CN105835374A

CN105835374A - 3D printing method for fiber-grade electric conduction product based on reactive extrusion

Info

Publication number: CN105835374A
Application number: CN201610250514.1A
Authority: CN
Inventors: 陈烨; 王朝生; 王华平; 汤廉
Original assignee: Donghua University
Current assignee: Donghua University; National Dong Hwa University
Priority date: 2016-04-21
Filing date: 2016-04-21
Publication date: 2016-08-10

Abstract

The invention relates to a 3D printing method for a fiber-grade electric conduction product based on reactive extrusion. After a lactam monomer and/or a lactone monomer are/is fused with an assistant and a plasticizer, the polymerization reaction is conducted under the action of a catalyst, an electric conduction filler is added before polymerization or in the polymerization process, fusion deposition 3D printing is conducted, and a final product is obtained after heat treatment. A high-precision and high-adaptability 3D printer is adopted, the forming precision and efficiency are high, the mechanical performance of the product is good, and the dispensability of functional components is good. The technology directly from polymerization monomers to the product is adopted, and the product flexibility is improved. Meanwhile, edge warping of nylon, polyester and other hypocrystalline polymers due to crystallization and the large temperature difference, and even unavailable printing are avoided. The kinds of fusion deposition 3D printing materials are widened, the quality of the product is improved, and the 3D printing method is widely applied to the fields of automobile materials, electronic devices, engineering materials, electromagnetic shielding materials and the like.

Description

A kind of 3D Method of printing of fibre-grade conductive articles based on reactive extrursion

Technical field

The invention belongs to 3D printing technique field, relate to the 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, Particularly relate to a kind of from monomer directly to the 3D Method of printing of goods.

Background technology

3D printing technique is a kind of rapid shaping technique of the most popular rise, and this is a kind of greenization desktop Quick-forming skill The advantages such as art, has volume little, low cost, pollutes low, easy to use.Its general principle is with macromolecular material as base material, Use Deformation In The Fdm Process or fused glass pellet technology, complete object by successively printing type and to structure and formed, successively fold Add and ultimately form product, can successively pile up under being accurately positioned and build various three-dimensional bodies.

Utilize the feature that 3D prints, can be controlled by software, and by the transformation of equipment, print and there is specific function Material.Be currently used for 3D print polymeric material have acrylonitrile butadiene styrene terpolymer (ABS), PLA (PLA), Nylon (PA), Merlon (PC) and polyvinyl alcohol (PVA) etc., predominantly polymeric articles.At present, along with 3D printer skill Art gradually develops, and product range is gradually widened, and the requirement of product is not only rested in bulk properties, to 3D by market The functionalization of printed product requires the most day by day to increase.

Patent " has the 3D printed material of automatically cleaning conductive fill function and preparation method and application " (CN104530668A) Disclose a kind of method preparing functionalization 3D printed material: this 3D printed material comprises following component: PLA or acrylonitrile The high polymer 70-85 parts such as-butadiene-styrene terpolymer；The pigment powder 1-5 part such as titanium white, red, calcium carbonate superfine powder, The inorganic filler 1-5 part such as superfine silicon dioxide and talcum powder, conductive nano filler titanium dioxide 0.5-1.5 part, isoprene rubber, Thermoplastic polyester elastomer binding material 10-20 part.This invention is by mixing aforementioned component；The material that will mix again Put in single-screw extruder, extrusion, cooling and shaping, be dried, traction, coiling, obtain having automatically cleaning conduction and fill out Fill the 3D printed material of function.Patent " a kind of flame-proof composite material for 3D printing and preparation method thereof " (CN104479349A) a kind of flame-proof composite material printed for 3D is provided, including the raw material of following weight portion: 60-95 The nylon resin of weight portion；The lubricant of the ABS resin 0.3-2 weight portion of 5-40 weight portion；The compatilizer of 5-20 weight portion； The antioxidant of 0.2-1 weight portion；The unformed red phosphorus of 5-30 weight portion, the 3D prepared by the method prints raw material and goods thereof There is certain fire resistance.Patent " a kind of electric conductivity 3D prints plastics lines and production method thereof " (CN103788565A), A kind of electric conductivity 3D of this disclosure of the invention prints plastics lines and production method thereof, includes following components according to mass fraction ratio: The conductive nano carbon black of the ABS of 100 parts, 35-55 part, the titanate coupling agent of 0.5-3 part, this invention obtains 3D and prints plastics Wire rod has electric conductivity.

From the prior art, for 3D print functional composite material and goods it has been reported that but still suffer from some problems, Mainly there is the following aspects: in macromolecule raw material, the material being mainly polymerized in advance, it is impossible to the quickly body of controlled material Performance；In 3D prints process, need polymer remelt, and owing to the melting tube of conventional 3D printing is shorter, In order to ensure polymer melting, heating-up temperature need to bring up to above 20-50 DEG C of melting point polymer, this secondary processing process is to poly- The performance of compound own impacts, and easily produces low molecule, bubble etc. easily occurs, affect the performance of product in print procedure, Meanwhile, remelted process is also the waste to energy.During doing functionalization 3D printing raw material, generally use blended Method, it is easy in Blending Processes that the method is difficult to the function powder of being uniformly distributed of function ingredients, especially Nano grade Reunite, thus cause functional effect to reduce and the instability of product quality, it is also possible to owing to the accumulation of function ingredients causes The blocking of nozzle.For nylon and polyester material, its water imbibition is relatively strong, and chemical stability is relatively poor, and material stores not Just, not being suitable for industrialization, this is all to limit 3D to print nylon and the key factor of polyester material development.

