CN114479188B - Edge-modified graphene, polyolefin composition, polyolefin foam beads and polyolefin foam bead molded body - Google Patents
Edge-modified graphene, polyolefin composition, polyolefin foam beads and polyolefin foam bead molded body Download PDFInfo
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- CN114479188B CN114479188B CN202011148389.6A CN202011148389A CN114479188B CN 114479188 B CN114479188 B CN 114479188B CN 202011148389 A CN202011148389 A CN 202011148389A CN 114479188 B CN114479188 B CN 114479188B
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Abstract
The invention belongs to the field of foamed polyolefin, and relates to edge modified graphene, a polyolefin composition, polyolefin foamed beads and a polyolefin foamed bead forming body. The average sheet diameter of the edge modified graphene is 2-30 mu m, and the average aspect ratio is 600-10000:1, a step of; the conductivity is 200-800S/m; in the edge modified graphene, the oxygen content is 3-30at% calculated by oxygen element, and the hydrogen content is 1-10at% calculated by hydrogen element. The edge modified graphene disclosed by the invention has the advantages that the sheet integrity is good, a good conductive network is easy to form, and the preparation method of the edge modified graphene is environment-friendly and low in production cost; meanwhile, the method has the advantages of short reaction period, simple process and the like. The method for preparing the foaming beads by using the graphene as the cell nucleating agent and the antistatic agent is simple and operable, is easy to industrialize and popularize, and has good economic and social benefits.
Description
Technical Field
The present invention belongs to the field of foamed polyolefin, and more specifically relates to an edge-modified graphene, a polyolefin composition, a polyolefin expanded bead and a polyolefin expanded bead molded body.
Background
Compared with polystyrene-based expanded beads (EPS), polypropylene expanded beads (EPP) have excellent rigidity, corrosion resistance and thermal stability, and can be molded into various lightweight articles. EPP has been increasingly demanded in recent years, and is widely used in the fields of automobile parts, packaging materials, children entertainment appliances, other impact energy absorption and the like. However, like other synthetic resin products, the EPP molded products also generate static electricity due to friction, which causes adhesion of dust and affects the application thereof in fields with high requirements on appearance. In addition, when a human body contacts the EPP molded body with static electricity, an electric shock feeling is generated, and the static electricity can cause malfunction of electronic equipment, and more serious, static electricity accumulation can generate electrostatic attraction or repulsion and spark discharge phenomena, which can cause huge disasters under flammable and explosive conditions. When EPP is used as a liquid crystal panel turnover box, a solar cell workshop ground is paved and related electronic materials are packaged, the EPP has higher requirements on antistatic performance. Accordingly, it is desired to develop polypropylene expanded beads having an antistatic function.
Compared with polystyrene expanded beads (EPS), the polyethylene expanded beads (EPE) have better rebound resilience, can be processed into various lightweight parts by using a molding process, are not easy to generate scraps due to external force, have higher mechanical strength, have increasingly higher requirements in recent years, and are widely used in the fields of home mattresses, precise electronic packaging materials, children entertainment appliances, other impact energy absorption and the like. However, like other synthetic resin products, the shaped products of EPE also generate static electricity due to friction, which causes adhesion of dust, and affects the application thereof in fields with high requirements on appearance (such as furniture mattresses). Therefore, it is also desired to develop polyethylene expanded beads having an antistatic function.
In industrial production, a surfactant is usually blended in polypropylene or polyethylene base resin or a surfactant is coated on the surface of a molded article of expanded beads to realize an antistatic function. However, in the antistatic method using a surfactant as an antistatic agent, the antistatic agent is liable to peel off due to washing with water or friction, and a long-lasting antistatic performance cannot be imparted to the foamed molded article. On the other hand, a method of continuously imparting antistatic properties to a molded article is known, which is industrially used, by adding a polymer type antistatic agent to a polypropylene or polyethylene base resin, thereby imparting a durable antistatic property to the molded article. Such polymer antistatic agents include polyethylene glycol-methacrylate copolymers, polyetheresteramides, polyetheramidimides. However, the polymer antistatic agent also has a problem of decomposition failure due to the environmental decomposition. CN200510004023.0 reports that antistatic polyolefin resin foam is prepared using a high molecular antistatic agent having a surface intrinsic resistivity of 10 8-1013 Ω·cm, the high molecular antistatic agent used mainly includes polyether-polypropylene block copolymer, a mixture of polyether ester amide and polyamide, etc., but the antistatic additive amount is 4 to 6wt%, and is a short-acting antistatic agent.
The addition of antistatic or conductive functional bodies (such as conductive carbon black) to a polymer base material is one of the main methods for solving the problem of long-acting antistatic of polymer-based composite materials, but in general, the addition amount of antistatic agents or the filling amount of conductive fillers required for forming a conductive network are relatively large, so that the mechanical properties of the polymer are obviously reduced, and the system viscosity of the composition during melt blending processing is increased, thereby improving the production cost and the process difficulty of the material, and therefore, the reduction of the use amount of the conductive fillers is an important content for developing and applying the antistatic composite materials. CN200710192215.8 reports a preparation method of antistatic and conductive polypropylene, the surface inherent resistivity of the obtained polypropylene sheet is 10 10-1011 Ω -cm, the addition amount of carbon black is 5-40wt%, but the apparent density of carbon black is low, the addition amount is larger, and blending with polypropylene base resin is difficult, and the method increases the complexity of the process and the product cost.
Graphene has found itself to have been known to have good conductive and antistatic properties. When added in small amounts, the polymer has good antistatic performance, but because of the inert surface of graphene, the graphene lacks effective chemical bond or hydrogen bond connection with polymer molecules, and surface functionalization treatment is often needed. Functionalized graphene refers to the introduction of functional groups, such as carboxyl groups, amine groups, epoxy groups, on the surface or edge of graphene through chemical reaction. The main purpose of introducing functional groups is to increase the polarity of graphene or provide chemical reaction sites, enhancing the interaction between graphene and other materials. However, the active groups are introduced and the conjugated system on the surface of the graphene is destroyed, so that the good conductivity of the graphene is certainly weakened, and the more the modification groups are introduced, the larger the loss of the electronic conductivity of the graphene is. If the functional groups are only introduced at the edges of the graphene, the conjugated system on the surface of the graphene is not destroyed, so that the basic performance of the graphene is ensured. Thus, active groups are introduced and the performance of the graphene is ensured. However, such selectively modified graphene is difficult to prepare. At present, few application documents are reported. The method of ball milling graphite and dry ice in US 2013/0018204 A1 can be used for modifying carboxyl at the edge of a graphite sheet, firstly preparing graphite with the carboxyl modified at the edge, and dispersing the graphite with the carboxyl modified at the edge in water after introducing enough carboxyl to obtain the graphene with the carboxyl modified at the edge. In the method, enough strong polar groups (i.e. modified edge carboxyl groups) are required to be introduced, and water is required to be added to peel off graphite into graphene, and the obtained graphene has a nano-scale size and is easy to agglomerate when being blended with a polymer, so that the antistatic effect is affected.
Disclosure of Invention
The invention aims to solve the problems of poor antistatic performance, high antistatic agent addition amount, structural damage after graphene functionalization and the like of a foam bead forming body in the prior art, and provides edge modified graphene, a polyolefin composition, a polyolefin foam bead and a polyolefin foam bead forming body.
The first aspect of the present invention provides an edge-modified graphene having an average sheet diameter of 2 to 30 μm and an average aspect ratio of 600 to 10000:1, a step of; the conductivity is 200-800S/m; in the edge modified graphene, the oxygen content is 3-30at% calculated by oxygen element, and the hydrogen content is 1-10at% calculated by hydrogen element.
A second aspect of the invention provides the use of the edge modified graphene as an antistatic agent.
A third aspect of the invention provides the use of the edge modified graphene as a cell nucleating agent.
