CN100455866C - Pipeline of polar polymer and poleless polymer composing with metal reinforcement - Google Patents
Pipeline of polar polymer and poleless polymer composing with metal reinforcement Download PDFInfo
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- CN100455866C CN100455866C CNB2006100204733A CN200610020473A CN100455866C CN 100455866 C CN100455866 C CN 100455866C CN B2006100204733 A CNB2006100204733 A CN B2006100204733A CN 200610020473 A CN200610020473 A CN 200610020473A CN 100455866 C CN100455866 C CN 100455866C
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Abstract
The invention provides a polar polymer and a non-polar polymer and a metallic reinforcement combined canal, the combined canal wall is formed by firm gluing and coating of grafting modified polyolefin polymer continuum with polar group with inner-outer surfaces of apertures on metallic reinforcement frame, a non-polar polyolefin polymer layer is coated on inner or outer layer of the canal wall. The invention solves technical problem of hard integral gluing of metallic and polyethylene combination interface, and reduces the cost and has a appreciable economic benefit, which provides reliable and convenient connections.
Description
Technical field:
The present invention relates to the graft modification of polyolefine material, it is modified as polar polymer by non-polar polymer, relate to the compound pipe production technology of metal and polyolefin, go on foot pertusate relevant especially as the compound pipeline of the metal cylindrical skeleton that strengthens body and the polyolefine material that polarity is arranged and nonpolarity polyolefine material.
Background technique:
The compound pipeline of metal and polymer thing comprises tubing and existing many technology and the patent reports of pipe fitting, also has a large amount of products and engineering to use in practical engineering application, and this multiple tube has become important industry at continuous development and progress.
Metallic conduit has higher intensity and the lower hot line coefficient that expands, but it is not corrosion-resistant, not only can not carry corrosive fluid, even carry not corrupt liquid, etc. at least also will do the preservative treatment of surperficial anti-electrocorrosion during application with burying.Polymer pipe has Corrosion Protection preferably, also convenient the connection, carry at potable water and corrosive fluid, the chemical engineering application facet, extraordinary usability is arranged, but have relatively high expectations, the bearing capacity reduction greatly of simple polymerisation pipe when the conveyance fluid temperature is higher than 50 ℃～80 ℃ at discharge pressure, particularly the bloated coefficient of hot line is more than ten times of metal tube, and the application of simple polymerisation pipe is restricted.
Because above-mentioned two kinds of pipes respectively have excellent performance, but each has unsurmountable problem to exist again, so the compound pipeline of metal and polymer is as a kind of advantages, and the pipeline that shortcoming overcomes has had significant progress.This composite pipe many with metal tube or skeleton as strengthening body, according to requirement of engineering wall and/or outer wall composite pipe polymer material within it.Because inside and outside wall composition polymer at pipe, this polymer is mainly born anti-corrosion function, so the connection between tube and tube, the tube and tube spare also mainly relies on being welded to connect or being threaded between metal tube and the skeleton, can't stand the system pressure requirement with docking also to hold by the melting welding between the polymer.Particularly diameter is at the pipeline of φ more than 630, being welded to connect between the basic dependence metal tube, even the pipe of φ below 630 welded, but inwall is because soldered can't enter personnel, composition polymer butt joint place is anticorrosion once more, and metal tube and polymer pipe are encountered difficulties in the engineering application less than the composite pipe of φ below 630.If because to metal tube and skeleton butt welding or be threaded, the local inwall of the ruinate polymer composite layer in joint can't be repaired.Therefore under this background, as strengthening body multiple tube of composition polymer on skeleton sufficient development has been arranged with pertusate metal frame.This pipe intensity mainly strengthens skeleton by metal and bears, the polymer continuum is mainly born anticorrosion and tube and tube, fusion between the tube and tube uncle connects, but polymer and metal tube, compound many important techniques difficulties and the problem of also existing between the metal cylindrical skeleton.General antiseptic property is good, chemical resistance is good, carry the standard compliant polymer of potable water all to belong to non-polar polymer such as polyethylene (PE) and polypropylene (PP), but interface compound with it or surface are the metal surfaces, as the aluminium sheet band, the steel plate band, these surfaces are typical polar surfaces, can not bond and affinity between the two at all, though the polymer continuum coats its surface and is compound, separate but the interface is actual, people are when producing and using this multiple tube for this reason, the bonding at the two interface, affinity is realized having adopted a lot of ways on truly compound.Because do not solve the affinity at the two interface, can not make the two interface really bonding, firmly compound is one, in fact the common composite material of bringing into play of our inreal the two excellent properties of acquisition.
