CN103242645B - High wear resistant polymer blend material or goods and preparation method thereof - Google Patents
High wear resistant polymer blend material or goods and preparation method thereof Download PDFInfo
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Abstract
Ultrahigh molecular weight polyethylene(UHMWPE) containing fluorine-contained surface in High wear resistant polymer blend material disclosed by the invention or goods, wherein matrix polymer is 100 parts, the ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is 5 ~ 30 parts, its preparation method first ultrahigh molecular weight polyethylene(UHMWPE) is placed in airtight vacuum reactor to carry out fluoridation 0.1 ~ 2 hour to it at 25 ~ 75 DEG C, wherein fluorine gas dividing potential drop is in the reactor 5 ~ 50kPa, then matrix polymer 100 parts and polyethylene 5 ~ 30 parts processing mode conveniently fluoridizing ultra-high molecular weight are prepared into material or goods.Because ultrahigh molecular weight polyethylene(UHMWPE) can stable dispersion in the polymer after fluorinated surface process; resulting materials or goods wearability, tear strength or shock strength is not only made greatly to improve; and the polymer materials scope of blended its wear resistance of raising with it can also be expanded; the method is simple to operate; with low cost, be easy to accomplish scale 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 wear resistant polymer blend material or goods and preparation method thereof containing fluorine-contained surface ultrahigh molecular weight polyethylene(UHMWPE).
Background technology
With the develop rapidly seeing national economy, the objects in polymeric material of excellent performance gains great popularity, especially as this kind of engineering superpolymer such as urethane, epoxy resin, resol, they are because of the performance such as have excellent mechanical property and wear-resisting, oil resistant, tear-resistant, resistance to chemical attack, resistance to x radiation x, binding property is good, damping capaicty is strong, progressively substitute traditional material goods at present, and be widely used in the fields such as various matrix material, tire, rubber tire, rubber roll, copper-clad plate, binding agent.
Although these polymkeric substance have had very outstanding performance, but along with the popularization of its use and increasing sharply of usage quantity, the annual cost consumption that material upgrades and renewal and renovation of equipment brings caused because of wearing and tearing is also surprisingly high, if the scratch-resistant performance of this kind of engineering superpolymer can be promoted further, so huge economic benefit and social benefit will be brought.
The method of current raising polymkeric substance wear resistance is multifarious, but drawback is also fairly obvious separately, and end is got up, and its main method has: 1) to polymer molecule modification, namely improves wear resisting property by design molecular structure.As (petrochemical complex, 2008.37(11) such as South China Science & Engineering University Zhou Nanqiao: 1181-1186) by soft, the hard section ratio that changes in polyurethane elastomer and change the wear resisting property that different soft segment structure improves urethane.This kind of method usually limit types of polyurethane, and need design specifically soft section of monomer, thus cost is higher simultaneously, and monomer synthesize is complicated, and structure control difficulty is difficult to commercialization and promotes.2) in polymer synthesis process, add other components and carry out in-situ blending modification.Carry out in-situ blending modification as added flexible composition in foaming polyurethanes elastomer building-up process, disclosed document has: the patent (CN102344541A) of Bayer science and technology application is by introducing a certain amount of polyisoprene in polyurethane elastomer; The patent (CN1192757A) of DOW Chemical application is by adding liquid polybutadiene when synthesis of polyurethane.This kind of method is usually just for polyurethane elastomer, and thus applicable surface is narrow.3) in polymer processing, add other wear resistant components and carry out blending and modifying, these class methods are the main stream approach increasing now polymkeric substance wear resisting property, are widely used in blending polymeric system.As (plastics such as HeFei University of Technology Xu soldiers; 1995; 24(1): 5-9) by the frictional dissipation performance of polytetrafluoroethylmodified modified polyoxymethylene; although result shows that the frictional dissipation performance of its matrix material increases; but because the ptfe surface added is nonpolar; so not only cause itself and basal body interface poor compatibility, be difficult to disperse, and usually also can reduce the mechanical property of integral material.
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is a kind of thermoplastic engineering plastic with Good All-around Property of linear structure.Ultrahigh molecular weight polyethylene(UHMWPE) molecular weight usually 100 ~ 5,000,000,2 orders of magnitude higher than 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, more wear-resisting than nylon 4 times, ultrahigh molecular weight polyethylene(UHMWPE) has lower frictional coefficient and good self-lubricating property simultaneously.