According to a fourth aspect of the present invention, there is provided a polyolefin composition comprising a polyolefin and the edge-modified graphene according to the first aspect of the present invention, wherein the edge-modified graphene is contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the polyolefin.
In a fifth aspect, the present invention provides a polyolefin expanded bead produced by granulating and then expanding a polyolefin composition according to the fourth aspect of the present invention.
In a sixth aspect of the present invention, there is provided a polyolefin expanded bead molded article obtained by molding the polyolefin expanded bead according to the fifth aspect of the present invention.
The invention provides novel edge modified graphene, which has the advantages of good sheet integrity, easiness in forming a good conductive network, capability of further preparing polypropylene foaming beads from a polypropylene composition containing the edge modified graphene as a cell nucleating agent and a long-acting antistatic agent, compact and uniform cell structure, uniform pore diameter, complete and unbroken appearance and lower density. The foaming beads are of a non-crosslinking structure, so that the foaming beads can be recycled, secondary pollution is avoided, and the requirements of recycling economy are met. In addition, the molded articles produced from the expanded beads of the present invention can have higher antistatic properties with lower amounts of antistatic agents added.
The preparation method of the edge modified graphene is environment-friendly and low in production cost; meanwhile, the method has the advantages of short reaction period, simple process and the like. The method for preparing the foaming beads by using the graphene as the cell nucleating agent and the antistatic agent is simple and operable, is easy to industrialize and popularize, and has good economic and social benefits.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings.
Fig. 1 shows a scanning electron microscope image of graphene G102 in an embodiment of the present invention.
Fig. 2 shows a scanning electron microscope image of graphene prepared according to the method of US20130018204 used in comparative example 4.
FIG. 3 shows a scanning electron micrograph of cells of the polyolefin foam beads prepared in example 7.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides edge modified graphene, wherein the average sheet diameter of the edge modified graphene is 2-30 mu m, preferably 5-15 mu m; average aspect ratio of 600-10000:1, preferably 1200-4500:1, more preferably 1500-3800:1, a step of; the conductivity is 200-800S/m, preferably 300-600S/m; in the edge modified graphene, the oxygen content calculated by oxygen element is 3-30at%, preferably 5-18at%; the hydrogen content is 1 to 10at%, preferably 3 to 8at%, in terms of hydrogen element.
The edge modified graphene has the sheet diameter size of micron level, has adjustable aspect ratio and content of carbon and oxygen elements, has higher conductivity, can be obviously different from the existing nanoscale graphene (such as US 20130018204), and can overcome the problem that the nanoscale graphene is easy to aggregate.
In the present invention, the "aspect ratio" refers to the ratio of the long side (sheet diameter) to the thickness of graphene.
According to the present invention, preferably, the edge-modified graphene is prepared by grinding graphite by a grinding disc under supercritical carbon dioxide.
Under the condition of supercritical carbon dioxide, the property of the carbon dioxide is greatly changed, the density is close to that of liquid, the viscosity is close to that of gas, and the diffusion coefficient is 100 times that of liquid. The inventor of the present invention has found that in this state, carbon dioxide is intercalated into the graphite flake layers, pi-pi interaction between the graphite flake layers is reduced, and graphite is exfoliated into graphene after it is sheared by the grinding disc; meanwhile, graphite or graphene is crushed by the shearing action of the grinding disc, the newly generated high-activity edge reacts with carbon dioxide, and as a result, carboxyl groups are modified at the edge of the graphene. Compared with the common ball milling method, the method can prepare the graphene with carboxylated edges without grinding graphite to be particularly fine, and the common ball milling method has to grind the graphite to the nano-scale, otherwise, the graphene cannot be prepared.
In the present invention, the terms "edge modified graphene", "carboxylated graphene", "edge carboxylated modified graphene" are the same in reference.
The edge modified graphene provided by the invention is prepared by a method comprising the following steps: the graphite powder is milled in a high pressure millstone kettle in the presence of supercritical carbon dioxide.
According to a specific embodiment of the invention, the edge-modified graphene is prepared by a method comprising the following steps:
step S1, adding purified or unpurified graphite powder into a high-pressure millstone kettle;
Step S2, introducing carbon dioxide into a high-pressure millstone kettle, and enabling the carbon dioxide to be in a supercritical state to form a material containing graphite powder and supercritical carbon dioxide;
and step S3, grinding the material containing graphite powder and supercritical carbon dioxide.
According to some embodiments of the invention, the graphite powder is selected from the group consisting of crystalline flake graphite powder and expanded graphite powder, preferably the graphite powder has a particle size of 10-80 mesh, preferably 20-60 mesh.
According to some embodiments of the present invention, the graphite powder is preferably subjected to a purification treatment in advance, such as by ultrasonic cleaning and/or chemical treatment, to remove impurities, such as impurity substances and impurity elements, prior to grinding.
According to some embodiments of the invention, in step S2, carbon dioxide is brought into a supercritical state by bringing the temperature inside the tank to over 32.26 ℃ and the pressure to over 72.9 atm.
According to some embodiments of the invention, in step S3, after finishing the grinding, the pressure in the high-pressure millstone kettle is rapidly reduced; preferably, the pressure in the autoclave is reduced to below 1atm in 5-20 seconds.
According to some embodiments of the invention, the temperature in the autoclave is 35-200 ℃, preferably 35-100 ℃, more preferably 35-70 ℃.
According to some embodiments of the invention, the pressure in the autoclave is 75-165atm, preferably 75-165atm, more preferably 75-125atm.
According to some embodiments of the invention, the stirring speed in the high-pressure millstone kettle is 500-10000r/min, preferably 500-5000r/min.
According to some embodiments of the invention, the milling time is from 6 to 48 hours.
Through the setting of the specific grinding conditions, the prepared edge modified graphene can meet the structural and performance characteristics.
In the invention, the graphite and the supercritical carbon dioxide can be fully mixed by adopting a high-pressure millstone kettle, and the graphite is ground and peeled off.
According to a preferred embodiment of the invention, the high-pressure millstone kettle is a self-circulation millstone device used in a high-pressure environment.
The edge modified graphene of the present invention can be used as an antistatic agent, preferably as an antistatic agent for polyolefin articles. When the edge modified graphene is used as the antistatic agent, a better antistatic effect can be achieved by adopting a lower additive amount than that of a conventional antistatic agent.
The edge modified graphene of the present invention may also be used as a cell nucleating agent, preferably as a cell nucleating agent for polyolefin articles.
In the present invention, the term "polyolefin" includes, but is not limited to, polyethylene and polypropylene, and other terms containing "polypropylene" are correspondingly given the above meaning, e.g., polyolefin compositions including polyethylene compositions, as well as polypropylene compositions.
The polyolefin product comprises a polyethylene product or a polypropylene product, and the edge modified graphene can be added in a conventional additive adding mode in the process of preparing the polyolefin product.
The invention also provides a polyolefin composition, which contains polyolefin and the edge modified graphene, wherein the content of the edge modified graphene is 0.05-5 parts by weight, preferably 0.1-2 parts by weight, based on 100 parts by weight of polyolefin.
The polyolefin composition of the invention may further contain other components such as various conventional auxiliary agents, specifically, based on 100 parts by weight of polyolefin, at least one of the following components:
0.1-0.3 part by weight of an antioxidant;
0.05-1 parts by weight of a dispersing agent;
1-5 parts by weight of grafted polyolefin;
the olefin structural unit of the grafted polyolefin and the olefin structural unit of the polyolefin are the same olefin structural unit, namely, if the polyolefin is polypropylene, the grafted polyolefin is grafted polypropylene; if the polyolefin is polyethylene, the grafted polyolefin is grafted polyethylene and the polyolefin base resin of the grafted polyolefin is the same as the corresponding polyolefin.
