CN102952309A - Improved short carbon fiber reinforced polyolefin composite material and preparation method thereof - Google Patents
Improved short carbon fiber reinforced polyolefin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an improved short carbon fiber reinforced polyolefin composite material and a preparation method thereof. With the adoption of the method, 20-75wt% of polyolefin, 7-40wt% of short carbon fibers, 2-20wt% of compatibilizer, 5-20% of epoxy resin and 0.2-5% of curing agent are mixed or extruded to be pelleted, so as to obtain the short carbon fiber reinforced polyolefin composite material. With the adoption of the method, the epoxy resin is cured on the surface of the short carbon fibers to form a coating layer, roughness of the short carbon fibers is improved, and even the epoxy resin is cured between the short carbon fibers and is connected with a plurality of short carbon fibers to form continuous spatial networks in a small range, thus greatly enhancing the interface effect between matrices of composition materials and the short carbon fibers, and being beneficial to transmission of stress between the short carbon fibers, thereby obviously improving mechanical performance of the material.
Description
Technical field
The present invention relates to carbon fiber and strengthen the composite polyolefine material technical field, particularly a kind of modification chopped carbon fiber strengthens composite polyolefine material and preparation method thereof.
Background technology
Carbon fiber is that carbon content is higher than 90% inorganic polymer fiber, is a kind of novel material of mechanical property excellence.Along with the development of China's carbon fiber industry, carbon fiber-reinforced resin composite materials is just with the strong and vigorous paces civilian industry of marching toward.Carbon fiber-reinforced resin composite materials is a kind of high performance lightweight structural material, has broad application prospects in fields such as the vehicles and wind-powered electricity generations.Traditional carbon fiber-reinforced resin composite materials is that continuous fibre is as strengthening body, take thermosetting resin as body material take macrofiber mainly.In recent years, because high, the good combination property of material preparation efficiency, product molding and welding and reprocessing technique are simple and low cost and other advantages, chopped carbon fiber strengthens the thermoplas tic resin composite such as chopped carbon fiber strengthens composite polyolefine material, is paid close attention to more and more widely.Along with the development of carbon fiber recovery technology, more carbon fibers are recovered with the form of chopped strand, and this is so that the research that chopped carbon fiber is strengthened the thermoplas tic resin composite has practical significance more.But, chopped carbon fiber is often inferior a lot of than the enhancing ability of continuous carbon fibre, mainly is because chopped carbon fiber can not form continuous network, can not become the continuous main body of bearing stress, stress is only born by single fiber, the as easy as rolling off a log fracture of fiber or be pulled out from matrix.Therefore, enhancing ability how to improve chopped carbon fiber remains needs a major issue solving.
Strengthen composite polyolefine material for chopped carbon fiber, it is considered to replace the high-performance light novel material of carbon steel in automotive industry.But, because the smooth surface of chopped carbon fiber, the surface oxy radical is less, and polyolefinic molecular chain is apolar chain, but and lack reactive group, a little less than causing both interface interactions, be difficult to set up effective stress transmission at interface zone, the mechanical property that chopped carbon fiber strengthens composite polyolefine material often can not get Effective Raise.In order to solve above technical problem, Granted publication number discloses a kind of preparation method of rare earth modified carbon fiber/polypropylene composite material for the Chinese patent literature of CN100368471C, the method immerses carbon fiber first and soaks 2 ~ 4 hours in the rare-earth modifier, filters post-drying; With the carbon fiber after processing by weight percentage 10% ~ 20% with 79% ~ 89% polypropylene, 1% ~ 10% molybdenumdisulphide carries out mechanical blending, then mixed powder is put into plate vulcanization machine die for molding, furnace temperature is warming up to 110 ℃ first, kept 60 minutes, the premolding blank is carried out preformed, pressure-controlling is at 10MPa ~ 14MPa, and then be warming up to 190 ℃ ~ 220 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding, pressure is removed after adopting subsequently mode with stove cooling to cool to 80 ℃, the matrix material after the compression molding is come along together with mould remove, with the room temperature cooling, obtain rare earth modified carbon fiber/polypropylene composite material; The weight percentages of components of described rare-earth modifier is: rare earth compound 0.1% ~ 2%, alcohol 95 % ~ 99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05% ~ 0.5%, ammonium chloride 0.1% ~ 1%, nitric acid 0.02% ~ 0.5%, urea 0.03% ~ 1%; Wherein, described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide; Described carbon fiber is PAN-based carbon fiber, and polypropylene is homopolymerization type polypropylene or copolymerized type propene polymer.