According to general reasoning, if can by ultrahigh molecular weight polyethylene(UHMWPE) stable dispersion in continuous polymer phase, the wear resisting property of the matrix material obtained and mechanical property must increase.But regrettably, ultrahigh molecular weight polyethylene(UHMWPE) surface polarity is weak, shows very inertia, is difficult to stable dispersion in polar polymer recited above, thus to the wear resisting property of matrix material and mechanical property contribution very limited, so need to carry out surface modification to ultrahigh molecular weight polyethylene(UHMWPE).Also some are had to report to modified with ultrahigh molecular weight polyethylene method at present, as Chinese Academy of Sciences's Ningbo material the patent (CN102250370) of being applied for come the surface of modified ultra-high molecular weight polyethylene with regard to the method that have employed interfacial polycondensation, utilize chemical method at ultrahigh molecular weight polyethylene(UHMWPE) surface polycondensation one deck polyureas and/or urethane and/or polyamide layer, thus increase ultrahigh molecular weight polyethylene(UHMWPE) surface polarity, and then improve its consistency in superpolymer and cohesiveness.But because the method needs to use multiple polyfunctionality reaction monomers to carry out successive reaction, need to consume a large amount of solvent simultaneously, so certainly exist the problems such as complex operation, high expensive, the recovery of solvent difficulty and environmental pollution, be difficult to accomplish scale production.
Summary of the invention
Primary and foremost purpose of the present invention is for the deficiencies in the prior art, provides the preparation method of a kind of High wear resistant polymer blend material or goods.
Another object of the present invention be to provide a kind of have aforesaid method to prepare High wear resistant polymer blend material or goods.
The preparation method of High wear resistant polymer blend material provided by the invention or goods, processing step and the condition of the method are as follows:
1) ultrahigh molecular weight polyethylene(UHMWPE) is placed in airtight vacuum reactor to vacuumize and after using the remaining air of inert gas replacement reactor, fluorine gas gas mixture is filled with in vacuum reactor, to its fluoridation 0.1 ~ 2 hour at 25 ~ 75 DEG C, after using the remaining fluorinated gas of nitrogen replacement again, namely obtain the polyethylene fluoridizing ultra-high molecular weight, wherein fluorine gas dividing potential drop is in the reactor 5 ~ 50kPa;
2) first that matrix polymer 100 parts is even with polyethylene 5 ~ 30 parts of premixs fluoridizing ultra-high molecular weight, then processing mode is conveniently prepared into material or goods.
In aforesaid method, fluorine gas dividing potential drop is in the reactor preferably 20 ~ 30KPa, is more preferably 25 KPa, and temperature of reaction is preferably 25 ~ 50 DEG C, and the reaction times is preferably 0.5 ~ 1 hour.
Ultrahigh molecular weight polyethylene(UHMWPE) used in aforesaid method be powder or/and short fiber, the particle diameter of powder is 10 ~ 100 μm, be preferably 20 ~ 50 μm, staple length is 1 ~ 10mm, be preferably 1 ~ 5mm, short fiber diameter is 10 ~ 25 μm, be preferably 15 ~ 20 μm.
Fluorine gas gas mixture used in aforesaid method is made up of at least one in fluorine gas and oxygen, nitrogen and argon gas, preferred fluorine gas and nitrogen.
Matrix polymer used in aforesaid method is any one in urethane, epoxy resin, resol or nylon.
The ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface used in aforesaid method preferably 10 ~ 20 parts.
The processing mode of routine used in aforesaid method obtains intermingling material or shaping goods further for ultrahigh molecular weight polyethylene(UHMWPE) and matrix polymer being put into screw extrusion press melt blending extruding pelletization, or carry out blended with the prepolymer of thermosetting polymer by a certain percentage, then curing molding obtains goods.
The invention provides High wear resistant polymer blend material or goods, it is characterized in that the ultrahigh molecular weight polyethylene(UHMWPE) containing fluorine-contained surface in this blended polymer material or 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 goods is urethane, its frictional dissipation is 8 ~ 15.2mm
3, tear strength is 97.4 ~ 112.4 kNm
-1; When the matrix polymer in this blended polymer material or goods is thermosetting resin, its frictional dissipation is 1132.6 ~ 1890.2mm
3, shock strength is 8.9 ~ 9.2kJm
-2; When the matrix polymer in this blended polymer material or goods is nylon, its frictional dissipation is 75.0 ~ 99.2mm
3, shock strength is 6.9 ~ 7.4 kJm
-2.