The polyolefin composition according to the present invention, preferably, the grafted polyolefin is a polar monomer grafted modified polyolefin; the polar monomer is preferably at least one selected from glycidyl methacrylate, maleic anhydride and methyl acrylate, and more preferably glycidyl methacrylate.
According to the polyolefin composition of the invention, the grafted polyolefin preferably has a grafting ratio of 0.5 to 6wt%, more preferably 1 to 3wt%.
According to one embodiment of the invention, the polyolefin is polypropylene and the grafted polyolefin is grafted polypropylene; preferably, the polypropylene is a random copolymer polypropylene having a melt index of 5 to 9g/10min and a molecular weight distribution M w/Mn to 20 at a temperature of 190℃and a load of 2.16 kg.
Specifically, the random copolymer polypropylene is selected from ethylene propylene random copolymer polypropylene, propylene Ding Mogui copolymer polypropylene and ethylene propylene Ding Mogui copolymer polypropylene. That is, the comonomer used in the random copolymer polypropylene is one or two of ethylene and butene. The above random copolymer polypropylene is commercially available.
According to another embodiment of the invention, the polyolefin is polyethylene and the grafted polyolefin is grafted polyethylene.
According to the invention, preferably, the polyethylene contains component a, component B and component C; the component A is linear low density polyethylene copolymerized by ethylene-alpha olefin, the melt index MI A of the component A measured at 190 ℃ under 2.16kg load is 0.01-2g/10min, and the density rho A of the component A is 0.880-0.936g/cm 3; the component B is linear low-density polyethylene copolymerized by ethylene-alpha olefin, the melt index MI B measured at 190 ℃ and 2.16kg load is 2.1-14.9g/10min, and the density rho B of the component B is 0.910-0.930g/cm 3; the component C is linear low density polyethylene copolymerized with ethylene-alpha olefin, the melt index MI C of the component C measured at 190 ℃ and 2.16kg load is 15-150g/10min, and the density rho C of the component C is 0.880-0.930g/cm 3.
In a preferred embodiment of the invention, the melt index MI A of component A at 190℃and 2.16kg load is 0.01-1.5g/10min, the melt index MI B of component B at 190℃and 2.16kg load is 3-10g/10min, and the melt index MI C of component C at 190℃and 2.16kg load is 15-100g/10min.
More preferably, the melt index MI A of component A at 190℃and 2.16kg load is 0.01-1g/10min, the melt index MI B of component B at 190℃and 2.16kg load is 3-5g/10min, and the melt index MI C of component C at 190℃and 2.16kg load is 20-60g/10min.
In the present invention, the melt index was measured according to the method specified in GB/T3682-2000.
Preferably, the density ρ A of the component a is 0.910-0.930g/cm 3, the density ρ B of the component B is 0.913-0.928g/cm 3, and the density ρ C of the component C is 0.905-0.928g/cm 3.
More preferably, the density ρ A of component A is 0.915-0.926g/cm 3, the density ρ B of component B is 0.913-0.924g/cm 3, and the density ρ C of component C is 0.910-0.926g/cm 3.
Further preferably, the relationship between the densities ρ A、ρB and ρ C of the component A, component B and component C satisfies-0.04.ltoreq.ρ A-ρB.ltoreq.0.02 and-0.04.ltoreq.ρ A-ρC.ltoreq.0.02. This enables the polyethylene to have better foaming properties, and the polyethylene expanded beads made from the composition composed of the polyethylene have a more dense and uniform cell structure, and the molded article made from the polyethylene expanded beads has higher compressive strength.
In the present invention, the linear structures of the component A, the component B and the component C refer to the structures of only short branched chains, but not long branched chains and cross-linked structures in the molecular chain, and the linear structures are determined by the polymerization monomers and the polymerization process conditions, are well known to those skilled in the art, and are not described herein.
According to the present invention, in order to give a polyethylene base resin having better foaming properties, preferably, in the polyethylene base resin, the part by mass of the component a, W A, is 25 to 90 parts by weight, the part by mass of the component B, W B, is 0.1 to 10 parts by weight, and the part by mass of the component C, W C, is 10 to 75 parts by weight; more preferably, in the polyethylene base resin, the weight part of the component A W A is 30 to 80 parts by weight, the weight part of the component B W B is 0.5 to 8 parts by weight, and the weight part of the component C W C is 20 to 70 parts by weight.
Further preferably, the parts by weight of component a W A, the parts by weight of component C W C and the melt index MI A of component a satisfy 5.2× lgMI A+11.6≥WA/WC≥0.9×lgMIA +2.1, further preferably satisfy 2.9× lgMI A+6.8≥WA/WC≥1.1×lgMIA +2.7. This enables the polyethylene base resin to have better foaming properties, and the polyethylene expanded beads made from the composition composed of the polyethylene base resin have a more compact and uniform cell structure, and the resulting polyethylene expanded bead molded body has higher compressive strength.
According to the invention, the polyethylene base resin has a melt index of 0.1 to 20g/10min, preferably 0.5 to 10g/10min, at a temperature of 190℃and a load of 2.16 kg. On the basis of the combination of the component A, the component B and the component C having the above specific melt index and density, controlling the melt index of the entire polyethylene base resin within the above range enables the resulting polyethylene composition to have very excellent foaming properties.
According to the invention, the molecular weight distribution indices of component A, component B and component C all satisfy M w/Mn.ltoreq.4.5, preferably 2.0.ltoreq.M w/Mn.ltoreq.4.2. In order to obtain the component a, the component B and the component C having the above molecular weight distribution, it is preferable that the component a, the component B and the component C are all polymerized using a metallocene catalyst. The metallocene catalyst may be selected as usual in the art, and is generally composed of a metallocene compound and an organoaluminum compound, and optionally an electron donor, and is known to those skilled in the art, and is not described herein.
The inventors of the present invention have conducted intensive studies and have found that, when a component A, a component B and a component C having the above melt index and density obtained by polymerization using a metallocene catalyst are used in combination, a composition composed of the polyethylene base resin has good foaming properties and the obtained foam beads have good cell structures when the foam beads are prepared by a reaction tank impregnation method, and a molded article obtained from the obtained foam beads also has very high compression strength.
According to the present invention, the content of the α -olefin copolymerization units in the component a, the component B, and the component C is not particularly limited, and for example, the molar content of the α -olefin copolymerization units in the component a, the component B, and the component C may each independently be 0.2 to 15mol%, preferably 1.5 to 10mol%. In the present invention, the molar content of the alpha olefin copolymer unit means a ratio of the molar amount of the structural unit formed by polymerization of the alpha olefin to the molar amount of the total monomer structural unit. In addition, the alpha-olefins in component a, component B and component C are each independently selected from at least one of the C 3-C20 olefins. The alpha olefin in the component a, the component B and the component C is preferably at least one selected from propylene, 1-butene, 2-butene, 3-methyl-1-butene, 4-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-dimethyl-1-pentene, 3, 4-dimethyl-1-pentene, 4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 1-heptene, 2-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, more preferably at least one selected from 1-butene, 1-hexene and 1-octene, from the viewpoint of raw material availability.
Preferably, the antioxidant is at least one selected from hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants. Specifically, the hindered phenol antioxidant may be a monophenol, a bisphenol, or a polyphenol; the phosphite antioxidant comprises alkyl phosphite and aryl phosphite; the sulfur ester antioxidant comprises a sulfur ester antioxidant, a thioether phenol antioxidant and a thiobisphenol antioxidant. Preferably, the antioxidant is a composite antioxidant, more preferably, the antioxidant is a composite antioxidant of two or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants according to a certain mass ratio.
The dispersant is, for example, glycerol monostearate (formula: C 21H42O4). The material is dispersed into polypropylene or polyethylene during processing. In order to advantageously improve the dispersibility of graphene in polypropylene or polyethylene base resin, it is preferable that the glycerol monostearate is added in an amount of 1 to 10% by weight of the edge-modified graphene.
