Deodorant as well as preparation method and application thereof

Abstract

The invention provides a deodorant and a preparation method thereof. The deodorant comprises polyolefin and an auxiliary agent, the auxiliary agents comprise a first auxiliary agent, a second auxiliary agent and a third auxiliary agent; in the deodorant, polyolefin forms a shell which wraps the first auxiliary agent, the second auxiliary agent and the third auxiliary agent. The problem that in the prior art, an odor removal method capable of considering the removal efficiency and low pollution is lacked for removing VOC in polyolefin can be solved. The invention is applicable to the technical field of polymer materials.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a deodorant and a preparation method and application thereof. Background Art

[0002] Polyolefins are widely used in various fields due to their excellent performance. However, polyolefin materials will produce a large amount of low-molecular volatiles due to problems such as monomer residues in the polymerization process and thermal oxidation degradation during the molding process. These low-molecular volatiles will be adsorbed in the polymer matrix and will continue to emit from the resin matrix over time, producing a bad odor, which seriously affects the use of polyolefin products, especially in confined spaces.

[0003] In the prior art, the processes for deodorizing the polyolefin material include physical adsorption processes and chemical deodorization processes. The physical adsorption process mainly uses porous inorganic substances to adsorb odors, but there is adsorption saturation, and VOC (Volatile Organic Compound) desorption will occur over time, causing secondary pollution. In addition, the adsorbents used in physical adsorption are mainly inorganic substances, such as intercalated montmorillonite, zeolite powder, diatomaceous earth, etc., which are easy to cause pollution to the polyolefin material preparation system, especially the transparent material system.

[0004] Chemical deodorization processes generally use photocatalysts to catalyze the degradation of organic molecules of VOCs in polyolefin materials. However, due to the limited contact between photocatalysts and VOCs, and the fact that the degradation of photocatalysts can only be effective under the condition of light energy input, the deodorization effect is difficult to guarantee.

[0005] At present, the most commonly used chemical deodorization process is the devolatilization process, which uses the low boiling point characteristics of low molecular weight substances such as water and alcohol to generate bubbles in the melt formed during the preparation of polyolefin materials, while carrying VOC molecules to remove them, thereby achieving the purpose of deodorization. However, the devolatilization process can only remove VOC molecules on the surface of the melt, while the VOC molecules wrapped in the melt cannot be removed and will continue to emit during long-term use. In addition, during the extraction process of the devolatilization process, the extract at high temperature often causes the yellow value of the polyolefin material to increase, affecting the use of the material.

[0006] Therefore, the prior art lacks a deodorization method that can take into account both removal efficiency and low pollution to remove VOCs from polyolefins. Summary of the invention

[0007] The main purpose of the present invention is to provide a deodorant and a preparation method and application thereof, so as to solve the problem that the prior art lacks a deodorization method that can take into account both removal efficiency and low pollution to remove VOCs in polyolefins.

[0008] In order to achieve the above-mentioned object, according to the first aspect of the present invention, a deodorant is provided, which comprises polyolefin and an auxiliary agent; the auxiliary agent comprises a first auxiliary agent, a second auxiliary agent and a third auxiliary agent; in the deodorant, the polyolefin forms an outer shell, covering the first auxiliary agent, the second auxiliary agent and the third auxiliary agent.

[0009] Furthermore, the deodorant comprises, by weight, 10 to 30 parts of polyolefin, 30 to 70 parts of the first auxiliary agent, 5 to 10 parts of the second auxiliary agent and 0.01 to 0.5 parts of the third auxiliary agent; preferably, the diameter of the deodorant is 1-3 mm.

[0010] Furthermore, the relative molecular weight of the polyolefin is 80,000 to 120,000; preferably, the polyolefin is a polyolefin powder; the diameter of the polyolefin powder is 1 to 500 nm; preferably, the polyolefin includes polypropylene or polyethylene.

[0011] Further, the viscosity of the first auxiliary agent is 0.1 to 5 cp, the saturated vapor pressure of the first auxiliary agent is 1 KPa to 20 KPa, and the boiling point of the first auxiliary agent is 80 to 150° C.;

[0012] Preferably, the first auxiliary agent includes one or more of water, diisopropyl ether or methyl ethyl ketone.

[0013] Further, the second auxiliary agent has a structural formula as shown in Formula I, or the second auxiliary agent is epoxy propionic acid;

[0014]

[0015] Wherein, Y is a normal alkyl group of C1 to C6, and the terminal C atom of Y away from the epoxy structure is optionally combined with 1 or 2 oxygen-containing functional groups; preferably, the oxygen-containing functional group includes one or more of -OH, -COOH or alkoxy; more preferably, the above-mentioned alkoxy includes ethyl alkoxy and methyl alkoxy; preferably, the second auxiliary agent includes propylene oxide and / or 1,2-octane oxide; preferably, the third auxiliary agent includes a surfactant; preferably, the surfactant contains both a hydrophilic structure and a hydrophobic structure; more preferably, the surfactant includes one or more of disodium lauryl sulfosuccinate, disodium coconut oil monoethanolamide sulfosuccinate or monolauryl phosphate.

[0016] In order to achieve the above object, according to the second aspect of the present invention, a method for preparing a deodorant is provided, the method comprising: S1) mixing a first auxiliary agent, a second auxiliary agent and a third auxiliary agent to obtain a first liquid; S2) spraying the first liquid onto polyolefin to obtain a deodorant.

[0017] Furthermore, in S1), the mixing includes ultrasonic water bath mixing; preferably, the ultrasonic water bath mixing includes mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent under the condition of an ultrasonic water bath; preferably, the mixing time is 0.2-0.5 hours, and the mixing temperature is 0-30°C.

