Thermoplastic elastomer and modified polypropylene thereof

Abstract

The invention relates to a thermoplastic elastomer and modified polypropylene thereof, and belongs to the technical field of polypropylene modified materials, and the key point of the technical scheme is that the thermoplastic elastomer comprises the following components in parts by weight: 35-65 parts of thermoplastic polyurethane; 25 to 35 parts of glue micro powder; 0.1 to 0.5 part of ethylene acrylic acid copolymer; 0.1 to 0.3 part of fatty alcohol-polyoxyethylene ether; 1-3 parts of maleic anhydride; 10 to 15 parts of spherical silica powder; 0.2 to 0.3 part of an antioxidant; 0.1 to 0.2 part of an active agent; the thermoplastic elastomer modified polypropylene comprises the following components in parts by mass: 100 parts of polypropylene particles; 10-15 parts of a thermoplastic elastomer; 2-4 parts of a composite compatilizer; 20-35 parts of an inorganic filler; 0.15 to 0.8 part of an antioxidant; the thermoplastic elastomer provided by the invention is applied to a modified polypropylene system, polypropylene can be well toughened and modified, and especially the low-temperature impact strength of polypropylene is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polypropylene modified materials, and particularly relates to a thermoplastic elastomer and modified polypropylene thereof. BACKGROUND

[0002] Polypropylene is a common engineering plastic, which has small density and good heat resistance, and is widely applied in the fields of household appliances, daily necessities and automobile parts. The toughness of polypropylene is poor, especially the low-temperature toughness. In order to improve the performance of polypropylene, elastomer toughening modification has always been considered as the most effective way. At present, a common method is to use POE elastomer to toughen and modify polypropylene. For details, refer to the Chinese patent application file with the application publication number CN 116693764 A, which uniformly mixes polypropylene, POE, an initiator and a crosslinking monomer to obtain a mixture, and then melts and extrudes the mixture by using a double-screw extruder to obtain a high-toughness polypropylene composite material.

[0003] Although the POE elastomer can well toughen polypropylene, the rigidity and strength of polypropylene are greatly lost, the dispersed phase particle size is not easy to control, the compatibility between the POE particles and the matrix is poor, and the particles are not good at stably deforming locally as stress concentration points. In order to improve the rigidity and strength, talc and more compatibilizers are generally added to the formula, and the talc will affect the low-temperature toughness and transparency of the material. SUMMARY

[0004] One of the purposes of the present application is to provide a thermoplastic elastomer which can be well applied to the toughening modification of polypropylene.

[0005] The above technical purpose of the present application is achieved by the following technical scheme: a thermoplastic elastomer, by weight, comprises:

[0006]

[0007]

[0008] By the technical scheme, the thermoplastic polyurethane and the rubber micro-powder are used as the main materials, the spherical silica micro-powder is used to fill the voids of the rubber micro-powder, the first is to form the reinforcing phase in the network structure of the polyurethane elastomer / rubber micro-powder, and the second is to improve the wear resistance of the system by using the wear resistance of the rigid particles; the dispersibility of the rubber micro-powder, the spherical silica micro-powder and the like is adjusted by using the active agent and the fatty alcohol polyoxyethylene ether, so as to avoid the agglomeration of the rubber micro-powder, and to form the stress concentration point; and after the surface modification of the rubber micro-powder by the active agent, more active sites and new functional groups are generated on the surface of the rubber micro-powder; the ethylene acrylic acid copolymer and the maleic anhydride are used as the compatibilizers, the maleic anhydride and the phenolic hydroxyl on the surface of the rubber micro-powder are subjected to the ring-opening esterification reaction, the new functional groups on the surface of the rubber micro-powder are subjected to the physical and chemical action with the ethylene acrylic acid copolymer at the phase interface, and the co-crosslinking is formed, the two compatibilizers and the high-activity rubber micro-powder penetrate each other between the interfaces, the interpenetrating polymer network structure is formed, the interface interaction force between the rubber phase and the plastic phase in the modified elastomer is increased, and the tensile strength and the toughness are improved; the antioxidant is added, and the anti-aging performance and the processing stability of the material are improved.

[0009] Preferably, the particle size of the rubber micro-powder is 10-50 μm.

[0010] By the technical scheme, the small-particle-size rubber micro-powder is mixed into the polyurethane elastomer, the interface interaction between the two phases of the polyurethane elastomer / rubber micro-powder blend is enhanced, the balanced torque, the tensile strength and the elongation at break are improved (compared with a single material), and the tensile strength of the original material is not reduced after the 10-50 μm rubber micro-powder in the technical scheme is added into the polyurethane elastomer, the melt performance is good during processing, and the stress concentration point is not generated.

[0011] Preferably, the particle size of the spherical silica micro-powder is 1-5 μm.

[0012] By the technical scheme, the particle size of the rubber micro-powder is one order of magnitude larger than that of the spherical silica micro-powder, and therefore the spherical silica micro-powder can be used to fill the voids of the rubber micro-powder.

[0013] Preferably, the active agent is diethylene glycol.

