CN110744743A - Polypropylene material and preparation method thereof - Google Patents
Polypropylene material and preparation method thereof Download PDFInfo
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- CN110744743A CN110744743A CN201911006500.5A CN201911006500A CN110744743A CN 110744743 A CN110744743 A CN 110744743A CN 201911006500 A CN201911006500 A CN 201911006500A CN 110744743 A CN110744743 A CN 110744743A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a polypropylene material and a preparation method thereof. The raw materials of the polypropylene material provided by the invention comprise a main material and an odor detergent, wherein the odor detergent is a mixed solution of water and ethanol, the weight of the ethanol is 3 wt% -10 wt% of the odor detergent, and the weight of the odor detergent is 3 wt% -10 wt% of the main material; the main materials comprise: 50-90 parts of polypropylene; 0-30 parts of mineral filler; 5-25 parts of a toughening agent; 0.1-2 parts of antioxidant; 0-0.5 part of light stabilizer. Effectively reduces the unpleasant odor and volatile organic compounds emitted from the polypropylene material.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polypropylene material and a preparation method thereof.
Background
The polypropylene material has the excellent characteristics of small density, excellent mechanical property, good chemical stability, high thermal stability, good weather resistance, high cost performance and the like, and is widely applied to various fields of automobiles, illumination, electronic and electric appliances, instruments and meters, machinery, aerospace and the like. Among them, various automobile interior parts made of polypropylene materials are found to release some Volatile Organic Compounds (VOCs) containing bad smells or harmful to human health to various degrees during application, which limits the deep application of polypropylene materials.
In the prior art, the method of adjusting the source of raw materials, adding an adsorbent, devolatilizing and the like is generally adopted to reduce the unpleasant odor and volatile organic compounds emitted by the modified polypropylene material. For example, CN101691435B prepares a low-VOC high-performance PP composite material for automotive upholstery by using hydrogen-blended polypropylene, which reduces the VOC content in the material by reducing the VOC in the raw material, but it cannot solve the VOC substances newly generated during the processing. CN101817953B adopts a method of adding an odor adsorbent to prepare a modified polypropylene composite material with low emission, wherein the odor adsorbent comprises: clay, bentonite, porous silica, activated alumina or molecular sieves, however, both physical and chemical adsorption suffer from selectivity and balance of adsorption and are not effective in removing VOCs from materials.
In conclusion, the existing methods are still not ideal for reducing the unpleasant odor and volatile organic compounds emitted from polypropylene materials, and further improvement is still needed.
Disclosure of Invention
The invention mainly aims to provide a polypropylene material and a preparation method thereof, aiming at reducing the unpleasant odor and volatile organic compounds emitted in the polypropylene material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a polypropylene material, wherein the preparation raw materials of the polypropylene material comprise a main material and an odor detergent, the odor detergent is a mixed solution of water and ethanol, the weight of the ethanol is 3 wt% -10 wt% of the odor detergent, and the weight of the odor detergent is 3 wt% -10 wt% of the main material;
the main material comprises the following components in parts by weight based on 100 parts by weight:
in another aspect, the present invention provides a method for preparing a polypropylene material, comprising the following steps:
providing polypropylene, mineral filler, toughening agent, antioxidant, light stabilizer and odor detergent according to the polypropylene material;
first mixing the polypropylene, the mineral filler, the toughening agent, the antioxidant and the light stabilizer to obtain a first mixture;
and carrying out melt extrusion on the odor detergent and the first mixture by adopting a hot melt extrusion process to obtain the polypropylene material.
In the polypropylene material provided by the invention, the mixed liquid of water and ethanol with a specific weight ratio is used as an odor detergent, so that volatile organic compounds in the polypropylene material with the specific weight ratio and the component composition can be furthest removed, and the polypropylene material with ideal effects of low odor emission and low harmful volatile organic compound residue is obtained.