[0018] Furthermore, the preparation method of polyolefin comprises: grinding the polyolefin to be purified and then performing supercritical fluid extraction using a supercritical fluid to obtain the polyolefin; preferably, the grinding time is 2 to 5 hours; preferably, the supercritical fluid extraction time is 5 to 10 hours, the supercritical fluid extraction pressure is 8-12 MPa, and the supercritical fluid extraction temperature is 100-150°C; preferably, the supercritical fluid comprises one or more of carbon dioxide or nitrogen; preferably, spraying comprises spraying using an inkjet printing device, and more preferably, the spraying pressure is 0.1-0.5 MPa; preferably, the polyolefin to be purified comprises polypropylene or polyethylene.

[0019] Furthermore, in the preparation method of the deodorant, the amount of the first auxiliary agent added is 30 to 70 parts by mass, the amount of the second auxiliary agent added is 5 to 10 parts by mass, the amount of the third auxiliary agent added is 0.01 to 0.5 parts by mass, and the amount of the polyolefin added is 10 to 30 parts by mass.

[0020] In order to achieve the above-mentioned purpose, according to the third aspect of the present invention, there is provided a method for preparing a polyolefin product, the preparation method comprising mixing the above-mentioned deodorant, or the deodorant prepared by the above-mentioned deodorant preparation method, with the polyolefin to be deodorized to obtain the polyolefin product; the mass ratio of the deodorant to the polyolefin raw material is 0.5:99.5 to 5:95; preferably, the mixing temperature is 100 to 300°C, and the mixing time is 1 to 10 minutes.

[0021] In order to achieve the above objectives, according to the third aspect of the present invention, there is provided the above deodorant, or a deodorant prepared by the above deodorant preparation method, or the use of the above polyolefin product preparation method in the preparation of polyolefin products.

[0022] By applying the technical solution of the present invention, a polyolefin material with a low odor level and low VOC content can be prepared by using the deodorant in the present application, which is formed of a polyolefin shell and covers the first auxiliary agent, the second auxiliary agent and the third auxiliary agent, and mixing and processing with a polyolefin raw material. The deodorant of the present application is used in the deodorization of polyolefins, and the deodorization efficiency is higher than that of the polyolefin deodorization method in the prior art, and secondary pollution will not be caused, and the pollution to the environment is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0024] Figure 1 A schematic diagram of the microscopic morphology of polyolefin nanopowder according to Example 1 of the present invention is shown.

[0025] Figure 2 A schematic diagram of the morphology of a polypropylene product according to Example 1 of the present invention is shown.

[0026] Figure 3 A schematic diagram of the microscopic morphology of polyolefin nanopowder according to Example 4 of the present invention is shown. DETAILED DESCRIPTION

[0027] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0028] Terminology explanation:

[0029] Pickering emulsion: Pickering emulsion is a stable emulsion composed of solid particles adsorbed to the interface between two phases.

[0030] Melt index: refers to the fluidity value of plastic materials during processing.

[0031] TVOC: Total Volatile Organic Compounds. VOC is volatile organic compound; TVOC refers to organic matter with a saturated vapor pressure exceeding 133.32KPa at room temperature, with a boiling point between 50℃ and 250℃. It can exist in the air in the form of evaporation at room temperature. Its toxicity, irritation, carcinogenicity and special odor will affect the skin and mucous membranes and cause acute damage to the human body.

[0032] As mentioned in the background technology, problems such as monomer residues in the polymerization process and thermal oxidation degradation during the molding process of polyolefin materials will produce a large amount of low-molecular volatiles, which will continue to volatilize over time. In the prior art, it is difficult to achieve both low pollution and high-efficiency deodorization effects in the process of adsorbing these low-molecular volatiles from polyolefin materials. Therefore, in this application, the inventors try to develop a new deodorizer, which can reduce pollution and improve deodorization efficiency when used in the deodorization adsorption process of polyolefin materials, so a series of protection schemes of this application are proposed.

[0033] In a first typical embodiment of the present application, a deodorant is provided, which includes polyolefin and an auxiliary agent; the auxiliary agent includes a first auxiliary agent, a second auxiliary agent and a third auxiliary agent; in the deodorant, the polyolefin forms an outer shell, covering the first auxiliary agent, the second auxiliary agent and the third auxiliary agent.

[0034] In the prior art, in the process of deodorizing and adsorbing VOC for polyolefin products that continuously emit low-molecular volatiles, the physical adsorption process has the defect of adsorption saturation, which is easy to cause secondary pollution, and the raw materials of the physical adsorbent are easy to pollute the polyolefin material preparation system; however, the chemical adsorption process has the disadvantages of poor adsorption effect and incomplete deodorization. Moreover, the deodorizer in the chemical adsorption process is generally a liquid deodorizer. The huge difference in viscosity and surface tension between the deodorizer and the polyolefin material melt causes the liquid directly injected to stay on the surface of the polymer melt and is more difficult to mix evenly with the melt, that is, only the VOC molecules on the surface of the melt can be removed, while the VOC molecules wrapped in the melt cannot be removed, which will cause the continuous emission of VOC during long-term use. Moreover, the liquid deodorizer will have difficulties in adding and metering during the processing of polyolefin materials. There are large differences in the morphology and density of the liquid and the plastic particles, which leads to the inability to evenly feed the liquid and the polyolefin material particles in proportion when mixing and feeding, resulting in poor removal effect.

[0035] The deodorant of the present application is a solid granular deodorant, which uses polyolefin nanopowder as a carrier of the additive to achieve a coating effect on the functional additive, forming solid particles with a structure such as Pickering emulsion. The functional additives in the present application include a first additive, a second additive and a third additive. By mixing and blending them with polyolefin materials, a polyolefin material with significant deodorizing effect and unaffected mechanical properties can be obtained. Among them, the first additive is used to azeotropize with the polyolefin material to remove VOCs on the surface; the second additive is used to fix the VOCs in the polyolefin material; and the third additive is used to adjust the surface tension between the polyolefin material and the deodorant of the present application, so that the deodorant can be evenly mixed with the polyolefin material.

