CN103242645A - High wear resistant polymer blend material or product and preparation method thereof - Google Patents
High wear resistant polymer blend material or product and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high wear resistant polymer blend material or product, which contains ultra high molecular weight polyethylene of which the surface contains fluorine, wherein the material or product is prepared from 100 parts of matrix polymer and 5-30 parts of ultra high molecular weight polyethylene of which the surface contains fluorine. A preparation method of the material or product comprises the steps: firstly, the ultra high molecular weight polyethylene is placed into a closed vacuum reactor, and fluoridation is carried out on the ultra high molecular weight polyethylene at the temperature of 25-75 DEG C for 0.1-2 hours, wherein partial pressure of the fluorine in the reactor is 5-50kPa; and then the 100 parts of matrix polymer and the 5-30 parts of fluorinated ultra high molecular weight polyethylene are processed into the material or product according to a conventional processing method. After the surface of the ultra high molecular weight polyethylene is subjected to fluoridation, the ultra high molecular weight polyethylene can be dispersed stably in the polymer, so not only are the wear resistance, the tear strength and the impact strength of the material or product improved, but also the range of polymer materials which are blended with the ultra high molecular weight polyethylene for improving wear resistance is greatly expanded. The method is simple to operate, low in cost, and easy for realizing bulk production.
Description
Technical field
The invention belongs to blending and modifying polymkeric substance wear resistance and preparing technical field thereof, be specifically related to a kind of high abrasion blended polymer material that contains the fluorine-contained surface ultrahigh molecular weight polyethylene(UHMWPE) or goods and preparation method thereof.
Background technology
With the develop rapidly of seeing national economy, the polymers of excellent properties material product gains great popularity, especially as this class engineering superpolymer such as urethane, Resins, epoxy, resol, they are because of performance such as have excellent mechanical property and wear-resisting, oil resistant, tear-resistant, resistance to chemical attack, anti-x radiation x, binding property is good, damping capaicty is strong, progressively substitute the traditional material goods at present, and be widely used in fields such as various matrix materials, tire, rubber tire, rubber roll, copper-clad plate, binding agent.
Though these polymkeric substance have had very outstanding performance, but along with the popularization of its use and increasing sharply of usage quantity, it is annual because the cost consumption that the material that wearing and tearing cause upgrades and renewal and renovation of equipment brings is also surprisingly high, if can further promote the scratch-resistant performance of this class engineering superpolymer, will bring huge economic benefit and social benefit so.
The method that improves the polymkeric substance wear resistance at present is multifarious, but drawback is also fairly obvious separately, and end is got up, and its main method has: 1) to the polymer molecule modification, namely improve wear resisting property by the design molecular structure.As the Zhou Nanqiao of South China Science ﹠ Engineering University etc. (petrochemical complex, 2008.37(11): 1181-1186) by changing soft, the hard section ratio in the polyurethane elastomer and changing the wear resisting property that different soft segment structures improve urethane.This kind method has limited types of polyurethane usually, need the specific soft section monomer of design simultaneously, thereby cost is higher, and monomer is synthetic complicated, and the structure control difficulty is difficult to commercialization and promotes.2) in the polymkeric substance building-up process, add other components and carry out the in-situ blending modification.Carry out the in-situ blending modification as add flexible composition in the foaming polyurethanes elastomer building-up process, disclosed document has: the patent (CN102344541A) of Bayer science and technology application is by introduce a certain amount of polyisoprene in polyurethane elastomer; The patent of DOW Chemical application (CN1192757A) is by adding liquid polybutadiene when the synthesis of polyurethane.This kind method just is used for polyurethane elastomer usually, thereby applicable surface is narrow.3) in polymer processing, to add other wear resistant components and carry out blending and modifying, these class methods are the main stream approach that increase the polymkeric substance wear resisting property now, are widely used in blending polymeric system.As (plastics such as the Xu soldiers of HeFei University of Technology; 1995; 24(1): 5-9) with the frictional dissipation performance of polytetrafluoroethylmodified modified polyoxymethylene; though the result shows the frictional dissipation performance of its matrix material and increases; but because the ptfe surface that adds is nonpolar; so not only cause itself and basal body interface consistency poor, be difficult to disperse, and also can reduce the mechanical property of integral material usually.