According to the invention, mixed liquor of ethanol and water is used as the odor detergent, on one hand, the ethanol and the water have different polarities, and the ethanol and the water with specific weight percentage are mixed, so that the odor detergent is compatible with the main material with specific weight proportion and component composition, and most of volatile organic compounds can be volatilized from a material system by using the water and the ethanol as carriers in the process, so that the volatile organic compounds in the polypropylene material are removed more completely, and the unpleasant odor emitted from the polypropylene material is effectively reduced; on the other hand, the ethanol and the water have different boiling points, and have a certain sequence of volatilization in the process, so that the volatile organic compounds in the material system can be washed and removed in multiple stages, meanwhile, the requirement of the preparation process of the polypropylene material is met, and the problem that the odor detergent is prematurely volatilized in the process due to the low boiling point is avoided, so that the volatile organic compounds in the polypropylene material with the specific weight ratio and the components are furthest removed; on the other hand, the polypropylene material has higher volatility, no solvent residue, no introduction of new impurities, and no influence on the mechanical property and the weather resistance of the polypropylene material; on the other hand, water and ethanol are green solvents, and the health and safety of human bodies are not threatened.
In the preparation method of the polypropylene material, the hot-melt extrusion process is adopted to melt and extrude the odor detergent and other components, and the preparation method is simple, simple and convenient to operate, low in process difficulty and cost and easy for large-scale preparation of the polypropylene material with ideal low emission effect.
Tests prove that the polypropylene material prepared by the preparation method not only has excellent mechanical property and weather resistance, but also has good volatile organic compound expelling effect, wherein the total volatile organic compound residual in the material is less than or equal to 20 microgram/g, and the odor grade is less than or equal to 3.5 grade.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The parts by weight of each component mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the mass between each component, and therefore, it is within the scope of the disclosure of the description of the embodiments of the present invention to scale up or down the content of each component of the composition according to the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a unit of weight known in the medical field, such as μ g, mg, g, kg.
In the description of the present invention, it is to be understood that the terms "first", "second" and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
The polypropylene material is prepared from main materials and an odor detergent, wherein the odor detergent is a mixed solution of water and ethanol, the weight of the ethanol is 3 wt% -10 wt% of the odor detergent, and the weight of the odor detergent is 3 wt% -10 wt% of the main materials;
the main material comprises the following components in parts by weight based on 100 parts by weight:
specifically, the raw materials for preparing the polypropylene material comprise main materials and an odor detergent, wherein the main materials are main raw materials of the polypropylene material and directly influence the mechanical property and the weather resistance of the polypropylene material workpiece.
The polypropylene (PP) is a matrix of the main material, and the polypropylene accounts for 50-90 parts by weight based on 100 parts by weight of the main material. In some embodiments, the polypropylene is 50.3, 52.5, 55.4, 57.1, 60.2, 63.8, 66.1, 68.4, 70.3, 72.6, 75.7, 76.5, 79.3, 83.2, 85.1, 88.7, 90 parts by weight based on 100 parts by weight of the main material.
In one embodiment, the polypropylene is a co-polypropylene and/or a homo-polypropylene, and the polypropylene has a melt index of 2 to 150g/10min at 230 ℃ under 2.16 kg. In some embodiments, the polypropylene is a co-polypropylene. In some embodiments, the polypropylene is a homopolypropylene. In some embodiments, the polypropylene has a melt index of 2, 5, 10, 16, 20, 23, 29, 30, 35, 39, 42, 47, 49, 50, 55, 60, 64, 71, 77, 80, 85, 90, 96, 100, 107, 111, 116, 122, 128, 131, 137, 142, 148, 150g/10min at 230 ℃ under 2.16 kg.
The mineral filler is used for enhancing the mechanical property of the polypropylene, so that the polypropylene material has good mechanical property. And 0-30 parts of mineral filler by taking 100 parts of the main material by weight. In some embodiments, the mineral filler is 1, 5, 7, 10, 12, 15, 16, 18, 19, 20, 21, 23, 25, 27, 30 parts by weight based on 100 parts by weight of the main material.