[0036] The present application utilizes the preparation principle of Pickering emulsion to prepare the deodorant of the present application, forming a deodorant with a polyolefin as the shell, coating the first auxiliary agent, the second auxiliary agent and the third auxiliary agent, which can convert the traditional liquid deodorant into a solid particle state, so that the deodorant is easier to measure when used in the deodorization process of polyolefin products, and the mixing ratio can be calculated more accurately, and the deodorant and polypropylene material can be mixed evenly, and the deodorization effect is improved. When the deodorant of the present application is used to deodorize the polyolefin material, the first auxiliary agent and the polyolefin raw material to be deodorized are removed by azeotropy or extraction to remove the VOC on the surface of the polyolefin melt. The second auxiliary agent fixes the VOC in the melt, reacts with the polar VOC molecules, forms a substance with a larger molecular weight, and suppresses the emission of the original VOC emission source. When the deodorant of the present application is applied to the adsorption deodorization process of polyolefin materials, the efficiency of adsorption deodorization is improved, and the raw materials are non-polluting, the adsorption effect is stable, and no secondary pollution will be caused.

[0037] In a preferred embodiment, the deodorant includes 10-30 parts of polyolefin (including but not limited to 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 parts), 30-70 parts of the first auxiliary agent (including but not limited to 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 or 70 parts), a second auxiliary agent 5-10 parts (including but not limited to 5, 6, 7, 8, 9 or 10 parts), and a third auxiliary agent 0.01-0.5 parts, (including but not limited to 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3 or 0.4, 0.5 parts); preferably, the diameter of the deodorant is 1-3mm, including but not limited to 1, 1.3, 2, 2.3, 2.5, 2.6, 3mm.

[0038] The present application uses an inkjet printer to load the first auxiliary agent, the second auxiliary agent and the third auxiliary agent into polyolefin to form a spherical structure solid deodorant within the above-mentioned particle size range. The surface layer of the spherical structure is polyolefin, and the core is the above-mentioned three auxiliary agents. The spherical structure solid deodorant with a particle size of 1-3mm cannot be formed by simple mixing and spraying. Controlling the mass fraction of each component of the deodorant in the present application within the above-mentioned range is conducive to the deodorant being mixed more evenly with the raw materials when the polyolefin material is deodorized, and the effect of removing and inhibiting VOCs in the polyolefin material is better, thereby improving the deodorization efficiency. By adjusting the particle size of the deodorant of the present application to be kept within the above-mentioned range, it is close to the material size in the actual production process, so that the polyolefin to be deodorized can be mixed more evenly with the deodorant of the present application, which is conducive to the deodorant exerting a deodorizing effect.

[0039] In a preferred embodiment, the relative molecular weight of the polyolefin is 80000-120000, including but not limited to 80000, 820000, 85000, 90000, 96000, 10000, 110000 or 120000; preferably, the polyolefin is a polyolefin powder, and the diameter of the polyolefin powder is 1-500nm, more preferably, the diameter of the polyolefin powder is 200-500nm, including Preferably, the polyolefin comprises polypropylene or polyethylene. More preferably, the polyolefin comprises one or more of homopolymer polypropylene powder, copolymer polypropylene powder, high density polyethylene powder, low density polyethylene powder or linear low density polyethylene powder.

[0040] The nano powder of polyolefin used in the deodorant of the present application is used as a carrier for coating auxiliary agents, and finally carries the auxiliary agents together to be integrated into the polymer matrix of polyolefin. Therefore, its microstructure needs to match that of commercially available polyolefin products. Among them, the relative molecular weight is a significant mark representing its microstructure. Although polyolefins with too low molecular weight can play an external lubricating role in the polyolefin matrix, the melt index of the polymer matrix is ​​increased, which will cause the material fluidity to be too high and affect the mechanical properties of the material; at the same time, low molecular weight polyolefins are more easily oxidized and degraded during processing to produce various low molecular weight organics, resulting in bad odors. Polyolefins with too high molecular weight remain in the polymer matrix. Due to the large difference in the melting point between their high molecular weight and the polymer matrix, they cannot be fused under the processing conditions of the polymer matrix, resulting in blockage problems during the molding process. The present application controls the relative molecular weight of polyolefin within the above range, which is beneficial to achieving co-fusion with polyolefin materials during processing, has little effect on their melt index, is not easily oxidized and degraded, and can better coat the three additives, thereby achieving efficient deodorization of polyolefin materials without affecting their mechanical properties, thereby avoiding adverse effects on the original properties of the polyolefin materials.

[0041] In the prior art, in order to obtain stable and independently dispersed Pickering emulsion deodorant particles, it is necessary to select a coating carrier with a small particle size. Polyolefins need to be cryogenically processed when they are crushed. When the particle size reaches the submicron scale, the energy consumption and efficiency of cryogenic processing will increase exponentially. In the present application, by controlling the diameter of the polyolefin powder within the above range, the formation of a stable Pickering emulsion deodorant can be ensured, and the processing energy consumption and cost can be reduced.

[0042] When selecting the carrier of the deodorant, the corresponding carrier material should be selected for different types of polyolefin materials to avoid introducing heterogeneous resins to affect the performance of the base resin. For example, if the polypropylene material needs to be deodorized, the polyolefin is preferably polypropylene.

[0043] In a preferred embodiment, the viscosity of the first auxiliary agent is 0.1-5cp (including but not limited to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4 or 5cp), the saturated vapor pressure of the first auxiliary agent is 1KPa-20KPa (including but not limited to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20KPa), and the boiling point of the first auxiliary agent is 80-150°C (including but not limited to 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C); preferably, the first auxiliary agent includes one or more of water, diisopropyl ether or methyl ethyl ketone.