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is a kind of thermoplastic engineering plastic with excellent over-all properties of linear structure.The ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is usually 100～5,000,000, than high 2 orders of magnitude of common polythene, degree of crystallinity 65～85%, density 0.92～0.96g/cm
3, and its abrasion resistance properties is very remarkable, is one of best superpolymer of frictional behaviour, than the wear-resisting several times of metal such as general carbon steel and steel, wear-resisting 4 times than nylon, ultrahigh molecular weight polyethylene(UHMWPE) has lower frictional coefficient and good self-lubricating property simultaneously.
According to general reasoning, if can be with the ultrahigh molecular weight polyethylene(UHMWPE) stable dispersion in polymkeric substance external phase, the wear resisting property of the matrix material that obtains and mechanical property must increase.But regrettably, a little less than the ultrahigh molecular weight polyethylene(UHMWPE) surface polarity, performance is inertia very, is difficult to stable dispersion in the above in the described polar polymer, thereby very limited to wear resisting property and the mechanical property contribution of matrix material, so need carry out surface modification to ultrahigh molecular weight polyethylene(UHMWPE).At present the modified with ultrahigh molecular weight polyethylene method also there are some reports, the patent (CN102250370) of applying for as Chinese Academy of Sciences's Ningbo material is come the surface of modified ultra-high molecular weight polyethylene with regard to the method that has adopted interfacial polycondensation, utilize chemical method at ultrahigh molecular weight polyethylene(UHMWPE) surface polycondensation one deck polyureas and/or urethane and/or polyamide layer, thereby increase the ultrahigh molecular weight polyethylene(UHMWPE) surface polarity, and then improve its consistency and cohesiveness in superpolymer.But because this method need use multiple polyfunctionality reaction monomers to come successive reaction, need to consume a large amount of solvents simultaneously, so certainly exist that complex operation, cost are higher, problems such as the difficult recovery of solvent and environmental pollution, be difficult to accomplish scale production.
Summary of the invention
Primary and foremost purpose of the present invention is at the deficiencies in the prior art, and the preparation method of a kind of high abrasion blended polymer material or goods is provided.
Another object of the present invention provides a kind of high abrasion blended polymer material or goods that method for preparing is arranged.
The preparation method of high abrasion blended polymer material provided by the invention or goods, processing step and the condition of this method are as follows:
1) ultrahigh molecular weight polyethylene(UHMWPE) is placed the enclosed vacuum reactor vacuumize and with behind the remaining air of inert gas replacement reactor, in vacuum reactor, charge into the fluorine gas gas mixture, under 25～75 ℃ to its fluoridation 0.1～2 hour, after using the remaining fluorinated gas of nitrogen replacement again, namely obtain fluoridizing the polyethylene of ultra-high molecular weight, wherein the dividing potential drop of fluorine gas in reactor is 5～50kPa;
2) earlier that 100 parts of matrix polymers is even with 5～30 parts of premixs of the polyethylene of fluoridizing ultra-high molecular weight, the processing mode according to routine is prepared into material or goods then.
The dividing potential drop of fluorine gas in reactor is preferably 20～30KPa in the aforesaid method, 25 KPa more preferably, and temperature of reaction is preferably 25～50 ℃, and the reaction times is preferably 0.5～1 hour.
Used ultrahigh molecular weight polyethylene(UHMWPE) is powder or/and short fiber in the aforesaid method, and the particle diameter of powder is 10～100 μ m, is preferably 20～50 μ m, and staple length is 1～10mm, is preferably 1～5 mm, and the short fiber diameter is 10～25 μ m, is preferably 15～20 μ m.