The mineral filler may be referred to minerals conventional in the art, such as talc, calcium carbonate, mica, and the like. As an embodiment, the mineral filler is selected from talc having a particle size of 1000-10000 mesh.
The toughening agent is used for improving the brittleness of the polypropylene material so as to improve the mechanical properties of the polypropylene material in the aspects of tensile strength, flexural modulus, notch impact strength and the like. And 5-25 parts of the toughening agent by taking 100 parts of the main material by weight. In some embodiments, the toughening agent is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 parts by weight based on 100 parts by weight of the main material.
The toughening agent may be referenced to toughening materials conventional in the art, such as in some embodiments the toughening agent is selected from at least one of ethylene-propylene block copolymers, ethylene-propylene-diene copolymers, ethylene-hexene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers.
The antioxidant is used for protecting the polypropylene material from being thermally degraded in the material forming process, the service life of the polypropylene material is prolonged, and the weather resistance of the polypropylene material can be further improved by compounding the light stabilizer. And 0.1-2 parts of antioxidant by taking 100 parts of the main material by weight. In some embodiments, the antioxidant is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 parts based on 100 parts by weight of the main material.
The antioxidant can refer to antioxidant materials conventional in the art, such as hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants, and the like. As an embodiment, the antioxidant is selected from a mixture of hindered phenolic antioxidants and phosphite antioxidants. In some embodiments, the hindered phenol antioxidant and the phosphite antioxidant are mixed in a ratio of (0.1-0.5) to (0.1-0.5).
And the light stabilizer is used for improving the light aging speed of the polypropylene material, and can be compounded with the antioxidant to synergistically enhance the weather resistance of the polypropylene material. And 0-0.5 part of light stabilizer by taking 100 parts of main material by weight. In some embodiments, the light stabilizer is 0.1, 0.2, 0.3, 0.4, 0.5 parts based on 100 parts by weight of the main material.
The light stabilizers may be referred to as light stabilizers conventional in the art, such as in some embodiments, selected from hindered amine light stabilizers.
Specifically, the odor detergent is a mixed solution of water and ethanol, is used as a carrier of volatile organic compounds in a material system, and when the odor detergent is applied to the preparation process of the polypropylene material with a specific weight ratio and component composition, the odor detergent can effectively wash and remove the volatile organic compounds brought by raw materials in the material system or formed in the production process, so that the polypropylene composite material with low emission and excellent weather resistance is obtained, and the polypropylene material is ensured to have no emission of harmful small-molecule volatile organic compounds during processing, and is green and safe.
Different from the existing odor detergent, the embodiment of the invention takes the mixed liquid of ethanol and water as the odor detergent, on one hand, the ethanol and the water have different polarities, and the ethanol and the water with specific weight percentage content are mixed, so that the odor detergent is compatible with the main material with specific weight proportion and component composition, and most of volatile organic compounds can be volatilized from a material system by taking the water and the ethanol as carriers in the process, so that the volatile organic compounds in the polypropylene material are removed more completely, and the unpleasant odor emitted from the polypropylene material is effectively reduced; on the other hand, the ethanol and the water have different boiling points, and have a certain sequence of volatilization in the process, so that the volatile organic compounds in the material system can be washed and removed in multiple stages, meanwhile, the requirement of the preparation process of the polypropylene material is met, and the problem that the odor detergent is prematurely volatilized in the process due to the low boiling point is avoided, so that the volatile organic compounds in the polypropylene material with the specific weight ratio and the components are furthest removed; on the other hand, the polypropylene material has higher volatility, no solvent residue, no introduction of new impurities, and no influence on the mechanical property and the weather resistance of the polypropylene material; on the other hand, water and ethanol are green solvents, and the health and safety of human bodies are not threatened. Therefore, compared with the technical scheme of singly adopting water as the odor detergent, the technical scheme of the embodiment of the invention which takes the mixed solution of ethanol and water as the odor detergent obviously improves the efficiency of washing and removing the volatile organic compounds in the material system; meanwhile, the potential safety hazard that the inflammable reagent ethanol easily generates spontaneous combustion under the high-temperature condition when acting alone is avoided.