Summary of the invention

For overcoming the deficiencies in the prior art, the present invention provides the 3D printing side of a kind of fibre-grade conductive articles based on reactive extrursion Method, be a kind of from monomer directly to the 3D Method of printing of goods.The present invention uses the 3D with high-accuracy high-efficiency high-adaptability to beat Print machine, with polymer monomer as raw material, adds a certain amount of function ingredients, obtains through the shaping of 3D printer and has specific function 3D prints goods.The method directly to goods from monomer, decreases in conventional 3D printing step and cools down remelted step, fall Low cost, it also avoid the second melting process degraded impact on product quality simultaneously, it also avoid material due to water suction simultaneously Deng and the degraded in the process that causes and hydraulic performance decline；From the direct goods of monomer, machine-shaping temperature can be reduced, it is to avoid The problem causing the change in size caused because of percent thermal shrinkage due to excessive temperature differentials；Meanwhile, function ingredients can be realized to beat with monomer Slurry homogeneous blend, or polymerization process add function ingredients, it is achieved the in-situ polymerization of function ingredients, are blended relative to conventional screw, Improve the dispersion effect of function ingredients, it is to avoid the reunion of function ingredients, improve product quality, it is to avoid spray nozzle clogging；And it is adjustable Control property is strong, can require regulation and control production technology according to product quality, it is achieved single line multi-item production, continuous production is good；Use simultaneously There is the 3D printer of high-accuracy high-efficiency high-adaptability, improve the shaping free degree, manufacturing speed and profiled member precision.

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion of the present invention, by lactam monomers and/or lactone Under catalyst action, carry out polymerisation after monomer and auxiliary agent, plasticizer are melted, before polymerization or during add conductive fill Agent, it is thus achieved that subject polymer；Then described subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece； Described 3 D workpiece after heat treatment obtains final products；

Described plasticizer is in dibutyl phthalate, citrate, gallium chloride, lithium chloride, calcium chloride, clay, rare earth More than one；In printing raw material, add appropriate plasticizer, reduce the degree of crystallinity of semi-crystalline polymer, reduce polymerization The fusing point of thing so that it is can realize at a lower temperature printing, simultaneously plasticizer in system can simultaneously with a plurality of strand phase interaction With, making to be formed between strand network structure, reduce the locomotivity of strand, plasticizer is crosslinking center, plays micro-crosslinking Effect so that polymer before melting after difference of flowability reduce.

Described heat treatment refers to keep 3-60min at 100-180 DEG C.The product that 3D prints, polymerisation is the completeest Become；The present invention use polymerization reaction system, at a certain temperature, polymer of the present invention under the effect of catalyst still There is polymerization activity, polymerisation can be made to proceed by being heat-treated a period of time at a certain temperature, thus obtain specific The product of molecular weight, has the controllability producing properties of product.

As preferred technical scheme:

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, described lactam monomers is penta Lactams, caprolactam, oenantholcatam, spicy inner formyl amine, certain herbaceous plants with big flowers lactams, ten lactams, 11 lactams, lauric lactam In more than one；Described internal ester monomer be valerolactone, caprolactone, heptalactone, caprylolactone, certain herbaceous plants with big flowers lactone, ten lactones, 11 More than one in lactone, dodecalactone；Described catalyst is in NaOH, potassium hydroxide, organo-metallic compound More than Zhong；Described organo-metallic compound is the one in methyl, ethyl, propyl group, butyl, phenyl and sodium, potassium, calcium, magnesium In a kind of combination formed stable compound；Described auxiliary agent is vinylcaprolactam, isocyanates, carbamate, carbon More than one in acid esters and sulphonic acid ester.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, before polymerization or during, Can add conductive filler, imparting goods are antistatic, radiation proof function.Described conductive filler is conductive carbon black, metal fragment Or powder, stainless steel wire, carbon fiber, graphite fibre, copper fiber, aluminize in glass one or more；Described metal fragment Or powder is copper, nickel, silver, CuI, SnO₂、SnO₂/Sb、SnO₂/In、CuS、CuCl、ZnO、TiO₂In one or Several.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, the temperature of described polymerisation For 150-300 DEG C, catalyst loading is 0.01-1wt%, and additive dosage is 0.1-5wt%, and described plasticizer addition is 10-40wt%, described conductive filler addition is the 0.01-30wt% of monomer, and the number-average molecular weight of described subject polymer is 1000-20000。

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, described polymerisation is at screw rod Extruder completes, by controlling extruder temperature, catalyst content, the number-average molecular weight of accuracy controlling polymer；Described screw rod Extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and measuring pump；Described screw rod be single screw rod, One in twin-screw, three screw rods, draw ratio is 12-48, uniform pitch, and helical angle is 14-18 °, and spiral groove depth is 1.5-3.5mm, Surface roughness is Ra0.4-0.8；The extruder motor of described connection screw rod is fixedly mounted on the right side of screw rod, solid by vertical support shaft Fixed；Described heating collar and temperature sensor are arranged on outside screw rod.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, the step bag that described 3D prints Include:

(1) use CAD or CAM Software for Design product figure on computers, then carry out at the AUTOMATIC ZONING section of model Reason, obtains the panel data information of each processing aspect, and is converted into the coordinate G code of shaping；

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and flat to shaping by nozzle system extrusion Platform, shaped platform makees X-Y plane motion under computer system control；After the temperature of the polymer of extrusion is less than solidification temperature Start curing molding, become the cross section of profiled member a layer thickness, terminates the deposition material of a layer and solidify rapidly and viscous with adjacent material Forming type, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form three-dimensional Workpiece.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, the shifting of described shaped platform Dynamic speed is 10-10000mm/s；Described measuring pump melt flow is 0.1-3000L/h, and precision is ± 0.1%, so that it is guaranteed that becoming The accurate control of extrusion capacity during type, it is ensured that whole mechanism stability in work continuously, simultaneously works as the effect of supercharging, Guarantee the smooth extrusion molding of high viscosity thermoplastic.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, described 3D prints and uses three-dimensional Print apparatus, including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer control with Drive system, described Screw Extrusion mechanism maintains static relative to workbench and profiled member；Described workbench mechanism peace It is contained on three-dimensional motion mechanism；It is automatically controlling and driving for complete machine that described computer controls with drive system.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, described three-dimensional motion mechanism is by X Shaft movement mechanism, Y-axis motion and Z axis motion composition；Described X-axis motion includes that X-axis motor and leading screw are led Rail forms；Described Y-axis motion includes y-axis motor and lead screw guide rails composition；Described Z axis motion includes Z axis electricity Machine and lead screw guide rails composition；Described X-axis is supported and fixed on Y-axis feed screw nut, and Y-axis is supported and fixed on shaping work platform and props up On support, Z axis is vertically fixed on pedestal.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, described workbench mechanism by Shaping work platform, shaping work platform frame and leveling nut composition；Described shaping work stage+module is in described X-axis On motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Described shaping work platform props up Support is connected with described Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down； Described leveling nut can regulate the height of shaping workbench, it is ensured that the shaping work platform plane perpendicularity to shower nozzle discharging opening Requirement.