The matrix material that aforesaid method makes has good mechanical property and tribological property, but, aforesaid method only carries out simple surface treatment to chopped carbon fiber, chopped carbon fiber has discontinuity, the stress of material can only transmit in short range, so that the amplitude that the mechanical property of material improves is limited, still be further improved.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of modification chopped carbon fiber and strengthen composite polyolefine material and preparation method thereof, the modification chopped carbon fiber of the method preparation strengthens composite polyolefine material and has higher mechanical property.
The invention provides a kind of modification chopped carbon fiber and strengthen composite polyolefine material, made through mixing or extruding pelletization by the chopped carbon fiber polyolefin blend, described chopped carbon fiber polyolefin blend comprises:
The polyolefine of 20wt% ~ 75wt%;
The chopped carbon fiber of 7wt% ~ 40wt%;
The expanding material of 2wt% ~ 20wt%;
The Resins, epoxy of 5wt% ~ 20wt%;
The solidifying agent of 0.2wt% ~ 5wt%.
The invention provides the preparation method that a kind of modification chopped carbon fiber strengthens composite polyolefine material, may further comprise the steps:
The polyolefine of 20wt% ~ 75wt%, the chopped carbon fiber of 7wt% ~ 40wt%, the expanding material of 2wt% ~ 20wt%, the Resins, epoxy of 5wt% ~ 20wt% and the solidifying agent of 0.2wt% ~ 5wt% are carried out mixing or extruding pelletization, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
Preferably, described mixing comprising:
Described polyolefine and expanding material are carried out blend under 160 ℃ ~ 200 ℃ condition, after 2 minutes ~ 5 minutes, obtain the first blend;
Described the first blend and described Resins, epoxy and chopped carbon fiber are carried out blend, after 2 minutes ~ 8 minutes, obtain the second blend;
Described the second blend and described solidifying agent are carried out blend, after 2 minutes ~ 8 minutes, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
Preferably, described extruding pelletization comprises:
Described polyolefine, expanding material, chopped carbon fiber and Resins, epoxy are mixed under 80 ℃ ~ 120 ℃ condition, then under 160 ℃ ~ 210 ℃ condition, carry out extruding pelletization, obtain extruding particle;
The described particle of extruding is mixed under 80 ℃ ~ 120 ℃ condition with described solidifying agent, then under 160 ℃ ~ 210 ℃ condition, carry out extruding pelletization, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
Preferably, when carrying out mixing or extruding pelletization, also comprise adding at least a in lubricant and the oxidation inhibitor.
Preferably, described solidifying agent is selected from one or more in dicyanamide, imidazoles, 2-ethyl-4 Methylimidazole and the adipic dihydrazide.
Preferably, described expanding material is selected from one or more in maleic anhydride stem grafting polyolefin, maleic anhydride graft terpolymer EP rubber and the ethylene vinyl acetate.
Preferably, the length of described chopped carbon fiber is 2mm ~ 20mm.
Preferably, described polyolefine is at least a in polyethylene and the polypropylene.
Preferably, described Resins, epoxy is Resins, epoxy E51.
Compared with prior art, the present invention carries out mixing or extruding pelletization with the polyolefine of 20wt% ~ 75wt%, the chopped carbon fiber of 7wt% ~ 40wt%, the expanding material of 2wt% ~ 20wt%, the Resins, epoxy of 5wt% ~ 20wt% and the solidifying agent of 0.2wt% ~ 5wt%, obtains the modification chopped carbon fiber and strengthens composite polyolefine material.The present invention adds the Resins, epoxy of above-mentioned amount ranges in the course of processing of chopped carbon fiber enhancing composite polyolefine material, oxy radical by the epoxide group in the Resins, epoxy and chopped carbon fiber surface reacts on the one hand, make epoxy resin graft on the chopped carbon fiber surface, the recycling expanding material improves the consistency between polyolefine and the Resins, epoxy, thereby set up effective stress pipeline between polyolefine-expanding material-Resins, epoxy-chopped carbon fiber interface, the stress transfer efficiency is improved greatly; On the other hand, the Resins, epoxy that the present invention adds is cured by solidifying agent, make epoxy resin cure on the chopped carbon fiber surface, thereby form coating layer, improved the roughness of chopped carbon fiber, even be solidificated between the chopped carbon fiber, connect a plurality of chopped carbon fibers, form continuous space network among a small circle, greatly strengthened the interface interaction between matrices of composite material and the chopped carbon fiber, and be conducive to stress and between carbon fiber, transmit, thereby significantly improve the mechanical property of material.Experimental result shows, the mechanical property excellence of modification chopped carbon fiber enhancing composite polyolefine material provided by the invention.