The steel metal surface of known and disclosed non-polar polymer (as PE or PP) and polarity and the secure bond on aluminum metal surface, be combined with each other, up to the present also mainly be to rely between the two interface, increase one deck adhesive layer or apply the transition layer that one deck can make the two affinity and firmly be combined with each other.Concrete technological scheme has many kinds.A kind of be between the interface, use polar group arranged but the Bond that can merge and be bonded as one with non-polar polymer, ethylene-ethyl acrylate copolymer such as commercially available binary copolymerization, ethylene-acrylic acid copolymer, with ethene-vinyl acetate-ethenol copolymer of ternary polymerization or the like, another kind is to apply one deck transition layer in advance in the metal surface such as epoxy resin, compound again one deck ethylene-vinyl acetate copolymer on it, compound with nonpolar polymer again.
The transition layer of these adhesive layers or coating can both be better with polarity metal surface and firm being combined with each other of nonpolar polymer.But owing to need the special coating equipment of extruding to apply this layer binder layer, on the production line of composite pipe, need at least two of many increases to extrude the equipment of coating at metal tube or skeleton inner and outer surface respectively, investment is increased, cost of production increases, technology is wayward, special in the less production line of diameter such as φ 200 pipes, be difficult.In order to make Bond can effectively be coated in the metal frame surface, and abundant moistening metal polar surfaces, the processing fusing point person of general these Bonds is lower, melt index is higher, though on the interface, can be easy to the two interface bonding compound, but when composite pipe during in higher serviceability temperature, this layer binder layer can produce on the interface again because of the low not enough slippage of temperature resistant capability of fusing point, destroyed to combine and born pressure-bearing and excellent function anticorrosion and that be connected as the two, make the nonpolar compound polymeric layer and the compound also corresponding generation slippage of metal surface, reduced the heatproof engineering application of temperature of composite pipe, reality has reduced the engineering property of pipe.This in addition adhesive layer complex technique is in the application on pertusate metal frame surface, can make by hole and coat of not heatproof fusion and the slippage of the polymer continuum of skeleton because of adhesive layer, reduce the heatproof engineering property of composite pipe greatly, when serious even can make of hole the internal and external layer of skeleton between the slippage of non-polar polymer continuum by skeleton, destroyed and combined as the two that to have born pressure anticorrosion and link firm excellent properties, and reduce the bearing capacity of this composite pipe delivering hot water's medium and aggressive medium greatly, therefore promptly to strengthen the body skeleton and produce the pipeline compound with polymer by pertusate metal, so that solve the composite pipe of the aforesaid φ of convenience 630 following calibers, utilize the polymer continuum to realize tube and tube, fusion between the tube and tube spare connects, utilize simultaneously the hole of skeleton that the bloated expansion of hot line that the continuum that coats is higher than ten times of metallic material is pinned again, make continuum and composite pipe have class formula metal and and the line of metal frame expand rate and give full play to the excellent properties of the compound composite pipe of the polymer of pertusate metal frame, make polymer continuum and metal polar surfaces secure bond and compound again, prevent that the two interface and section from having infirm compound the infiltrate through combination interface of flowing medium because of the interface, pipeline corrosion protection and leakproof linkage function were lost efficacy, better for using at the two interface, cost is lower, compound more reliable, produce more convenient, the interface secure bond that can give full play to again for the composite pipe function and compound new technological scheme, the emphasis that has become industry to pursue.The author had once applied for many patents and had made many conceptual designs for this reason, but all fail to jump out aforesaid those several basic schemes, more there is not scheme, the market industry does not have scheme to relate to utilize the polymer continuum can adopt the modify and graft polar group to make non-polar polymer directly have polarity yet and can directly coat metal frame with the secure bond combined polarity, the technological scheme of pertusate metal frame particularly, so, even the two interface secure bond and compound be one, pertusate metal frame and polymer continuum are connected as a single entity by hole, prevent that promptly the polymer continuum from producing the bloated or thermal expansion of the line that is higher than ten times of metal frames of polymer, can be one because of it is firmly compound again, can couple together by pipe or the hot melt of pipe fitting outer wall or the molten internal and external layer polymer melting of electric heating and be pipe network its skeleton hole, realize that reliable pipe network fusion connects, solve the compound pipeline of metal and polymer and can not give full play to its excellent properties, can not conveniently connect, the two interface be difficult for secure bond compound for one or compound for one must relate to adhesive layer or the coating transition layer investment big, a cost high-technology difficult problem.