The composition according to the invention may preferably also contain other adjuvants. The other adjuvants do not adversely affect polyolefin properties including, but not limited to, at least one of a slip agent, a lubricant, a plasticizer, and the like. In addition, the amounts of the other adjuvants are all conventional in the art and will be known to those skilled in the art.
Because the edge modified graphene can serve as an antistatic agent and a cell nucleating agent at the same time, the edge modified graphene can replace the original cell nucleating agent of the foaming bead, namely, the composition does not need to be added with other cell nucleating agents except the edge modified graphene.
The invention provides a polyolefin expanded bead which is prepared by granulating and then expanding the polyolefin composition.
The pelletization may be carried out in various ways known per se, for example, the polyolefin composition may be extruded into strands and cut through one or more dies of a twin-screw or single-screw extruder to obtain polyolefin pellets, or an underwater micropellet pelletizing system may be used, the specific operation of which is well known to those skilled in the art.
According to one embodiment of the present invention, a method for preparing a polyolefin composition into polyolefin resin pellets comprises:
Pathway one:
(1) Mixing the components of the polyolefin composition in a mixer according to a proportion to obtain a blend;
(2) Adding the blend into an extruder for extrusion and granulation; the granulating mode comprises strand cutting or underwater cutting.
Pathway two:
(1) Proportionally adding the components of the polyolefin composition to an extruder via a plurality of metering feeders;
(2) The extruder is used for pelleting after melt blending, and the modes comprise strand pelleting or underwater pelleting.
Preferably, in step (2) of pathway one, the strand die-cut extrusion temperature is 200-230 ℃ (for polypropylene), or 180-200 ℃ (for polyethylene); in step (2) of pathway two, the underwater pelletizing extrusion temperature is 240-260 ℃ (for polypropylene), or 200-220 ℃ (for polyethylene).
The underwater pelletizing step comprises the following steps: after hot cutting, the mixture is introduced into water at 75 ℃ or lower, preferably 70 ℃ or lower, more preferably 55 to 65 ℃ to cut the microparticles so that the length/diameter ratio of each of the microparticles is 0.5 to 2.0, preferably 0.8 to 1.3, more preferably 0.9 to 1.1, and the average weight is 0.1 to 20mg, preferably 0.2 to 10mg, more preferably 1 to 3mg. The length/diameter ratio described herein is an average of 200 arbitrarily selected polypropylene composition particles.
According to the invention, the foaming can be carried out in various existing modes, for example, an extrusion foaming method can be adopted, a reaction kettle dipping foaming method is preferred, and the foaming beads obtained in the mode are of non-crosslinked structures, so that the foaming beads can be recycled according to polyolefin modified materials, secondary pollution is avoided, and the requirement of recycling economy is met.
According to a preferred embodiment of the present invention, the reaction kettle dipping foaming method comprises the following steps:
(1) Uniformly mixing polyolefin resin particles with dispersing medium, surfactant, dispersing agent, dispersion enhancer and other assistants in an autoclave;
(2) Closing the autoclave lid, evacuating the residual air from the autoclave by means of an evacuating gas method, i.e. using a foaming agent, after which the foaming agent is fed into the autoclave, heating is started and the pressure is initially adjusted until it stabilizes, and the autoclave is subsequently stirred at a stirring speed of 50-150rmp, preferably 90-110rmp, to heat it at a constant speed to a temperature of 0.1-5 ℃, preferably 0.5-1 ℃ lower than the expansion stability;
(3) Adjusting the pressure in the autoclave to the pressure required for foaming, wherein the pressure is 1-10MPa, preferably 3-5MPa, and the temperature is increased to the foaming temperature at the average heating speed of 0.1 ℃/min, the foaming temperature is 0.1-5 ℃ lower, preferably 0.5-1 ℃ lower than the melting temperature of the microparticles, and stirring is continuously carried out for 0.1-2 hours, preferably 0.25-0.5 hours under the conditions of the foaming temperature and the pressure;
(4) The discharge port of the autoclave was opened to allow the material in the autoclave to drain into the collection tank to obtain polyolefin foam beads, and carbon dioxide gas was fed while discharging was performed so that the pressure in the autoclave was maintained near the foaming pressure before all the particles were completely foamed and entered into the collection tank.
In this context, the pressures are referred to as gauge pressures unless otherwise indicated.
According to the method for producing polyolefin expanded beads of the present invention, the dispersion medium may be any of various existing dispersion media capable of dispersing polyolefin resin fine particles therein without dissolving components thereof, and for example, may be at least one of deionized water, ethylene glycol, glycerin, methanol, ethanol, etc., and deionized water is particularly preferred. Preferably, the dispersion medium is used in an amount of 1000 to 5000 parts by weight, preferably 2500 to 3500 parts by weight, relative to 100 parts by weight of the polyolefin resin particles.
According to the method for producing polyolefin foam beads of the present invention, the surfactant may be any of various existing components capable of promoting dispersion of polyolefin resin fine particles in a dispersion medium, and for example, may be at least one of stearic acid, sodium dodecylbenzenesulfonate, quaternium, lecithin, amino acid, betaine, fatty acid glyceride, fatty acid sorbitan, polysorbate, etc., with sodium dodecylbenzenesulfonate being particularly preferred. Preferably, the surfactant is used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 0.5 parts by weight, relative to 100 parts by weight of the polyolefin resin particles.
According to the method for preparing polyolefin expanded beads of the present invention, the dispersing agent may be an organic dispersing agent or an inorganic dispersing agent, preferably an inorganic dispersing agent. The inorganic dispersant may be at least one of natural or synthetic clay minerals (e.g., kaolin, mica, magnesium aluminum garnet, clay, etc.), alumina, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, silica, zinc borate, iron oxide, etc., and particularly preferably kaolin. In order to effectively prevent the polyolefin resin particles from being melt-adhered to each other during foaming, it is preferable that the dispersant is used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 1 to 6 parts by weight, relative to 100 parts by weight of the polyolefin resin particles.
According to the method for producing polyolefin expanded beads of the present invention, the dispersion enhancer is added for the purpose of improving the dispersion efficiency of the dispersant, that is, to reduce the amount of the dispersant while retaining its function of preventing inter-particle fusion bonding. The dispersion enhancing agent may be any of a variety of existing inorganic compounds having a solubility of 1mg in 100mL of water at 40 ℃ and providing a divalent or trivalent anion or cation. Examples of the dispersion enhancer include, but are not limited to, at least one of magnesium nitride, magnesium nitrate, aluminum phosphate, magnesium sulfate, aluminum nitride, aluminum nitrate, aluminum sulfate, ferric chloride, ferric sulfate, ferric nitrate, and the like, and aluminum sulfate is preferable. In order to obtain polyolefin expanded beads having an apparent density of 100g/L or more, the dispersion-enhancing agent is preferably used in an amount of 0.0001 to 1 part by weight, preferably 0.01 to 0.2 part by weight, relative to 100 parts by weight of the polyolefin particles.