Fluorine gas gas mixture used in the aforesaid method is by at least a composition the in fluorine gas and oxygen, nitrogen and the argon gas, preferred fluorine gas and nitrogen.
Used matrix polymer is any in urethane, Resins, epoxy, resol or the nylon in the aforesaid method.
The ultrahigh molecular weight polyethylene(UHMWPE) of used fluorine-contained surface is preferred 10～20 parts in the aforesaid method.
In the aforesaid method processing mode of used routine for ultrahigh molecular weight polyethylene(UHMWPE) and matrix polymer are put into screw extrusion press melt blending extruding pelletization get intermingling material or further moulding get goods, or carrying out blend with the prepolymer of thermosetting polymer by a certain percentage, curing molding gets goods again.
The invention provides high abrasion blended polymer material or goods, it is characterized in that containing in this blended polymer material or the goods ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface, wherein matrix polymer is 100 parts, the ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is 5～30 parts, when the matrix polymer in this blended polymer material or the goods was urethane, its frictional dissipation was 8 ~ 15.2mm
3, tear strength is 97.4 ~ 112.4 kNm
-1When the matrix polymer in this blended polymer material or the goods was thermosetting resin, its frictional dissipation was 1132.6 ~ 1890.2mm
3, shock strength is 8.9 ~ 9.2kJm
-2When the matrix polymer in this blended polymer material or the goods was nylon, its frictional dissipation was 75.0 ~ 99.2mm
3, shock strength is 6.9 ~ 7.4 kJm
-2
The ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is preferred 10～20 parts in above high abrasion blended polymer material or the goods.
The ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is powder or/and short fiber in above high abrasion blended polymer material or the goods, and when existing powder, when also short fiber being arranged, the weight ratio of the two is 80～60:20～40.
Carbon-fluorine covalent bond structure and carboxylic, oh group are contained in the surface of ultrahigh molecular weight polyethylene(UHMWPE) in above high abrasion blended polymer material or the goods, and its attenuated total reflectance infrared spectrogram is at 1100cm
-1About the absorption peak of carbon-fluorine covalent linkage is arranged; 3000cm
-1～3500cm
-1Between broad peak and 1700cm
-1There is the absorption peak of hydroxyl and carboxylic group near peak, at the 687eV bound energy place of x-ray photoelectron energy spectrogram fluorine element power spectrum peak is arranged.
The present invention compared with prior art has following beneficial effect:
1, owing to contained ultrahigh molecular weight polyethylene(UHMWPE) in high abrasion blended polymer material provided by the invention or the goods is handled through direct fluorinated surface, a large amount of carbon-fluorine covalent bond structure and carboxylic, oh group have just been introduced like this on its surface, thereby not only solved a little less than the ultrahigh molecular weight polyethylene(UHMWPE) surface polarity, the problem that is difficult to stable dispersion in polymkeric substance can be given full play to its remarkable abrasion resistance properties and good self-lubricating property again.
2, owing to contained ultrahigh molecular weight polyethylene(UHMWPE) in high abrasion blended polymer material provided by the invention or the goods has the excellent comprehensive performance, especially its wearability, frictional property, thereby the frictional dissipation that the polymer materials that makes the blend gained does not add the ultrahigh molecular weight polyethylene(UHMWPE) system of fluorine-contained surface has reduced by 30～60%, tear strength has improved 5～25%, shock strength has improved 20～50%, and the economic benefit of bringing therefrom and social benefit are all very considerable.
3, owing to contained ultrahigh molecular weight polyethylene(UHMWPE) in high abrasion blended polymer material provided by the invention or the goods also has good self-lubricating property, thereby with the matrix polymer blend course of processing in not only can not have a negative impact, also can bring into play the effect of lubricant, save the lubricant that adds other again, to reduce cost.