The application number 200510020523 of the applicant's application, in in September, 2005 disclosed steel-plastic composite pipe production method and device the polymer continuum that adopts maleic anhydride or acrylic ester grafted polymer to make the clad metal skeleton was once disclosed in specification, and the weight ratio and the polyethylene or the polypropylene blending modified technological scheme that is used as continuum that do not have grafting that adopt the above-mentioned graft polymer 15～30% of more economical usefulness, but in the industry the professional person only all know with the blend ratio realize firm bonding and compound be disclose inadequate, because of different polymer materials and the percent grafting of the different unsaturated carboxylic acid that contains utmost point polar group are big differences very, can produce percent grafting in 0.3～6% scope, to realize real secure bond and compound with the polar surfaces of metal such as steel and aluminium, under there is certain condition on the surface, the percent grafting of above-mentioned polymer and unsaturated carboxylic acid will reach the percent grafting more than 0.12% at least, if simply with 15～30% weight blend recently, technological scheme does not realize purpose, with nonpolar polyolefine material graft modification is the polyolefine material that polarity is arranged, at least relate to unsaturated carboxylic acid and peroxide grafted initator, the supplementary material prescription of these modifications, formulation cost for each ton material is higher than 1000 yuan of the same materials of not modification at least, pass through the reaction extruding pelletization of extruder in addition, it is per ton more than 1000 yuan also need to increase direct cost, so all produce composite metal plastic pipe with being modified as the polar polyolefin material, though performance improves a lot, but in order to enlarge its engineering application area and to reduce engineering cost, how to reduce the cost of material of pipe wall and maintain advantage and the superperformance that polar polyolefin and metal frame strengthen the pipeline of bluk recombination again, adopt MULTILAYER COMPOSITE on the structure of tube wall, adopting the non-polar polyolefinic material of low-cost non-modified to produce especially is the very effective technological scheme that reduces cost.
Summary of the invention:
The objective of the invention is in order to overcome above deficiency, provide a kind of metal and compound the two interface of polyethylene of solving to be difficult for that secure bond is compound to be the technical barrier of one, the pipeline that polar polymer and nonpolarity polymer enhancing body metal composite are arranged that reduces cost, have tangible economic benefit, can reliable, conveniently be connected.
The object of the present invention is achieved like this:
The present invention has polar polyolefin polymer and nonpolarity polyolefin polymer and metal to strengthen the pipeline of bluk recombination, the tube wall of multiple tube is to be strengthened the hole secure bond surperficial with it on the body skeleton and coat by porose hole metal by the polyolefin polymer continuum with polar group through graft modification to form, internal layer or skin at this tube wall are compounded with one deck non-polar polyolefinic polymeric layer, compound pipeline, polar group being arranged or the polar group of the polyolefin continuum of polarity being arranged of composite pipe tube wall is carboxyl or hydroxyl or carbonyl or anhydride group, its percent grafting is that 0.12%～3% also promptly to measure its gel fraction be 0.12%～3%, and its infrared spectrogram has the characteristic absorption peak of typical above-mentioned polar group.Adopting this scheme that nearly 50% material is arranged in the polymer material of tube wall is the nonpolar polymer that does not need graft modification, if the tube wall design is thicker, there is nearly 65% material not need modification, the cost of material of polymer is reduced by 8～15% at least, tangible economic benefit is arranged, if adopt the unmodified nonpolar polyolefine material of compound one deck at the internal layer of carrying drinking-water pipe, will make its sanitary index better, the superoxide and the organic acid of the residual trace of the polymer that polarity is arranged of modification had better obstruct and shielding.
Above-mentioned compound pipeline, the continuum of compound tube wall is that poly polymer with polar group forms through extruder extruding graft reaction modifying by a kind of in a kind of and high density polyethylene (HDPE) (HDPE) in maleic anhydride (MAH), the acrylic acid series (MMA, AA), the non-crosslinked heat-proof polythene (PE-RT) arranged under the effect of peroxide grafted initator, is high density polyethylene (HDPE) (HDPE) or non-crosslinked heat-proof polythene (PE-RT) at the internal layer or the compound one deck nonpolar polyolefin hydrocarbon polymer of skin of this tube wall.This scheme has ripe disclosed prescription and technology, with maleic anhydride (MAH) and PE-RT grafting, there are ripe disclosed prescription and technology can obtain the good polyethylene that polarity is arranged of temperature tolerance, on hot water pipe net, use, compound interface is being higher than 80 ℃, and pressure uses greater than 0.8Mpa special impermeable ability.Because non-crosslinked heat-proof polythene (PE-RT) has the excellent heat resistance energy, be only second to crosslinked polyethylene in polyethylene product kind, but it has processibility easily and needn't must be through the trouble operation of hydrolytie polycondensation cross-linking reaction as organosilane crosslinked polyethylene, the performance that makes things convenient for melting to connect is arranged again than peroxide crosslinked polyethylene, percent grafting can reach more than 0.5%, after the grafting not only heat resistance do not descend, owing to metal frame better bonding is arranged after being modified as polarity, more can reduce 5%, promptly improve bearing capacity with strengthening reduction that body bears the heatproof long-time running of hot water pipe net and bearing capacity composite pipe than the PE-RT of not modification.Owing to saved this expensive cost of material greatly at tube wall internal layer or the outer compound nonpolar non-crosslinked heat-proof polythene of one deck (PE-RT), can enlarge its applying at northern hot water pipe net.In this scheme since on the HDPE of polarity material the compound nonpolar HDPE of one deck particularly compound at internal layer, improved its sanitation performance index greatly and saved cost of material.