The ultrahigh molecular weight polyethylene(UHMWPE) preferably 10 ~ 20 parts of fluorine-contained surface in above High wear resistant polymer blend material or goods.
In above High wear resistant polymer blend material or goods the ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface be powder or/and short fiber, when existing powder, when also having short fiber, the weight ratio of the two is 80 ~ 60:20 ~ 40.
In above High wear resistant polymer blend material or goods, carbon-fluorine covalent bond structure and carboxylic, oh group are contained in the surface of ultrahigh molecular weight polyethylene(UHMWPE), and its attenuated total reflectance infrared spectrogram is at 1100cm
-1there is the absorption peak of carbon-fluorine covalent linkage left and right; 3000cm
-1~ 3500cm
-1between broad peak and 1700cm
-1there is the absorption peak of hydroxyl and carboxylic group at neighbouring peak, combines can have fluorine element power spectrum peak in place at the 687eV of x-ray photoelectron energy spectrogram.
The present invention compared with prior art, has following beneficial effect:
1, because ultrahigh molecular weight polyethylene(UHMWPE) contained in High wear resistant polymer blend material provided by the invention or goods is through direct fluorinated surface process, a large amount of carbon-fluorine covalent bond structure and carboxylic, oh group is just introduced like this on its surface, thus ultrahigh molecular weight polyethylene(UHMWPE) surface polarity is not only solved weak, be difficult to the problem of stable dispersion in the polymer, the abrasion resistance properties of its brilliance and good self-lubricating property can be given full play to again.
2, because ultrahigh molecular weight polyethylene(UHMWPE) contained in High wear resistant polymer blend material provided by the invention or goods has excellent over-all properties, especially its wearability, frictional property, thus the frictional dissipation making the polymer materials of blended gained not add the ultrahigh molecular weight polyethylene(UHMWPE) system of fluorine-contained surface reduces 30 ~ 60%, tear strength improves 5 ~ 25%, shock strength improves 20 ~ 50%, and the economic benefit brought therefrom and social benefit are all very considerable.
3, because ultrahigh molecular weight polyethylene(UHMWPE) contained in High wear resistant polymer blend material provided by the invention or goods also has good self-lubricating property, thus with the blended course of processing of matrix polymer in not only can not have a negative impact, also can play the effect of lubricant, save the lubricant adding other again, to reduce costs.
4, owing to containing 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 process, thus can the polymer materials of blended its wear resistance of raising with it in extensive range, can be the thermosetting resins such as casting type polyurethane, epoxy resin, resol, also can be the thermoplastic resin such as nylon, polycarbonate, can also be the elastomerics such as polyethers or PAUR.
5, because preparation method provided by the invention is with fluoridizing gas mixture process by ultrahigh molecular weight polyethylene(UHMWPE); treating processes is simple to operate; Be very effective; thus prior art not only can be avoided to adopt multiple polyfunctionality reaction monomers to carry out successive reaction; need to consume complex operation that a large amount of solvent brings simultaneously, high expensive, solvent difficulty reclaim and the problem such as environmental pollution; and cost is lower; be easy to accomplish scale production, simultaneously also for the surface treatment of ultrahigh molecular weight polyethylene(UHMWPE) provides a new approach.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum figure of high abrasion polymer blend section prepared by the embodiment of the present invention 1, and the ultrahigh molecular weight polyethylene(UHMWPE) powder of fluorine-contained surface is dispersed in polyurethane elastomer as seen from the figure.
Fig. 2 is the Electronic Speculum figure of intermingling material section prepared by comparative example 2, and untreated ultrahigh molecular weight polyethylene(UHMWPE) powder disperses not to be very even in polyurethane elastomer as seen from the figure.
The infrared spectrogram of the ultrahigh molecular weight polyethylene(UHMWPE) powder of the fluorine-contained surface of Fig. 3 obtained by the embodiment of the present invention 1, shows in figure, 1100cm
-1there is the absorption peak of carbon-fluorine covalent linkage left and right; 3000cm
-1~ 3500cm
-1between broad peak and 1700cm
-1there is the absorption peak of hydroxyl and carboxylic group at neighbouring peak.