According to the method for preparing polyolefin expanded beads of the present invention, the foaming agent may be an organic-based physical foaming agent or an inorganic-based physical foaming agent. Examples of the organic-based physical blowing agent include, but are not limited to, aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane, alicyclic hydrocarbons such as cyclobutane and cyclohexane, and halogenated hydrocarbons such as at least one of chlorofluoromethane, trifluoromethane, 1, 2-difluoroethane, 1, 2-tetrafluoroethane, methyl chloride, ethyl chloride and methylene chloride, etc. Examples of the inorganic-based physical blowing agent include, but are not limited to, at least one of air, nitrogen, carbon dioxide, oxygen, and water. In order to ensure good stability (uniformity), low cost and environmental friendliness of the apparent density of the obtained polyolefin expanded beads, the blowing agent is preferably carbon dioxide and/or nitrogen, particularly preferably carbon dioxide. In addition, the amount of the blowing agent may be determined according to the specific kind of the blowing agent, the foaming temperature, and the apparent density of the polypropylene expanded beads to be produced. For example, when nitrogen is used as a foaming agent and water is used as a dispersion medium, the pressure in the closed vessel (i.e., the pressure in the upper space in the closed vessel (gauge pressure)) is controlled to be 1 to 12MPa when the foaming device is depressurized; when carbon dioxide is used as the blowing agent, the gauge pressure is controlled to 1-7MPa. In general, the desired pressure in the upper space within the closed vessel increases as the apparent density of the polyolefin particles to be obtained decreases.
The polyolefin expanded beads of the present invention have a relatively low density, less than 0.9g/cm 3, and may be, for example, 0.01 to 0.49g/cm 3. The polyolefin foaming bead has compact cells, uniform pore diameter, complete appearance, no rupture, lower density and good antistatic effect.
The invention also provides a polyolefin foam bead molded body, which is obtained by molding the polyolefin foam beads.
According to the present invention, the molding may be performed in various existing molding machines, and the molding conditions may be selected conventionally in the art, and those skilled in the art will be aware of this, and detailed description thereof will be omitted herein.
In the following examples and comparative examples, the data were obtained as follows:
(1) Melt index MI: the measurement was carried out according to the method prescribed in GB/T3682-2000, wherein the polypropylene resin was tested at 230℃and the polyethylene resin was tested at 190℃with a load of 2.16kg.
(2) Density of polypropylene and composition: the measurement was carried out according to the method specified in GB/T1033.2-2010 and using a density gradient column method; the density of the expanded polypropylene beads was measured according to ASTM D792.
(3) Surface resistivity of the expanded bead molded body: measured according to the method specified in GB/T1410-2006.
(4) The cell density was measured as follows:
firstly, observing the section of the polypropylene foaming beads by using a scanning electron microscope, selecting a certain area from the obtained electron microscope photograph, obtaining the information of the area, the number of cells and the like, and obtaining the cell density of the beads by using the following formula:
wherein: n is the number of cells in the SEM, M is the magnification, A is the area of the selected region (unit: cm 2) on the SEM, Is the expansion ratio of the polypropylene expanded beads.
(5) The 50% compression strength is determined according to the method described in the national standard GB/T8813-2020.
(6) The average sheet diameter and aspect ratio of graphene were determined by Scanning Electron Microscopy (SEM).
(7) The oxygen and hydrogen content of graphene are characterized by X-ray photoelectron spectroscopy (XPS).
(8) The conductivity of graphene was measured using a powder resistivity conductivity tester as described in DB 13/T2768.3-2018.
In the following examples and comparative examples, the materials used were as follows:
glycerol monostearate: purchased from Heda, ATMER 129V.
Ethylene propylene random copolymer polypropylene 4908: purchased from China petrochemical Yanshan division (melt index: 8.0.+ -. 0.5g/10min (230 ℃ C., 2.16 kg); molecular weight distribution: 5.7).
Propylene Ding Mogui copolymer polypropylene E680E: purchased from Shanghai petrochemical China (melt index 8.0.+ -. 0.5g/10min (230 ℃ C., 2.16 kg); molecular weight distribution 5.0).
Ethylene propylene Ding Mogui copolymerized polypropylene 5608: purchased from China petrochemical Yanshan division (melt index 6.0.+ -. 0.5g/10min (230 ℃ C., 2.16 kg); molecular weight distribution 4.5).
Chemically exfoliated graphene, purchased from nanjing ji cang nanotechnology limited, 32% oxygen content.
Polyethylene composition PE101
The polyethylene base resin of this preparation contains component A, component B, component C and a lubricant. Wherein, the component A, the component B and the component C are all Linear Low Density Polyethylene (LLDPE) copolymerized by ethylene-alpha olefin and are prepared by adopting the same catalyst system (metallocene catalyst) and polymerization process, and the difference is that the amount of hydrogen added and the types and the molar contents of alpha-olefin comonomers are different when preparing different components. The method comprises the following specific steps:
Ethylene, alpha olefin, hydrogen and nitrogen (all of which are polymerization grades, are used after water and oxygen are removed, and the same applies below) are added into a fluidized bed gas phase reactor, then a metallocene catalyst system (the metallocene catalyst system is a supported metallocene catalyst prepared by CN102453124A example 1, and the same applies below) is added, and then polymerization is carried out at a temperature of 84-88 ℃ and a pressure of 1.8-2MPa, so as to obtain a component A, a component B and a component C respectively. Wherein, the control of the melt index of the component A, the component B and the component C is realized by adjusting the addition amount of hydrogen, and the control of the density is realized by adjusting the type and the addition amount of alpha olefin. The alpha olefin used in the process of preparing the component A is 1-hexene, the alpha olefin used in the process of preparing the component B is 1-hexene, and the alpha olefin used in the process of preparing the component C is 1-butene.
The properties of the component A, the component B and the component C prepared by the method are as follows:
Component a has a melt index MI A =1.5 g/10min, a density ρ A＝0.913g/cm3, a molecular weight distribution index M w/Mn =3.4, a molar content of alpha olefin comonomer=7.5 mol%;
Component B has a melt index MI B =2.1 g/10min, a density ρ B＝0.913g/cm3, a molecular weight distribution index M w/Mn =3.2, a molar content of alpha-olefin comonomer=7.5 mol%;
Component C has a melt index MI C =15 g/10min, a density ρ C＝0.905g/cm3, a molecular weight distribution index M w/Mn =3.5, a molar content of alpha-olefin comonomer=9.1 mol%.
The lubricant was a PEG lubricant produced by Switzerland Corp, having a number average molecular weight of 10000.
Weighing and mixing the component A, the component B and the component C according to a proportion, wherein the weight part W A of the component A is 80 weight parts, the weight part W B of the component B is 10 weight parts, the weight part W C of the component C is 20 weight parts, and the weight part W A/WC =4 (5.2× lgMI A+11.6≥WA/WC≥0.9×lgMIA +2.1 is satisfied and 2.9× lgMI A+6.8≥WA/WC≥1.1×lgMIA +2.7 is also satisfied); adding a lubricant (the addition amount of the lubricant is 0.1 part by weight based on 100 parts by weight of the total weight of the component A, the component B and the component C), adding the mixture into a high-speed stirrer, uniformly mixing, adding the mixed material into a feeder of a double-screw extruder manufactured by Nanjac ploung company, feeding the material into a double-screw through the feeder, keeping the temperature of the screw between 180 ℃ and 240 ℃ in the processing process, melting and uniformly mixing through the screw, extruding, granulating and drying to obtain polyethylene base resin granules (PE 101), and detecting the melt index MI=2.4 g/10min.
Polyethylene composition PE102
The polyethylene base resin of this preparation contains component A, component B, component C and a lubricant. Wherein, the component A, the component B and the component C are all Linear Low Density Polyethylene (LLDPE) copolymerized by ethylene-alpha olefin and are prepared by adopting the same catalyst system (metallocene catalyst) and polymerization process, and the difference is that the amount of hydrogen added in the preparation of different components and the types and the molar contents of alpha-olefin comonomer are different. The method comprises the following specific steps:
Ethylene, alpha olefin, hydrogen and nitrogen are added into a fluidized bed gas phase reactor, then a metallocene catalyst system is added, and then polymerization is carried out under the conditions that the temperature is 84-88 ℃ and the pressure is 1.8-2MPa, so that a component A, a component B and a component C are respectively obtained. Wherein, the control of the melt index of the component A, the component B and the component C is realized by adjusting the addition amount of hydrogen, and the control of the density is realized by adjusting the type and the addition amount of alpha olefin. The alpha olefin used in the process of preparing the component A is 1-butene, the alpha olefin used in the process of preparing the component B is 1-butene, and the alpha olefin used in the process of preparing the component C is 1-hexene.