Above-mentioned compound pipeline, the continuum of multiple tube tube wall is by maleic anhydride (MAH) is arranged, methyl methacrylate (MMA), acrylic acid (AA), methacrylic acid carboxylic acetate (HEMA), a kind of and polypropylene (PPB in the methyl propenoic acid glycidyl fat (GMA), PPH), a kind of under the effect of peroxide grafted initator in the atactic copolymerized polypropene (PP-R), through extruder extruding graft reaction modifying is that the polyacrylic polymer with polar group is formed, and is polypropylene (PPB at internal layer or outer compound one deck nonpolar polyolefin hydrocarbon polymer of this tube wall, PPH) or atactic copolymerized polypropene (PP-R).This scheme has ripe disclosed prescription and technology, obtained the conveyance conduit of hot water pipe net and heat-resisting chemical fluid medium with this scheme, PP-R pipeline particularly, owing to the humidification of metal frame and the heat-resisting excellent properties of PP-R are arranged, have enlarged the application of polypropylene pipe on the chemical fluid engineering.
Above-mentioned compound pipeline, the continuum of multiple tube tube wall is organosilane crosslinked polyethylene or the silane cross-linkable polyethylene continuum that polar group is arranged, at the internal layer or the outer compound crosslinked heat-proof polythenes of one deck nonpolar polyolefin hydrocarbon polymer right and wrong (PE-RT) of this tube wall.Crosslinked with silicane (or silane-crosslinkable) is PE modified for the polymer of polar group is arranged, carry out the first step in two steps: be to be silane cross-linkable polyethylene by maturation disclosed silane grafting prescription and technology with its grafting with polyethylene respectively; Be the polyethylene that polar group is arranged with polyethylene by disclosed prescription of maturation and method grafting on one side in addition; Second step: the two mixes and extrudes to the silane cross-linkable polyethylene of polarity is arranged, and the material gel rate that obtains like this is lower than 60%.If being the polyethylene with the hexasilane grafting, the 2nd step directly adds unsaturated carboxylic acids such as maleic anhydride, utilizing remaining initator and already present free radicals is the material that polar group is arranged with the polycthylene grafted reaction of hexasilane grafting, and this kind method silane percent grafting (or being gel fraction) is greater than 60%.
Above-mentioned compound pipeline, the continuum of multiple tube tube wall are crosslinked with silicane polypropylene or the silane-crosslinkable polypropylene continuuies that polar group is arranged, at the internal layer or the outer compound crosslinked polypropylene of one deck nonpolar polyolefin hydrocarbon polymer right and wrong of this tube wall.Its technology and production method are same as crosslinked with silicane (or silane-crosslinkable) polyethylene substantially.
Above-mentioned compound pipeline, the continuum of multiple tube tube wall is the polyolefin of polar group to be arranged and do not have the nonpolar polyolefin blend of graft modification to make, and its blend percent grafting is at least greater than 0.12% (gel fraction of also promptly measuring its polymer that polar group is arranged is at least greater than 0.12%).Graft modification has the polyethylene of polar group, its percent grafting is generally 0.5%～0.8%, if the polypropylene that has styrene monomer to participate in graft reaction is 2～3%, if hole steel band metal frame surface is arranged handles through cleaning and texturing, the percent grafting of general carboxyl or hydroxyl or carbonyl or anhydride group polar group reaches 0.12% above continuum just can the firm and compound good skeleton surface of effective adhesive, therefore the polyolefin and the nonpolar polyolefinic mixed proportion of polarity are arranged, can in certain proportion, adjust according to the adhesive property on metal frame surface fully.If the polar polyethylene percent grafting is arranged greater than 0.72%, the nonpolar polyethylene of mixed proportion can be 70～80%, it is greater than 20% that polar polyethylene is arranged, just can bond through the tubular metal frame of cleaning and coat firmly, if the polypropylene grafted rate of polarity is arranged is 3%, the mixed proportion non-polar polypropylene can be 90%～95%, it is 5%～10% that polar polypropylene is arranged, should be able to and coat firmly the skeleton bonding, and can bear 20 ℃ of water temperatures of compound interface (section), the pressure-bearing impermeable, that tear, tear compound interface of 0.6Mpa hydraulic pressure is tested.With former in application number 200510020523 a scheme comparative descriptions of disclosed additional proportion 15～30% weight ratios, former scheme is not definite, say at 0.4% polyethylene for percent grafting because of being lower than 20% ratio, represent that promptly the blend composition percent grafting is lower than 0.12%, actual be can not with metal polar surfaces secure bond and compound and bear of the test of the water of certain pressure to the pressure permeation at interface.For the polypropylene that percent grafting is 2%～3%, be lower than 15% and participate in ratio, connect the skill rate and still be higher than 0.12% and still can pass through pressure test.This scheme can coat skeleton than tube wall and all use grafted material to save cost, makes this kind coat pipeline that skeleton forms tube wall by polar polyolefin and has the market competition ability and widely applied.