The 3D Method of printing of a kind of fibre-grade as above conductive articles based on reactive extrursion, described Screw Extrusion mechanism is Vertical or horizontal, it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Described confession Barrel includes the material feed drum being connected with screw extrusion apparatus, and the rounded funnel-form of material feed drum, outside arranges drying heater；Described Nozzle system is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Described nozzle is installed on conveyance conduit end, Nozzle number at least includes one, and it is generally circular in shape, one or more in rectangle, triangle, rhombus, and nozzle comprises 1-1000 spray orifice, spray orifice is generally circular in shape, one in rectangle, triangle, rhombus, cross, in-line, Y shape or Several, spray orifice outlet diameter is 10-500 μm, simultaneously nozzle cooling device installed above, and cooling device is ring blowing or side-blown Wind, wind-warm syndrome is 15-25 DEG C, and wind speed is 0.01-0.1m/s；Described stop valve is installed on above the cooling device of shower nozzle, is used for controlling The duty of many shower nozzles.

Beneficial effect:

The present invention compared with prior art, has and the most obviously highlights substantive distinguishing features and remarkable advantage:

(1) present invention is by using screw rod and the combination of measuring pump, it is achieved in forming process, shower nozzle raw silk percentage of cocoon accurately controls and go out The stability of silk, improves formed precision；Simultaneously by the pressurization of measuring pump, it is achieved shaping high viscosity thermoplastic polymer, Thus widen the range of choice of moulding material so that it is there is high-adaptability.

(2) present invention pressurization by measuring pump, can be effectively improved the material extruded velocity from nozzle, faster heap Long-pending profiled member, thus improve shaping efficiency；Additionally, supercharging can use the nozzle that diameter is less, reduce the transversal of extruded material Area, obtains more preferable formed precision, simultaneously because extrude being greatly increased of silk material specific surface area, its cooling velocity increases, and enters And shaping speed can be improved further, and the raising of shaping speed, the degree of orientation of extrusion silk material can be greatly increased, thus carry The mechanical property of high profiled member.

(3) present invention is by using many shower nozzles multiinjector, can be molded multiple profiled member, such that it is able to be effectively improved shaping simultaneously Efficiency, meets the requirement of batch shaping.

(4) owing to fusion sediment 3D prints, to add heat pipe shorter, in order to make polymer the most melted, it is necessary to melt temperature must be improved, And the present invention from monomer directly to goods, decrease and conventional 3D printing step cool down remelted step, reduce cost； Second melting process easily produces little molecule and causes degraded, and little molecule can form stress concentration point in product, greatly reduces The mechanical property of product, and degrade and can reduce the molecular weight of polymer, molecular weight reduces the fall meaning the mechanical property of material own Low, bring is the reduction of Mechanical Properties of Products, and the present invention then eliminates second melting process, thus with avoiding second melting The little molecule of process generation and the impact on product quality of other degradation processes.

(5) present invention is from monomer directly to goods, decreases in conventional 3D printing step and cools down remelted step, it is to avoid Remelted process of cutting into slices can reduce machine-shaping temperature, it also avoid what printed material caused due to water suction etc. during storing The degraded declining and causing of quality of materials；The present invention can pass through accuracy controlling polymerization temperature, and when regulation and control print, polymer divides Son amount, then obtain finished product by post processing, so can reduce print temperature, it is to avoid cause because of thermal contraction due to excessive temperature differentials Rate and the problem of change in size that causes；The present invention is also by regulation and control aftertreatment technology, it is thus achieved that the goods of different performance, simultaneously Also act as elimination thermal history, thermal finalization, improve the effect of part performance further.

(6) conventional melt deposition 3D prints, and usual a kind of raw material can only print the product of a kind of performance, and the present invention is straight from monomer Receive goods, different product can be obtained by regulation polymerization technique and formula, substantially increase the flexibility of production, reduce Properties of product dependences to raw material.

(7) present invention introduces appropriate plasticizer in printing raw material, reduces the degree of crystallinity of semi-crystalline polymer, reduces The fusing point of polymer so that it is can realize at a lower temperature printing, reduce the difference between print temperature and environment temperature, keep away The problems such as the product contraction owing to crystallization and temperature difference cause, hydraulic performance decline are exempted from；Plasticizer can be simultaneously with many in system simultaneously Bar strand interacts, and makes to be formed between strand network structure, reduces the locomotivity of strand, and plasticizer is in crosslinking The heart, plays the effect of micro-crosslinking so that polymer before melting after difference of flowability reduce, be conducive to from nozzle extrusion Silk reaches conformality.Meanwhile, plasticizer can play the effect of lubrication, so that not havinging blocking in FDM forming process Nozzle phenomenon, and the product that printed of 3D is prone to the separation of backing material or forming platform, is molded more stable.

(8) present invention realizes function ingredients and addition function ingredients in monomer making beating homogeneous blend, or polymerization process, it is achieved function The in-situ polymerization of component, is blended relative to conventional screw, improves the dispersion effect of function ingredients, it is to avoid the reunion of function ingredients, Improve product quality, it is to avoid spray nozzle clogging.

(9), compared with printing with conventional melt deposition 3D, the diameter of spray orifice of the present invention outlet can be as small as 10 μm, Reaching fibre-grade standard, this design can be greatly improved the precision that 3D prints, and makes 3D print finer and smoother, improves 3D and prints The quality of goods and fineness, also improve the scope of application that 3D prints simultaneously.

Detailed description of the invention

Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and It is not used in restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art Can make various changes or modifications the present invention, these equivalent form of values fall within the model that the application appended claims is limited equally Enclose.