[0044] The existing technology cannot simultaneously take into account the complete removal of VOC molecules in polyolefin materials and not adversely affecting their performance. When deodorizing polyolefin materials, the first auxiliary agent combines with VOCs through azeotropy or extraction, which can remove VOC molecules from the polyolefin material and eliminate VOCs from the source. By screening the viscosity, saturated vapor pressure and boiling point of the first auxiliary agent within the above range, it can be combined with and removed from the VOCs without adversely affecting the performance of the polyolefin material. The above-mentioned viscosity and saturated vapor pressure limit ranges are all under normal temperature and pressure (25°C, 101.325kPa).

[0045] In a preferred embodiment, the second auxiliary agent has a structural formula as shown in Formula I, or the second auxiliary agent is epoxypropionic acid;

[0046]

[0047] Wherein, Y is a normal alkyl group of C1 to C6, and the terminal C atom of Y away from the epoxy structure is optionally combined with 1 or 2 oxygen-containing functional groups; preferably, the oxygen-containing functional group includes one or more of -OH, -COOH or alkoxy; more preferably, the above-mentioned alkoxy includes ethyl alkoxy and methyl alkoxy; preferably, the second auxiliary agent includes propylene oxide and / or 1,2-octane oxide; preferably, the third auxiliary agent includes a surfactant; preferably, the surfactant contains both a hydrophilic structure and a hydrophobic structure; more preferably, the surfactant includes one or more of disodium lauryl sulfosuccinate, disodium coconut oil monoethanolamide sulfosuccinate or monolauryl phosphate.

[0048] Due to the high viscosity of the polyolefin material melt, when the first auxiliary agent is used to remove VOC, extraction or azeotropy can only be effective on the surface of the melt, while the VOC molecules inside the melt are difficult to remove quickly. Most of the VOCs inside the melt are substances with oxygen-containing functional groups, and their volatility is lower than that of alkane VOCs on the surface. They will continue to emit during subsequent long-term use, polluting the air and damaging the health of consumers. For the VOC molecules inside this kind of melt, in view of their slow emission rate and long duration, the second auxiliary agent of the present application can fix this kind of VOC molecules inside the melt, inhibit their emission, and reduce the spillage of harmful substances in the later stage. The epoxy structure has good reactivity to aldehydes, ketones, alcohols, amines, etc., and can directly react with polar VOC molecules to form substances with larger molecular weight fixed inside the material, thereby inhibiting their emission, and will not have a harmful effect on the polyolefin material, such as the reactions shown in the following reaction formulas A, B and C. Among them, the compound of formula II is the structural formula of the second auxiliary agent of the present application, R 1That is, it represents the part of the second auxiliary agent except the epoxy structure; Formula III, Formula IV and Formula V represent the VOC molecules present in the melt, and R represents an alkyl group, including but not limited to one or more of methyl, ethyl, propyl or isopropyl; Formula VI, Formula VII and VIII represent compounds with higher molecular weight produced after the VOC molecules in the melt react with the second auxiliary agent.

[0049]

[0050] The third auxiliary agent of the present application, namely the surface tension regulator, can adjust the tension difference between the deodorant of the present application and the polyolefin material fused therewith, so that the deodorant can be mixed with the material more evenly, can achieve co-fusion, improve the deodorization efficiency, and avoid secondary pollution.

[0051] In a second typical embodiment of the present application, a method for preparing any of the above-mentioned deodorants is provided, the method comprising: S1) mixing a first auxiliary agent, a second auxiliary agent and a third auxiliary agent to obtain a first liquid; S2) spraying the first liquid onto polyolefin to obtain a deodorant.

[0052] The present application utilizes the spraying technology to spray a mixed liquid (first liquid) of the first auxiliary agent, the second auxiliary agent and the third auxiliary agent onto the nano powder of polyolefin, thereby obtaining a Pickering emulsion deodorant in which the mixed liquid is coated by the nano powder of polyolefin. The deodorant of the present application is in the form of solid particles. Compared with liquid auxiliary agents, the coating structure in the present application can enable each auxiliary agent to play its role synergistically. The first auxiliary agent and the polyolefin material melt are azeotropic to remove the VOC molecules on the surface; the second auxiliary agent combines with the VOC inside the polyolefin material melt to react and generate a compound with a larger molecular weight, which is fixed inside the melt to avoid its subsequent continuous emission; the third auxiliary agent adjusts the tension between the deodorant of the present application and the polyolefin material to make the mixing more uniform and achieve co-melting. Moreover, the deodorant in the present application is a solid particle, which is easier to measure when participating in the deodorization process of polyolefin materials.

[0053] In a preferred embodiment, in S1), mixing includes ultrasonic water bath mixing; preferably, ultrasonic water bath mixing includes mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent under the condition of an ultrasonic water bath; preferably, the mixing time is 0.2-0.5, including but not limited to 0.2, 0.3, 0.4 or 0.5 hours, and the mixing temperature is 0-30°C, including but not limited to 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C or 30°C.

[0054] By controlling the mixing time and temperature, the three additives can be mixed more fully, which is conducive to subsequent uniform spraying onto the nano powder of polyolefin to form the deodorant in the present application.

[0055] In a preferred embodiment, the preparation method of polyolefin comprises: grinding the polyolefin to be purified and then performing supercritical fluid extraction using a supercritical fluid to obtain the polyolefin; preferably, the grinding time is 2 to 5 hours (including but not limited to 2, 3, 4 or 5 hours); preferably, the supercritical fluid extraction time is 5 to 10 hours (including but not limited to 5, 6, 7, 8, 9 or 10 hours), the supercritical fluid extraction pressure is 8-12MPa (including but not limited to 8, 9, 10, 11 or 12MPa), and the supercritical fluid extraction temperature is 100-150°C (including but not limited to 100, 110, 120, 130, 140 or 150°C); preferably, the supercritical fluid comprises one or more of carbon dioxide or nitrogen; preferably, spraying comprises spraying using an inkjet printing device, and more preferably, the spraying pressure is 0.1-0.5MPa (including but not limited to 0.1, 0.2, 0.3, 0.4 or 0.5MPa); preferably, the polyolefin to be purified comprises polypropylene or polyethylene.