In the polypropylene material, the weight of the odor detergent is 3 wt% -10 wt% of the main material, and the weight of the ethanol is 3 wt% -10 wt% of the odor detergent. In some embodiments, the weight of the odor detergent is 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt% of the main material. In some embodiments, the weight of the ethanol is 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt% of the odor detergent.
Tests show that when the weight of the odor detergent is 3 wt% -10 wt% of the main material and the weight of the ethanol is 3 wt% -10 wt% of the odor detergent, the odor detergent has a good volatile organic matter dispelling effect, the total volatile organic matters remained in the prepared polypropylene material are less than or equal to 20 microgram/g, the odor grade is less than or equal to 3.5 grade, and excellent mechanical properties and weather resistance are maintained. When the weight of the odor detergent is less than 3 wt% of the main material, the odor detergent does not play a role in sufficiently washing small-molecule volatile organic compounds in a material system; when the weight of the odor detergent is more than 10 wt% of the main material, the addition of the odor detergent increases certain process difficulty, causes production difficulty and unstable blanking, and causes the obtained polypropylene material to have poor mechanical properties, such as obviously reduced tensile strength and flexural modulus, and unequal material density. When the weight percentage of the ethanol in the odor detergent is less than 3 wt% or more than 10 wt%, its volatile organic compound-repelling effect on the polypropylene material is deteriorated.
In summary, the embodiment of the present invention uses the mixed solution of water and ethanol with a specific weight ratio as the odor detergent, which can remove the volatile organic compounds in the polypropylene material with the specific weight ratio and the composition to the maximum extent, thereby obtaining the polypropylene material with ideal effects of low odor emission and low harmful volatile organic compound residue.
The following is a method for preparing the polypropylene material.
Correspondingly, the preparation method of the polypropylene material comprises the following steps:
s01, providing polypropylene, mineral filler, toughening agent, antioxidant, light stabilizer and odor detergent according to the polypropylene material;
s02, carrying out first mixing on the polypropylene, the mineral filler, the toughening agent, the antioxidant and the light stabilizer to obtain a first mixture;
s03, performing melt extrusion on the odor detergent and the first mixture by adopting a hot melt extrusion process to obtain the polypropylene material.
The polypropylene, the mineral filler, the toughening agent, the antioxidant, the light stabilizer and the odor detergent used in the step S01 are substantially the same as those of the polypropylene, the mineral filler, the toughening agent, the antioxidant, the light stabilizer and the odor detergent, and are not described in detail herein for the sake of brevity.
In step S02, the polypropylene, the mineral filler, the toughening agent, the antioxidant, and the light stabilizer are first mixed to achieve a pre-mixing among the polypropylene, the mineral filler, the toughening agent, the antioxidant, and the light stabilizer.
The step of first mixing the polypropylene, the mineral filler, the toughening agent, the antioxidant and the light stabilizer may refer to conventional operations in the art, for example, a part of the raw materials may be first mixed, and then the rest of the raw materials may be added for blending, which is not specifically limited in the present invention. In some embodiments, the first mixing step is performed in a high speed blender. In some embodiments, the first mixing is performed in a high speed blender at a speed of 800rpm for 30 minutes.
In step S03, the odor detergent and the first mixture are melt-extruded using a hot melt extrusion process to prepare the polypropylene material.
Mixing the polypropylene, the mineral filler, the toughening agent, the antioxidant and the light stabilizer in the first mixture at a molecular level during melt extrusion; meanwhile, the odor detergent is fully mixed with volatile organic compounds in the system, the volatile organic compounds in the system are dissolved in the odor detergent, and the volatile organic compounds volatilize out of the system by taking the odor detergent as a carrier along with the progress of a melt extrusion process.
The step of melt extruding the odor detergent with the first mixture using a hot melt extrusion process may be performed with reference to operations of melt extrusion that are conventional in the art, such as in some embodiments, melt extruding the odor detergent with the first mixture using a twin screw extrusion apparatus.