Ultrahigh molecular weight polyethylene(UHMWPE) X-ray powder photoelectron spectrum figure (XPS) of the fluorine-contained surface of Fig. 4 obtained by the embodiment of the present invention 1, in figure, 687eV combines the peak that can locate is fluorine element power spectrum peak.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; 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, the wear resistance of following embodiment and comparative example resulting materials measures according to GB/T 9867-2008 or GB 3960-83 respectively; Tear strength is the mensuration according to GB/T529-1999, and shock strength measures and measures according to GB/T 2571-1995, and test result sees attached list.
Embodiment 1
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 10 μm is placed in airtight vacuum reactor by particle diameter, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of delivery of fluorine/nitrogen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 25kPa, to its fluoridation 0.5 hour at 25 DEG C, after then adopting the remaining fluorinated gas of nitrogen replacement, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that namely reactor obtains surface fluorination; First by 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dried 100 parts of PAUR elastomerics premixs evenly and melt blending granulations.
Embodiment 2
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 50 μm is placed in airtight vacuum reactor by particle diameter, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/argon gas is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 5kPa, to its fluoridation 1 hour at 40 DEG C, after then adopting the remaining fluorinated gas of nitrogen replacement, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that namely reactor obtains surface fluorination; First by 15 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dried 100 parts of PAUR premixs evenly and melt blending granulations.
Embodiment 3
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 100 μm is placed in airtight vacuum reactor by particle diameter, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/oxygen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 20kPa, to its fluoridation 2 hours at 50 DEG C, after then adopting the remaining fluorinated gas of nitrogen replacement, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that namely reactor obtains surface fluorination; First by 30 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dried 100 parts of PAUR premixs evenly and melt blending granulations.
Embodiment 4
Be 3mm by length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 15 μm is placed in airtight vacuum reactor, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with the gas mixture of delivery of fluorine/nitrogen, control fluorine gas in the reactor dividing potential drop be 25kPa, to its fluoridation 0.5 hour at 50 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that namely reactor obtains surface fluorination is opened; First by 5 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dried 100 parts of PAUR premixs evenly and melt blending granulations.
Embodiment 5
Be 5mm by length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 20 μm is placed in airtight vacuum reactor, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with the gas mixture of delivery of fluorine/nitrogen, control fluorine gas in the reactor dividing potential drop be 25kPa, to its fluoridation 0.5 hour at 75 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that namely reactor obtains surface fluorination is opened; First by 5 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dried 100 parts of PAUR premixs evenly and melt blending granulations.
Embodiment 6
Be 10mm by length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 25 μm is placed in airtight vacuum reactor, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with the gas mixture of delivery of fluorine/nitrogen, control fluorine gas in the reactor dividing potential drop be 25kPa, to its fluoridation 0.75 hour at 25 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that namely reactor obtains surface fluorination is opened; First by 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dried 100 parts of PAUR premixs evenly and melt blending granulations.
Embodiment 7
Be 1mm by length, to be the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 15 μm and particle diameter be diameter that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 20 μm is placed in airtight vacuum reactor simultaneously, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/oxygen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 30kPa, to its fluoridation 1 hour at 50 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, ultrahigh molecular weight polyethylene(UHMWPE) short fiber and powder that namely reactor obtains surface fluorination is opened; First by 5 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber, 20 parts fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dried 100 parts of PAUR premixs evenly and melt blending granulations.
Embodiment 8
Be 3mm by length, to be the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 10 μm and particle diameter be diameter that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 20 μm is placed in airtight vacuum reactor simultaneously, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/oxygen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 40kPa, to its fluoridation 1 hour at 25 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, ultrahigh molecular weight polyethylene(UHMWPE) short fiber and powder that namely reactor obtains surface fluorination is opened; First by 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber, 20 parts fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dried 100 parts of polyether(poly)urethane premixs evenly and melt blending granulations.
Embodiment 9
Be 5mm by length, to be the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 20 μm and particle diameter be diameter that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 30 μm is placed in airtight vacuum reactor simultaneously, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/oxygen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 20kPa, to its fluoridation 2 hours at 75 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, ultrahigh molecular weight polyethylene(UHMWPE) short fiber and powder that namely reactor obtains surface fluorination is opened; First by 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber, 10 parts fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dried 100 parts of polyether(poly)urethane premixs evenly and melt blending granulations.