4, owing to contain a large amount of carbon-fluorine covalent bond structure and carboxylic, oh group with the ultrahigh molecular weight polyethylene(UHMWPE) surface after the inventive method processing, thereby with it blend to improve the polymer materials of its wear resistance in extensive range, can be thermosetting resins such as casting type polyurethane, Resins, epoxy, resol, also can be thermoplastic resins such as nylon, polycarbonate, can also be elastomericss such as polyethers or PAUR.
5, because preparation method provided by the invention is with fluoridizing the gas mixture processing with ultrahigh molecular weight polyethylene(UHMWPE); treating processes is simple to operate; effect is remarkable; thereby not only can avoid prior art to adopt multiple polyfunctionality reaction monomers to come successive reaction; need simultaneously to consume that complex operation, cost that a large amount of solvents bring are higher, problem such as the difficult recovery of solvent and environmental pollution; and cost is lower; be easy to accomplish scale production, the while also provides a new approach for the surface treatment of ultrahigh molecular weight polyethylene(UHMWPE).
Description of drawings
Fig. 1 is the Electronic Speculum figure of the high abrasion polymer blend section of the embodiment of the invention 1 preparation, and the ultrahigh molecular weight polyethylene(UHMWPE) powder of fluorine-contained surface is to be dispersed in the polyurethane elastomer as seen from the figure.
Fig. 2 is the Electronic Speculum figure of the intermingling material section of Comparative Examples 2 preparation, and to disperse in polyurethane elastomer be not very even to untreated ultrahigh molecular weight polyethylene(UHMWPE) powder as seen from the figure.
Fig. 3 is the infrared spectrogram of the ultrahigh molecular weight polyethylene(UHMWPE) powder of the embodiment of the invention 1 prepared fluorine-contained surface, shows 1100cm among the figure
-1About the absorption peak of carbon-fluorine covalent linkage is arranged; 3000cm
-1～3500cm
-1Between broad peak and 1700cm
-1There is the absorption peak of hydroxyl and carboxylic group near peak.
Fig. 4 is the ultrahigh molecular weight polyethylene(UHMWPE) powder X-ray X-ray photoelectron spectroscopy X figure (XPS) of the embodiment of the invention 1 prepared fluorine-contained surface, and the peak at 687eV bound energy place is fluorine element power spectrum peak among the figure.
Embodiment
Carry out concrete description below by the present invention of embodiment; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
What deserves to be explained is in addition, below the wear resistance of each embodiment and Comparative Examples gained material be to measure according to GB/T 9867-2008 or GB 3960-83 respectively; Tear strength is the mensuration according to GB/T 529-1999, and shock strength is measured according to GB/T 2571-1995 and measured, and test result is seen attached list.
Embodiment 1
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 10 μ m places the enclosed vacuum reactor with particle diameter, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of delivery of fluorine/nitrogen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 25kPa, under 25 ℃ to its fluoridation 0.5 hour, adopt the remaining fluorinated gas of nitrogen replacement then after, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that reactor namely gets surface fluorination; Earlier with 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dry 100 parts of PAUR elastomerics premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 2
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 50 μ m places the enclosed vacuum reactor with particle diameter, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/argon gas in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 5kPa, under 40 ℃ to its fluoridation 1 hour, adopt the remaining fluorinated gas of nitrogen replacement then after, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that reactor namely gets surface fluorination; Earlier with 15 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dry 100 parts of PAUR premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 3
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 100 μ m places the enclosed vacuum reactor with particle diameter, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 20kPa, under 50 ℃ to its fluoridation 2 hours, adopt the remaining fluorinated gas of nitrogen replacement then after, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that reactor namely gets surface fluorination; Earlier with 30 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dry 100 parts of PAUR premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 4