Above-mentioned compound pipeline, the continuum of multiple tube tube wall is that the mass percent that polar group is arranged of graft modification is that 5～60% polypropylene and mass percent are the silane cross-linkable polyethylene of 40～95% unsaturated carboxylic acid graft modifications of no use, blend is extruded, becoming through crosslinked polycondensation reaction has the crosslinked with silicane of polarity polymer alloy, internal layer or the outer compound nonpolar polyolefin polymer of one deck at this tube wall are to have non-crosslinked heat-proof polythene (PE-RT) or the polypropylene (PPH that melting links performance, PPB) or atactic copolymerized polypropene (PP-R), nonpolar polyolefin polymer is compound before the uncrosslinked polycondensation reaction of pipe wall.Such as the weight of the percent grafting of getting polarity at 2.5～3% atactic copolymerized polypropene (PP-R) 10～15%.Get the weight of the silane cross-linkable polyethylene that does not have polarity 85～90% of non-modified, extrude with metal frame compound through blend, this blend composition is after the hydrolytic crosslinking polycondensation reaction, its crosslinked with silicane degree also is that gel fraction is more than 60%, still can fully guarantee its thermal characteristics, the intensity height of PP-R itself in addition, resistance to heat is good, its the two alloy also has sufficient performance to guarantee, with metal frame firm bonding and coating and compound are arranged, this pipe is having excellent performance aspect the chemical mediator conveying of hot water and heat in addition.Internal layer or outer compound one deck of the tube wall that forms at the skeleton of the crosslinked with silicane polymer overmold that polarity is arranged, PE-RT or PP-R, make can not welding pipeline become the pipeline that can make things convenient for melting to connect, the difficult problem that the polymer that has solved crosslinked with silicane and the secure bond of metal frame are connected with a compound difficult problem and melting thereof.
Above-mentioned compound pipeline, the pertusate metal of the tubing of multiple tube strengthen the body skeleton with pertusate steel plate or steel band through longitudinal curl or helix-coil again through being welded.
It is that the broadwise steel wire twines the warp-wise steel wire through being welded that above-mentioned compound pipeline, the pertusate metal of the tubing of multiple tube strengthen the body skeleton.
There are the electrodeposited coating of burning of preventing and erosion or the anti-corrosion of metal layer that plates with physical vacuum film plating process (PVD) in the surface that above-mentioned compound pipeline, the pertusate metal of multiple tube strengthen the body skeleton.For the antiseptic power that makes pipeline improves, the life-span is longer, to the copper coating or the zinc-plated or chromium plating of metal frame, so that skeleton strengthens the long-term maintenance of function.
Above-mentioned compound pipeline, the pipe fitting of multiple tube are the pipe fittings that two logical or threeways or four-way or 90 ° of elbows or 45 ° of elbows and reducing have CONCENTRIC REDUCER, and it is the metalwork of porose steel plate or steel wire welded product or precision casting that pertusate metal strengthens the body skeleton.
The present invention has polar polyolefin polymer and nonpolarity polyolefin polymer and metal to strengthen the pipeline of bluk recombination, both can make tubing, also can make pipe fitting, adopt surperficial secure bond and the coating formation tube wall of the polyolefin continuum with carboxyl or hydroxyl or carbonyl or anhydride group polar group of process graft modification with skeleton, the nonpolar polyolefin of compound one deck on the internal layer of tube wall or skin again, solve the compound pipeline of metal and polymer and can not give full play to its excellent properties, can not be conveniently bonding, the two interface be difficult for secure bond compound for one or compound for one must relate to adhesive layer or the coating transition layer investment big, the technical barrier that cost of material is high, the pipe network more reliable performance.
Description of drawings:
Fig. 1 is the pipeline connection diagram of the present invention that three-way connector is arranged.
Fig. 2 is a pipe structure schematic representation of the present invention.
Fig. 3 is another structural representation of tubing of the present invention.
Fig. 4 is a tubing of the present invention structural representation again.
Fig. 5 is the pipe structure schematic representation of the present invention that contains polar silanes crosslinked polypropylene tube wall.