[0014] By the technical scheme, the diethylene glycol is used as the active agent, the S-S bond and the C-S bond in the rubber micro-powder are broken, the three-dimensional network structure of the rubber micro-powder is destroyed, the surface activity of the rubber micro-powder is enhanced, and the functional groups such as the carboxyl and the hydroxyl on the surface of the rubber micro-powder are increased; on the interface, the crosslinking product of the functional groups of the rubber micro-powder and the ethylene acrylic acid copolymer, and the product of the ring-opening esterification reaction of the maleic anhydride and the surface of the rubber micro-powder form the interpenetrating polymer network structure, the molecular chains penetrate each other, the interface bonding force is improved, and the toughness and the strength of the system are improved.

[0015] The thermoplastic elastomer is prepared by the following method:

[0016] A thermoplastic elastomer preparation method comprises the following steps:

[0017] 1) The component raw materials are weighed according to the proportion;

[0018] 2) The glue micro powder is added to a proper amount of ethanol solution, and then ultrasonic oscillation is performed to make the glue micro powder fully dissolved in the ethanol solution to form a glue micro powder solution;

[0019] 3) The glue micro powder solution is filtered by using a filter membrane with a filter hole smaller than the particle size of the glue micro powder, and the glue micro powder in the glue micro powder solution is precipitated and dried;

[0020] 4) The precipitated glue micro powder is added to a sealed container provided with a microwave generator, and ozone is introduced into the container to irradiate the glue micro powder in the microwave environment for 15-20 minutes;

[0021] 5) The glue micro powder is added to a high-speed blender, and when the glue micro powder is heated to a temperature range of 70-90℃, ethylene acrylic acid copolymer is added, and the stirring is continued; when the glue micro powder is heated to a temperature range of 120-160℃, spherical silica micro powder and active agent are added, and the stirring is uniform to form a primary mixture, which is naturally cooled and used;

[0022] 6) The thermoplastic polyurethane elastomer, antioxidant, and maleic anhydride are added to a high-speed blender, and the stirring is performed at 70-90℃; after the stirring is uniform, the temperature is raised to 120-160℃, and the primary mixture and fatty alcohol polyoxyethylene ether are added to perform the stirring to form a blending raw material;

[0023] 7) The blending raw material is sent into a single-screw extruder to be extruded and granulated at 180-200℃ to obtain the thermoplastic elastomer.

[0024] Through the above technical solution, the glue micro powder is desulfurized by the mechanical shearing effect and ultrasonic cavitation effect of ultrasonic, so that the S-S bond and C-S bond on the surface of the glue micro powder are broken, slight degradation occurs, and the surface becomes rough. Under the action of ultrasonic, the carbon black contained in the glue powder is partially exposed, accompanied by the generation of a large number of free radicals. Subsequently, microwave irradiation is used for further desulfurization and activation to produce hydroxyl, carboxyl, carbonyl, and other polar functional groups on the main chain of the outermost molecules of the glue micro powder. The above steps synergistically modify the glue micro powder to produce polar functional groups and active reaction sites, which can react with the active groups in the ethylene acrylic acid copolymer, active agent, and maleic anhydride, improve the dispersibility and interfacial bonding force of the glue micro powder in the polyurethane elastomer, and realize the modification and reinforcement of the polyurethane elastomer by the glue micro powder.

[0025] The rubber micro powder is a random high molecular elastomer containing various sulfur bonds before use, and is incompatible with other plastic systems. The common mechanical desulfurization and activation method can only achieve partial desulfurization and partial activation. Compared with the common rubber micro powder and polyurethane elastomer blending scheme, the two-step desulfurization and activation mode of ultrasonic and microwave in the technical scheme improves the surface activity of the rubber micro powder. After melting, the polar functional groups such as free radicals, hydroxyl groups and carbonyl groups form an interpenetrating polymer network structure between the active agent and the compatibilizer on the phase interface, and the different phases are mutually integrated and penetrated, thereby improving the interfacial bonding force. This beneficial structure improves the comprehensive mechanical properties of the elastomer, and the elastomer can be used for modifying materials to improve the impact strength of the materials.

[0026] Another object of the present application is to provide a thermoplastic elastomer modified polypropylene with good impact resistance and low temperature toughness.

[0027] The above technical object of the application is achieved by the following technical scheme:

[0028] A thermoplastic elastomer modified polypropylene, comprising, in terms of the amount by weight:

[0029]

[0030] According to the above technical scheme, polypropylene and thermoplastic elastomer are used as main materials, a composite compatibilizer is used to compatibilize the polypropylene / thermoplastic elastomer / inorganic filler system, improve the dispersibility of the filler and the affinity of the system, the non-polar molecular main chain and the strong polar side chain of the compatibilizer are combined with PP and thermoplastic elastomer respectively, and the toughness of PP plastic is improved. Inorganic filler particles are used as rigid nucleating agents to promote the formation of β crystal phase with good impact strength in the PP material and improve the toughness of the material.

[0031] Preferably, the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and maleic acid dibutyl ester grafted polypropylene, and the mass ratio of maleic anhydride grafted polypropylene to maleic acid dibutyl ester grafted polypropylene is 2:1.