Be 3mm with length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 15 μ m places the enclosed vacuum reactor, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of delivery of fluorine/nitrogen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 25kPa, under 50 ℃ to its fluoridation 0.5 hour, after adopting the remaining fluorinated gas of nitrogen replacement then, open the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that reactor namely gets surface fluorination; Earlier with 5 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dry 100 parts of PAUR premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 5
Be 5mm with length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 20 μ m places the enclosed vacuum reactor, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of delivery of fluorine/nitrogen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 25kPa, under 75 ℃ to its fluoridation 0.5 hour, after adopting the remaining fluorinated gas of nitrogen replacement then, open the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that reactor namely gets surface fluorination; Earlier with 5 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dry 100 parts of PAUR premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 6
Be 10mm with length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 25 μ m places the enclosed vacuum reactor, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of delivery of fluorine/nitrogen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 25kPa, under 25 ℃ to its fluoridation 0.75 hour, after adopting the remaining fluorinated gas of nitrogen replacement then, open the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that reactor namely gets surface fluorination; Earlier with 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dry 100 parts of PAUR premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 7
Be 1mm with length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 15 μ m and ultrahigh molecular weight polyethylene(UHMWPE) powder that particle diameter is 20 μ m place the enclosed vacuum reactor simultaneously, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 30kPa, under 50 ℃ to its fluoridation 1 hour, after adopting the remaining fluorinated gas of nitrogen replacement then, open ultrahigh molecular weight polyethylene(UHMWPE) short fiber and powder that reactor namely gets surface fluorination; Earlier with 5 parts this fluoridize that ultrahigh molecular weight polyethylene(UHMWPE) short fiber, 20 parts are fluoridized ultrahigh molecular weight polyethylene(UHMWPE) powder and dry 100 parts of PAUR premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 8
Be 3mm with length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 10 μ m and ultrahigh molecular weight polyethylene(UHMWPE) powder that particle diameter is 20 μ m place the enclosed vacuum reactor simultaneously, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 40kPa, under 25 ℃ to its fluoridation 1 hour, after adopting the remaining fluorinated gas of nitrogen replacement then, open ultrahigh molecular weight polyethylene(UHMWPE) short fiber and powder that reactor namely gets surface fluorination; Earlier with 10 parts this fluoridize that ultrahigh molecular weight polyethylene(UHMWPE) short fiber, 20 parts are fluoridized ultrahigh molecular weight polyethylene(UHMWPE) powder and dry 100 parts of polyether(poly)urethane premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 9
Be 5mm with length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 20 μ m and ultrahigh molecular weight polyethylene(UHMWPE) powder that particle diameter is 30 μ m place the enclosed vacuum reactor simultaneously, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 20kPa, under 75 ℃ to its fluoridation 2 hours, after adopting the remaining fluorinated gas of nitrogen replacement then, open ultrahigh molecular weight polyethylene(UHMWPE) short fiber and powder that reactor namely gets surface fluorination; Earlier with 10 parts this fluoridize that ultrahigh molecular weight polyethylene(UHMWPE) short fiber, 10 parts are fluoridized ultrahigh molecular weight polyethylene(UHMWPE) powder and dry 100 parts of polyether(poly)urethane premixs crossing evenly and the melt blending granulation gets final product.
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 10 μ m places the enclosed vacuum reactor with particle diameter, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 25kPa, under 50 ℃ to its fluoridation 0.75 hour, adopt the remaining fluorinated gas of nitrogen replacement then after, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that reactor namely gets surface fluorination; With 100 parts of MDI type polyurethane performed polymers, fluoridize the ultrahigh molecular weight polyethylene(UHMWPE) powder after 90 ℃ of vacuum stirring blend and deaeration for 20 parts, add 20 parts of chainextenders 3,3'-two chloro-4,4'-diaminodiphenyl-methane or two adjacent chlorodiphenyl amine methane (MOCA), stir after 2～3 minutes fast, pour into rapidly in the mould, baking obtains pouring into a mould high abrasion blending polyester type polyurethane.