As an embodiment, the step of melt extruding the odor detergent with the mixture using a hot melt extrusion process comprises:
s031, providing a twin-screw extrusion device, wherein a screw barrel of the twin-screw extrusion device comprises a feeding section, a first mixing section, a second mixing section, a first vacuum exhaust section, a third mixing section and a second vacuum exhaust section which are sequentially arranged;
s032, adding the first mixture from the feeding section to the twin-screw extrusion device, and then adding the odor detergent in the first mixing section, so that the odor detergent is mixed with the first mixture in the first mixing section and the second mixing section to obtain a second mixture; thereafter, the second mixture passes through the first vacuum venting section, the third mixing section, and the second vacuum venting section in sequence until exiting the twin screw extrusion device.
More specifically, the twin-screw extrusion apparatus in step S031 includes a feeding section, a first mixing section, a second mixing section, a first vacuum exhaust section, a third mixing section and a second vacuum exhaust section, which are arranged in sequence, and the specific configuration of the twin-screw extrusion apparatus can refer to a conventional twin-screw extrusion apparatus in the art. In some embodiments, the twin-screw extrusion apparatus further comprises a melting section, a melt conveying section and a metering section, and the feeding section, the melting section, the melt conveying section, the first mixing section, the second mixing section, the first vacuum exhaust section, the third mixing section, the second vacuum exhaust section and the metering section are sequentially arranged, and the feeding section, the melting section, the melt conveying section, the first mixing section, the second mixing section, the first vacuum exhaust section, the third mixing section, the second vacuum exhaust section and the metering section are in one-to-one correspondence with a melting extrusion process of the material in the screw barrel.
More specifically, in step S032, the first mixture is added to the twin-screw extrusion device from the feeding section. Different from the prior art of adding a gas detergent in a feeding section, the feeding of the odor detergent in the first mixing section into the twin-screw extrusion equipment is controlled to avoid problems of premature volatilization, material emission and the like of the odor detergent which possibly occur earlier than the feeding in the first mixing section, so that the odor detergent and the first mixture are fully mixed and washed for the first time in the first mixing section and the second mixing section, and the polypropylene composite material with low emission and excellent weather resistance is ensured. In some embodiments, the odor detergent is added in the first mixing section of the twin-screw extrusion device by using a liquid flow pump, so that the addition amount of the odor detergent can be accurately controlled, and the operation is convenient.
More specifically, the odor detergent is mixed with the first mixture in the first mixing section and a second mixing section to obtain a second mixture; thereafter, the second mixture passes through the first vacuum venting section, the third mixing section, and the second vacuum venting section in sequence until exiting the twin screw extrusion device.
Mixing the odor detergent with the first mixture in the first mixing section and the second mixing section during melt extrusion, and performing first mixing washing on the odor detergent and volatile organic compounds in the first mixture; the second mixture obtained in the way passes through the first vacuum exhaust section, and a large amount of volatile organic compounds and odor detergent are sucked away due to vacuum negative pressure, so that the volatile organic compounds in the material system are removed for the first time; through a third mixing section, mixing and washing the residual odor detergent and the residual volatile organic compounds in the material system again; finally, the residual odor detergent and volatile organic compounds are absorbed by the vacuum negative pressure through the second vacuum exhaust section. Through the combination of two times of mixing and washing and two times of vacuum exhaust, volatile organic compounds in a material system are driven out more thoroughly, and further, the polypropylene material with ideal effects of low odor emission and low harmful volatile organic compound residue is obtained.
In further embodiments, the first vacuum pumping stage and/or the second vacuum pumping stage has a vacuum of ≦ -0.05bar, such as in some embodiments, the first vacuum pumping stage and/or the second vacuum pumping stage has a vacuum of-0.07 bar.