Embodiment:
Embodiment 1:
Fig. 1 has provided the embodiment of the invention 1 figure.Referring to Fig. 1, strengthen the compound φ 160mm composite pipe network 1 of body skeleton by the polymer of polarity and non-polar polymer and metal and form by tee pipe fitting 2, tubing 3,4.The tube wall of pipe fitting 2 passes by the polyolefin continuum 5 of the graft modification that polar group is arranged that pertusate steel plate strengthens the hole on the body skeleton 6 and surface adhesion inside and outside with it and coating form, and is compounded with the nonpolarity polyolefin layer 7 of one deck on tube wall internal layer surface.The tube wall of tubing 3,4 is to roll the cylindrical skeleton 10 of welding or broadwise steel wire 11 by pertusate steel plate respectively by the polyolefin continuum that polar group is arranged 8,9 of graft modification respectively to twine the cylindrical skeleton 13 that steel radials 12 form through welding and form with the bonding coating of cylindrical skeleton respectively.The tube wall periphery of tubing 3 is compounded with the non-polar polyolefin layer 14 of one deck.The tube wall inwall of tubing 4 is compounded with the non-polar polyolefin layer 15 of one deck.Tubing 3, an end of 4 stretches into respectively and is attached thereto in the joint socket at pipe fitting 2 two ends and forms φ 160mm pipe network, the polyolefin continuum that polar group is arranged of graft modification is high density polyethylene (HDPE) (HDPE) material, the polyolefin 4 of nonpolarity group is high density polyethylene (HDPE) (HDPE) material, to this pipe network with 60 ℃, 2.0Mpa pressure pressure testing, tubing 3,4 and the termination of pipe fitting 2 all cut off bare metal skeleton and the compound interface (section) of continuum, impermeable through the continuous pressure testing of 165h, do not reduce pressure, this composite pipe not only anti-corrosion capacity is strong, the bearing capacity height, also whole indexs reach the drinking-water pipe sanitary standard.
Tee pipe fitting also forms tube wall by pertusate steel plate frame or steel wire welded framework or precision casting skeleton with its secure bond and coating as continuum by the high density polyene (HDPE) that polar group is arranged, within it the layer compound one deck polarity HDPE and become pipe fitting, this pipe fitting can be made by the method for quadric injection mould, promptly become the tube wall of continuum coating skeleton earlier with mold injection, again with the nonpolar HDPE of another pair mould wall injection moulding within it one deck.Certainly if also can use the polymer that polar group is arranged as continuum earlier, in mould, coat skeleton shape tube wall,, utilize two shot process to finish the pipe fitting that skin is a non-polar polymer in the injection moulding of tube wall outer wall again with another pair mould because of the needs of engineering design.
Embodiment 2:
Fig. 2 has provided pipe structure schematic representation in the embodiment of the invention 2.Referring to Fig. 2, the structure of the skeleton 16 in the tubing 19 is identical with cylindrical skeleton among the embodiment 1, be the cylindrical skeleton of steel wire welding, the continuum that forms tube wall 17 by hole secure bond on the cylindrical skeleton and coating skeleton is the non-crosslinked heatproof polyethylene (PE-RT) (Korea S SK company produces PE-RT DX800) that polar group is arranged, by following prescription, adopting the polycthylene grafted rate of extruder extruding pelletization non-crosslinked heatproof is 0.5%-0.8%, weigh 100 parts by mass parts, maleic anhydride (MAH) 2-5 part, 0.1～0.4 part of peroxide grafted initator (DCP).Be compounded with nonpolarity non-crosslinked heatproof polyethylene layer 18 at tube wall 17 internal layers, this tubing 13 is connected with the pipe fitting of same structure and is pipe network, can bear the operation of 60～80 ℃ hot water long-term safety, can bear at the interface of metal frame and continuum (section) 0.6Mpa long-time running pressure and impermeable, tear.
Embodiment 3:
Fig. 3 has provided pipe structure schematic representation in the embodiment of the invention 3.Referring to Fig. 3, there is the broadwise steel wire to twine steel radial in the tubing 20 and strengthens body skeleton 21 through the tubular metal that welding forms, the continuum that forms tube wall 22 by hole secure bond and clad metal skeleton is the atactic copolymerized polypropene that polar group is arranged, compound atactic copolymerized polypropene (PP-R) layer 23 that does not have polarity of the internal layer of tube wall 22.Adopting the extruder extruding pelletization to obtain percent grafting by following prescription is 0.4%～0.7% the polypropylene that polar group is arranged, and this polypropylene can be produced the hot water pipe net composite pipe, at 80 ℃, and long-time running under the 0.6Mpa condition.Prescription is: Beijing Yanshan Petrochemical is produced atactic copolymerized polypropene (PP-R) 100 parts.Maleic anhydride (MAH) 2-4 part, grafting initator (DCP) 0.2-0.3 part.
Embodiment 4:
Fig. 4 has provided the embodiment of the invention 4 pipe structure schematic representation.Referring to Fig. 4, compound outside the polyolefin polymer tube wall 25 in tubing 24 is non-polar non-crosslinked heatproof polyethylene (PE-RT) outer 26, pertusate cylindrical skeleton 27 is welded through the moulding of steel band longitudinal curl, is crosslinked with silicane (crosslinkable) polyethylene that polar group is arranged by hole with the polyolefin polymer tube wall 25 of metal frame secure bond and coating, its percent grafting is 0.12%～0.3%, and this composite pipe network suits to move not being higher than under 90 ℃, 0.8Mpa pressure.