Embodiment 11
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 50 μ m places the enclosed vacuum reactor with particle diameter, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen/argon in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 50kPa, under 50 ℃ to its fluoridation 2 hours, adopt the remaining fluorinated gas of nitrogen replacement then after, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that reactor namely gets surface fluorination; With 100 parts of epoxy E-51 resins, fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder, 70 parts of maleic anhydride solidifying agent and a small amount of 1 part of N for 10 parts, N-dimethylbenzyl amine catalyst is warming up to 90 ℃ and continue stirred 1 hour, under the mixed solution vacuum after the deaeration cast cured explosive become goods.Curing process is followed successively by: 120 ℃/lh, 140 ℃/lh, l50 ℃/1.5h.
Embodiment 12
Be that ultrahigh molecular weight polyethylene(UHMWPE) powder and the length of 10 μ m is 5mm with particle diameter, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 17 μ m places the enclosed vacuum reactor simultaneously, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 30kPa, under 40 ℃ to its fluoridation 0.5 hour, after adopting the remaining fluorinated gas of nitrogen replacement then, open ultrahigh molecular weight polyethylene(UHMWPE) powder and short fiber that reactor namely gets surface fluorination; With 100 parts of heat-reactive phenolic resins, fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and short fiber and stirred 1 hour for each 5 parts, under the mixed solution vacuum after the deaeration cast cured explosive become goods.Condition of cure is 150 ℃ and solidified 4 hours.
Embodiment 13
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 10 μ m places the enclosed vacuum reactor with particle diameter, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of delivery of fluorine/nitrogen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 25kPa, under 40 ℃ to its fluoridation 0.5 hour, adopt the remaining fluorinated gas of nitrogen replacement then after, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that reactor namely gets surface fluorination; Earlier with 20 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dry 100 parts of Nylon 6 premixs crossing evenly and the melt blending granulation gets final product.
Embodiment 14
Be 1mm with length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 10 μ m places the enclosed vacuum reactor, vacuumize then, and with behind the air in the nitrogen replacement reactor three times, charge into the gas mixture of fluorine gas/oxygen in the vacuum reactor, control fluorine gas dividing potential drop in reactor is 25kPa, under 75 ℃ to its fluoridation 0.5 hour, after adopting the remaining fluorinated gas of nitrogen replacement then, open the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that reactor namely gets surface fluorination; Earlier with 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dry 100 parts of Nylon 66 premixs crossing evenly and the melt blending granulation, injection moulding gets goods then.
Comparative Examples 1
With 100 parts of dry PAUR elastomerics and 10 parts of direct blend granulations of ultrahigh molecular weight polyethylene(UHMWPE) powder that particle diameter is 10 μ m of crossing, injection moulding then.
Comparative Examples 2
The direct injection moulding of pure PAUR elastomerics that drying is crossed.
Comparative Examples 3
Be 1mm with 100 parts of dry polyether(poly)urethane elastomerics and length of crossing, diameter is the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 20 μ m and ultrahigh molecular weight polyethylene(UHMWPE) powder each 10 parts of blend granulations, injection mouldings then that particle diameter is 10 μ m.
Comparative Examples 4
The direct injection moulding of pure polyether(poly)urethane elastomerics that drying is crossed.
Comparative Examples 5
Be that 10 μ m ultrahigh molecular weight polyethylene(UHMWPE) powder directly vulcanize casting with the method for embodiment 10 with 100 parts of MDI type polyurethane performed polymers and 20 parts of particle diameters.
Comparative Examples 6
MDI type polyurethane performed polymer is directly vulcanized casting with the vulcanization process of embodiment 10.
Comparative Examples 7
The ultrahigh molecular weight polyethylene(UHMWPE) powder that is 50 μ m with 100 parts of epoxy E-51 resins and 10 parts of particle diameters directly is cured moulding with the curing of embodiment 11.
Comparative Examples 8
Epoxy E-51 resin directly is cured moulding with the curing of embodiment 11.