In a further embodiment, in the step of melt-extruding the odor detergent and the first mixture by using a hot-melt extrusion process, the odor detergent and the first mixture are subjected to hot-melt extrusion at a temperature of 190 ℃ and 230 ℃. In some embodiments, the process from feeding to melt extrusion comprises 11 heating zones, the temperature being in the order: 190-. Further, the heating working area corresponds to the feeding section, the first mixing section, the second mixing section, the first vacuum exhaust section, the third mixing section and the second vacuum exhaust section; according to the direction from the feeding section to the second vacuum exhaust section, the first mixing section corresponds to a 4 th heating working area, the second mixing section corresponds to a 5 th heating working area, the first vacuum exhaust section corresponds to a 6 th heating working area, the third mixing section corresponds to a 7 th-8 th heating working area, and the second vacuum exhaust section corresponds to a 9 th heating working area. In some embodiments, according to the direction from the feeding section to the second vacuum exhaust section, the temperature is 190 ℃, 195 ℃, 215 ℃, 205 ℃, 215 ℃, 205 ℃, 200 ℃ in sequence, and under the condition, the decomposition of the polypropylene in the processing process can be effectively controlled, which is beneficial to reducing the VOC content of the product.
In further embodiments, the twin-screw extrusion apparatus has a length to diameter ratio of (36-60):1, preferably (50-55):1, such as 52:1 in some embodiments, to ensure sufficient mixing and washing of the detergent and the polypropylene resin, and to promote uniform dispersion of the talc in the polypropylene resin.
In further embodiments, the screw speed in the twin screw extrusion device is 500-.
In summary, in the preparation method of the polypropylene material provided by the embodiment of the invention, the hot-melt extrusion process is adopted to melt and extrude the odor detergent and other components, and the preparation method is simple, simple and convenient to operate, low in process difficulty, low in cost and easy for large-scale preparation of the polypropylene material with ideal low emission effect.
Tests prove that the polypropylene material obtained by the preparation method disclosed by the embodiment of the invention not only has excellent mechanical property and weather resistance, but also has a good volatile organic compound expelling effect, wherein the total volatile organic compound residual in the material is less than or equal to 20 microgram/g, and the odor grade is less than or equal to 3.5 grade.
In order that the details of the above-described practice and operation of the present invention will be clearly understood by those skilled in the art, and the advanced properties of the polypropylene material and the method of making the same according to the embodiments of the present invention will be apparent, the practice of the present invention will now be illustrated by way of example.
The formulations of the polypropylene materials provided in examples 1-8 and comparative examples 1-8 are shown in Table 1:
TABLE 1
Examples 1-8 and comparative examples 1-5 provide polypropylene materials prepared by a process comprising the steps of:
s11, weighing the raw materials according to the formula shown in Table 1;
first mixing the polypropylene, the mineral filler, the toughening agent, the antioxidant and the light stabilizer to obtain a first mixture;
and carrying out melt extrusion on the odor detergent and the first mixture by adopting a hot melt extrusion process to obtain the polypropylene material.
S12, dry-mixing polypropylene (melt index of 30g/10min, copolymerized polypropylene), ethylene-butylene copolymer POE, hindered phenol antioxidant 1010 and light stabilizer in a high-speed mixer at the rotating speed of about 800rpm for 30S, adding talcum powder (3000 meshes) and mixing for 2 minutes to obtain a first mixture.
S13, providing a double-screw extrusion device, wherein a screw machine barrel of the double-screw extrusion device comprises a feeding section, a first mixing section, a second mixing section, a first vacuum exhaust section, a third mixing section and a second vacuum exhaust section which are sequentially arranged; wherein the vacuum degree of the first vacuum exhaust section is-0.07 MPa, and the vacuum degree of the second vacuum exhaust section is-0.07 MPa; the length-diameter ratio of the double-screw extrusion equipment is 52:1, and the rotating speed of a screw is 650 rpm; the double-screw extrusion equipment has 11 heating working areas, and the temperature is 190 ℃, 195 ℃, 215 ℃, 205 ℃, 215 ℃, 205 ℃ and 200 ℃ according to the feeding direction to the melt extrusion direction. The charging section corresponds to the 1 st to 3 rd heating working areas (190 ℃, 195 ℃, 215 ℃), the first mixing section corresponds to the 4 th heating working area (205 ℃), the second mixing section corresponds to the 5 th heating working area (205 ℃), the first vacuum exhaust section corresponds to the 6 th heating working area (215 ℃), the third mixing section corresponds to the 7 th to 8 th heating working areas (205 ℃ ), and the second vacuum exhaust section corresponds to the 9 th heating working area (215 ℃).