Embodiment 1

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers valerolactam and lactone list Body valerolactone and addition are the auxiliary agent vinylcaprolactam of 0.1wt% and addition is the plasticizer phthalic acid of 10wt% Dibutyl ester；Under the catalyst NaOH effect that addition is 0.01wt%, at temperature is 150 DEG C, polymerization is carried out anti-after Rong Rong Should, before polymerisation, add the conductive filler conductive carbon black of 0.01wt%, it is thus achieved that number-average molecular weight is the target polymerization of 1000 Thing, polymerisation completes in screw extruder, screw extruder include screw rod, connect the extruder motor of screw rod, heating collar, Temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 12, uniform pitch, and helical angle is 14 °, and spiral groove depth is 1.5mm, surface roughness is Ra0.4；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, solid by vertical support shaft Fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, successively heap Long-pending formation 3 D workpiece；3 D workpiece obtains final products after keeping 3min at 100 DEG C, and 3D prints and uses three-dimensional printer dress Put, control and drive system including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism；Meter It is automatically controlling and driving for complete machine that calculation machine controls with drive system；Three-dimensional motion mechanism is by X-axis motion, Y-axis fortune Motivation structure and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion bag Include y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on On Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Work is flat Platform mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module is transported in X-axis On motivation structure, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform frame with Described Y-axis motion is connected, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling spiral shell Female height that can regulate shaping workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw rod Extrusion mechanism is vertical, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum Including the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system It is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, nozzle number one Individual, it is generally circular in shape, and nozzle comprises 1 spray orifice, and spray orifice is generally circular in shape, and spray orifice outlet diameter is 10 μm, simultaneously Nozzle cooling device installed above, cooling device is ring blowing, and wind-warm syndrome is 15 DEG C, and wind speed is 0.01m/s；Stop valve is installed on Above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAD software deisgn product figure on computers, then carry out the AUTOMATIC ZONING slicing treatment of model, To the panel data information of each processing aspect, and it is converted into the coordinate G code of shaping；

(2) subject polymer is fed forward, and is controlled by measuring pump accurate quantification and flat to shaping by nozzle system extrusion Platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 10mm/s, meter Amount pump melt flow is 0.1L/h, and precision is 0.1%；Solidification is started after the temperature of the polymer of extrusion is less than solidification temperature Shaping, becomes the cross section of profiled member a layer thickness, terminate the deposition material of a layer solidify rapidly and with adjacent material molding bonded, Shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form 3 D workpiece.

Embodiment 2

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers caprolactam and lactone list Intimate lactone and addition are the auxiliary agent isocyanates of 5wt% and plasticizer citrate that addition is 40wt%；After Rong Rong Addition be 1wt% catalyst potassium hydroxide effect under at temperature is 300 DEG C, carry out polymerisation, in polymerization process, Add the conductive filler metal fragment copper of 30wt%, it is thus achieved that number-average molecular weight is the subject polymer of 20000, and polymerisation exists Completing in screw extruder, screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and meter Amount pump；Screw rod is twin-screw, and draw ratio is 48, uniform pitch, and helical angle is 18 °, and spiral groove depth is 3.5mm, rough surface Degree is Ra0.8；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar and temperature Sensor is arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece； 3 D workpiece obtains final products after keeping 60min at 180 DEG C, and 3D prints and uses 3 D-printing machine, including setting gradually Screw Extrusion mechanism, three-dimensional motion mechanism, workbench mechanism and computer control and drive system, Screw Extrusion mechanism phase Workbench and profiled member are maintained static；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer controls and drives System is automatically controlling and driving for complete machine；Three-dimensional motion mechanism is transported by X-axis motion, Y-axis motion and Z axis Motivation structure forms；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes y-axis motor and silk Thick stick guide rail forms；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Workbench mechanism is by shaping work Platform, shaping work platform frame and leveling nut composition；Shaping work stage+module, on X-axis motion, has conjunction Suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform frame is connected with Y-axis motion, The most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can regulate shaping workbench Highly, it is ensured that the perpendicularity requirement to shower nozzle discharging opening of the shaping work platform plane；Screw Extrusion mechanism is horizontal, and it includes supplying Barrel, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes being connected with screw extrusion apparatus Material feed drum, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by conveyance conduit, nozzle, rotating disk, Stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes 2, and it is shaped as rectangle, spray Comprising 1000 spray orifices on mouth, spray orifice is shaped as rectangle, and spray orifice outlet diameter is 500 μm, simultaneously nozzle cooling installed above Device, cooling device is cross air blasting, and wind-warm syndrome is 25 DEG C, and wind speed is 0.1m/s；Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAM Software for Design product figure on computers, then carry out the AUTOMATIC ZONING slicing treatment of model, Obtain the panel data information of each processing aspect, and be converted into the coordinate G code of shaping；

(2) subject polymer is fed forward, and is controlled by measuring pump accurate quantification and flat to shaping by nozzle system extrusion Platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 10000mm/s, Measuring pump melt flow is 3000L/h, and precision is-0.1%；Start solid after the temperature of the polymer of extrusion is less than solidification temperature Chemical conversion type, becomes the cross section of profiled member a layer thickness, and the deposition material terminating a layer solidifies rapidly and is bonded to adjacent material Type, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form three-dimensional work Part.

Embodiment 3

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers oenantholcatam and lactone list Body heptalactone and addition are the auxiliary agent carbamate of 0.5wt% and plasticizer gallium chloride that addition is 15wt%；After Rong Rong Addition be the catalyst methyl of 0.08wt% be combined with sodium formed stable compound effect under carry out at temperature is 250 DEG C Polymerisation, in the course of the polymerization process, adds the conductive filler stainless steel wire of 0.9wt%, it is thus achieved that number-average molecular weight is 10000 Subject polymer, polymerisation completes in screw extruder, screw extruder include screw rod, connect screw rod extruder motor, Heating collar, temperature sensor and measuring pump；Screw rod is three screw rods, and draw ratio is 45, uniform pitch, and helical angle is 16 °, screw channel The degree of depth is 1.8mm, and surface roughness is Ra0.6；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically Support shaft is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, Successively pile up and form 3 D workpiece；3 D workpiece obtains final products after keeping 10min at 120 DEG C, and 3D prints and uses three-dimensional to beat Print machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives Dynamic system, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion machine On structure；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling spiral shell Female height that can regulate shaping workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw rod Extrusion mechanism is vertical, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum Including the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system It is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, nozzle number bag Including 3, it is shaped as triangle, and nozzle comprises 800 spray orifices, and spray orifice is shaped as triangle, and spray orifice outlet diameter is 100 μm, simultaneously nozzle cooling device installed above, cooling device is ring blowing, and wind-warm syndrome is 20 DEG C, and wind speed is 0.05m/s；Cut-off Valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and by nozzle system extrusion to becoming Type platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 100mm/s, Measuring pump melt flow is 1000L/h, and precision is 0.1%；Start solid after the temperature of the polymer of extrusion is less than solidification temperature Chemical conversion type, becomes the cross section of profiled member a layer thickness, and the deposition material terminating a layer solidifies rapidly and is bonded to adjacent material Type, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form three-dimensional work Part.