Comparative Examples 9
Be that ultrahigh molecular weight polyethylene(UHMWPE) powder and the length of 10 μ m is 5mm with 100 parts of heat-reactive phenolic resins and particle diameter, diameter is that each 5 parts of the ultrahigh molecular weight polyethylene(UHMWPE) short fibers of 20 μ m directly are cured moulding with the curings of embodiment 12.
Comparative Examples 10
Heat-reactive phenolic resin directly is cured moulding with the curing of embodiment 12.
Comparative Examples 11
With 100 parts of dry Nylon 6s of crossing and 20 parts of evenly also melt blending granulation, injection mouldings then of ultrahigh molecular weight polyethylene(UHMWPE) powder premix that particle diameter is 10 μ m.
Comparative Examples 12
The Nylon 6 that drying is crossed directly carries out injection moulding.
Comparative Examples 13
Comparative Examples 14
The Nylon 66 that drying is crossed directly carries out injection moulding.
| Embodiment | Frictional dissipation/mm 3 | Tear strength/kNm -1 | Shock strength/kJm -2 |
| 1 | 10.4 | 100.9 | |
| 2 | 12.7 | 103.0 | |
| 3 | 15.2 | 97.4 | |
| 4 | 15.0 | 110.8 | |
| 5 | 13.4 | 111.6 | |
| 6 | 10.1 | 107.3 | |
| 7 | 12.7 | 101.7 | |
| 8 | 10.0 | 104.2 | |
| 9 | 10.8 | 100.6 | |
| 10 | 8.0 | 112.4 | |
| 11 | 1890.2 | 9.2 | |
| 12 | 1132.6 | 8.9 | |
| 13 | 99.2 | 7.4 | |
| 14 | 75.0 | 6.9 | |
| Comparative Examples 1 | 20.1 | 92.0 | |
| Comparative Examples 2 | 23.2 | 90.2 | |
| Comparative Examples 3 | 21.5 | 91.0 | |
| Comparative Examples 4 | 25.8 | 88.1 | |
| Comparative Examples 5 | 14.2 | 75.2 | |
| Comparative Examples 6 | 20.1 | 97.7 | |
| Comparative Examples 7 | 2400.9 | 7.4 | |
| Comparative Examples 8 | 3679.2 | 6.5 | |
| Comparative Examples 9 | 1687.5 | 7.1 | |
| Comparative Examples 10 | 2015.1 | 6.0 | |
| Comparative Examples 11 | 136.0 | 5.6 | |
| Comparative Examples 12 | 162.4 | 5.2 | |
| Comparative Examples 13 | 94.6 | 6.4 | |
| Comparative Examples 14 | 126.7 | 5.4 |
Claims (10)
1. the preparation method of a high abrasion blended polymer material or goods, processing step and the condition of this method are as follows:
1) ultrahigh molecular weight polyethylene(UHMWPE) is placed the enclosed vacuum reactor vacuumize and with behind the remaining air of inert gas replacement reactor, in vacuum reactor, charge into the fluorine gas gas mixture, under 25～75 ℃ to its fluoridation 0.1～2 hour, after using the remaining fluorinated gas of nitrogen replacement again, namely obtain fluoridizing the polyethylene of ultra-high molecular weight, wherein the dividing potential drop of fluorine gas in reactor is 5～50kPa;
2) earlier that 100 parts of matrix polymers is even with 5～30 parts of premixs of the polyethylene of fluoridizing ultra-high molecular weight, the processing mode according to routine is prepared into material or goods then.
2. the preparation method of high abrasion blended polymer material according to claim 1 or goods, the dividing potential drop of fluorine gas in reactor is 20～30KPa in this method.
3. the preparation method of high abrasion blended polymer material according to claim 1 or goods, the dividing potential drop of fluorine gas in reactor is 25 KPa in this method.
4. according to the preparation method of claim 1 or 2 or 3 described high abrasion blended polymer materials or goods, temperature of reaction is 25～50 ℃ in this method, and the reaction times is 0.5～1 hour.