[0032] According to the above technical scheme, maleic anhydride grafted polypropylene and maleic acid dibutyl ester grafted polypropylene are grafted with polypropylene, and are connected to the main chain of polypropylene in the form of short branches, forming a stable transition zone between the elastomer and polypropylene in the system. In the prior art, maleic anhydride grafted polypropylene is often used as a single compatibilizer. When the amount of maleic anhydride grafted polypropylene exceeds a certain amount, the grafting rate of the grafted polypropylene to the polypropylene free radical will decrease due to the homopolymerization of maleic anhydride grafted polypropylene, that is, the grafting rate will decrease, which will affect the compatibilization effect of the system and reduce the impact strength of the modified polypropylene material. Therefore, a composite compatibilizer is used to avoid the decrease in grafting rate caused by homopolymerization of a single compatibilizer.

[0033] Preferably, the inorganic filler is nano calcium carbonate powder or white carbon black.

[0034] The thermoplastic elastomer modified polypropylene described above is prepared by the following method:

[0035] A thermoplastic elastomer modified polypropylene preparation method comprises the following method steps:

[0036] Step S1, the components are weighed according to the proportion.

[0037] Step S2, the weighed materials are put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0038] Step S3, the mixture is added to a twin-screw extruder for melt extrusion and granulation; the material stays in the barrel for 3-5 minutes.

[0039] The twin-screw extrusion process conditions are as follows: Zone 1: 220-240℃; Zone 2: 220-240℃; Zone 3: 220-240℃; Zone 4: 220-240℃; Zone 5: 220-240℃; Zone 6: 220-240℃; die temperature: 220-240℃; screw speed: 300-350r / min. DETAILED DESCRIPTION

[0040] In order to more clearly illustrate the present application, the following embodiments are further described in detail. Those skilled in the art should understand that the following description is a detailed description of the content of the application, not a limitation, therefore, the protection scope of the present application should not be limited by this.

[0041] Preparation Example:

[0042] Preparation Example 1

[0043] A thermoplastic elastomer preparation method comprises the following steps:

[0044] 1) The component raw materials are weighed according to the proportion: thermoplastic polyurethane 35 parts; glue micro powder 25 parts; ethylene acrylic acid copolymer 0.1 part; fatty alcohol polyoxyethylene ether 0.1 part; maleic anhydride 1 part; spherical silica micro powder 10 parts; antioxidant 0.2 part; active agent 0.1 part;

[0045] The particle size of the glue micro powder is 10-50μm; the particle size of the spherical silica micro powder is 1-5μm; the antioxidant is antioxidant 1076; and the active agent is diethylene glycol.

[0046] 2) The glue micro powder is added to an appropriate amount of ethanol solution, and then ultrasonic oscillation is performed to fully dissolve the glue micro powder in the ethanol solution to form a glue micro powder solution.

[0047] 3) using a filter membrane with a filter hole smaller than the particle size of the glue micro powder to filter the glue micro powder solution, precipitating the glue micro powder in the glue micro powder solution and drying.

[0048] 4) adding the precipitated glue micro powder to a sealed container provided with a microwave generator, and introducing ozone into the container, so that the glue micro powder is irradiated in a microwave environment for 15 minutes.

[0049] 5) adding the glue micro powder to a high-speed blender, when the glue micro powder is heated to 70°C, adding ethylene acrylic acid copolymer and continuing to stir; when the glue micro powder is heated to 120°C, adding spherical silica micro powder and active agent, stirring uniformly to form a primary mixture, and naturally cooling before use.

[0050] 6) adding thermoplastic polyurethane elastomer, antioxidant, maleic anhydride to a high-speed blender, stirring at 70°C, after uniform stirring, heating to 120°C, adding the primary mixture and fatty alcohol polyoxyethylene ether for stirring to form a blending raw material.

[0051] 7) feeding the blending raw material into a single-screw extruder for extrusion granulation at 180°C to obtain No. 1 thermoplastic elastomer.

[0052] Preparation Example 2

[0053] A method for preparing a thermoplastic elastomer, comprising the following steps:

[0054] 1) weighing the component raw materials according to the proportion: thermoplastic polyurethane 35 parts; glue micro powder 35 parts; ethylene acrylic acid copolymer 0.1 part; fatty alcohol polyoxyethylene ether 0.1 part; maleic anhydride 1 part; spherical silica micro powder 10 parts; antioxidant 0.2 parts; active agent 0.1 part;

[0055] Among them, the particle size of the glue micro powder is 10-50 μm; the particle size of the spherical silica micro powder is 1-5 μm; the antioxidant is antioxidant 1076; the active agent is diethylene glycol.

[0056] 2) adding the glue micro powder to an appropriate amount of ethanol solution, and then performing ultrasonic oscillation to fully dissolve the glue micro powder in the ethanol solution to form a glue micro powder solution.

[0057] 3) using a filter membrane with a filter hole smaller than the particle size of the glue micro powder to filter the glue micro powder solution, precipitating the glue micro powder in the glue micro powder solution and drying.

[0058] 4) adding the precipitated glue micro powder to a sealed container provided with a microwave generator, and introducing ozone into the container, so that the glue micro powder is irradiated in a microwave environment for 15 minutes.