[0056] Preferably, the present application utilizes an inkjet printer device to spray the first liquid onto polyolefin to obtain the deodorant of the present application. In the inkjet printer device used for spraying in the present application, there are many tiny nozzles inside the inkjet head, each nozzle is connected to an ink storage tank, and the ink is pushed to the nozzle through a pressure system to form tiny water droplets. The present application loads the above-mentioned first liquid into the ink storage tank, and when the inkjet head is working, each row of nozzles sprays out water droplets of the first liquid in sequence, which drip onto the polyolefin powder to form small spherical solid particles, which are the deodorant of the present application. By controlling the pressure of the inkjet within the above range, solid deodorant particles similar to the Pickering emulsion structure of the present application can be formed, that is, a deodorant with a shell of polyolefin and a core of the above three auxiliary agents. The deodorant with the Pickering emulsion structure cannot be formed by simple mixing and spraying, and it is also difficult to form a stable solid particle structure.

[0057] By controlling the grinding time, the diameter of the final polyolefin nanopowder is controlled within the range of 1 to 500 nm, and the polyolefin powder obtained after grinding is subjected to supercritical fluid extraction. In the reactor of the supercritical fluid extraction of the present application, the supercritical fluid is a combination of carbon dioxide and nitrogen in any proportion. By using supercritical fluid extraction, the VOC in the original polyolefin and the small molecular substances produced during grinding are extracted and removed, and purified so that they do not affect the smell of subsequent polyolefin products. The present application also utilizes the super strong penetration ability of the supercritical fluid to penetrate the supercritical fluid into the matrix of the polyolefin, so that the surface of the nanospheres is roughened. Based on the Lotus effect, when the deodorant is sprayed out by inkjet and falls on the powder, solid particles can be quickly formed. By controlling the extraction time, pressure and temperature, the extraction efficiency can be further improved. By controlling the spraying pressure, it is beneficial for the first liquid to be evenly sprayed onto the above-mentioned polyolefin, and fully combined with it to form the Pickering emulsion deodorant finally obtained in the present application.

[0058] The lotus effect refers to the super-hydrophobicity and self-cleaning properties of the lotus leaf surface. This property causes water droplets falling on the leaf surface to form water droplets due to surface tension. In the present application, it refers to water droplets of the first liquid, which, when dropped on the polyolefin surface, can quickly form "water droplets" with a polyolefin surface and the above-mentioned three additives as the core, i.e., the solid particle deodorant in the present application.

[0059] In a preferred embodiment, in the preparation method of the deodorant, the amount of the first auxiliary agent added is 30 to 70 parts by weight, the amount of the second auxiliary agent added is 5 to 10 parts by weight, the amount of the third auxiliary agent added is 0.01 to 0.5 parts by weight, and the amount of the polyolefin added is 10 to 30 parts by weight.

[0060] In a third typical embodiment of the present application, a method for preparing a polyolefin product is provided, the method comprising mixing any one of the above-mentioned deodorants, or a deodorant prepared by any of the above-mentioned deodorant preparation methods, with a polyolefin to be deodorized to obtain a polyolefin product; the mass ratio of the deodorant to the polyolefin raw material is 0.5:100 to 5:100.

[0061] In a fourth typical embodiment of the present application, there is provided a use of any of the above deodorants, or a deodorant prepared by the preparation method of any of the above deodorants, in the preparation of polyolefin materials.

[0062] The beneficial effects of the present application will be further explained in detail below in conjunction with specific embodiments.

[0063] The polyolefins used in the following examples are polypropylene 1100N produced from Shenhua Ningmei, polyethylene 2426H produced from Shenhua Ningmei, and polypropylene T30S produced from Zhenhai Refining and Chemical.

[0064] The first auxiliary agent includes water, diisopropyl ether (108-20-3) and methyl ethyl ketone (78-93-3), which are purchased from McLean Chemical Reagent Co., Ltd.;

[0065] The second auxiliary agents include propylene oxide (556-52-5), 1,2-epoxyoctane (2984-50-1), and epoxypropionic acid (503-11-7) purchased from Gaide Chemical Network.

[0066] The third auxiliary agents include disodium lauryl sulfosuccinate (19040-44-9), disodium coconut oil monoethanolamide sulfosuccinate (61791-66-0), and monolauryl phosphate (12751-23-4), which are purchased from Gaide Chemical Network.

[0067] Unless otherwise specified, the reagents in the examples of this application are conventional commercially available products.

[0068] Example 1

[0069] The formula components of the deodorant of this embodiment are shown in Table 1.

[0070] Table 1

[0071] name Polypropylene 1100N water Glycidol Disodium lauryl sulfosuccinate Mass(g) 10 70 10 0.05

[0072] The preparation method of the deodorant of this embodiment comprises the following steps:

[0073] S1. Grind polypropylene 1100N in liquid nitrogen for 3 hours to obtain polypropylene nanopowder with a size of 380nm and a molecular weight of 110000;

[0074] S2. The polypropylene nanopowder is placed in a supercritical carbon dioxide fluid extraction kettle for extraction for 8 hours at a pressure of 8 MPa and a temperature of 140°C. The microscopic morphology of the obtained polyolefin nanopowder is shown in FIG. Figure 1 As shown;

[0075] S3, mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent in the proportion shown in Table 1 in an ultrasonic water bath for 0.2 hours at a temperature of 25° C. to obtain a first liquid;

[0076] S4. Spray the first liquid onto the polypropylene nanopowder substrate using an inkjet printer (Hangzhou Thales, CAJ) at a pressure of 0.4 MPa to obtain a deodorant with a size of 2.3 mm.