Description of drawings
Fig. 1 is the composite manufacture method flow diagram that one embodiment of the invention provides;
Fig. 2 is the composite manufacture method flow diagram that another embodiment of the present invention provides;
Fig. 3 is the profile scanning electromicroscopic photograph of the matrix material that obtains of the embodiment of the invention 1;
To be the embodiment of the invention 1 matrix material fall carbon fiber surface stereoscan photograph behind the polypropylene with xylene soluble to Fig. 4;
Fig. 5 is the profile scanning electromicroscopic photograph of the matrix material that obtains of comparative example 1 of the present invention;
To be comparative example 1 matrix material of the present invention fall carbon fiber surface stereoscan photograph behind the polypropylene with xylene soluble to Fig. 6.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The invention provides a kind of modification chopped carbon fiber and strengthen composite polyolefine material, made through mixing or extruding pelletization by the chopped carbon fiber polyolefin blend, described chopped carbon fiber polyolefin blend comprises:
The polyolefine of 20wt% ~ 75wt%;
The chopped carbon fiber of 7wt% ~ 40wt%;
The expanding material of 2wt% ~ 20wt%;
The Resins, epoxy of 5wt% ~ 20wt%;
The solidifying agent of 0.2wt% ~ 5wt%.
The present invention adopts Resins, epoxy that chopped carbon fiber is strengthened composite polyolefine material and assists enhancing, has further improved the mechanical property of matrix material, is beneficial to application.
In the present invention, described chopped carbon fiber polyolefin blend comprises the polyolefine of 20wt% ~ 75wt%, preferably comprises the polyolefine of 40wt% ~ 60wt%.The present invention is take polyolefine as body material, polyolefine is as thermoplastics, have that chemical resistance is strong, tenacity excellent, stress cracking resistance is good and flexible life than advantages of higher, it is a kind of comparatively ideal body material that chopped carbon fiber strengthens the thermoplas tic resin composite for preparing, and the polyolefine low price, raw material is easy to get.The present invention adopts this area polyolefine commonly used to get final product, and described polyolefine is preferably at least a in polyethylene and the polypropylene.
Described chopped carbon fiber polyolefin blend comprises the chopped carbon fiber of 7wt% ~ 40wt%, preferably comprises the chopped carbon fiber of 10wt% ~ 30wt%.The chopped carbon fiber mechanical property is excellent, can bear load, plays the effect of reinforced composite, make composites present the feature of high strength, high-modulus, and chopped carbon fiber is easy to reclaim.The present invention adopts this area chopped carbon fiber commonly used to get final product, and the length of described chopped carbon fiber is preferably 2mm ~ 20mm, more preferably 5mm ~ 15mm.
Described chopped carbon fiber polyolefin blend comprises the Resins, epoxy of 5wt% ~ 20wt%, preferably comprises the Resins, epoxy of 10wt% ~ 15wt%.In the present invention, epoxide group in the Resins, epoxy can react with the oxy radical on chopped carbon fiber surface, make epoxy resin graft on the chopped carbon fiber surface, the recycling expanding material improves the consistency between polyolefine and the Resins, epoxy, thereby set up effective stress pipeline between polyolefine-expanding material-Resins, epoxy-chopped carbon fiber interface, the stress transfer efficiency is improved greatly; Simultaneously, Resins, epoxy is cured by solidifying agent, make the Resins, epoxy after the curing be coated on the chopped carbon fiber surface, even between a plurality of chopped carbon fibers, solidify, thereby chopped carbon fiber is linked together, form spacial framework, stress can directly be transmitted between a plurality of carbon fibers, greatly improved the mechanical property of matrix material.The present invention does not have particular restriction to described Resins, epoxy, and described Resins, epoxy is preferably Resins, epoxy E51.
Described chopped carbon fiber polyolefin blend comprises the expanding material of 2wt% ~ 20wt%, preferably comprises the expanding material of 10wt% ~ 15wt%.In the present invention, expanding material can impel polyolefine to combine with Resins, epoxy, and then is beneficial to the mechanical property that improves material.Described expanding material is preferably one or more in maleic anhydride stem grafting polyolefin, maleic anhydride graft terpolymer EP rubber and the ethylene vinyl acetate, more preferably maleic anhydride stem grafting polyolefin such as maleic anhydride inoculated polypropylene and maleic anhydride grafted polyethylene etc., or the maleic anhydride graft terpolymer EP rubber, compatible effect is better.