The properties of the component A, the component B and the component C prepared by the method are as follows:
Component a has a melt index MI A =0.01 g/10min, a density ρ A＝0.930g/cm3, a molecular weight distribution index M w/Mn =3.0, a molar content of alpha olefin comonomer=1.6 mol%;
Component B has a melt index MI B =10.0 g/10min, a density ρ B＝0.930g/cm3, a molecular weight distribution index M w/Mn =2.8, a molar content of alpha-olefin comonomer=1.9 mol%;
Component C has a melt index MI C =60 g/10min, a density ρ C＝0.922g/cm3, a molecular weight distribution index M w/Mn =2.9, and a molar content of alpha-olefin comonomer=3.8 mol%.
Weighing and mixing the component A, the component B and the component C according to a proportion, wherein the weight part W A of the component A is 55 weight parts, the weight part W B of the component B is 5 weight parts, the weight part W C of the component C is 55 weight parts, and the weight part W A/WC =1 (5.2× lgMI A+11.6≥WA/WC≥0.9×lgMIA +2.1 is satisfied and 2.9× lgMI A+6.8≥WA/WC≥1.1×lgMIA +2.7 is also satisfied); adding a lubricant (the addition amount of the lubricant is 0.1 part by weight based on 100 parts by weight of the total weight of the component A, the component B and the component C), adding the mixture into a high-speed stirrer, uniformly mixing, adding the mixed material into a feeder of a double-screw extruder manufactured by Nanjac ploung company, feeding the material into a double-screw through the feeder, keeping the temperature of the screw between 180 ℃ and 240 ℃ in the processing process, melting and uniformly mixing through the screw, extruding, granulating and drying to obtain polyethylene base resin granules (PE 102), and detecting the melt index MI=0.9 g/10min.
Polyethylene composition PE103
The polyethylene base resin of the preparation example is obtained by polymerization in a multi-reactor parallel device, wherein a first reactor 1 is used for preparing a component A by polymerization, a second reactor 2 is used for preparing a component B by polymerization, and a third reactor 3 is used for preparing a component C by polymerization, and the three components are all Linear Low Density Polyethylene (LLDPE) copolymerized by ethylene-alpha olefin, wherein the three components are prepared by adopting the same catalyst system (metallocene catalyst) and polymerization process, and the difference is that the amount of hydrogen, the types and mole contents of alpha olefin comonomer and the unit time yield of each reactor are different when different components are prepared. The method comprises the following specific steps:
Alpha-olefin, normal hexane and hydrogen were added to a polymerization reactor, and the polymerization reactor was heated to a preset polymerization temperature, after which ethylene monomer and a catalyst system were simultaneously added to the polymerization reactor, and polymerized at a temperature of 140C and a pressure of 2.5MPa for 30 minutes, to obtain component a, component B and component C, respectively. Wherein, the control of the melt index of the component A, the component B and the component C is realized by adjusting the addition amount of hydrogen, and the control of the density is realized by adjusting the type and the addition amount of alpha olefin. The alpha olefin used in the process of preparing the component A is 1-octene, the alpha olefin used in the process of preparing the component B is 1-butene, and the alpha olefin used in the process of preparing the component C is 1-butene.
The weight ratio of the yield per unit time W A of component a in the first reactor 1, the yield per unit time W B of component B in the second reactor 2 and the yield per unit time W C of component C in the third reactor 3 was maintained at W A：WB：WC =75 during the preparation process: 2:35, wherein W A/WC = 2.1 (5.2 x lgMI A+11.6≥WA/WC≥0.9×lgMIA +2.1 is satisfied, as is 2.9 x lgMI A+6.8≥WA/WC≥1.1×lgMIA + 2.7).
The properties of the component A, the component B and the component C prepared by the method are as follows:
component a has a melt index MI A =0.1 g/10min, a density ρ A＝0.92g/cm3, a molecular weight distribution index M w/Mn =3.1, a molar content of alpha olefin comonomer=2.1 mol%;
Component B has a melt index MI B.0 g/10min, a density ρ B＝0.92g/cm3, a molecular weight distribution index M w/Mn =3.5, a molar content of alpha olefin comonomer=5.1 mol%;
Component C has a melt index MI C =25 g/10min, a density ρ C＝0.92g/cm3, a molecular weight distribution index M w/Mn =3.2, and a molar content of alpha-olefin comonomer=5.1 mol%.
The lubricant was a PEG lubricant produced by Switzerland Corp, having a number average molecular weight of 10000.
The above-mentioned component A, component B and component C are respectively transferred into different solid/liquid (gas) separators 4 according to the yield ratio of unit time to make phase separation, then transferred into homogenizing bin 5 with stirring, then the lubricant is added according to the ratio to make mixing homogenization. Wherein the lubricant is added in an amount of 0.1 parts by weight based on 100 parts by weight of the total weight of the above-mentioned component A, component B and component C. And then adding the homogenized mixture in a homogenizing bin 5 into a feeder of a double-screw extruder manufactured by Nanjac plong company, feeding the materials into a double screw through the feeder, keeping the temperature of the screw between 160 and 210 ℃ in the processing process, extruding after the materials are melted and mixed uniformly by the screw, granulating and drying to obtain polyethylene base resin granules (PE 103), and detecting the melt index MI=0.6 g/10min.
Edge modified graphene G101
And (3) ultrasonically cleaning 100G of 32-mesh flake graphite powder (washing 1 time with water and 2 times with ethanol) to remove impurity substances and impurity elements, then placing the flake graphite in a high-pressure millstone kettle, sealing the high-pressure millstone kettle, then heating the high-pressure millstone kettle to 40 ℃, pumping CO 2 to enable the pressure in the high-pressure millstone kettle to rise to 85atm, enabling the rotating speed to be 500r/min, grinding and stripping the graphite by utilizing the shearing force generated by the millstone, stirring for 24 hours, reducing the pressure to 1atm within 10 seconds, and sampling from the high-pressure millstone kettle to obtain the edge modified graphene G101.
The prepared edge modified graphene G101 is analyzed by a Scanning Electron Microscope (SEM), the average sheet diameter of the graphene is 12.6 mu m, the average thickness is 3.4nm, and the average aspect ratio is 3706:1, X-ray photoelectron spectroscopy (XPS) characterization, oxygen content of 5.60at%, hydrogen content of 3.22at%, conductivity of 506S/m.
Edge modified graphene G102
And (3) ultrasonically cleaning 40G of 32-mesh expanded graphite powder (washing with water for 1 time and ethanol for 2 times) to remove impurity substances and impurity elements, then placing the expanded graphite powder in a high-pressure millstone kettle, sealing the high-pressure millstone kettle, then heating the high-pressure millstone kettle to 40 ℃, pumping CO 2 to enable the pressure in the high-pressure millstone kettle to rise to 85atm, enabling the rotating speed to be 500r/min, grinding and stripping graphite by utilizing the shearing force generated by the millstone, stirring for 48 hours, reducing the pressure to 1atm within 10 seconds, and sampling from the high-pressure millstone kettle to obtain the edge modified graphene G102.
The prepared edge-modified graphene G102 was analyzed by Scanning Electron Microscopy (SEM), as shown in fig. 1, the graphene had an average sheet diameter of 9.6 μm, an average thickness of 3.2nm, and an average aspect ratio of 3000:1, X-ray photoelectron spectroscopy (XPS) characterization, oxygen content of 7.83at%, hydrogen content of 3.23at% and conductivity of 425S/m.