Embodiment 10
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 10 μm is placed in airtight vacuum reactor by particle diameter, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/oxygen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 25kPa, to its fluoridation 0.75 hour at 50 DEG C, after then adopting the remaining fluorinated gas of nitrogen replacement, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that namely reactor obtains surface fluorination; By 100 parts of MDI Type Polyurethane Prepolymers, 20 parts to fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder blended and after deaeration in 90 DEG C of vacuum stirring, add 20 parts of chainextenders 3,3'-bis-chloro-4,4'-diaminodiphenyl-methane or two adjacent chlorodiphenyl amine methane (MOCA), rapid stirring, after 2 ~ 3 minutes, is poured into rapidly in mould, and baking obtains cast high abrasion blending polyester type polyurethane.
Embodiment 11
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 50 μm is placed in airtight vacuum reactor by particle diameter, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/oxygen/argon is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 50kPa, to its fluoridation 2 hours at 50 DEG C, after then adopting the remaining fluorinated gas of nitrogen replacement, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that namely reactor obtains surface fluorination; By 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, N-dimethylbenzyl amine catalyst for 10 parts, be warming up to 90 DEG C and continue stirring 1 hour, under mixed solution vacuum, after deaeration, cast cured explosive becomes goods.Curing process is followed successively by: 120 DEG C/lh, 140 DEG C/lh, l50 DEG C/1.5h.
Embodiment 12
Be ultrahigh molecular weight polyethylene(UHMWPE) powder and the length of 10 μm by particle diameter be 5mm, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 17 μm is placed in airtight vacuum reactor simultaneously, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of fluorine gas/oxygen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 30kPa, to its fluoridation 0.5 hour at 40 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, ultrahigh molecular weight polyethylene(UHMWPE) powder and short fiber that namely reactor obtains surface fluorination is opened; By 100 parts of heat-reactive phenolic resins, fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and short fiber each 5 parts stir 1 hour, under mixed solution vacuum, after deaeration, cast cured explosive becomes goods.Condition of cure is 150 DEG C of solidifications 4 hours.
Embodiment 13
Be that the ultrahigh molecular weight polyethylene(UHMWPE) powder of 10 μm is placed in airtight vacuum reactor by particle diameter, then vacuumize, and with after the air in nitrogen replacement reactor three times, the gas mixture of delivery of fluorine/nitrogen is filled with in vacuum reactor, control fluorine gas in the reactor dividing potential drop is 25kPa, to its fluoridation 0.5 hour at 40 DEG C, after then adopting the remaining fluorinated gas of nitrogen replacement, open the ultrahigh molecular weight polyethylene(UHMWPE) powder that namely reactor obtains surface fluorination; First by 20 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) powder and dried 100 parts of Nylon 6 premixs evenly and melt blending granulations.
Embodiment 14
Be 1mm by length, diameter is that the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 10 μm is placed in airtight vacuum reactor, then vacuumize, and with after the air in nitrogen replacement reactor three times, in vacuum reactor, be filled with the gas mixture of fluorine gas/oxygen, control fluorine gas in the reactor dividing potential drop be 25kPa, to its fluoridation 0.5 hour at 75 DEG C, then, after adopting the remaining fluorinated gas of nitrogen replacement, the ultrahigh molecular weight polyethylene(UHMWPE) short fiber that namely reactor obtains surface fluorination is opened; First by 10 parts this fluoridize ultrahigh molecular weight polyethylene(UHMWPE) short fiber and dried 100 parts of Nylon 66 premixs evenly and melt blending granulations, then injection moulding obtains goods.
Comparative example 1
By the direct blended granulation of ultrahigh molecular weight polyethylene(UHMWPE) powder that 100 parts of dried PAUR elastomericss and 10 parts of particle diameters are 10 μm, then injection moulding.
Comparative example 2
By the dried direct injection moulding of pure PAUR elastomerics.
Comparative example 3
Be 1mm by 100 parts of dried polyether(poly)urethane elastomericss and length, diameter to be the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 20 μm and particle diameter be ultrahigh molecular weight polyethylene(UHMWPE) powder each 10 parts of blended granulations, the then injection mouldings of 10 μm.
Comparative example 4
By the dried direct injection moulding of pure polyether(poly)urethane elastomerics.
Comparative example 5
Be that 10 μm of ultrahigh molecular weight polyethylene(UHMWPE) powder directly carry out sulfuration casting by the method for embodiment 10 by 100 parts of MDI Type Polyurethane Prepolymers and 20 parts of particle diameters.
Comparative example 6
MDI Type Polyurethane Prepolymer is directly carried out sulfuration casting with the vulcanization process of embodiment 10.