Described chopped carbon fiber polyolefin blend comprises the solidifying agent of 0.2wt% ~ 5wt%, preferably comprises the solidifying agent of 1wt% ~ 4wt%.In the present invention, solidifying agent and Resins, epoxy react, and form netted space polymer, make epoxy resin cure and bring into play auxiliary enhancement, and then the mechanical property of matrix material is significantly increased.Described solidifying agent is preferably one or more in dicyanamide, imidazoles, 2-ethyl-4 Methylimidazole and the adipic dihydrazide.
For processing characteristics and the application performance that improves matrix material, described chopped carbon fiber polyolefin blend preferably also comprises at least a in lubricant and the oxidation inhibitor.The kind of described lubricant and consumption can be adjusted as required, lubricant commonly used comprises paraffin, polyethylene wax, metallic soap, hydro carbons, silicoorganic compound, lipid acid and ester and fatty acid amide etc., such as stearic acid, butyl stearate, oleylamide and ethylene bis stearamide, consumption is generally 0.5wt% ~ 1wt%.Described oxidation inhibitor can be in phenolic antioxidant, amine antioxidants and the phosphite ester kind antioxidant one or more, preferably with the Hinered phenols antioxidant in the phenolic antioxidant and the composite use of phosphite ester kind antioxidant, effect is better, and the present invention more preferably adopts composite antioxidant B215; Wherein, described phenolic antioxidant includes but not limited to antioxidant 1076, antioxidant 264, oxidation inhibitor 2264, antioxidant 1010 and antioxidant BHT, described amine antioxidants includes but not limited to oxidation inhibitor H, oxidation inhibitor 4010, oxidation inhibitor D and oxidation inhibitor DNP, and described phosphite ester kind antioxidant includes but not limited to oxidation inhibitor TPP, antioxidant TNP P, oxidation inhibitor ST-1500 and oxidation inhibitor 3010.
Modification chopped carbon fiber provided by the invention strengthens composite polyolefine material and mainly is comprised of polyolefine, chopped carbon fiber, expanding material, Resins, epoxy and solidifying agent, described modification chopped carbon fiber strengthens composite polyolefine material take polyolefine as body material, take chopped carbon fiber as strongthener, Resins, epoxy after the curing is coated on described chopped carbon fiber surface, thereby has preferably mechanical property.
The invention provides the preparation method that a kind of modification chopped carbon fiber strengthens composite polyolefine material, may further comprise the steps:
The polyolefine of 20wt% ~ 75wt%, the chopped carbon fiber of 7wt% ~ 40wt%, the expanding material of 2wt% ~ 20wt%, the Resins, epoxy of 5wt% ~ 20wt% and the solidifying agent of 0.2wt% ~ 5wt% are carried out mixing or extruding pelletization, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
It is raw material that the present invention mainly adopts polyolefine, chopped carbon fiber, expanding material, Resins, epoxy and solidifying agent, by mixing or extruding pelletization, prepares the modification chopped carbon fiber and strengthens composite polyolefine material, and it has preferably mechanical property, is beneficial to application.
In the present invention, described raw material is consistent with previously described content, gives unnecessary details no longer one by one at this.When carrying out mixing or extruding pelletization, the present invention preferably also comprises and adds at least a in lubricant and the oxidation inhibitor, can improve processing characteristics and the application performance of matrix material.
The present invention can carry out described raw material mixing, and described mixing can carrying out in Banbury mixer obtains the modification chopped carbon fiber and strengthen composite polyolefine material.In the present invention, described mixing preferably including:
Described polyolefine and expanding material are carried out blend under 160 ℃ ~ 200 ℃ condition, after 2 minutes ~ 5 minutes, obtain the first blend;
Described the first blend and described Resins, epoxy and chopped carbon fiber are carried out blend, after 2 minutes ~ 8 minutes, obtain the second blend;
Described the second blend and described solidifying agent are carried out blend, after 2 minutes ~ 8 minutes, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
Fig. 1 is the composite manufacture method flow diagram that one embodiment of the invention provides, referring to Fig. 1, the embodiment of the invention at first drops into polyolefine, expanding material, lubricant and oxidation inhibitor in the Banbury mixer, be 160 ℃ ~ 200 ℃ in temperature, be preferably mixed melting under 170 ℃ ~ 190 ℃ the condition, after 2 minutes ~ 5 minutes, add Resins, epoxy and chopped carbon fiber and continue blend, after 2 minutes ~ 8 minutes, add again solidifying agent and continue blend, after 2 minutes ~ 8 minutes, discharging, pelletizing obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
The present invention adds the later stage of solidifying agent at melt blending in the preparation method who uses Banbury mixer, namely utilizes the dynamical cure technology to prepare the modification chopped carbon fiber and strengthens composite polyolefine material.The present invention is by the control to the course of processing, make the Resins, epoxy after the curing be coated on the chopped carbon fiber surface, even between a plurality of chopped carbon fibers, solidify, chopped carbon fiber is linked together, form spacial framework, stress can directly be transmitted between a plurality of carbon fibers, greatly improved the mechanical property of matrix material.