[0077] 15g of deodorant and 985g of polypropylene composite material PP-T20 (Xinli New Materials, Article No.: 2203) were extruded through a twin-screw extruder (ZSK MEGAlab) to obtain a polypropylene product. The extrusion time was 5min and the extrusion temperature was 200°C. The morphology of the polypropylene product was as follows: Figure 2 shown.

[0078] Example 2

[0079] The formula components of the deodorant of this embodiment are shown in Table 2:

[0080] Table 2

[0081]

[0082]

[0083] The preparation method of the deodorant of this embodiment comprises the following steps:

[0084] S1, grinding polypropylene T30S in liquid nitrogen for 5 hours to obtain polypropylene nanopowder with a size of 200 nm and a molecular weight of 96000;

[0085] S2, putting the nano-powder of polypropylene into a supercritical nitrogen fluid extraction kettle for extraction for 5 hours at a pressure of 8 MPa and a temperature of 100°C;

[0086] S3, mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent in an ultrasonic water bath in the proportions shown in Table 2 for 0.5 hours at a temperature of 20° C. to obtain a first liquid;

[0087] S4. Spray the first liquid onto the polypropylene nanopowder substrate using an inkjet printer. The inkjet printing pressure is 0.5 MPa to obtain a deodorant with a size of 2.6 mm.

[0088] 15 g of deodorant and 985 g of polypropylene composite material PP-T20 were extruded through a twin-screw extruder to obtain a polypropylene product. The extrusion time was 10 min and the extrusion temperature was 200°C.

[0089] Example 3

[0090] The formula components of the deodorant of this embodiment are shown in Table 3:

[0091] Table 3

[0092] name Polypropylene 1100N Methyl Ethyl Ketone Glycidyl propionic acid Monolauryl phosphate Mass(g) 15 50 9 0.1

[0093] The preparation method of the deodorant of this embodiment comprises the following steps:

[0094] S1. Grind polypropylene 1100N in liquid nitrogen for 2 hours to obtain polypropylene nanopowder with a size of 470nm and a molecular weight of 110000;

[0095] S2, putting the nano-powder of polypropylene into an extraction kettle in a fluid of supercritical nitrogen and carbon dioxide (mass ratio 1:1) for extraction for 5 hours at a pressure of 8 MPa and a temperature of 150°C;

[0096] S3, mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent in an ultrasonic water bath in the proportions shown in Table 3 for 0.5 hours at a temperature of 30° C. to obtain a first liquid;

[0097] S4. Spray the deodorant onto the polypropylene nanopowder substrate using an inkjet printer. The inkjet printing pressure is 0.1 MPa to obtain a deodorant with a size of 1.3 mm.

[0098] 15g of deodorant and 985g of polypropylene composite material PP-T20 were extruded through a twin-screw extruder to obtain a polypropylene product. The extrusion time was 3 minutes and the extrusion temperature was 240°C.

[0099] Example 4

[0100] The formula components of the deodorant of this embodiment are shown in Table 4 by weight:

[0101] Table 4

[0102] name Polyethylene 2426H water Methyl Ethyl Ketone Glycidol Disodium lauryl sulfosuccinate Mass(g) 10 40 30 8 0.3

[0103] The preparation method of the deodorant of this embodiment comprises the following steps:

[0104] S1. Grind polyethylene 2426H in liquid nitrogen for 5 hours to obtain polyethylene nanopowder with a size of 493 nm and a molecular weight of 82,000;

[0105] S2. The polyethylene nanopowder is placed in a supercritical carbon dioxide fluid extraction kettle for extraction for 10 hours at a pressure of 8 MPa and a temperature of 140° C. The microscopic morphology of the polyolefin nanopowder is shown in FIG. Figure 3 As shown;

[0106] S3, mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent in an ultrasonic water bath in the proportions shown in Table 4 for 0.4 hours at a temperature of 2° C. to obtain a first liquid;

[0107] S4. Spray the deodorant onto the polyethylene nanopowder substrate using an inkjet printer. The inkjet printing pressure is 0.4 MPa to obtain a deodorant with a size of 2.5 mm.

[0108] 15 g of deodorant and 985 g of polyethylene material (Blonde material, PE-RH200) were extruded through a twin-screw extruder to obtain a polyethylene product. The extrusion time was 5 min and the extrusion temperature was 200°C.

[0109] Example 5

[0110] The difference from Example 1 is that the formula components of the deodorant of this example are shown in Table 5 in terms of mass fractions.

[0111] Table 5

[0112] name Polypropylene 1100N water Glycidol Disodium lauryl sulfosuccinate Mass(g) 10 60 10 0.05

[0113] Example 6

[0114] The difference from Example 1 is that the formula components of the deodorant in this example are shown in Table 6 in terms of mass fractions.

[0115] Table 6

[0116] name Polypropylene 1100N water Glycidol Disodium lauryl sulfosuccinate Mass(g) 10 70 7 0.05

[0117] Example 7

[0118] The difference from Example 1 is that the formula components of the deodorant in this example are shown in Table 7 in terms of mass fractions.

[0119] Table 7

[0120] name Polypropylene 1100N water Glycidol Disodium lauryl sulfosuccinate Mass(g) 10 70. 10 0.5

[0121] Example 8

[0122] The difference from Example 1 is that the formula components of the deodorant in this example are shown in Table 8 in terms of mass fractions.

[0123] Table 8

[0124] name Polypropylene 1100N water Glycidol Disodium lauryl sulfosuccinate Mass(g) 30 70 10 0.05

[0125] Example 9

[0126] The difference from Example 1 is that the molecular weight of the nano-powder of polypropylene is 70,000 and the size is 670 nm.