[0059] 5) Add the glue powder into the high-speed mixer, and when the glue powder is heated to 70°C, add the ethylene acrylic acid copolymer and continue to stir; when the glue powder is heated to 120°C, add the spherical silica powder and the active agent, stir uniformly to form a primary mixture, and naturally cool down for later use.

[0060] 6) Add the thermoplastic polyurethane elastomer, the antioxidant, and the maleic anhydride into the high-speed mixer, and stir at 70°C; after uniform stirring, heat to 120°C, add the primary mixture and the fatty alcohol polyoxyethylene ether, and stir to form a blending raw material.

[0061] 7) Send the blending raw material into a single-screw extruder to be extruded and granulated at 180°C to obtain the No. 2 thermoplastic elastomer.

[0062] Preparation Example 3

[0063] A method for preparing a thermoplastic elastomer, comprising the following steps:

[0064] 1) Weigh the component raw materials according to the proportion: 65 parts of thermoplastic polyurethane; 25 parts of glue powder; 0.5 parts of ethylene acrylic acid copolymer; 0.3 parts of fatty alcohol polyoxyethylene ether; 3 parts of maleic anhydride; 10 parts of spherical silica powder; 0.3 parts of antioxidant; and 0.2 parts of active agent.

[0065] Among them, the particle size of the glue powder is 10-50 μm; the particle size of the spherical silica powder is 1-5 μm; the antioxidant is antioxidant 1076; and the active agent is diethylene glycol.

[0066] 2) Add the glue powder into an appropriate amount of ethanol solution, and then perform ultrasonic oscillation to fully dissolve the glue powder in the ethanol solution to form a glue powder solution.

[0067] 3) Filter the glue powder solution using a filter membrane with a pore size smaller than the particle size of the glue powder to precipitate and dry the glue powder in the glue powder solution.

[0068] 4) Add the precipitated glue powder into a sealed container provided with a microwave generator, and introduce ozone into the container to irradiate the glue powder in the microwave environment for 15 minutes.

[0069] 5) Add the glue powder into the high-speed mixer, and when the glue powder is heated to 70°C, add the ethylene acrylic acid copolymer and continue to stir; when the glue powder is heated to 120°C, add the spherical silica powder and the active agent, stir uniformly to form a primary mixture, and naturally cool down for later use.

[0070] 6) Add the thermoplastic polyurethane elastomer, the antioxidant, and the maleic anhydride into the high-speed mixer, and stir at 70°C; after uniform stirring, heat to 120°C, add the primary mixture and the fatty alcohol polyoxyethylene ether, and stir to form a blending raw material.

[0071] 7) The blended raw materials are sent into a single screw extruder to be extruded and granulated at 180℃ to obtain the No. 3 thermoplastic elastomer.

[0072] Preparation Example 4

[0073] A thermoplastic elastomer preparation method comprises the following steps:

[0074] 1) The component raw materials are weighed according to the proportion: thermoplastic polyurethane 65 parts; glue micro powder 35 parts; ethylene acrylic acid copolymer 0.5 parts; fatty alcohol polyoxyethylene ether 0.3 parts; maleic anhydride 3 parts; spherical silica micro powder 10 parts; antioxidant 0.3 parts; active agent 0.2 parts;

[0075] The particle size of the glue micro powder is 10-50 μm; the particle size of the spherical silica micro powder is 1-5 μm; the antioxidant is antioxidant 1076; and the active agent is diethylene glycol.

[0076] 2) The glue micro powder is added to an appropriate amount of ethanol solution, and then ultrasonic oscillation is performed to fully dissolve the glue micro powder in the ethanol solution to form a glue micro powder solution.

[0077] 3) The glue micro powder solution is filtered using a filter membrane with a pore size smaller than the particle size of the glue micro powder, and the glue micro powder in the glue micro powder solution is precipitated and dried.

[0078] 4) The precipitated glue micro powder is added to a sealed container provided with a microwave generator, and ozone is introduced into the container to irradiate the glue micro powder in the microwave environment for 15 minutes.

[0079] 5) The glue micro powder is added to a high-speed mixer, and when the glue micro powder is heated to 70℃, the ethylene acrylic acid copolymer is added and continues to be stirred; when the glue micro powder is heated to 120℃, the spherical silica micro powder and the active agent are added and stirred uniformly to form a primary mixture, which is naturally cooled and used.

[0080] 6) The thermoplastic polyurethane elastomer, antioxidant, and maleic anhydride are added to a high-speed mixer and stirred at 70℃, and after uniform stirring, the temperature is raised to 120℃, the primary mixture and the fatty alcohol polyoxyethylene ether are added and stirred to form a blended raw material.

[0081] 7) The blended raw materials are sent into a single screw extruder to be extruded and granulated at 180℃ to obtain the No. 4 thermoplastic elastomer.