Embodiment 4

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers spicy inner formyl amine and lactone list Body caprylolactone and addition are the auxiliary agent carbonic ester of 2wt% and plasticizer lithium chloride that addition is 20wt%；At addition after Rong Rong Be combined under the stable compound effect formed with potassium for the ethyl of 0.07wt% and at temperature is 200 DEG C, carry out polymerisation, in polymerization In course of reaction, add the conductive filler carbon fiber of 2.5wt%, it is thus achieved that number-average molecular weight is the subject polymer of 1000, poly- Closing reaction to complete in screw extruder, screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature biography Sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 15, uniform pitch, and helical angle is 16 °, and spiral groove depth is 1.8mm, Surface roughness is Ra0.6；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating Circle and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, successively pile up formation three Dimension workpiece；3 D workpiece obtains final products after keeping 60min at 100 DEG C, and 3D prints and uses 3 D-printing machine, including The Screw Extrusion mechanism, three-dimensional motion mechanism, workbench mechanism and the computer that set gradually control and drive system, and screw rod squeezes Go out mechanism to maintain static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer control System is automatically controlling and driving for complete machine with drive system；Three-dimensional motion mechanism is by X-axis motion, Y-axis motion Form with Z axis motion；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes Y-axis Motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis silk On thick stick nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Workbench mechanism It is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module is at X-axis motion On, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform frame is with described Y-axis motion is connected, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can The height of regulation shaping workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw extruder Structure is horizontal, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum include with The material feed drum that screw extrusion apparatus is connected, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system is by carrying Pipeline, nozzle, rotating disk, stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes one, It is shaped as rhombus, and nozzle comprises 500 spray orifices, and spray orifice is shaped as rhombus, and spray orifice outlet diameter is 50 μm, sprays simultaneously Mouth cooling device installed above, cooling device is ring blowing, and wind-warm syndrome is 19 DEG C, and wind speed is 0.02m/s；Stop valve is installed on spray Above the cooling device of head；

The step that concrete 3D prints includes:

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and by nozzle system extrusion to becoming Type platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 6000mm/s, measuring pump melt flow is 1500L/h, and precision is-0.1%；When the temperature of the polymer of extrusion is less than solidification Start curing molding after temperature, become the cross section of profiled member a layer thickness, terminate the deposition material of a layer solidify rapidly and with week Enclosing material molding bonded, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively heap Long-pending formation 3 D workpiece.

Embodiment 5

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers certain herbaceous plants with big flowers lactams and lactone list Body certain herbaceous plants with big flowers lactone and addition are the auxiliary agent sulphonic acid ester of 3.5wt% and plasticizer calcium chloride that addition is 25wt%；Adding after Rong Rong The catalyst propyl group that amount is 0.3wt% is combined with calcium under the stable compound effect formed and carries out polymerization at temperature is 160 DEG C instead Should, in polymerization process, add the conductive filler graphite fibre of 3wt%, it is thus achieved that number-average molecular weight is the target of 1000 Polymer, polymerisation completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating Circle, temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 32, uniform pitch, and helical angle is 16 °, spiral groove depth For 1.5mm, surface roughness is Ra0.8；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically supporting Axle is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, by Layer stack is long-pending forms 3 D workpiece；3 D workpiece obtains final products after keeping 12min at 110 DEG C, and 3D prints and uses 3 D-printing Machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives System, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism On；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling spiral shell Female height that can regulate shaping workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw rod Extrusion mechanism is vertical, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum Including the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system It is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, nozzle number bag Including 10, it is shaped as rhombus, and nozzle comprises 600 spray orifices, and spray orifice is shaped as cross, and spray orifice outlet diameter is 80 μm, simultaneously nozzle cooling device installed above, cooling device is cross air blasting, and wind-warm syndrome is 22 DEG C, and wind speed is 0.09m/s；Cut-off Valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAD or CAM Software for Design product figure on computers, then carry out the AUTOMATIC ZONING section of model Process, obtain the panel data information of each processing aspect, and be converted into the coordinate G code of shaping；

(2) subject polymer is fed forward, and is controlled by measuring pump accurate quantification and flat to shaping by nozzle system extrusion Platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 6000mm/s, Measuring pump melt flow is 100L/h, and precision is 0.1%；Start solid after the temperature of the polymer of extrusion is less than solidification temperature Chemical conversion type, becomes the cross section of profiled member a layer thickness, and the deposition material terminating a layer solidifies rapidly and is bonded to adjacent material Type, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form three-dimensional work Part.

Embodiment 6

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers ten lactams and lactone list Body ten lactone and addition are the auxiliary agent vinylcaprolactam of 4wt% and plasticizer clay that addition is 23wt%；After Rong Rong Gather at temperature is 160 DEG C under the catalyst butyl that addition is 0.2wt% is combined the stable compound effect formed with magnesium Close reaction, in polymerization process, add the conductive filler copper fiber of 5wt%, it is thus achieved that number-average molecular weight is the mesh of 1200 Mark polymer, polymerisation completes in screw extruder, and screw extruder includes screw rod, the extruder motor connecting screw rod, adds Gas ket, temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 30, uniform pitch, and helical angle is 14 °, and screw channel is deep Degree is 1.8mm, and surface roughness is Ra0.5；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically propping up Support axle is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, Successively pile up and form 3 D workpiece；3 D workpiece obtains final products after keeping 30min at 130 DEG C, and 3D prints and uses three-dimensional to beat Print machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives Dynamic system, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion machine On structure；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling spiral shell Female height that can regulate shaping workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw rod Extrusion mechanism is horizontal, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum Including the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system It is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, nozzle number bag Include 8, its generally circular in shape, rectangle, nozzle comprises 650 spray orifices, spray orifice is generally circular in shape, rectangle, and spray orifice exports A diameter of 35 μm, simultaneously nozzle cooling device installed above, cooling device is cross air blasting, and wind-warm syndrome is 15 DEG C, and wind speed is 0.1m/s； Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and by nozzle system extrusion to becoming Type platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 30mm/s, Measuring pump melt flow is 120L/h, and precision is-0.1%；Start solid after the temperature of the polymer of extrusion is less than solidification temperature Chemical conversion type, becomes the cross section of profiled member a layer thickness, and the deposition material terminating a layer solidifies rapidly and is bonded to adjacent material Type, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form three-dimensional work Part.