Edge modified graphene G103
And (3) ultrasonically cleaning 100G of 32-mesh flake graphite powder (washing 1 time with water and 2 times with ethanol) to remove impurity substances and impurity elements, then placing the flake graphite in a high-pressure millstone kettle, sealing the high-pressure millstone kettle, then heating the high-pressure millstone kettle to 70 ℃, pumping CO 2 to enable the pressure in the high-pressure millstone kettle to rise to 125atm, enabling the rotating speed to be 1000r/min, grinding and stripping the graphite by utilizing the shearing force generated by the millstone, stirring for 24 hours, reducing the pressure to 1atm within 10 seconds, and sampling from the high-pressure millstone kettle to obtain the edge modified graphene G103.
The prepared edge modified graphene was analyzed by Scanning Electron Microscopy (SEM), the average sheet diameter of the graphene was 6.2 μm, the average thickness was 2.9nm, and the average aspect ratio was 2138:1, X-ray photoelectron spectroscopy (XPS) characterization, oxygen content 13.40at%, hydrogen content 7.3at% and conductivity 339S/m.
Edge modified graphene G104
And (3) ultrasonically cleaning 100G of 32-mesh flake graphite powder (washing 1 time with water and 2 times with ethanol) to remove impurity substances and impurity elements, then placing the flake graphite in a high-pressure millstone kettle, sealing the high-pressure millstone kettle, then heating the high-pressure millstone kettle to 70 ℃, pumping CO 2 to enable the pressure in the high-pressure millstone kettle to rise to 125atm, enabling the rotating speed to be 1000r/min, grinding and stripping the graphite by utilizing the shearing force generated by the millstone, stirring for 72h, reducing the pressure to 1atm within 10s, and sampling from the high-pressure millstone kettle to obtain the edge modified graphene G104.
The prepared edge-modified graphene was analyzed by Scanning Electron Microscopy (SEM), the average sheet diameter of the graphene was 4.3 μm, the average thickness was 3.18nm, and the average aspect ratio was 1352:1, X-ray photoelectron spectroscopy (XPS) characterization, oxygen content 19.40at%, hydrogen content 9.63at%, conductivity 286S/cm.
Edge modified graphene G105
And (3) ultrasonically cleaning 100G of 32-mesh flake graphite powder (washing 1 time with water and 2 times with ethanol) to remove impurity substances and impurity elements, then placing the flake graphite in a high-pressure millstone kettle, sealing the high-pressure millstone kettle, then heating the high-pressure millstone kettle to 40 ℃, pumping CO 2 to enable the pressure in the high-pressure millstone kettle to rise to 125atm, enabling the rotating speed to be 1000r/min, grinding and stripping the graphite by utilizing the shearing force generated by the millstone, stirring for 16h, reducing the pressure to 1atm within 10s, and sampling from the high-pressure millstone kettle to obtain the edge modified graphene G105.
The prepared edge modified graphene was analyzed by Scanning Electron Microscopy (SEM), the average sheet diameter of the graphene was 14.9 μm, the average thickness was 3.8nm, and the average aspect ratio was 3921:1, X-ray photoelectron spectroscopy (XPS) characterization, oxygen content 4.32at%, hydrogen content 2.35at% and conductivity 536S/m.
Expanded beads, molded article examples and comparative examples
Mixing edge modified graphene and an antioxidant (hindered phenol antioxidant 1010: phosphite antioxidant 168=1:1 (weight ratio)) uniformly in 0.1 weight part and glycerol monostearate uniformly in 0.5 weight part according to the proportion in table 1, and stirring by a dry powder machine to obtain uniformly mixed powder; the above mixed powder was mixed with polypropylene or polyethylene in the type and ratio of table 1 in a high-speed mixer. And (3) adding the mixed materials into a double-screw extruder for melting, wherein the rotation speed of the double screw is 300rpm, then, entering a LabLine microparticle preparation system, controlling the torque to be about 65%, and granulating under water to obtain polypropylene or polyethylene resin microparticles.
In an autoclave, 100 parts by weight of polypropylene or polyethylene resin fine particles were added and mixed with 3000 parts by weight of a dispersion medium (deionized water), 0.3 parts by weight of a surfactant (sodium dodecylbenzenesulfonate), 3 parts by weight of a dispersant (kaolin) and 0.2 parts by weight of a dispersion enhancer (aluminum sulfate) at once; discharging residual air in the reaction kettle by using an inert foaming agent (CO 2 or nitrogen, see table 1), removing the air in the reaction kettle, and then covering the kettle cover tightly; feeding an inert blowing agent into the autoclave, initially adjusting the pressure until it stabilizes; the dispersion in the autoclave was then stirred and heated at a constant speed to a temperature between 0.5 and 1 ℃ below the expansion temperature. Then, adjusting the pressure in the kettle to reach the pressure required by foaming; raising the temperature to a foaming temperature at an average heating rate of 0.1 ℃/min; stirring is continued for 0.25-0.5 hours under foaming temperature and pressure conditions. Then, opening a discharge hole of the autoclave to drain the materials in the autoclave to a collecting tank so as to obtain polyethylene or polypropylene foaming beads; the discharge was carried out while feeding carbon dioxide gas so that the pressure in the autoclave was kept around the foaming pressure before the whole particles were completely foamed and entered the collecting tank.
Test case
The density and cell density of the expanded beads were measured, and the compressive strength and surface resistivity of the expanded bead molded body were measured, and the results are shown in Table 1. The small-sized graphene used in comparative examples 4 and 11 was prepared by the method described in US20130018204, and the conductivity was 1.09S/m, the aspect ratio was 10:1 to 50:1, the average aspect ratio was 32:1, and the scanning electron microscope chart was shown in fig. 2. Examples 1-9, 21-23 relate to polypropylene grafts of glycidyl methacrylate grafted polypropylene (2.6% grafting), polypropylene matrix and polypropylene base resin, and examples 11-19, 24-25 relate to polyethylene grafts of glycidyl methacrylate grafted polyethylene (2.6% grafting), polyethylene matrix and polyethylene base resin. A scanning electron micrograph of the cells of the polyolefin foam beads obtained in example 7 is shown in FIG. 3.
As can be seen from the data shown in table 1, the polypropylene or polyethylene expanded beads of the present invention using the edge-modified graphene as the cell nucleating agent and the antistatic agent have lower density, have higher cell density, and have excellent antistatic property and mechanical property. Even if polypropylene or polyethylene graft copolymer is not added, the polypropylene or polyethylene expanded beads related in the examples show higher expansion ratio, antistatic property and mechanical property.
The polypropylene or polyethylene expanded bead molded body of the present invention using the edge-modified graphene is significantly better in compression performance and antistatic performance than the polypropylene or polyethylene expanded bead molded body using the chemically exfoliated graphene or carbon black as an antistatic agent at the same addition amount.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (33)
1. The polyolefin composition is characterized by comprising polyolefin and edge modified graphene, wherein the content of the edge modified graphene is 0.05-5 parts by weight based on 100 parts by weight of polyolefin; the average sheet diameter of the edge modified graphene is 5-15 mu m, and the average aspect ratio is 1500-3800:1, the conductivity is 300-600S/m; in the edge modified graphene, the oxygen content is 5-18at% calculated by oxygen element, and the hydrogen content is 3-8at% calculated by hydrogen element;
the polyolefin composition further comprises the following components:
0.1-0.3 part by weight of an antioxidant;
0.05-1 parts by weight of a dispersing agent;
1-5 parts by weight of grafted polyolefin;
the olefin structural unit of the grafted polyolefin and the olefin structural unit of the polyolefin are the same kind of olefin structural unit;
The grafted polyolefin is a polar monomer grafted modified polyolefin;
the polar monomer is at least one selected from glycidyl methacrylate, maleic anhydride and methyl acrylate;
the grafting rate of the grafted polyolefin is 0.5-6wt%.