[0082] Preparation Example 5

[0083] A thermoplastic elastomer preparation method comprises the following steps:

[0084] 1) According to the proportion, the component raw materials are weighed: thermoplastic polyurethane 35 parts; glue micro powder 35 parts; ethylene acrylic acid copolymer 0.1 part; fatty alcohol polyoxyethylene ether 0.1 part; maleic anhydride 1 part; spherical silica micro powder 10 parts; antioxidant 0.2 part; active agent 0.1 part;

[0085] Among them, the particle size of the glue micro powder is 10-50 μm; the particle size of the spherical silica micro powder is 1-5 μm; the antioxidant is antioxidant 1076; the active agent is diethylene glycol.

[0086] 2) The glue micro powder is added to an appropriate amount of ethanol solution, and then ultrasonic oscillation is carried out, so that the glue micro powder is fully dissolved in the ethanol solution to form a glue micro powder solution.

[0087] 3) The glue micro powder solution is filtered using a filter membrane with a pore size smaller than the particle size of the glue micro powder, and the glue micro powder in the glue micro powder solution is precipitated and dried.

[0088] 4) The precipitated glue micro powder is added to a sealed container provided with a microwave generator, and ozone is introduced into the container, so that the glue micro powder is irradiated in a microwave environment for 20 minutes.

[0089] 5) The glue micro powder is added to a high-speed blender, and when the glue micro powder is heated to 70℃, the ethylene acrylic acid copolymer is added, and the stirring is continued; when the glue micro powder is heated to 120℃, the spherical silica micro powder and the active agent are added, and the stirring is uniform to form a primary mixture, which is naturally cooled and used.

[0090] 6) The thermoplastic polyurethane elastomer, antioxidant, maleic anhydride is added to a high-speed blender, and stirred at 70℃, and after uniform stirring, the temperature is raised to 120℃, the primary mixture and the fatty alcohol polyoxyethylene ether are added and stirred to form a blended raw material.

[0091] 7) The blended raw material is sent into a single screw extruder to be extruded and granulated at 180℃ to obtain No. 5 thermoplastic elastomer.

[0092] Preparation Example 6

[0093] A thermoplastic elastomer preparation method, comprising the following steps:

[0094] 1) According to the proportion, the component raw materials are weighed: thermoplastic polyurethane 35 parts; glue micro powder 25 parts; ethylene acrylic acid copolymer 0.1 part; fatty alcohol polyoxyethylene ether 0.1 part; maleic anhydride 1 part; spherical silica micro powder 15 parts; antioxidant 0.2 part; active agent 0.1 part;

[0095] Among them, the particle size of the glue micro powder is 10-50 μm; the particle size of the spherical silica micro powder is 1-5 μm; the antioxidant is antioxidant 1076; the active agent is diethylene glycol.

[0096] 2) The glue micro powder is added to an appropriate amount of ethanol solution, and then ultrasonic oscillation is performed to fully dissolve the glue micro powder in the ethanol solution to form a glue micro powder solution.

[0097] 3) The glue micro powder solution is filtered using a filter membrane with a pore size smaller than the particle size of the glue micro powder to precipitate and dry the glue micro powder in the glue micro powder solution.

[0098] 4) The precipitated glue micro powder is added to a sealed container provided with a microwave generator, and ozone is introduced into the container to irradiate the glue micro powder in the microwave environment for 15 minutes.

[0099] 5) The glue micro powder is added to a high-speed blender, and when the glue micro powder is heated to 70°C, ethylene acrylic acid copolymer is added and stirring is continued; when the glue micro powder is heated to 120°C, spherical silica micro powder and active agent are added and stirred uniformly to form a primary mixture, which is naturally cooled and used.

[0100] 6) Thermoplastic polyurethane elastomer, antioxidant, maleic anhydride are added to a high-speed blender and stirred at 70°C. After uniform stirring, the temperature is raised to 120°C, and the primary mixture and fatty alcohol polyoxyethylene ether are added and stirred to form a blending raw material.

[0101] 7) The blending raw material is fed into a single-screw extruder and extruded at 180°C to obtain No. 6 thermoplastic elastomer.

[0102] Preparation Example 7

[0103] A method for preparing a thermoplastic elastomer, comprising the following steps:

[0104] 1) The component raw materials are weighed according to the ratio: thermoplastic polyurethane 35 parts; glue micro powder 25 parts; ethylene acrylic acid copolymer 0.1 part; fatty alcohol polyoxyethylene ether 0.1 part; maleic anhydride 1 part; spherical silica micro powder 10 parts; antioxidant 0.2 parts; active agent 0.1 part;

[0105] Wherein, the particle size of the glue micro powder is 10-50 μm; the particle size of the spherical silica micro powder is 1-5 μm; the antioxidant is antioxidant 1076; the active agent is diethylene glycol.

[0106] 2) The glue micro powder is added to an appropriate amount of ethanol solution, and then ultrasonic oscillation is performed to fully dissolve the glue micro powder in the ethanol solution to form a glue micro powder solution.

[0107] 3) The glue micro powder solution is filtered using a filter membrane with a pore size smaller than the particle size of the glue micro powder to precipitate and dry the glue micro powder in the glue micro powder solution.

[0108] 4) The precipitated glue micro powder is added to a sealed container provided with a microwave generator, and ozone is introduced into the container to irradiate the glue micro powder in the microwave environment for 15 minutes.