Embodiment 7

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers 11 lactams and lactone Monomer undecalactone and addition are the auxiliary agent vinylcaprolactam of 0.1wt% and isocyanates and addition is the increasing of 30wt% Mould agent rare earth；The mass ratio of vinylcaprolactam and isocyanates is 1:1；At the catalyst benzene that addition is 1wt% after Rong Rong Base is combined with sodium under the stable compound effect formed and carries out polymerisation at temperature is 300 DEG C, in polymerization process, The conductive filler adding 6wt% is aluminized glass, it is thus achieved that number-average molecular weight is the subject polymer of 1000, and polymerisation is at screw rod Completing in extruder, screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and measuring pump； Screw rod is three screw rods, and draw ratio is 48, uniform pitch, and helical angle is 18 °, and spiral groove depth is 1.5mm, and surface roughness is Ra0.8；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar and TEMP Device is arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece；Three-dimensional Workpiece obtains final products after keeping 40min at 160 DEG C, and 3D prints and uses 3 D-printing machine, including the spiral shell set gradually Bar extrusion mechanism, three-dimensional motion mechanism, workbench mechanism and computer control and drive system, Screw Extrusion mechanism relative to Workbench and profiled member maintain static；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer controls and drive system It is automatically controlling and driving for complete machine；Three-dimensional motion mechanism is by X-axis motion, Y-axis motion and Z axis fitness machine Structure forms；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes that y-axis motor and leading screw are led Rail forms；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis feed screw nut, Y Axle is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Workbench mechanism is put down by shaping work Platform, shaping work platform frame and leveling nut composition；Shaping work stage+module is on X-axis motion, and it is suitable to have Coefficient of friction, it is possible to well fixing ground floor printed material；Shaping work platform frame and described Y-axis motion It is connected, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can regulate shaping work The height of platform, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw Extrusion mechanism be vertical or Horizontal, it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes and screw rod The material feed drum that extrusion device is connected, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by conveyance conduit, Nozzle, rotating disk, stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes 10, its shape Shape is triangle, rhombus, and nozzle comprises 800 spray orifices, and spray orifice is shaped as cross, in-line, and spray orifice outlet diameter is 25 μm, simultaneously nozzle cooling device installed above, cooling device is ring blowing or cross air blasting, and wind-warm syndrome is 25 DEG C, and wind speed is 0.1m/s；Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and by nozzle system extrusion to becoming Type platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 10mm/s, Measuring pump melt flow is 0.1L/h, and precision is 0.1%；Start solid after the temperature of the polymer of extrusion is less than solidification temperature Chemical conversion type, becomes the cross section of profiled member a layer thickness, and the deposition material terminating a layer solidifies rapidly and is bonded to adjacent material Type, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form three-dimensional work Part.

Embodiment 8

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers lauric lactam and lactone Monomer dodecalactone and addition are auxiliary agent carbamate and the mixture of carbonic ester of 5wt%, wherein carbamate and carbonic acid The mass ratio of ester is 1:2, and plasticizer phthalic acid dibutyl ester that addition is 36wt% and the mixture of citrate, its The mass ratio 1:3 of middle dibutyl phthalate and citrate；At the catalyst NaOH that addition is 0.9wt% after Rong Rong Enter at temperature is 160 DEG C under acting on the mixture (wherein the mass ratio of NaOH and potassium hydroxide is 2:1) of potassium hydroxide Row polymerisation, adds the conductive filler nickel by powder of 7wt% before polymerisation, it is thus achieved that number-average molecular weight is the target of 10000 Polymer, polymerisation completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating Circle, temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 30, uniform pitch, and helical angle is 14 °, spiral groove depth For 3.5mm, surface roughness is Ra0.4；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically supporting Axle is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, by Layer stack is long-pending forms 3 D workpiece；3 D workpiece obtains final products after keeping 10min at 150 DEG C, and 3D prints and uses 3 D-printing Machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives System, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism On；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with described Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down； Leveling nut can regulate the height of shaping workbench, it is ensured that the perpendicularity requirement to shower nozzle discharging opening of the shaping work platform plane； Screw Extrusion mechanism is vertical or horizontal, and it includes material feed drum, screw extrusion apparatus and the shower nozzle being connected with screw extrusion apparatus System；Material feed drum includes the material feed drum being connected with screw extrusion apparatus, and the rounded funnel-form of material feed drum, outside arranges dry heat Device；Nozzle system is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, Nozzle number includes 6, and it is shaped as rhombus, and nozzle comprises 600 spray orifices, and spray orifice is shaped as Y shape, and spray orifice outlet is straight Footpath is 300 μm, simultaneously nozzle cooling device installed above, and cooling device is ring blowing, and wind-warm syndrome is 15 DEG C, and wind speed is 0.1m/s； Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and by nozzle system extrusion to becoming Type platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 10000mm/s, measuring pump melt flow is 0.1L/h, and precision is-0.1%；When the temperature of the polymer of extrusion is warm less than solidification Start curing molding after degree, become the cross section of profiled member a layer thickness, terminate the deposition material of a layer solidify rapidly and with surrounding Material molding bonded, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up Form 3 D workpiece.