S14, adding the first mixture into a double-screw extrusion device from a feeding section, and then adding the odor detergent into the first mixing section (the 4 th heating working area) by using a liquid flow pump to obtain a second mixture; and performing melt vacuum extrusion granulation on the second mixture by using a double-screw extrusion device to obtain the polypropylene composite material.
Comparative example 6 provides a method for preparing a polypropylene material, which is different from example 1 in that: the odorous detergent in step S14 was fed from the third mixing section (8 th heating work zone).
Comparative example 7 provides a method for preparing a polypropylene material, which is different from example 1 in that: in step S14, the odorous detergent is fed from the feeding section (3 rd heating work area).
Comparative example 8 provides a method for preparing a polypropylene material, which is different from example 1 in that: the odorous detergent in step S14 is fed from the second mixing section (5 th heating work zone).
Test example
The polypropylene materials of examples 1-8 and comparative examples 1-8 were injection molded to prepare test specimens, which were tested for their density, mechanical properties, odor rating, total volatile organic compounds and other performance parameters, table 2 is the standard for testing, table 3 is the odor rating table, and table 4 is the test results.
As shown in the test results in Table 4, the total volatile organic compounds in the test specimens prepared from the polypropylene materials of examples 1-8 are less than or equal to 20 μ g/g, the odor grade is less than or equal to 3.5, and the excellent mechanical properties and weather resistance are maintained, which shows that the method of the embodiment of the invention has good volatile organic compound expelling effect.
The odor detergent of comparative example 2 having an ethanol content of less than 3 wt% and the odor detergent of comparative example 3 having an ethanol content of more than 10 wt% each had a poor volatile organic compound-repelling effect on the polypropylene material.
The weight of the odor detergent of comparative example 4 was less than 3 wt% of the main material, and the total volatile organic content of the test specimen thus prepared was very high, indicating that the amount of odor detergent used affects the removal effect of small molecule volatile organic compounds in the material system.
The weight of the odor detergent of the comparative example 5 is more than 10 wt% of the main material, so that the tensile strength and the flexural modulus of the obtained polypropylene material are obviously reduced, and the material density is not equal.
The odor detergent of comparative example 6 was added in the second vacuum exhaust stage, and the odor detergent and the materials were not sufficiently mixed and were sucked away in vacuum, resulting in poor VOC-removing effect.
The odor detergent of comparative example 7 is added in the feeding section, because the region where the odor detergent is added is too close to the material melting section, the screw and the barrel are not completely and compactly filled by the melted PP material, the vaporized odor detergent is easy to flow reversely and overflows from the feeding opening, so that the odor detergent cannot be fully mixed with the PP material, meanwhile, the bridging of the feeding opening is easy to cause seriously, the normal production is influenced, the final product performance is low, the density is inaccurate, and the VOC effect is poor.
The odor detergent of comparative example 8 was added in the first mixing section and the second mixing section, and was close to the vacuuming area, and the odor detergent was not sufficiently mixed with the polypropylene resin and was sucked away by vacuum, and the effect of removing VOC was not good.
TABLE 2
TABLE 3
TABLE 4
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The polypropylene material is characterized in that raw materials for preparing the polypropylene material comprise a main material and an odor detergent, wherein the odor detergent is a mixed solution of water and ethanol, the weight of the ethanol is 3 wt% -10 wt% of the odor detergent, and the weight of the odor detergent is 3 wt% -10 wt% of the main material;
the main material comprises the following components in parts by weight based on 100 parts by weight:
2. the polypropylene material according to claim 1, wherein the polypropylene is a co-polypropylene and/or a homo-polypropylene, and the melt index of the polypropylene is 2-150g/10min at 230 ℃ under 2.16 kg.
