular chain, and extruding and granulating to obtain a modified polypropylene masterbatch;

[0049] 3) spinning the modified polypropylene masterbatch obtained in step 2) into filaments to obtain a uniform filament structure;

[0050] 4) Lay the filaments to form the initial structure of the geotextile, and then reinforce the structure of the geotextile through a needle punching process to improve its strength and stability;

[0051] 5) The geotextile after needle punching is subjected to heat setting treatment to obtain a durable antibacterial polypropylene filament non-woven geotextile.

[0052] Example 2

[0053] The preparation method of the double-bond organosilicon quaternary ammonium salt comprises the following steps:

[0054] 1 part of dimethylaminoethyl methacrylate, 500 parts of terminal chloromethyl epoxy silicone oil (Mn=10000) and 1169 parts of toluene were mixed evenly, heated to 80°C, stirred for reaction for 12 hours, and toluene was removed under reduced pressure to obtain a double-bond organic silicon quaternary ammonium salt.

[0055] The preparation of antibacterial polypropylene filament nonwoven geotextile is carried out according to Example 1.

[0056] Example 3

[0057] The preparation method of the double-bond organosilicon quaternary ammonium salt comprises the following steps:

[0058] 1 part of dimethylaminoethyl methacrylate, 800 parts of terminal chloromethyl epoxy silicone oil (Mn=10000) and 1869 parts of toluene were mixed evenly, heated to 80°C, stirred for reaction for 12 hours, and toluene was removed under reduced pressure to obtain a double-bond organic silicon quaternary ammonium salt.

[0059] The preparation of antibacterial polypropylene filament nonwoven geotextile is carried out according to Example 1.

[0060] Example 4

[0061] The preparation method of the double-bond organosilicon quaternary ammonium salt comprises the following steps:

[0062] 1 part of dimethylaminoethyl methacrylate, 200 parts of terminal chloromethyl epoxy silicone oil (Mn=10000) and 469 parts of toluene were mixed evenly, heated to 100° C., stirred for reaction for 12 hours, and toluene was removed under reduced pressure to obtain a double-bond organic silicon quaternary ammonium salt.

[0063] The preparation of antibacterial polypropylene filament nonwoven geotextile is carried out according to Example 1.

[0064] Example 5

[0065] The preparation method of the double-bond organosilicon quaternary ammonium salt comprises the following steps:

[0066] 1 part of dimethylaminoethyl methacrylate, 200 parts of terminal chloromethyl epoxy silicone oil (Mn=10000) and 469 parts of xylene were mixed evenly, heated to 80°C, stirred for reaction for 12 hours, and xylene was removed under reduced pressure to obtain a double-bond organic silicon quaternary ammonium salt.

[0067] The preparation of antibacterial polypropylene filament nonwoven geotextile is carried out according to Example 1.

[0068] Example 6

[0069] The preparation of the double bond-containing organosilicon quaternary ammonium salt was carried out according to Example 1.

[0070] Preparation of antibacterial polypropylene filament non-woven geotextile:

[0071] 1) melt blending 1 part of double-bond organosilicon quaternary ammonium salt and 1000 parts of polypropylene masterbatch in a screw extruder, wherein the blending temperature is controlled between the melting point of polypropylene and the thermal decomposition temperature of the organosilicon quaternary ammonium salt to ensure that the two are evenly mixed;

[0072] 2) adding 0.05 parts of benzoyl peroxide for 1 hour during the melt blending process to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and the polypropylene molecular chain, and extruding and granulating to obtain a modified polypropylene masterbatch;

[0073] 3) spinning the modified polypropylene masterbatch obtained in step 2) into filaments to obtain a uniform filament structure;

[0074] 4) Lay the filaments to form the initial structure of the geotextile, and then reinforce the structure of the geotextile through a needle punching process to improve its strength and stability;

[0075] 5) The geotextile after needle punching is subjected to heat setting treatment to obtain a durable antibacterial polypropylene filament non-woven geotextile.

[0076] Example 7

[0077] The preparation method of the double-bond organic silicon quaternary ammonium salt is carried out according to Example 1.