The present invention also can carry out extruding pelletization with described raw material, and described extruding pelletization can utilize kneader and screw extrusion press to carry out, and obtains the modification chopped carbon fiber and strengthens composite polyolefine material.In the present invention, described extruding pelletization preferably includes:
Described polyolefine, expanding material, chopped carbon fiber and Resins, epoxy are mixed under 80 ℃ ~ 120 ℃ condition, then under 160 ℃ ~ 210 ℃ condition, carry out extruding pelletization, obtain extruding particle;
The described particle of extruding is mixed under 80 ℃ ~ 120 ℃ condition with described solidifying agent, then under 160 ℃ ~ 210 ℃ condition, carry out extruding pelletization, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
Fig. 2 is the composite manufacture method flow diagram that another embodiment of the present invention provides, referring to Fig. 2, the embodiment of the invention is at first with polyolefine, expanding material, Resins, epoxy, chopped carbon fiber, lubricant and oxidation inhibitor are in 80 ℃ ~ 120 ℃, in kneader, mix under preferred 100 ℃ ~ 110 ℃, then put in the screw extrusion press, it is extruding pelletization under 160 ℃ ~ 210 ℃ the condition in each zone temperatures scope of screw rod, obtain extruding particle, what will obtain extrudes particle and solidifying agent in 80 ℃ ~ 120 ℃ again, in kneader, mix under preferred 100 ℃ ~ 110 ℃, carry out extruding pelletization with the screw extrusion press of each district's temperature between 160 ℃ ~ 210 ℃ again, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
The present invention is in the preparation method who uses screw extrusion press; first the material except solidifying agent is once extruded; then the particle of solidifying agent and the first step being extruded mixes; carry out again extruding the second time afterwards processing, namely utilize the dynamical cure technology to prepare the modification chopped carbon fiber and strengthen composite polyolefine material.In the course of processing, the Resins, epoxy that the present invention adds is cured by solidifying agent, make epoxy resin cure on the chopped carbon fiber surface, thereby form coating layer, improved the roughness of chopped carbon fiber, even be solidificated between the chopped carbon fiber, connect a plurality of chopped carbon fibers, form continuous space network among a small circle, greatly strengthened the interface interaction between matrices of composite material and the chopped carbon fiber, and be conducive to stress and between carbon fiber, transmit, thereby significantly improve the mechanical property of material.
After obtaining modification chopped carbon fiber enhancing composite polyolefine material, the present invention is to its structure and Performance Detection.The present invention observes the structure of described matrix material by sem test, and according to the mechanical property of the described matrix material of following standard detection: GB/T9341-2000 " Plastics-Oetermination of flexural properties method ", GB/T2918-1998 " standard environment of plastics testing status adjustment and test ", GB/T17037-2003 " preparation of thermoplastic material injection moulding sample ", ISO179-2000 " mensuration of plastics simple beam impact strength ", ISO 527-1993 " mensuration of plastic tensile performance ".Detected result shows, modification chopped carbon fiber provided by the invention strengthens composite polyolefine material and has excellent mechanical property.
In order further to understand the present invention, below in conjunction with embodiment modification chopped carbon fiber provided by the invention is strengthened composite polyolefine material and preparation method thereof and specifically describe.
Used polypropylene is PetroChina Company Limited.'s the Kunlun acrylic resin in following examples, trade mark T30S; Polyethylene is China Petrochemical Industry's Yanshan Mountain polyvinyl resin, trade mark LD400; Resins, epoxy is available from Lanxing Chemical New Material Co., Ltd., trade mark WSR618; Chopped carbon fiber is available from Shanghai Ying Jia special fibre Materials Co., Ltd.