The metal cylindrical skeleton also can adopt porosity ratio to account for 12%～25%, aperture φ 3mm～φ 6mm, the steel plate band of thickness 1～3mm is welded behind longitudinal curl or helix-coil, two runner ecto-entad extruded polymers that are communicated with two kinds of materials through the cross cross-head, the polymer that runner is extruded polarity earlier can be crossed hole and the skeleton internal and external layer is formed coat, continuum is with metal frame secure bond and the compound tube wall that is formed as one, extrude nonpolarity polymer at the nonpolar polymer of the compound one deck of the outer surface of tube wall by another runner, form composite pipe through cooling.
Embodiment 5:
Fig. 5 has provided the embodiment of the invention 5 figure.Present embodiment 5 is basic same with embodiment 3.Do not exist together is as shown in Figure 5, tube wall 29 in multiple tube 28 is for there being polar silanes crosslinked (crosslinkable) polypropylene material, the acquisition of material is to carry out the grafting of silane with the prescription and the technology of disclosed document, be crosslinked with silicane (crosslinkable) polypropylene that polar group is arranged again with its graft modification, because if its percent grafting of grafting that has styrene monomer to participate in polar group can reach 2.5%～3%, so the polyacrylic acquisition of crosslinked with silicane (crosslinkable) that polar group arranged is more suitable with the silane grafting with there is the polar group grafting to carry out respectively, the polyacrylic technological method of crosslinked with silicane (crosslinkable) that acquisition has polar group is extruded in the two mixing again.Extrude compound secure bond and be coated with hole tubular metal frame formation tube wall 29 with this material, at the compound more non-polar atactic copolymerized polypropene of one deck (PP-R) 30 of extruding of the internal layer of tube wall, the polyacrylic gel fraction of crosslinked with silicane (crosslinkable) that polarity is arranged is generally below 50%, controlling during the course wherein that the requirement of polar group percent grafting reaches more than 0.12% can secure bond and clad metal skeleton, 80 ℃ of water temperatures, the hydrostatic test of 0.8Mpa just can be born in skeleton and continuum interface.
Tube wall 29 is also got 20 weight portions with the material of the polar polyethylene (percent grafting is 0.6%～0.8%) of maleic anhydride (MAH) graft modification, do not get 80 weight portions with having the nonpolar polyethylene HDPE material of modification, blend forms the polymer continuum through extruding, the actual percent grafting of this pipe continuum is 0.12%～0.16%, the cylindrical skeleton that pertusate roll of steel plate boxing is connect firmly coats and bonding and forming, continuum can not separate with the metal surface and peel off, compound interface (section) can bear 20 ℃ of water temperatures, 2.0Mpa 165 hours pressure testing of hydraulic pressure, the normal operation that can bear the long-term pipe network of 1.6Mpa.
All there is the characteristic absorption peak of typical above-mentioned polar group in the infrared spectrum group of the polyolefin continuum that polar group is arranged in the various embodiments described above.
The various embodiments described above are that foregoing of the present invention is further described, but this should be interpreted as that the protection domain of the above-mentioned theme of the present invention only limits to the foregoing description.All technology that realizes based on foregoing all belong to scope of the present invention.
Claims (10)
1, there are polar polymer and nonpolarity polymer and metal to strengthen the pipeline of bluk recombination, the tube wall that it is characterized in that multiple tube is by strengthening in hole on the body skeleton and its by porose hole metal through the polyolefin polymer continuum with polar group of graft modification, outer surface secure bond and coating form, internal layer or skin at this tube wall are compounded with one deck non-polar polyolefinic polymeric layer, the polar group of the polyolefin continuum that polar group is arranged in the composite pipe tube wall is carboxyl or hydroxyl or carbonyl or anhydride group, and its percent grafting is the characteristic absorption peak that 0.12%～3% its infrared spectrogram has typical above-mentioned polar group.
2, compound pipeline as claimed in claim 1, the continuum that it is characterized in that compound tube wall is that a kind of in a kind of and high density polyethylene (HDPE), non-crosslinked heat-proof polythene in maleic anhydride, the acrylic acid series is that the poly polymer with polar group is formed through extruder extruding graft reaction modifying under the effect of peroxide grafted initator, is high density polyethylene (HDPE) or non-crosslinked heat-proof polythene at internal layer or outer compound one deck nonpolar polyolefin hydrocarbon polymer of this tube wall.