Embodiment 9

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by valerolactam that mass ratio is 1:1, in oneself Acid amides and addition are the auxiliary agent vinylcaprolactam of 5wt% and plasticizer that addition is 35wt% is the mixed of clay and rare earth Compound, wherein the mass ratio 4:3 of clay and rare earth；After Rong Rong under the catalyst NaOH effect that addition is 0.01wt% Temperature is to carry out polymerisation at 300 DEG C, adds 8wt% conductive filler silver fragment, it is thus achieved that number is divided equally in polymerization process Son amount is the subject polymer of 20000, and polymerisation completes in screw extruder, and screw extruder includes screw rod, connects spiral shell The extruder motor of bar, heating collar, temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 12, uniform pitch, spiral Angle is 14 °, and spiral groove depth is 1.5mm, and surface roughness is Ra0.8；The extruder motor connecting screw rod is fixedly mounted on screw rod Right side, vertical support shaft fix；Heating collar and temperature sensor are arranged on outside screw rod；Then by subject polymer through molten Thaw collapse amasss 3D and prints, and successively piles up and forms 3 D workpiece；3 D workpiece obtains final products, 3D after keeping 60min at 100 DEG C Print use 3 D-printing machine, including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and Computer controls and drive system, and Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is pacified It is contained on three-dimensional motion mechanism；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism It is made up of X-axis motion, Y-axis motion and Z axis motion；X-axis motion includes that X-axis motor and leading screw are led Rail forms；Y-axis motion includes y-axis motor and lead screw guide rails composition；Z axis motion includes that Z axis motor and leading screw are led Rail forms；X-axis is supported and fixed on Y-axis feed screw nut, and Y-axis is supported and fixed on shaping work platform frame, and Z axis erects Directly it is fixed on pedestal；Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Become Type workbench is arranged on X-axis motion, has suitable coefficient of friction, it is possible to the most fixing ground floor printed material； Shaping work platform frame is connected with described Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis Move along a straight line up and down；Leveling nut can regulate the height of shaping workbench, it is ensured that shaping work platform plane is to shower nozzle discharging The perpendicularity requirement of mouth；Screw Extrusion mechanism is vertical or horizontal, and it includes material feed drum, screw extrusion apparatus and squeezes with screw rod Go out the nozzle system that device is connected；Material feed drum includes the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, Outside arranges drying heater；Nozzle system is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is pacified Being loaded on conveyance conduit end, nozzle number includes one, and it is generally circular in shape, and nozzle comprises 1 spray orifice, and spray orifice is shaped as circle Shape, spray orifice outlet diameter is 500 μm, nozzle cooling device installed above simultaneously, and cooling device is ring blowing, and wind-warm syndrome is 15 DEG C, Wind speed is 0.01m/s；Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and by nozzle system extrusion to becoming Type platform, shaped platform make under computer system control X-Y plane motion, the translational speed of shaped platform is 500mm/s, Measuring pump melt flow is 3000L/h, and precision is 0.1%；Start solid after the temperature of the polymer of extrusion is less than solidification temperature Chemical conversion type, becomes the cross section of profiled member a layer thickness, and the deposition material terminating a layer solidifies rapidly and is bonded to adjacent material Type, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively piles up and form three-dimensional work Part.

Embodiment 10

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers valerolactam and lactone list Body valerolactone and addition are the auxiliary agent vinylcaprolactam of 0.1wt% and addition is the plasticizer phthalic acid of 10wt% Dibutyl ester；Under the catalyst NaOH effect that addition is 0.01wt%, at temperature is 150 DEG C, polymerization is carried out anti-after Rong Rong Should, in polymerization process, add the conductive filler CuI fragment of 11wt%, it is thus achieved that number-average molecular weight is the target of 1000 Polymer, polymerisation completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating Circle, temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 12, uniform pitch, and helical angle is 14 °, spiral groove depth For 1.5mm, surface roughness is Ra0.4；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically supporting Axle is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, by Layer stack is long-pending forms 3 D workpiece；3 D workpiece obtains final products after keeping 3min at 100 DEG C, and 3D prints and uses 3 D-printing Machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives System, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism On；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with described Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down； Leveling nut can regulate the height of shaping workbench, it is ensured that the perpendicularity requirement to shower nozzle discharging opening of the shaping work platform plane； Screw Extrusion mechanism is vertical, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Supply Barrel includes the material feed drum being connected with screw extrusion apparatus, and the rounded funnel-form of material feed drum, outside arranges drying heater；Shower nozzle System is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, nozzle Several one, it is generally circular in shape, and nozzle comprises 1 spray orifice, and spray orifice is generally circular in shape, and spray orifice outlet diameter is 10 μm, Nozzle cooling device installed above simultaneously, cooling device is ring blowing, and wind-warm syndrome is 15 DEG C, and wind speed is 0.01m/s；Stop valve is pacified It is loaded on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Embodiment 11

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers caprolactam and lactone list Intimate lactone and addition are the auxiliary agent isocyanates of 5wt% and plasticizer citrate that addition is 40wt%；After Rong Rong Addition be 1wt% catalyst potassium hydroxide effect under at temperature is 300 DEG C, carry out polymerisation, in polymerization process Add the conductive filler SnO of 15wt%₂Powder, it is thus achieved that number-average molecular weight is the subject polymer of 20000, and polymerisation is at spiral shell Completing in bar extruder, screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and metering Pump；Screw rod is twin-screw, and draw ratio is 48, uniform pitch, and helical angle is 18 °, and spiral groove depth is 3.5mm, surface roughness For Ra0.8；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar and temperature pass Sensor is arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece；Three Dimension workpiece obtains final products after keeping 60min at 180 DEG C, and 3D prints and uses 3 D-printing machine, including set gradually Screw Extrusion mechanism, three-dimensional motion mechanism, workbench mechanism and computer control and drive system, and Screw Extrusion mechanism is relative Maintain static in workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer controls and drivetrain System is automatically controlling and driving for complete machine；Three-dimensional motion mechanism is moved by X-axis motion, Y-axis motion and Z axis Mechanism forms；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes y-axis motor and leading screw Guide rail forms；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Workbench mechanism is by shaping work Platform, shaping work platform frame and leveling nut composition；Shaping work stage+module, on X-axis motion, has conjunction Suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform frame is connected with Y-axis motion, The most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can regulate shaping workbench Highly, it is ensured that the perpendicularity requirement to shower nozzle discharging opening of the shaping work platform plane；Screw Extrusion mechanism is horizontal, and it includes supplying Barrel, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes being connected with screw extrusion apparatus Material feed drum, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by conveyance conduit, nozzle, rotating disk, Stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes 2, and it is shaped as rectangle, spray Comprising 1000 spray orifices on mouth, spray orifice is shaped as rectangle, and spray orifice outlet diameter is 500 μm, simultaneously nozzle cooling installed above Device, cooling device is cross air blasting, and wind-warm syndrome is 25 DEG C, and wind speed is 0.1m/s；Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Embodiment 12