Comparative example 7
The ultrahigh molecular weight polyethylene(UHMWPE) powder being 50 μm by 100 parts of epoxy E-51 resins and 10 parts of particle diameters is directly cured shaping with the curing of embodiment 11.
Comparative example 8
Epoxy E-51 resin is directly cured shaping with the curing of embodiment 11.
Comparative example 9
Be ultrahigh molecular weight polyethylene(UHMWPE) powder and the length of 10 μm by 100 parts of heat-reactive phenolic resins and particle diameter be 5mm, diameter is that each 5 parts of the ultrahigh molecular weight polyethylene(UHMWPE) short fiber of 20 μm is directly cured shaping with the curing of embodiment 12.
Comparative example 10
Heat-reactive phenolic resin is directly cured shaping with the curing of embodiment 12.
Comparative example 11
By 100 parts of dried Nylon 6s and 20 parts of particle diameters be the ultrahigh molecular weight polyethylene(UHMWPE) powder premix of 10 μm evenly and melt blending granulation, then injection moulding.
Comparative example 12
Dried Nylon 6 is directly carried out injection moulding.
Comparative example 13
Be 1mm by 100 parts of dried Nylon 66s and 10 parts of length, diameter be the ultrahigh molecular weight polyethylene(UHMWPE) short fiber premix of 10 μm evenly and melt blending granulation, then injection moulding.
Comparative example 14
Dried Nylon 66 is directly carried 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 example 1 | 20.1 | 92.0 | |
| Comparative example 2 | 23.2 | 90.2 | |
| Comparative example 3 | 21.5 | 91.0 | |
| Comparative example 4 | 25.8 | 88.1 | |
| Comparative example 5 | 14.2 | 75.2 | |
| Comparative example 6 | 20.1 | 97.7 | |
| Comparative example 7 | 2400.9 | 7.4 | |
| Comparative example 8 | 3679.2 | 6.5 | |
| Comparative example 9 | 1687.5 | 7.1 | |
| Comparative example 10 | 2015.1 | 6.0 | |
| Comparative example 11 | 136.0 | 5.6 | |
| Comparative example 12 | 162.4 | 5.2 | |
| Comparative example 13 | 94.6 | 6.4 | |
| Comparative example 14 | 126.7 | 5.4 |
Claims (18)
1. a preparation method for High wear resistant polymer blend material, processing step and the condition of the method are as follows:
1) ultrahigh molecular weight polyethylene(UHMWPE) is placed in airtight vacuum reactor to vacuumize and after using the remaining air of inert gas replacement reactor, fluorine gas gas mixture is filled with in vacuum reactor, to its fluoridation 0.1 ~ 2 hour at 25 ~ 75 DEG C, after using the remaining fluorinated gas of nitrogen replacement again, namely obtain the polyethylene fluoridizing ultra-high molecular weight, wherein fluorine gas dividing potential drop is in the reactor 5 ~ 50kPa;
2) first that matrix polymer 100 parts is even with polyethylene 5 ~ 30 parts of premixs fluoridizing ultra-high molecular weight, then processing mode is conveniently prepared into material,
Ultrahigh molecular weight polyethylene(UHMWPE) wherein used be powder or/and short fiber, the particle diameter of powder is 10 ~ 100 μm, and staple length is 1 ~ 10mm, and diameter is 10 ~ 25 μm.
2. the preparation method of High wear resistant polymer blend material according to claim 1, in the method, fluorine gas dividing potential drop is in the reactor 20 ~ 30KPa.
3. the preparation method of High wear resistant polymer blend material according to claim 1, in the method, fluorine gas dividing potential drop is in the reactor 25KPa.
4. the preparation method of the High wear resistant polymer blend material according to claim 1 or 2 or 3, in the method, temperature of reaction is 25 ~ 50 DEG C, and the reaction times is 0.5 ~ 1 hour.
5. the preparation method of High wear resistant polymer blend material according to claim 4, ultrahigh molecular weight polyethylene(UHMWPE) used in the method be powder or/and short fiber, the particle diameter of powder is 20 ~ 50 μm, and staple length is 1 ~ 5mm, and diameter is 15 ~ 20 μm.
6. the preparation method of the High wear resistant polymer blend material according to claim 1 or 2 or 3, fluorine gas gas mixture used in the method is made up of at least one in fluorine gas and oxygen, nitrogen and argon gas.