[0127] Example 10

[0128] The difference from Example 1 is that the molecular weight of the nano-powder of polypropylene is 200,000 and the size is 5430 nm.

[0129] Embodiment 11

[0130] The difference from Example 1 is that in this example, the first liquid is loaded onto the nano-powder of polypropylene by spraying.

[0131] Comparative Example 1

[0132] The formula components of the deodorant of this comparative example and the weight parts are shown in Table 9.

[0133] Table 9

[0134] name water Glycidol Disodium lauryl sulfosuccinate Mass(g) 70 10 0.05

[0135] The preparation method of the deodorant of this comparative example comprises the following steps:

[0136] S1. Mix water, glycidol and disodium lauryl sulfosuccinate in an ultrasonic water bath in the proportions shown in Table 9 for 0.2 hours at a temperature of 25° C. to obtain a first liquid. The first liquid in this comparative example is the deodorant used in this comparative example.

[0137] 15g of deodorant and 985g of polypropylene composite material PP-T20 were extruded through a twin-screw extruder to obtain a polypropylene product. The extrusion time was 5 minutes and the extrusion temperature was 200°C.

[0138] Comparative Example 2

[0139] The formula components of the deodorant of this comparative example are shown in Table 10 by weight.

[0140] Table 10

[0141] name Polypropylene T30S Diisopropyl ether Disodium Cocoyl Monoethanolamide Sulfosuccinate Mass(g) 15 45 0.01

[0142] The preparation method of the deodorant of this comparative example comprises the following steps:

[0143] S1, grinding polypropylene in liquid nitrogen for 5 hours to obtain a nano powder of polypropylene with a size of 200 nm and a molecular weight of 96000;

[0144] S2, putting the nano-powder of polypropylene into a supercritical nitrogen fluid extraction kettle for extraction for 5 hours at a pressure of 8 MPa and a temperature of 100°C;

[0145] S3, diisopropyl ether and disodium cocoyl monoethanolamide sulfosuccinate were mixed uniformly in an ultrasonic water bath according to the ratio shown in Table 10, for 0.5 hours at a temperature of 20° C. to obtain a first liquid;

[0146] S4. Spray the deodorant onto the polypropylene nanopowder substrate using an inkjet printer at a pressure of 0.5 MPa to obtain the deodorant.

[0147] 15g of deodorant and 985g of polypropylene composite material PP-T20 were extruded through a twin-screw extruder to obtain a polypropylene product. The extrusion time was 5 minutes and the extrusion temperature was 200°C.

[0148] Comparative Example 3

[0149] The formula components of the deodorant of this comparative example and the weight parts are shown in Table 11.

[0150] Table 11

[0151]

[0152] The preparation method of the deodorant of this comparative example comprises the following steps:

[0153] S1, grinding polypropylene in liquid nitrogen for 5 hours to obtain a nano powder of polypropylene with a size of 200 nm and a molecular weight of 96000;

[0154] S2, putting the nano-powder of polypropylene into a supercritical nitrogen fluid extraction kettle for extraction for 5 hours at a pressure of 8 MPa and a temperature of 100°C;

[0155] S3, polypropylene, 1,2-octane oxide, and disodium cocoyl monoethanolamide sulfosuccinate are uniformly mixed in an ultrasonic water bath according to the ratio shown in Table 11 for 0.5 hours at a temperature of 20° C. to obtain a first liquid;

[0156] S4. Spray the deodorant onto the polypropylene nanopowder substrate using an inkjet printer at a pressure of 0.5 MPa to obtain the deodorant.

[0157] 15 g of deodorant and 985 g of polyethylene material were extruded through a twin-screw extruder to obtain a polyethylene product. The extrusion time was 5 min and the extrusion temperature was 200°C.

[0158] Comparative Example 4

[0159] The polyethylene milk flake bottle material (Green Cycle, PE L330) was crushed to obtain polyethylene recycled material, and the polyethylene recycled material was extruded by a twin-screw extruder for 5 minutes at a temperature of 200°C to obtain a polyethylene product.

[0160] Comparative Example 5

[0161] The formula components of the deodorant of this comparative example, the weight parts are shown in Table 12:

[0162] Table 12

[0163] name Polyethylene 2426H water Methyl Ethyl Ketone Glycidol Mass(g) 10 40 30 7

[0164] The preparation method of the deodorant of this comparative example comprises the following steps:

[0165] S1, grinding polyethylene in liquid nitrogen for 5 hours to obtain polyethylene nanopowder with a size of 493 nm and a molecular weight of 82000;

[0166] S2, placing the polyethylene nanopowder into a supercritical carbon dioxide fluid extraction kettle for extraction for 10 hours at a pressure of 8 MPa and a temperature of 140° C.;

[0167] S3, polyethylene 2426H, water, methyl ethyl ketone and glycidol were mixed uniformly in an ultrasonic water bath according to the proportions shown in Table 12 for 0.4 hours at a temperature of 20° C. to obtain a first liquid;

[0168] S4. Spray the deodorant onto the polyethylene nanopowder using an inkjet printer at a pressure of 0.4 MPa to obtain the deodorant.

[0169] 15 g of deodorant and 985 g of polyethylene were extruded through a twin-screw extruder to obtain a polyethylene product. The extrusion time was 5 min and the extrusion temperature was 200°C.

[0170] The odor level (PV3900), TVOC (μg / g) (GB / T18883), melt index (g / 10min) (GB / T 3682.1), tensile strength (MPa) (GB / T 1040), flexural strength (MPa) (GB / T 9341), flexural modulus (MPa) (GB / T 9341) and notched impact strength (kJ / m) of the polyolefin materials obtained in the above examples and comparative examples are as follows: 2 )(GB / T 1843) was tested, and the results are shown in Tables 13 and 14.