3. The polypropylene material according to claim 1, wherein the mineral filler is selected from talc having a particle size of 1000-10000 mesh.
4. The polypropylene material of claim 1, wherein the toughening agent is selected from at least one of ethylene-propylene block copolymers, ethylene-propylene-diene copolymers, ethylene-hexene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers.
5. The polypropylene material of claim 1, wherein the antioxidant is selected from the group consisting of a mixture of hindered phenolic antioxidants and phosphite antioxidants.
6. The method according to claim 1, wherein the light stabilizer is selected from hindered amine light stabilizers.
7. The preparation method of the polypropylene material is characterized by comprising the following steps:
the polypropylene material according to any one of claims 1 to 6 providing polypropylene, mineral fillers, toughening agents, antioxidants, light stabilizers and odor detergents;
first mixing the polypropylene, the mineral filler, the toughening agent, the antioxidant and the light stabilizer to obtain a first mixture;
and carrying out melt extrusion on the odor detergent and the first mixture by adopting a hot melt extrusion process to obtain the polypropylene material.
8. The method of claim 7, wherein the step of melt extruding the odor detergent with the mixture using a hot melt extrusion process comprises:
providing a double-screw extrusion device, wherein the double-screw extrusion device comprises a feeding section, a first mixing section, a second mixing section, a first vacuum exhaust section, a third mixing section and a second vacuum exhaust section which are sequentially arranged;
feeding said first mixture from said feeding section into said twin-screw extrusion device, and then feeding said odor detergent in said first mixing section, such that said odor detergent is mixed with said first mixture in said first mixing section and said second mixing section, obtaining a second mixture; thereafter, the second mixture passes through the first vacuum venting section, the third mixing section, and the second vacuum venting section in sequence until exiting the twin screw extrusion device.
9. The method of claim 8, wherein the first vacuum degassing stage and/or the second vacuum degassing stage has a vacuum degree of ≦ -0.05 bar.
10. The method as claimed in any one of claims 7 to 9, wherein in the step of melt-extruding the odor detergent and the first mixture by a hot-melt extrusion process, the odor detergent and the first mixture are hot-melt extruded at 230 ℃ and 190 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602096A (en) * | 2014-11-21 | 2016-05-25 | 合肥杰事杰新材料股份有限公司 | Low-volatility polypropylene composite material used for automobile inner-decoration material and preparation method thereof |
| CN106751680A (en) * | 2016-12-27 | 2017-05-31 | 上海长伟锦磁工程塑料有限公司 | Ultralow PC/ABS alloys for distributing of a kind of ultra-low-smell and preparation method thereof |
| CN107501734A (en) * | 2017-09-13 | 2017-12-22 | 北京航天试验技术研究所 | It is a kind of it is low distribute, low smell long glass fiber-reinforced polypropylene materials |
| WO2018234222A1 (en) * | 2017-06-19 | 2018-12-27 | Ineos Styrolution Group Gmbh | Vinyl aromatic/diene-block copolymers having good organoleptic properties |
-
2019
- 2019-10-22 CN CN201911006500.5A patent/CN110744743A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602096A (en) * | 2014-11-21 | 2016-05-25 | 合肥杰事杰新材料股份有限公司 | Low-volatility polypropylene composite material used for automobile inner-decoration material and preparation method thereof |
| CN106751680A (en) * | 2016-12-27 | 2017-05-31 | 上海长伟锦磁工程塑料有限公司 | Ultralow PC/ABS alloys for distributing of a kind of ultra-low-smell and preparation method thereof |
| WO2018234222A1 (en) * | 2017-06-19 | 2018-12-27 | Ineos Styrolution Group Gmbh | Vinyl aromatic/diene-block copolymers having good organoleptic properties |
| CN107501734A (en) * | 2017-09-13 | 2017-12-22 | 北京航天试验技术研究所 | It is a kind of it is low distribute, low smell long glass fiber-reinforced polypropylene materials |
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