27g polypropylene and 4.4g maleic anhydride inoculated polypropylene are dropped in the Banbury mixer, it is mixed melting under 190 ℃ the condition in temperature, after 2 minutes, adding 5.2g Resins, epoxy E51 and 13.2g length is the chopped carbon fiber continuation blend of 6mm, after 2 minutes, add the 0.2g imidazoles again and continue blend, after 4 minutes, discharging obtains modification chopped carbon fiber reinforced polypropylene compound material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Fig. 3 is the profile scanning electromicroscopic photograph of the matrix material that obtains of the embodiment of the invention 1, to be the embodiment of the invention 1 matrix material fall carbon fiber surface stereoscan photograph behind the polypropylene with xylene soluble to Fig. 4, by Fig. 3 and Fig. 4 as can be known, described matrix material is take polypropylene as body material, take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on the surface of described chopped carbon fiber.
The tensile strength of described matrix material is 95MPa, and tensile modulus is 3.5GPa, and flexural strength is 102MPa, and notched Izod impact strength is 4.2kJ/m
2, show that it has excellent mechanical property.
Comparative example 1
32.4g polypropylene and 4.4g maleic anhydride inoculated polypropylene are dropped in the Banbury mixer, be mixed melting under 190 ℃ the condition in temperature, after 2 minutes, the chopped carbon fiber that adds 13.2g length and be 6mm continues blend, after 4 minutes, discharging obtains the chopped carbon fiber reinforced polypropylene compound material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Fig. 5 is the profile scanning electromicroscopic photograph of the matrix material that obtains of comparative example 1 of the present invention, to be comparative example 1 matrix material of the present invention fall carbon fiber surface stereoscan photograph behind the polypropylene with xylene soluble to Fig. 6, by Fig. 5 and Fig. 6 as can be known, described matrix material is take polypropylene as body material, take chopped carbon fiber as strongthener, described chopped carbon fiber smooth surface.
The tensile strength of described matrix material is 52MPa, and tensile modulus is 1.2GPa, and flexural strength is 59MPa, and notched Izod impact strength is 2.2kJ/m
2Comparative example 1 does not add Resins, epoxy and assists enhancing, and the mechanical property of the matrix material that makes is starkly lower than the mechanical property of the matrix material of embodiment 1 preparation.
Comparative example 2
27.2g polypropylene and 4.4g maleic anhydride inoculated polypropylene are dropped in the Banbury mixer, it is mixed melting under 190 ℃ the condition in temperature, after 2 minutes, adding 5.2g Resins, epoxy E51 and 13.2g length is the chopped carbon fiber continuation blend of 6mm, after 4 minutes, discharging obtains the chopped carbon fiber reinforced polypropylene compound material.
After obtaining described matrix material, according to method mentioned above to its Performance Detection.The detected result demonstration, the tensile strength of described matrix material is 44MPa, and tensile modulus is 1.0GPa, and flexural strength is 48MPa, and notched Izod impact strength is 1.9kJ/m
2Comparative example 2 has added Resins, epoxy, but Resins, epoxy is not cured processing, and the mechanical property of the matrix material that makes is starkly lower than the mechanical property of the matrix material of embodiment 1 preparation.
Embodiment 2
10g polyethylene, 10g maleic anhydride grafted polyethylene, 0.2g composite antioxidant B215 and 1g paraffin are dropped in the Banbury mixer, it is mixed melting under 160 ℃ the condition in temperature, after 2 minutes, adding 10g Resins, epoxy E51 and 16.3g length is the chopped carbon fiber continuation blend of 20mm, after 8 minutes, add 2.5g2-ethyl-4 Methylimidazole again and continue blend, after 8 minutes, discharging obtains modification chopped carbon fiber enhanced polyethylene matrix material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Described matrix material is take polyethylene as body material, and take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on the surface of described chopped carbon fiber.
The tensile strength of described matrix material is 72MPa, and tensile modulus is 2.4GPa, and flexural strength is 75MPa, and notched Izod impact strength is 3.2kJ/m
2, show that it has excellent mechanical property.
Comparative example 3
10g polyethylene, 10g maleic anhydride grafted polyethylene, 0.2g composite antioxidant B215 and 1g paraffin are dropped in the Banbury mixer, it is mixed melting under 160 ℃ the condition in temperature, after 2 minutes, adding 10g Resins, epoxy E51 and 16.3g length is the chopped carbon fiber continuation blend of 20mm, after 8 minutes, discharging obtains chopped carbon fiber enhanced polyethylene matrix material.