[0171] Table 13

[0172]

[0173] Table 14

[0174]

[0175] The pre-test treatment conditions in Tables 13 and 14 are as follows: A means standing at 30°C for 12 hours before testing; B means standing at 30°C for 72 hours; C means standing at 30°C for 240 hours; D means standing at 30°C for one month; E means standing at 30°C for two months; F means standing at 30°C for six months.

[0176] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: the deodorant in the present application is in the form of solid particles, and the carrier of the coating structure is formed by the nano-powder of polyolefin, which coats the first auxiliary agent, the second auxiliary agent and the third auxiliary agent. The deodorant of the present application is blended with the polyolefin material to achieve co-melting, and it can effectively remove VOCs on the surface and outside of the material, and will not be continuously emitted to cause secondary pollution, and has no negative impact on its melt index and mechanical properties. Compared with liquid deodorizing auxiliary agents, it is easier to measure during the deodorizing process of polyolefin materials. Therefore, the deodorant of the present application can not only improve the deodorizing efficiency, but also reduce pollution, is easy to measure, and has no harmful effect on the properties of the raw materials. Compared with the deodorizing process of polyolefin materials in the prior art, it is more conducive to promotion.

[0177] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A deodorant, characterized in that: The deodorant comprises polyolefin and an auxiliary agent; The auxiliary agent includes a first auxiliary agent, a second auxiliary agent and a third auxiliary agent; In the deodorant, the polyolefin forms a shell that covers the first auxiliary agent, the second auxiliary agent and the third auxiliary agent.

2. The deodorant according to claim 1, characterized in that The deodorant comprises, by weight, 10 to 30 parts of the polyolefin, 30 to 70 parts of the first auxiliary agent, 5 to 10 parts of the second auxiliary agent, and 0.01 to 0.5 parts of the third auxiliary agent; Preferably, the deodorant has a diameter of 1-3 mm.

3. The deodorant according to claim 1, characterized in that The relative molecular weight of the polyolefin is 80,000 to 120,000; Preferably, the polyolefin is polyolefin powder; Preferably, the diameter of the polyolefin powder is 1 to 500 nm; Preferably, the polyolefin comprises polypropylene or polyethylene.

4. The deodorant according to claim 1, characterized in that The viscosity of the first auxiliary agent is 0.1-5 cp, the saturated vapor pressure of the first auxiliary agent is 1 KPa-20 KPa, and the boiling point of the first auxiliary agent is 80-150° C.; Preferably, the first auxiliary agent includes one or more of water, diisopropyl ether or methyl ethyl ketone.

5. The deodorant according to claim 1, characterized in that The second auxiliary agent has a structure shown in Formula I, or the second auxiliary agent is epoxy propionic acid; Wherein, Y is a C1-C6 normal alkyl group, and the terminal C atom of Y away from the epoxy structure may be optionally combined with one or two oxygen-containing functional groups; Preferably, the oxygen-containing functional group includes one or more of -OH, -COOH or alkoxy; Preferably, the second auxiliary agent includes propylene oxide and / or 1,2-octyl oxide; Preferably, the third auxiliary agent includes a surfactant; preferably, the surfactant contains both a hydrophilic structure and a hydrophobic structure; more preferably, the surfactant includes one or more of disodium lauryl sulfosuccinate, disodium coconut oil monoethanolamide sulfosuccinate or monolauryl phosphate.

6. A method for preparing the deodorant according to any one of claims 1 to 5, characterized in that: The preparation method comprises: S1) mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent to obtain a first liquid; S2) spraying the first liquid onto the polyolefin to obtain the deodorant.

7. The preparation method according to claim 6, characterized in that: In said S1), said mixing comprises ultrasonic water bath mixing; Preferably, the ultrasonic water bath mixing comprises mixing the first auxiliary agent, the second auxiliary agent and the third auxiliary agent under the condition of an ultrasonic water bath; Preferably, the mixing time is 0.2-0.5 hours, and the mixing temperature is 0-30°C.

8. The preparation method according to claim 6, characterized in that: The preparation method of the polyolefin comprises: Grinding the polyolefin to be purified and performing supercritical fluid extraction using a supercritical fluid to obtain the polyolefin; Preferably, the grinding time is 2 to 5 hours; Preferably, the supercritical fluid extraction time is 5 to 10 hours, the supercritical fluid extraction pressure is 8-12 MPa, and the supercritical fluid extraction temperature is 100-150° C.; Preferably, the supercritical fluid includes one or more of carbon dioxide or nitrogen; preferably, the spraying includes spraying using an inkjet printing device, and more preferably, the spraying pressure is 0.1-0.5 MPa; Preferably, the polyolefin to be purified comprises polypropylene or polyethylene.

9. The preparation method according to claim 6, characterized in that: In the preparation method of the deodorant, the first auxiliary agent is added in an amount of 30 to 70 parts by mass, the second auxiliary agent is added in an amount of 5 to 10 parts by mass, the third auxiliary agent is added in an amount of 0.01 to 0.5 parts by mass, and the polyolefin is added in an amount of 10 to 30 parts by mass.

10. A method for preparing a polyolefin product, characterized in that: The preparation method comprises: mixing the deodorant according to any one of claims 1 to 5, or the deodorant prepared by the preparation method of the deodorant according to any one of claims 6 to 9, with a polyolefin to be deodorized to obtain the polyolefin product; The mass ratio of the deodorant to the polyolefin raw material is 0.5:99.5 to 5:95; Preferably, the mixing temperature is 200-240° C., and the mixing time is 1-10 min.

11. Use of the deodorant according to any one of claims 1 to 5, or the deodorant prepared by the method for preparing a deodorant according to any one of claims 6 to 9, or the method for preparing a polyolefin product according to claim 10 in preparing a polyolefin product.

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