5. according to the preparation method of claim 1 or 2 or 3 described high abrasion blended polymer materials or goods, used ultrahigh molecular weight polyethylene(UHMWPE) is that powder is or/and short fiber in this method, the particle diameter of powder is 10～100 μ m, and staple length is 1～10mm, and diameter is 10～25 μ m.
6. the preparation method of high abrasion blended polymer material according to claim 4 or goods, used ultrahigh molecular weight polyethylene(UHMWPE) is that powder is or/and short fiber in this method, the particle diameter of powder is 20～50 μ m, and staple length is 1～5 mm, and diameter is 15～20 μ m.
7. according to the preparation method of claim 1 or 2 or 3 described high abrasion blended polymer materials or goods, fluorine gas gas mixture used in this method is by at least a composition the in fluorine gas and oxygen, nitrogen and the argon gas.
8. the preparation method of high abrasion blended polymer material according to claim 6 or goods, fluorine gas gas mixture used in this method is by at least a composition the in fluorine gas and oxygen, nitrogen and the argon gas.
9. high abrasion blended polymer material or goods by a method for preparing, the ultrahigh molecular weight polyethylene(UHMWPE) that contains fluorine-contained surface in this blended polymer material or the goods, wherein matrix polymer is 100 parts, the ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is 5～30 parts, when the matrix polymer in this blended polymer material or the goods was urethane, its frictional dissipation was 8 ~ 15.2mm
3, tear strength is 97.4 ~ 112.4 kNm
-1When the matrix polymer in this blended polymer material or the goods was thermosetting resin, its frictional dissipation was 1132.6 ~ 1890.2mm
3, shock strength is 8.9 ~ 9.2kJm
-2When the matrix polymer in this blended polymer material or the goods was nylon, its frictional dissipation was 75.0 ~ 99.2mm
3, shock strength is 6.9 ~ 7.4 kJm
-2
10. high abrasion blended polymer material according to claim 9 or goods, the ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is 10～20 parts in this blended polymer material or the goods.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104909034A (en) * | 2015-06-01 | 2015-09-16 | 铜陵方正塑业科技有限公司 | Wear-resistant paper-plastic composite bag and preparation method for same |
| CN110845644A (en) * | 2019-12-03 | 2020-02-28 | 祁娟 | Preparation method of oil-water amphiphilic polymer powder and polymer powder prepared by preparation method |
| CN110888312A (en) * | 2018-09-11 | 2020-03-17 | 柯尼卡美能达株式会社 | Cleaning member, method of manufacturing the same, and image forming apparatus |
| CN114133525A (en) * | 2021-12-16 | 2022-03-04 | 胡先海 | Preparation method and application of self-repairing high-temperature-resistant polyurethane elastomer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101875736A (en) * | 2010-06-24 | 2010-11-03 | 王崇高 | Modified ultra-high molecular weight polyethylene resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101875736A (en) * | 2010-06-24 | 2010-11-03 | 王崇高 | Modified ultra-high molecular weight polyethylene resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909034A (en) * | 2015-06-01 | 2015-09-16 | 铜陵方正塑业科技有限公司 | Wear-resistant paper-plastic composite bag and preparation method for same |
| CN104909034B (en) * | 2015-06-01 | 2018-01-09 | 铜陵方正塑业科技有限公司 | Wear-resistant paper and plastics compound bag and preparation method thereof |
| CN110888312A (en) * | 2018-09-11 | 2020-03-17 | 柯尼卡美能达株式会社 | Cleaning member, method of manufacturing the same, and image forming apparatus |
| CN110845644A (en) * | 2019-12-03 | 2020-02-28 | 祁娟 | Preparation method of oil-water amphiphilic polymer powder and polymer powder prepared by preparation method |
| CN114133525A (en) * | 2021-12-16 | 2022-03-04 | 胡先海 | Preparation method and application of self-repairing high-temperature-resistant polyurethane elastomer |
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