2. The polyolefin composition of claim 1, wherein the edge-modified graphene is prepared by grinding graphite by a grinding disc under supercritical carbon dioxide.
3. The polyolefin composition of claim 2, wherein the edge-modified graphene is made by a process comprising the steps of: the graphite powder is milled in a high pressure millstone kettle in the presence of supercritical carbon dioxide.
4. A polyolefin composition according to claim 3 wherein the graphite powder is selected from flake graphite powder and/or expanded graphite powder.
5. The polyolefin composition according to claim 4, wherein the particle size of the graphite powder is 10 to 80 mesh.
6. The polyolefin composition according to claim 5, wherein the graphite powder has a particle size of 20 to 60 mesh.
7. A polyolefin composition according to claim 3, wherein the edge modified graphene is made by a process comprising the steps of:
step S1, adding purified or unpurified graphite powder into a high-pressure millstone kettle;
Step S2, introducing carbon dioxide into a high-pressure millstone kettle, and enabling the carbon dioxide to be in a supercritical state to form a material containing graphite powder and supercritical carbon dioxide;
and step S3, grinding the material containing graphite powder and supercritical carbon dioxide.
8. The polyolefin composition according to claim 7, wherein in step S2, carbon dioxide is brought into a supercritical state by bringing the temperature in the tank to over 32.26 ℃ and the pressure to over 72.9 atm.
9. The polyolefin composition according to claim 8, wherein in step S3, after finishing the grinding, the pressure in the autoclave is rapidly decreased.
10. The polyolefin composition according to claim 9, wherein the pressure in the autoclave is reduced to below 1atm in 5-20 seconds.
11. The polyolefin composition according to claim 7, wherein the temperature in the autoclave is from 35 to 200 ℃; a pressure of 75-165atm; the stirring speed is 500-10000r/min; the grinding time is 6-48 hours.
12. The polyolefin composition according to claim 11, wherein the temperature is from 35 to 100 ℃ and the stirring speed is from 500 to 5000r/min.
13. The polyolefin composition according to claim 12, wherein the temperature is 35-70 ℃ and the pressure is 75-125atm.
14. The polyolefin composition according to claim 1, wherein the edge-modified graphene is contained in an amount of 0.1to 2 parts by weight based on 100 parts by weight of the polyolefin.
15. The polyolefin composition according to claim 1, wherein the grafted polyolefin has a grafting ratio of 1 to 3wt%.
16. The polyolefin composition of claim 1, wherein the polyolefin is polypropylene and the grafted polyolefin is grafted polypropylene; or alternatively
The polyolefin is polyethylene, and the grafted polyolefin is grafted polyethylene.
17. The polyolefin composition according to claim 16, wherein the polypropylene is a random copolymer polypropylene having a melt index of 5-9g/10min and a molecular weight distribution of 5-20 at a temperature of 230 ℃ and a load of 2.16 kg.
18. The polyolefin composition of claim 16, wherein the polyethylene has a melt index of 0.1-20g/10min at 190 ℃ and 2.16kg load.
19. The polyolefin composition according to claim 18, wherein the polyethylene has a melt index of 0.5-10g/10min at 190 ℃ and 2.16kg load.
20. The polyolefin composition of claim 16, wherein the polyethylene contains component a, component B, and component C;
The component A is linear low density polyethylene copolymerized by ethylene-alpha olefin, and the melt index MI A measured at 190 ℃ and 2.16kg load of the component A is 0.01-2g/10min; the density ρ A of the component A is 0.880-0.936g/cm 3;
The component B is linear low density polyethylene copolymerized by ethylene-alpha olefin, and the melt index MI B measured at 190 ℃ and 2.16kg load is 2.1-14.9g/10min; the density ρ B of the component B is 0.910-0.930g/cm 3;
The component C is linear low density polyethylene copolymerized by ethylene-alpha olefin, and the melt index MI C of the component C measured at 190 ℃ under 2.16kg load is 15-150g/10min; the density ρ C of the component C is 0.880-0.930g/cm 3.
21. The polyolefin composition of claim 20, wherein the component a is an ethylene-alpha olefin copolymerized linear low density polyethylene having a melt index MI A of 0.01-1.5g/10min measured at a temperature of 190 ℃ and a load of 2.16 kg; the density ρ A of the component a is 0.910-0.930g/cm 3;
The component B is linear low density polyethylene copolymerized by ethylene-alpha olefin, and the melt index MI B measured at 190 ℃ and 2.16kg load of the component B is 3-10g/10min; the density rho B of the component B is 0.913-0.928g/cm 3;
The component C is linear low density polyethylene copolymerized by ethylene-alpha olefin, and the melt index MI C of the component C measured at 190 ℃ under 2.16kg load is 15-100g/10min; the density ρ C of the component C is 0.905-0.928g/cm 3.
22. The polyolefin composition according to claim 21, wherein the component a is a linear low density polyethylene copolymerized with ethylene-a-olefins, the component a having a melt index MI A of 0.01-1g/10min measured at a temperature of 190 ℃ and a load of 2.16 kg; the density rho A of the component A is 0.915-0.926g/cm 3;
The component B is linear low density polyethylene copolymerized by ethylene-alpha olefin, and the melt index MI B measured at 190 ℃ and under 2.16kg load is 3-5g/10min; the density rho B of the component B is 0.913-0.924g/cm 3;
The component C is linear low density polyethylene copolymerized by ethylene-alpha olefin, and the melt index MI C of the component C measured at 190 ℃ under 2.16kg load is 20-60g/10min; the density ρ C of the component C is 0.910-0.926g/cm 3.
23. The polyolefin composition of claim 20, wherein the relationship between the densities ρ A、ρB and ρ C of component a, component B and component C satisfies-0.04+.ρ A-ρB +.0.02 and-0.04+.ρ A-ρC +.0.02.
24. The polyolefin composition according to claim 20, wherein in the polyethylene base resin, the part by weight of the component a, W A, is 25 to 90 parts by weight, the part by weight of the component B, W B, is 0.1 to 10 parts by weight, and the part by weight of the component C, W C, is 10 to 75 parts by weight.
25. The polyolefin composition according to claim 24, wherein in the polyethylene base resin, the part by weight of W A of the component a is 30 to 80 parts by weight, the part by weight of W B of the component B is 0.5 to 8 parts by weight, and the part by weight of W C of the component C is 20 to 70 parts by weight.
26. The polyolefin composition according to claim 24, wherein the parts by weight of component a W A, the parts by weight of component C W C and the melt index MI A of component a satisfy 5.2 x lgMI A+11.6≥WA/WC≥0.9×lgMIA +2.1.
27. The polyolefin composition according to claim 26, wherein the parts by weight of component a W A, the parts by weight of component C W C and the melt index MI A of component a satisfy 2.9 x lgMI A+6.8≥WA/WC≥1.1×lgMIA +2.7.
28. The polyolefin composition according to claim 20, wherein the molecular weight distribution index of each of the component A, component B and component C satisfies M w/Mn.ltoreq.4.5.
29. The polyolefin composition of claim 28, wherein the molecular weight distribution index of each of component a, component B, and component C satisfies 2.0.ltoreq.m w/Mn.ltoreq.4.2.
30. Polyolefin expanded beads, characterized in that they are obtained by granulating and then expanding the polyolefin composition according to any one of claims 1to 29.
31. The polyolefin expanded beads of claim 30 wherein the foaming process is a kettle dip foaming process.
32. The polyolefin expanded beads of claim 31, wherein the blowing agent is carbon dioxide or nitrogen.
33. A polyolefin expanded bead molded body obtained by molding the polyolefin expanded beads according to any one of claims 30 to 32.
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| CN107651669A (en) * | 2017-09-22 | 2018-02-02 | 北京化工大学 | A kind of method reacted mill method and prepare edge carboxylated graphene and graphene |
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