7. the preparation method of High wear resistant polymer blend material according to claim 5, fluorine gas gas mixture used in the method is made up of at least one in fluorine gas and oxygen, nitrogen and argon gas.
8. the High wear resistant polymer blend material prepared by method described in claim 1, ultrahigh molecular weight polyethylene(UHMWPE) containing fluorine-contained surface in this blended polymer material, 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 is urethane, its frictional dissipation is 8 ~ 15.2mm
3, tear strength is 97.4 ~ 112.4kNm
-1; When the matrix polymer in this blended polymer material is thermosetting resin, its frictional dissipation is 1132.6 ~ 1890.2mm
3, shock strength is 8.9 ~ 9.2kJm
-2; When the matrix polymer in this blended polymer material is nylon, its frictional dissipation is 75.0 ~ 99.2mm
3, shock strength is 6.9 ~ 7.4kJm
-2.
9. High wear resistant polymer blend material according to claim 8, in this blended polymer material, the ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is 10 ~ 20 parts.
10. a preparation method for high abrasion blending polymerization Tetramune, processing step and the condition of the method are as follows:
1) ultrahigh molecular weight polyethylene(UHMWPE) is placed in airtight vacuum reactor to vacuumize and after using the remaining air of inert gas replacement reactor, fluorine gas gas mixture is filled with in vacuum reactor, to its fluoridation 0.1 ~ 2 hour at 25 ~ 75 DEG C, after using the remaining fluorinated gas of nitrogen replacement again, namely obtain the polyethylene fluoridizing ultra-high molecular weight, wherein fluorine gas dividing potential drop is in the reactor 5 ~ 50kPa;
2) first that matrix polymer 100 parts is even with polyethylene 5 ~ 30 parts of premixs fluoridizing ultra-high molecular weight, then processing mode is conveniently prepared into goods,
Ultrahigh molecular weight polyethylene(UHMWPE) wherein used be powder or/and short fiber, the particle diameter of powder is 10 ~ 100 μm, and staple length is 1 ~ 10mm, and diameter is 10 ~ 25 μm.
The preparation method of 11. high abrasion blending polymerization Tetramunes according to claim 10, in the method, fluorine gas dividing potential drop is in the reactor 20 ~ 30KPa.
The preparation method of 12. high abrasion blending polymerization Tetramunes according to claim 10, in the method, fluorine gas dividing potential drop is in the reactor 25KPa.
The preparation method of 13. high abrasion blending polymerization Tetramunes according to claim 10 or 11 or 12, in the method, temperature of reaction is 25 ~ 50 DEG C, and the reaction times is 0.5 ~ 1 hour.
The preparation method of 14. high abrasion blending polymerization Tetramunes according to claim 13, ultrahigh molecular weight polyethylene(UHMWPE) used in the method be powder or/and short fiber, the particle diameter of powder is 20 ~ 50 μm, and staple length is 1 ~ 5mm, and diameter is 15 ~ 20 μm.
The preparation method of 15. high abrasion blending polymerization Tetramunes according to claim 10 or 11 or 12, fluorine gas gas mixture used in the method is made up of at least one in fluorine gas and oxygen, nitrogen and argon gas.
The preparation method of 16. high abrasion blending polymerization Tetramunes according to claim 14, fluorine gas gas mixture used in the method is made up of at least one in fluorine gas and oxygen, nitrogen and argon gas.
17. 1 kinds of high abrasion blending polymerization Tetramunes prepared by method described in claim 10, ultrahigh molecular weight polyethylene(UHMWPE) containing fluorine-contained surface in this blending polymerization Tetramune, 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 blending polymerization Tetramune is urethane, its frictional dissipation is 8 ~ 15.2mm
3, tear strength is 97.4 ~ 112.4kNm
-1; When the matrix polymer in this blending polymerization Tetramune is thermosetting resin, its frictional dissipation is 1132.6 ~ 1890.2mm
3, shock strength is 8.9 ~ 9.2kJm
-2; When the matrix polymer in this blending polymerization Tetramune is nylon, its frictional dissipation is 75.0 ~ 99.2mm
3, shock strength is 6.9 ~ 7.4kJm
-2.
18. high abrasion blending polymerization Tetramunes according to claim 17, in this blending polymerization Tetramune, the ultrahigh molecular weight polyethylene(UHMWPE) of fluorine-contained surface is 10 ~ 20 parts.
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