[0109] 5) Add the glue micro powder into the high-speed mixer, when the glue micro powder is heated to 90℃, add the ethylene acrylic acid copolymer, continue to stir; when the glue micro powder is heated to 160℃, add the spherical silica micro powder and the active agent, stir uniformly to form a primary mixture, and wait for use after natural cooling.

[0110] 6) Add the thermoplastic polyurethane elastomer, the antioxidant, and the maleic anhydride into the high-speed mixer, stir at 90℃, after uniform stirring, heat to 160℃, add the primary mixture and the fatty alcohol polyoxyethylene ether to stir to form a blending raw material.

[0111] 7) Send the blending raw material into the single screw extruder to be extruded and granulated at 200℃ to obtain the No. 7 thermoplastic elastomer.

[0112] Example

[0113] Example 1

[0114] A method for preparing an elastomer modified polypropylene, comprising the following method steps:

[0115] Step S1, weigh each component material according to the following ratio:

[0116]

[0117] Among them, the inorganic filler is white carbon black; the antioxidant is antioxidant 1010; the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and maleic acid dibutyl ester grafted polypropylene, wherein the mass ratio of maleic anhydride grafted polypropylene to maleic acid dibutyl ester grafted polypropylene is 2:1.

[0118] Step S2, put the weighed materials into the high-speed mixer and stir for 10-20 minutes to form a mixture.

[0119] Step S3, add the mixture into the twin-screw extruder to melt extrude and granulate; the material stays in the barrel for 3-5 minutes.

[0120] The twin-screw extrusion process conditions are: Zone 1: 220-240℃; Zone 2: 220-240℃; Zone 3: 220-240℃; Zone 4: 220-240℃; Zone 5: 220-240℃; Zone 6: 220-240℃; Die temperature: 220-240℃; Screw speed: 300-350r / min.

[0121] Examples 2-7

[0122] Examples 2-7 and Example 1 are the same in material ratio and preparation method, and the only difference is that the No. 1 thermoplastic elastomer in the example is replaced by the No. 2-7 thermoplastic elastomer, respectively.

[0123] Example 8

[0124] A method for preparing an elastomer modified polypropylene, comprising the following method steps:

[0125] Step S1, the components are weighed according to the following ratio:

[0126]

[0127] The inorganic filler is white carbon black; the antioxidant is antioxidant 1010; the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and dibutyl maleate grafted polypropylene, and the mass ratio of the maleic anhydride grafted polypropylene to the dibutyl maleate grafted polypropylene is 2:1.

[0128] Step S2, the weighed materials are put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0129] Step S3, the mixture is added to a twin-screw extruder for melt extrusion and granulation; the material stays in the barrel for 3-5 minutes.

[0130] The process conditions of the twin-screw extruder are as follows: Zone 1: 220-240℃; Zone 2: 220-240℃; Zone 3: 220-240℃; Zone 4: 220-240℃; Zone 5: 220-240℃; Zone 6: 220-240℃; die temperature: 220-240℃; screw speed: 300-350r / min.

[0131] Example 9

[0132] A method for preparing an elastomer modified polypropylene, comprising the following method steps:

[0133] Step S1, the components are weighed according to the following ratio:

[0134]

[0135] The inorganic filler is white carbon black; the antioxidant is antioxidant 1010; the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and dibutyl maleate grafted polypropylene, and the mass ratio of the maleic anhydride grafted polypropylene to the dibutyl maleate grafted polypropylene is 2:1.

[0136] Step S2, the weighed materials are put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0137] Step S3, the mixture is added to a twin-screw extruder for melt extrusion and granulation; the material stays in the barrel for 3-5 minutes.

[0138] The twin-screw extrusion process conditions are as follows: zone 1: 220-240 DEG C; zone 2: 220-240 DEG C; zone 3: 220-240 DEG C; zone 4: 220-240 DEG C; zone 5: 220-240 DEG C; zone 6: 220-240 DEG C; head temperature: 220-240 DEG C; and screw rotation speed: 300-350 r / min.

[0139] Example 10

[0140] The method comprises the following steps:

[0141] In step S1, the components are weighed according to the following proportions:

[0142]

[0143] The inorganic filler is white carbon black, the antioxidant is antioxidant 1010, and the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and maleic acid dibutyl ester grafted polypropylene, wherein the mass ratio of maleic anhydride grafted polypropylene to maleic acid dibutyl ester grafted polypropylene is 2:1.

[0144] In step S2, the weighed materials are put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0145] In step S3, the mixture is added to a twin-screw extruder for melt extrusion and granulation, and the material stays in the barrel for 3-5 minutes.

[0146] The twin-screw extrusion process conditions are as follows: zone 1: 220-240 DEG C; zone 2: 220-240 DEG C; zone 3: 220-240 DEG C; zone 4: 220-240 DEG C; zone 5: 220-240 DEG C; zone 6: 220-240 DEG C; head temperature: 220-240 DEG C; and screw rotation speed: 300-350 r / min.

[0147] Example 11

[0148] The method comprises the following steps:

[0149] In step S1, the components are weighed according to the following proportions:

[0150]

[0151] The inorganic filler is nano calcium carbonate, the antioxidant is antioxidant 1010, and the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and maleic acid dibutyl ester grafted polypropylene, wherein the mass ratio of maleic anhydride grafted polypropylene to maleic acid dibutyl ester grafted polypropylene is 2:1.