3, compound pipeline as claimed in claim 1, the continuum that it is characterized in that the multiple tube tube wall is a kind of under the effect of peroxide grafted initator by in a kind of and polypropylene in maleic anhydride, methyl methacrylate, acrylic acid, methacrylic acid carboxylic acetate, the methyl propenoic acid glycidyl fat, the atactic copolymerized polypropene, through extruder extruding graft reaction modifying is that the polyacrylic polymer with polar group is formed, and is polypropylene or atactic copolymerized polypropene at internal layer or outer compound one deck nonpolar polyolefin hydrocarbon polymer of this tube wall.
4, compound pipeline as claimed in claim 1, the continuum that it is characterized in that the multiple tube tube wall is organosilane crosslinked polyethylene or the silane cross-linkable polyethylene continuum that polar group is arranged, at the internal layer or the outer compound crosslinked heat-proof polythene of one deck nonpolar polyolefin hydrocarbon polymer right and wrong of this tube wall.
5, compound pipeline as claimed in claim 1, the continuum that it is characterized in that the multiple tube tube wall is crosslinked with silicane polypropylene or the silane-crosslinkable polypropylene continuum that polar group is arranged, at the internal layer or the outer compound crosslinked polypropylene of one deck nonpolar polyolefin hydrocarbon polymer right and wrong of this tube wall.
6, compound pipeline as claimed in claim 1, the continuum that it is characterized in that the multiple tube tube wall are the polyolefin of polar group to be arranged and do not have the nonpolar polyolefin blend of graft modification to make.
7, compound pipeline as claimed in claim 1, the continuum that it is characterized in that the multiple tube tube wall is that mass percent is that the blend of the silane cross-linkable polyethylene of the polypropylene that polar group is arranged of graft modification of 5-60% and the unsaturated carboxylic acid graft modification of no use that mass percent is 40-95% is extruded, becoming through crosslinked polycondensation reaction has the crosslinked with silicane of polar group polymer alloy, internal layer or the outer compound nonpolar polyolefin polymer of one deck at this tube wall are to have non-crosslinked heat-proof polythene or the atactic copolymerized polypropene that melting links performance, and nonpolar polyolefin polymer is compound before the uncrosslinked polycondensation reaction of pipe wall.
8, compound pipeline as claimed in claim 1 or 2, the pertusate metal that it is characterized in that the tubing in the multiple tube strengthen the body skeleton with pertusate steel plate or steel band through longitudinal curl or helix-coil again through being welded.
9, compound pipeline as claimed in claim 1 or 2 is characterized in that the pertusate metal enhancing body skeleton of the tubing in the multiple tube is that the broadwise steel wire twines the warp-wise steel wire through being welded.
10, compound pipeline as claimed in claim 1 or 2 is characterized in that there are the electrodeposited coating of burning of preventing and erosion or the anti-corrosion of metal layer that plates with the physical vacuum film plating process in the surface of the pertusate metal enhancing body skeleton in the multiple tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100204733A CN100455866C (en) | 2006-03-13 | 2006-03-13 | Pipeline of polar polymer and poleless polymer composing with metal reinforcement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100204733A CN100455866C (en) | 2006-03-13 | 2006-03-13 | Pipeline of polar polymer and poleless polymer composing with metal reinforcement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101038049A CN101038049A (en) | 2007-09-19 |
| CN100455866C true CN100455866C (en) | 2009-01-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100204733A Expired - Fee Related CN100455866C (en) | 2006-03-13 | 2006-03-13 | Pipeline of polar polymer and poleless polymer composing with metal reinforcement |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102767652A (en) * | 2012-07-31 | 2012-11-07 | 厦门立霖卫浴有限公司 | Heat-resisting polyethylene composite pipe and preparation method thereof |
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| CN102181246B (en) * | 2011-03-15 | 2012-12-12 | 广东联塑科技实业有限公司 | Heat-resistant hot melt adhesive and preparation method and application thereof |
| CN102252900B (en) * | 2011-04-13 | 2013-10-30 | 河南科技大学 | Inert gas protection method and apparatus for self-heating high temperature compression quenching experiment |
| CN103318578B (en) * | 2013-05-24 | 2014-12-10 | 无锡新开河储罐有限公司 | Forming method of large-scale metal storage tank with high bonding strength inner wall anticorrosive layer |
| CN103419329A (en) * | 2013-07-04 | 2013-12-04 | 余姚市河姆渡庆发实业有限公司 | Forming technology for steel-plastic composite high-pressure-resistant type PE electric melting pipe fitting of secondary injection moulding forming |
| DE112015002298T5 (en) * | 2014-05-16 | 2017-04-13 | Magna International Inc. | Method and system for producing a composite pipe node |
| CN110527233B (en) * | 2019-08-01 | 2022-11-15 | 威海联桥新材料科技股份有限公司 | TPE (thermoplastic elastomer) coated silane crosslinked polyethylene composite material and preparation method thereof |
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| CN101038049A (en) | 2007-09-19 |
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