[0078] Preparation of antibacterial polypropylene filament non-woven geotextile:

[0079] 1) melt blending 1 part of double-bond organosilicon quaternary ammonium salt and 800 parts of polypropylene masterbatch in a screw extruder, wherein the blending temperature is controlled between the melting point of polypropylene and the thermal decomposition temperature of the organosilicon quaternary ammonium salt to ensure that the two are uniformly mixed;

[0080] 2) adding 0.05 parts of benzoyl peroxide for 1 hour during the melt blending process to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and the polypropylene molecular chain, and extruding and granulating to obtain a modified polypropylene masterbatch;

[0081] 3) spinning the modified polypropylene masterbatch obtained in step 2) into filaments to obtain a uniform filament structure;

[0082] 4) Lay the filaments to form the initial structure of the geotextile, and then reinforce the structure of the geotextile through a needle punching process to improve its strength and stability;

[0083] 5) The geotextile after needle punching is subjected to heat setting treatment to obtain a durable antibacterial polypropylene filament non-woven geotextile.

[0084] Example 8

[0085] The preparation method of the double-bond organic silicon quaternary ammonium salt is carried out according to Example 1.

[0086] Preparation of antibacterial polypropylene filament non-woven geotextile:

[0087] 1) melt blending 1 part of double-bond organosilicon quaternary ammonium salt and 500 parts of polypropylene masterbatch in a screw extruder, wherein the blending temperature is controlled between the melting point of polypropylene and the thermal decomposition temperature of the organosilicon quaternary ammonium salt to ensure that the two are uniformly mixed;

[0088] 2) adding 0.05 parts of lauroyl peroxide for 1 hour during the melt blending process to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and the polypropylene molecular chain, and extruding and granulating to obtain a modified polypropylene masterbatch;

[0089] 3) spinning the modified polypropylene masterbatch obtained in step 2) into filaments to obtain a uniform filament structure;

[0090] 4) Lay the filaments to form the initial structure of the geotextile, and then reinforce the structure of the geotextile through a needle punching process to improve its strength and stability;

[0091] 5) The geotextile after needle punching is subjected to heat setting treatment to obtain a durable antibacterial polypropylene filament non-woven geotextile.

[0092] Example 9

[0093] The preparation method of the double-bond organic silicon quaternary ammonium salt is carried out according to Example 1.

[0094] Preparation of antibacterial polypropylene filament non-woven geotextile:

[0095] 1) melt blending 1 part of double-bond organosilicon quaternary ammonium salt and 500 parts of polypropylene masterbatch in a screw extruder, wherein the blending temperature is controlled between the melting point of polypropylene and the thermal decomposition temperature of the organosilicon quaternary ammonium salt to ensure that the two are uniformly mixed;

[0096] 2) adding 0.1 parts of benzoyl peroxide for 1 hour during the melt blending process to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and the polypropylene molecular chain, and extruding and granulating to obtain a modified polypropylene masterbatch;

[0097] 3) spinning the modified polypropylene masterbatch obtained in step 2) into filaments to obtain a uniform filament structure;

[0098] 4) Lay the filaments to form the initial structure of the geotextile, and then reinforce the structure of the geotextile through a needle punching process to improve its strength and stability;

[0099] 5) The geotextile after needle punching is subjected to heat setting treatment to obtain a durable antibacterial polypropylene filament non-woven geotextile.

[0100] Comparative Example 1

[0101] Polypropylene filament nonwoven geotextile without any latex modification.

[0102] Experimental example

[0103] Antibacterial performance test:

[0104] The antibacterial performance test method is as follows: First, the S. aureus bacterial suspension is placed in a constant temperature incubator for 18 hours (37°C, 150rmp / min) to obtain a bacterial solution with an initial concentration of (1-5)×108CFU / ml. Then cut a 2×2cm size polypropylene filament geotextile material and irradiate it under ultraviolet light for 1 hour to kill the original bacteria on the material. After diluting the prepared bacterial solution 10 times, take 100μL of the bacterial solution and drop it on the material. After standing for 2 hours, transfer the material to a test tube containing 10mL PBS solution, ultrasonicate for 2 minutes, and dilute the ultrasonicated PBS solution and inoculate it on the agar plate. After incubation in a 37°C constant temperature incubator for 24 hours, record the number of bacteria on each plate. Finally, the antibacterial activity of the polypropylene filament geotextile material sample is calculated using the following formula:

[0105]

[0106] Where N and N0 are the colony counts of samples treated with geotextile materials and those without treatment, respectively. Figure 1 shown.