[0152] Step S2, the weighed material is put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0153] Step S3, the mixture is added into a twin-screw extruder for melt extrusion granulation; the material stays in the barrel for 3-5 minutes.

[0154] The twin-screw extrusion process conditions are as follows: Zone 1: 220-240°C; Zone 2: 220-240°C; Zone 3: 220-240°C; Zone 4: 220-240°C; Zone 5: 220-240°C; Zone 6: 220-240°C; die temperature: 220-240°C; screw speed: 300-350 r / min.

[0155] Comparative Example

[0156] Comparative Example 1

[0157] A method for preparing an elastomer-modified polypropylene, comprising the following method steps:

[0158] Step S1, the components are weighed according to the following proportions:

[0159]

[0160] The inorganic filler is white carbon black; the antioxidant is antioxidant 1010; the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and maleic acid dibutyl ester grafted polypropylene, wherein the mass ratio of maleic anhydride grafted polypropylene to maleic acid dibutyl ester grafted polypropylene is 2:1.

[0161] Step S2, the weighed material is put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0162] Step S3, the mixture is added into a twin-screw extruder for melt extrusion granulation; the material stays in the barrel for 3-5 minutes.

[0163] The twin-screw extrusion process conditions are as follows: Zone 1: 220-240°C; Zone 2: 220-240°C; Zone 3: 220-240°C; Zone 4: 220-240°C; Zone 5: 220-240°C; Zone 6: 220-240°C; die temperature: 220-240°C; screw speed: 300-350 r / min.

[0164] Comparative Example 2

[0165] A method for preparing an elastomer-modified polypropylene, comprising the following method steps:

[0166] Step S1, the components are weighed according to the following proportions:

[0167]

[0168] The inorganic filler is nano calcium carbonate; the antioxidant is antioxidant 1010; the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and dibutyl maleate grafted polypropylene, wherein the mass ratio of the maleic anhydride grafted polypropylene and the dibutyl maleate grafted polypropylene is 2:1.

[0169] Step S2, the weighed materials are put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0170] Step S3, the mixture is added to a twin-screw extruder for melt extrusion and granulation; the material stays in the barrel for 3-5 minutes.

[0171] The twin-screw extrusion process conditions are as follows: Zone 1: 220-240℃; Zone 2: 220-240℃; Zone 3: 220-240℃; Zone 4: 220-240℃; Zone 5: 220-240℃; Zone 6: 220-240℃; die temperature: 220-240℃; screw speed: 300-350r / min.

[0172] Comparative Example 3

[0173] A method for preparing an elastomer-modified polypropylene, comprising the following method steps:

[0174] Step S1, the components are weighed according to the following proportions:

[0175]

[0176] The inorganic filler is white carbon black; the antioxidant is antioxidant 1010.

[0177] Step S2, the weighed materials are put into a high-speed mixer and stirred for 10-20 minutes to form a mixture.

[0178] Step S3, the mixture is added to a twin-screw extruder for melt extrusion and granulation; the material stays in the barrel for 3-5 minutes.

[0179] The twin-screw extrusion process conditions are as follows: Zone 1: 220-240℃; Zone 2: 220-240℃; Zone 3: 220-240℃; Zone 4: 220-240℃; Zone 5: 220-240℃; Zone 6: 220-240℃; die temperature: 220-240℃; screw speed: 300-350r / min.

[0180] Comparative Example 4

[0181] A method for preparing an elastomer-modified polypropylene, comprising the following method steps:

[0182] Step S1, weigh each component material according to the following ratio;

[0183]

[0184]

[0185] Among them, the inorganic filler is white carbon black; the antioxidant is antioxidant 1010.

[0186] Step S2, put the weighed materials into a high-speed mixer and stir for 10-20 minutes to form a mixture.

[0187] Step S3, add the mixture to a twin-screw extruder for melt extrusion and granulation; the material stays in the barrel for 3-5 minutes.

[0188] The twin-screw extrusion process conditions are as follows: Zone 1: 220-240℃; Zone 2: 220-240℃; Zone 3: 220-240℃; Zone 4: 220-240℃; Zone 5: 220-240℃; Zone 6: 220-240℃; Die temperature: 220-240℃; Screw speed: 300-350r / min.

[0189] Comparative Example 5

[0190] Put 100 parts of polypropylene, 10 parts of POE, 5 parts of divinylbenzene, and 0.1 parts of 2,5-dimethyl-2,5-(bis-tert-butyl peroxide) hexane into a blender and mix uniformly, then pour them into a twin-screw extruder, the working temperature of the twin-screw extruder is 220℃, and the screw speed is 350r / min. Through high temperature and screw shearing, the raw materials react with each other. Through extrusion, cooling and granulation, high-toughness polypropylene pellets are prepared. The pellets are injected into an injection molding machine at 210℃ to obtain samples for testing toughness.

[0191] This method is excerpted from the background art of Chinese invention patent application file with application publication number CN 116693764 A.