After obtaining described matrix material, according to method mentioned above to its Performance Detection.The detected result demonstration, the tensile strength of described matrix material is 27MPa, and tensile modulus is 0.6GPa, and flexural strength is 31MPa, and notched Izod impact strength is 1.31kJ/m
2Comparative example 3 has added Resins, epoxy, but Resins, epoxy is not cured processing, and the mechanical property of the matrix material that makes is starkly lower than the mechanical property of the matrix material of embodiment 2 preparations.
Embodiment 3
37.5g polypropylene, 1g maleic anhydride graft terpolymer EP rubber and 0.3g antioxidant 1076 are dropped in the Banbury mixer, it is mixed melting under 180 ℃ the condition in temperature, after 5 minutes, adding 2.5g Resins, epoxy E51 and 9.6g length is the chopped carbon fiber continuation blend of 2mm, after 4 minutes, add the 0.1g adipic dihydrazide again and continue blend, after 2 minutes, discharging obtains modification chopped carbon fiber reinforced polypropylene compound material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Described matrix material is take polypropylene as body material, and take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on the surface of described chopped carbon fiber.
The tensile strength of described matrix material is 75MPa, and tensile modulus is 2.6GPa, and flexural strength is 84MPa, and notched Izod impact strength is 3.4kJ/m
2, show that it has excellent mechanical property.
Embodiment 4
17.5g polyethylene, 6.5g ethylene-vinyl acetate, 0.2g antioxidant 1076 and 0.3g sodium stearate are dropped in the Banbury mixer, it is mixed melting under 200 ℃ the condition in temperature, after 3 minutes, adding 5.3g Resins, epoxy E51 and 20g length is the chopped carbon fiber continuation blend of 3mm, after 6 minutes, add the 0.2g dicyanamide again and continue blend, after 6 minutes, discharging obtains modification chopped carbon fiber enhanced polyethylene matrix material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Described matrix material is take polyethylene as body material, and take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on the surface of described chopped carbon fiber.
The tensile strength of described matrix material is 86MPa, and tensile modulus is 3.5GPa, and flexural strength is 94MPa, and notched Izod impact strength is 3.8kJ/m
2, show that it has excellent mechanical property.
Embodiment 5
30g polypropylene, 6.5g maleic anhydride inoculated polypropylene, 0.2g antioxidant 1076 and 0.1g sodium oleate are dropped in the Banbury mixer, it is mixed melting under 190 ℃ the condition in temperature, after 2 minutes, adding 9.5g Resins, epoxy E51 and 3.5g length is the chopped carbon fiber continuation blend of 20mm, after 2 minutes, add the 0.2g imidazoles again and continue blend, after 4 minutes, discharging obtains modification chopped carbon fiber reinforced polypropylene compound material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Described matrix material is take polypropylene as body material, and take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on the surface of described chopped carbon fiber.
The tensile strength of described matrix material is 71MPa, and tensile modulus is 2.7GPa, and flexural strength is 76MPa, and notched Izod impact strength is 3.1kJ/m
2, show that it has excellent mechanical property.
Embodiment 6
With the 1000g polypropylene, the 180g maleic anhydride inoculated polypropylene, the 10g antioxidant 1010, the 15g oleylamide, 200g Resins, epoxy E51 and 530g length are that the chopped carbon fiber of 8mm mixes in 120 ℃ of lower kneaders, then put in the screw extrusion press, it is extruding pelletization under 160 ℃ ~ 210 ℃ the condition in each zone temperatures scope of screw rod, obtain extruding particle, the particle of extruding that will obtain again mixes in kneader under 120 ℃ with 65g2-ethyl-4-methylimidazole, carry out extruding pelletization with the screw extrusion press of each district's temperature between 160 ℃ ~ 210 ℃ again, obtain modification chopped carbon fiber reinforced polypropylene compound material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Described matrix material is take polypropylene as body material, and take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on the surface of described chopped carbon fiber.
The tensile strength of described matrix material is 83MPa, and tensile modulus is 3.2GPa, and flexural strength is 89MPa, and notched Izod impact strength is 3.4kJ/m
2, show that it has excellent mechanical property.