[0107] It can be seen from the above antibacterial test results that the polypropylene filament geotextile modified with double-bond organosilicon quaternary ammonium salt has obvious antibacterial effect.

Claims

1. A durable antibacterial polypropylene filament nonwoven geotextile, prepared by melt blending a double-bond organic silicon quaternary ammonium salt and a polypropylene masterbatch in a mass ratio of (1-3): (200-1500), graft copolymerizing under an initiator, and undergoing a needle punching process; The double-bond-containing organosilicon quaternary ammonium salt has a structure shown in Formula I:

2. The durable antibacterial polypropylene filament nonwoven geotextile according to claim 1, characterized in that: The number average molecular weight Mn of the double-bond organic silicon quaternary ammonium salt is 4000-30000.

3. The durable antibacterial polypropylene filament nonwoven geotextile according to claim 1, characterized in that: The double-bond organic silicon quaternary ammonium salt is prepared by reacting terminal chloromethyl epoxy silicone oil II with dimethylaminoethyl methacrylate III under certain temperature and solvent conditions through nucleophilic substitution reaction; 4. The durable antibacterial polypropylene filament nonwoven geotextile according to claim 3, characterized in that: The solvent for the preparation reaction of the double-bond organic silicon quaternary ammonium salt is one or two of 1,4-dioxane, toluene, xylene, 1,2-dichloroethane, tetrahydrofuran and water.

5. The durable antibacterial polypropylene filament nonwoven geotextile according to claim 3, characterized in that: The temperature of the reaction for preparing the double-bond organic silicon quaternary ammonium salt is 50-150°C.

6. The durable antibacterial polypropylene filament nonwoven geotextile according to claim 3, characterized in that: The mass ratio of terminal chloromethyl epoxy silicone oil II to dimethylaminoethyl methacrylate III is (50-1000):

1.

7. The durable antibacterial polypropylene filament nonwoven geotextile according to claim 3, characterized in that: The mass ratio of the total mass of the chloromethyl-terminated epoxy silicone oil II and dimethylaminoethyl methacrylate III to the solvent is 1:(1-9).

8. The method for preparing the durable antibacterial polypropylene filament nonwoven geotextile according to any one of claims 1 to 7, comprising the following steps: 1) melt blending the above-mentioned double-bond organosilicon quaternary ammonium salt and polypropylene masterbatch in a screw extruder, wherein the blending temperature is controlled between the melting point of polypropylene and the thermal decomposition temperature of the organosilicon quaternary ammonium salt to ensure that the two are uniformly mixed; 2) During the melt blending process, an initiator is added to promote the graft copolymerization reaction between the double bonds of the organosilicon quaternary ammonium salt and the polypropylene molecular chain to form a stable graft copolymer; 3) spinning the graft copolymer obtained in step 2) into filaments to obtain a uniform filament structure; 4) Lay the filaments to form the initial structure of the geotextile, and then reinforce the structure of the geotextile through a needle punching process to improve its strength and stability; 5) The geotextile after needle punching is subjected to heat setting treatment to obtain a durable antibacterial polypropylene filament non-woven geotextile.

9. The preparation method according to claim 8, characterized in that: In step 1), the mass ratio of the double-bond organic silicon quaternary ammonium salt to the polypropylene masterbatch is (1-3): (200-1500).

10. The preparation method according to claim 8, characterized in that: In step 2), the amount of initiator used is 1-10% of the mass of the double-bond organosilicon quaternary ammonium salt, and the initiator is one or two of dibenzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, Ziegler-Natta catalyst, and metallocene catalyst.

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