[0192] Test method

[0193] The modified polypropylenes prepared in Examples 1-11 and Comparative Examples 1-5 were respectively tested for tensile strength, flexural strength, notched impact strength, Izod impact strength, and elongation at break.

[0194] The tensile strength test, the elongation at break test are tested according to the GB / T1040-2018 standard; the bending strength is tested according to the GB / T9341-2008 standard; the notched impact strength, the cantilever beam impact strength test are tested according to the GB / T 1843-2008 standard;

[0195] The detection results are shown in Table 1.

[0196]

[0197]

[0198] Table 1 Test item detection results of examples 1-11 and comparative examples 1-5

[0199] By comparing the test data of examples 1-11 and comparative example 5, it can be concluded that the prepared thermoplastic elastomer modified polypropylene system of the present application has improved room temperature impact resistance and significantly improved low temperature impact resistance compared with the existing POE elastomer polypropylene toughening modification system.

[0200] By comparing the test data of examples 1 and comparative example 1, and examples 2 and comparative example 2, it can be concluded that the thermoplastic elastomer prepared by the present application has better toughening modification effect than POE elastomer under the same toughening system and the same addition amount, especially the low temperature impact resistance of the material.

[0201] By comparing the test data of examples 1 and comparative examples 3 and 4, it can be concluded that the composite compatibilizer (the composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and maleic acid dibutyl ester grafted polypropylene, and the mass ratio of maleic anhydride grafted polypropylene to maleic acid dibutyl ester grafted polypropylene is 2:1) used in the present application can better disperse and compatibilize the thermoplastic elastomer in the material than single maleic anhydride grafted polypropylene or maleic acid dibutyl ester grafted polypropylene, so that the material obtains better toughening effect.

[0202] Although some specific embodiments of the present application have been described in detail by examples, those skilled in the art should understand that the above examples are only for illustration, not for limiting the scope of the present application. Those skilled in the art should understand that the above embodiments can be modified without departing from the scope and spirit of the present application. The scope of the present application is defined by the appended claims.

Claims

1. A thermoplastic elastomer, characterized in that Calculated by measurement score, including:

2. The thermoplastic elastomer according to claim 1, characterized in that: The particle size of the rubber micropowder is 10-50 μm.

3. The thermoplastic elastomer according to claim 1, characterized in that: The particle size of the spherical silicon powder is 1-5 μm.

4. The thermoplastic elastomer according to claim 1, characterized in that: The active agent is diethylene glycol.

5. A method for preparing a thermoplastic elastomer, characterized in that: The following steps are involved: 1) Weigh the component raw materials according to the ratio; 2) adding the gelatin powder to an appropriate amount of ethanol solution, and then performing ultrasonic oscillation to fully dissolve the gelatin powder in the ethanol solution to form a gelatin powder solution; 3) filtering the glue powder solution using a filter membrane with a pore size smaller than the glue powder particle size, separating the glue powder in the glue powder solution and drying it; 4) adding the precipitated rubber powder into a sealed container equipped with a microwave generator, introducing ozone into the container, and irradiating the rubber powder in a microwave environment for 15-20 minutes; 5) Add the rubber powder to a high-speed mixer. When the temperature of the rubber powder reaches 70-90°C, add the ethylene acrylic acid copolymer and continue stirring. When the temperature of the rubber powder reaches 120-160°C, add the spherical silica powder and the active agent and stir evenly to form a primary mixture. Cool naturally and set aside. 6) adding the thermoplastic polyurethane elastomer, antioxidant, and maleic anhydride to a high-speed mixer, stirring at 70-90° C., and after stirring evenly, heating to 120-160° C., adding the primary mixture and fatty alcohol polyoxyethylene ether, and stirring to form a blended raw material; 7) feeding the blended raw materials into a single screw extruder for extrusion and granulation at 180-200° C. to obtain the thermoplastic elastomer.

6. A thermoplastic elastomer-modified polypropylene, using the thermoplastic elastomer according to any one of claims 1 to 4, characterized in that: Measured in parts, including:

7. The elastomer-modified polypropylene according to claim 6, characterized in that: The composite compatibilizer is a mixture of maleic anhydride grafted polypropylene and dibutyl maleate grafted polypropylene, wherein the mass ratio of maleic anhydride grafted polypropylene to dibutyl maleate grafted polypropylene is 2:

1.

8. The elastomer-modified polypropylene according to claim 7, characterized in that: The inorganic filler is nano calcium carbonate powder or white carbon black.

9. A method for preparing elastomer-modified polypropylene, characterized in that: The method comprises the following steps: Step S1, weighing each component material according to the ratio; Step S2: putting the weighed materials into a high-speed blender and stirring for 10-20 minutes to form a mixture; Step S3, adding the mixture into a twin-screw extruder, and melt-extruding and granulating; the material stays in the barrel for 3-5 minutes; The twin-screw extrusion process conditions are: Zone 1: 220-240°C; Zone 2: 220-240℃; Zone 3: 220-240℃; Zone 4: 220-240℃; Zone 5: 220-240℃; Zone 6: 220-240℃; Die head temperature: 220-240℃; Screw speed: 300-350r / min.

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