Embodiment 7
With the 800g polyethylene, the 240g maleic anhydride grafted polyethylene, the 20g antioxidant 1076, the 20g oleylamide, 280g Resins, epoxy E51 and 600g length are that the chopped carbon fiber of 15mm mixes in 80 ℃ of lower kneaders, then put in the screw extrusion press, it is extruding pelletization under 160 ℃ ~ 190 ℃ the condition in each zone temperatures scope of screw rod, obtain extruding particle, the particle of extruding that will obtain again mixes in kneader under 80 ℃ with the 40g dicyanamide, carry out extruding pelletization with the screw extrusion press of each district's temperature between 160 ℃ ~ 190 ℃ again, obtain modification chopped carbon fiber enhanced polyethylene matrix material.
After obtaining described matrix material, according to method mentioned above it is carried out structure and Performance Detection.Described matrix material is take polyethylene as body material, and take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on the surface of described chopped carbon fiber.
The tensile strength of described matrix material is 72MPa, and tensile modulus is 3.0GPa, and flexural strength is 81MPa, and notched Izod impact strength is 3.6kJ/m
2, show that it has excellent mechanical property.
By above embodiment and comparative example as can be known, modification chopped carbon fiber provided by the invention strengthens composite polyolefine material and mainly is comprised of polyolefine, chopped carbon fiber, expanding material, Resins, epoxy and solidifying agent, described modification chopped carbon fiber strengthens composite polyolefine material take polyolefine as body material, take chopped carbon fiber as strongthener, the Resins, epoxy after the curing is coated on described chopped carbon fiber surface.Modification chopped carbon fiber provided by the invention strengthens composite polyolefine material and has preferably mechanical property, is beneficial to application.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a modification chopped carbon fiber strengthens composite polyolefine material, is made through mixing or extruding pelletization by the chopped carbon fiber polyolefin blend, and described chopped carbon fiber polyolefin blend comprises:
The polyolefine of 20wt% ~ 75wt%;
The chopped carbon fiber of 7wt% ~ 40wt%;
The expanding material of 2wt% ~ 20wt%;
The Resins, epoxy of 5wt% ~ 20wt%;
The solidifying agent of 0.2wt% ~ 5wt%.
2. a modification chopped carbon fiber strengthens the preparation method of composite polyolefine material, may further comprise the steps:
The polyolefine of 20wt% ~ 75wt%, the chopped carbon fiber of 7wt% ~ 40wt%, the expanding material of 2wt% ~ 20wt%, the Resins, epoxy of 5wt% ~ 20wt% and the solidifying agent of 0.2wt% ~ 5wt% are carried out mixing or extruding pelletization, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
3. preparation method according to claim 2 is characterized in that, described mixing comprising:
Described polyolefine and expanding material are carried out blend under 160 ℃ ~ 200 ℃ condition, after 2 minutes ~ 5 minutes, obtain the first blend;
Described the first blend and described Resins, epoxy and chopped carbon fiber are carried out blend, after 2 minutes ~ 8 minutes, obtain the second blend;
Described the second blend and described solidifying agent are carried out blend, after 2 minutes ~ 8 minutes, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
4. preparation method according to claim 2 is characterized in that, described extruding pelletization comprises:
Described polyolefine, expanding material, chopped carbon fiber and Resins, epoxy are mixed under 80 ℃ ~ 120 ℃ condition, then under 160 ℃ ~ 210 ℃ condition, carry out extruding pelletization, obtain extruding particle;
The described particle of extruding is mixed under 80 ℃ ~ 120 ℃ condition with described solidifying agent, then under 160 ℃ ~ 210 ℃ condition, carry out extruding pelletization, obtain the modification chopped carbon fiber and strengthen composite polyolefine material.
5. preparation method according to claim 2 is characterized in that, when carrying out mixing or extruding pelletization, also comprises adding at least a in lubricant and the oxidation inhibitor.
6. each described preparation method is characterized in that according to claim 2 ~ 5, and described solidifying agent is selected from one or more in dicyanamide, imidazoles, 2-ethyl-4 Methylimidazole and the adipic dihydrazide.
7. each described preparation method is characterized in that according to claim 2 ~ 5, and described expanding material is selected from one or more in maleic anhydride stem grafting polyolefin, maleic anhydride graft terpolymer EP rubber and the ethylene vinyl acetate.
8. each described preparation method is characterized in that according to claim 2 ~ 5, and the length of described chopped carbon fiber is 2mm ~ 20mm.
9. each described preparation method is characterized in that according to claim 2 ~ 5, and described polyolefine is at least a in polyethylene and the polypropylene.
10. each described preparation method is characterized in that according to claim 2 ~ 5, and described Resins, epoxy is Resins, epoxy E51.
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Effective date of registration: 20161216 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Applied Chemistry Inst., Chinese Academy of Sciences |