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers oenantholcatam and lactone list Body heptalactone and addition are the auxiliary agent carbamate of 0.5wt% and plasticizer gallium chloride that addition is 15wt%；After Rong Rong Addition be the catalyst methyl of 0.08wt% be combined with sodium formed stable compound effect under carry out at temperature is 250 DEG C Polymerisation, adds the conductive filler SnO of 18wt% in the course of the polymerization process₂/ Sb fragment, it is thus achieved that number-average molecular weight is 10000 Subject polymer, polymerisation completes in screw extruder, screw extruder include screw rod, connect screw rod extruder motor, Heating collar, temperature sensor and measuring pump；Screw rod is three screw rods, and draw ratio is 45, uniform pitch, and helical angle is 16 °, screw channel The degree of depth is 1.8mm, and surface roughness is Ra0.6；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically Support shaft is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, Successively pile up and form 3 D workpiece；3 D workpiece obtains final products after keeping 10min at 120 DEG C, and 3D prints and uses three-dimensional to beat Print machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives Dynamic system, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion machine On structure；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling spiral shell Female height that can regulate shaping workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw rod Extrusion mechanism is vertical, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum Including the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system It is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, nozzle number bag Including 3, it is shaped as triangle, and nozzle comprises 800 spray orifices, and spray orifice is shaped as triangle, and spray orifice outlet diameter is 100 μm, simultaneously nozzle cooling device installed above, cooling device is ring blowing, and wind-warm syndrome is 20 DEG C, and wind speed is 0.05m/s；Cut-off Valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Embodiment 13

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers spicy inner formyl amine and lactone list Body caprylolactone and addition are the auxiliary agent carbonic ester of 2wt% and plasticizer lithium chloride that addition is 20wt%；At addition after Rong Rong Be combined under the stable compound effect formed with potassium for the ethyl of 0.07wt% and at temperature is 200 DEG C, carry out polymerisation, in polymerization During add the conductive filler SnO of 18wt%₂/ In powder, it is thus achieved that number-average molecular weight is the subject polymer of 1000, polymerization Reaction completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, TEMP Device and measuring pump；Screw rod is single screw rod, and draw ratio is 15, uniform pitch, and helical angle is 16 °, and spiral groove depth is 1.8mm, table Surface roughness is Ra0.6；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar It is arranged on outside screw rod with temperature sensor；Then subject polymer is printed through fusion sediment 3D, successively pile up and form three-dimensional Workpiece；3 D workpiece obtains final products after keeping 60min at 100 DEG C, and 3D prints and uses 3 D-printing machine, including depending on The Screw Extrusion mechanism of secondary setting, three-dimensional motion mechanism, workbench mechanism and computer control and drive system, Screw Extrusion Mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer controls It is automatically controlling and driving for complete machine with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion forms；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes Y-axis electricity Machine and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis leading screw On nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Workbench mechanism by Shaping work platform, shaping work platform frame and leveling nut composition；Shaping work stage+module on X-axis motion, There is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform frame and described Y-axis Motion is connected, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can regulate The height of shaping work platform, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw Extrusion mechanism is Horizontal, it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes and screw rod The material feed drum that extrusion device is connected, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by conveyance conduit, Nozzle, rotating disk, stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes one, its shape Shape is rhombus, and nozzle comprises 500 spray orifices, and spray orifice is shaped as rhombus, and spray orifice outlet diameter is 50 μm, simultaneously on nozzle Cooling device is installed by side, and cooling device is ring blowing, and wind-warm syndrome is 19 DEG C, and wind speed is 0.02m/s；Stop valve is installed on shower nozzle Above cooling device；

The step that concrete 3D prints includes:

Embodiment 14

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers certain herbaceous plants with big flowers lactams and lactone list Body certain herbaceous plants with big flowers lactone and addition are the auxiliary agent sulphonic acid ester of 3.5wt% and plasticizer calcium chloride that addition is 25wt%；Adding after Rong Rong The propyl group that amount is 0.3wt% is combined with calcium under the stable compound effect formed and carries out polymerisation at temperature is 160 DEG C, poly- Close the conductive filler CuS fragment adding 20wt% in course of reaction, it is thus achieved that number-average molecular weight is the subject polymer of 1000, Polymerisation completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature Sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 32, uniform pitch, and helical angle is 16 °, and spiral groove depth is 1.5mm, Surface roughness is Ra0.8；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating Circle and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, successively pile up formation three Dimension workpiece；3 D workpiece obtains final products after keeping 12min at 110 DEG C, and 3D prints and uses 3 D-printing machine, including The Screw Extrusion mechanism, three-dimensional motion mechanism, workbench mechanism and the computer that set gradually control and drive system, and screw rod squeezes Go out mechanism to maintain static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer control System is automatically controlling and driving for complete machine with drive system；Three-dimensional motion mechanism is by X-axis motion, Y-axis motion Form with Z axis motion；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes Y-axis Motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis silk On thick stick nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Workbench mechanism It is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module is at X-axis motion On, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform frame is transported with Y-axis Motivation structure is connected, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can be adjusted to The height of type workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw Extrusion mechanism is vertical Formula, it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes squeezing with screw rod Going out the material feed drum that device is connected, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by conveyance conduit, Nozzle, rotating disk, stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes 10, its shape Shape is rhombus, and nozzle comprises 600 spray orifices, and spray orifice is shaped as cross, and spray orifice outlet diameter is 80 μm, simultaneously nozzle Cooling device installed above, cooling device is cross air blasting, and wind-warm syndrome is 22 DEG C, and wind speed is 0.09m/s；Stop valve is installed on shower nozzle Cooling device above；

The step that concrete 3D prints includes:

Embodiment 15

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers ten lactams and lactone list Body ten lactone and addition are the auxiliary agent vinylcaprolactam of 4wt% and plasticizer clay that addition is 23wt%；After Rong Rong Gather at temperature is 160 DEG C under the catalyst butyl that addition is 0.2wt% is combined the stable compound effect formed with magnesium Close reaction, add the conductive filler CuCl powder of 22wt% in the course of the polymerization process, it is thus achieved that number-average molecular weight is the target of 1200 Polymer, polymerisation completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating Circle, temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 30, uniform pitch, and helical angle is 14 °, spiral groove depth For 1.8mm, surface roughness is Ra0.5；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically supporting Axle is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, by Layer stack is long-pending forms 3 D workpiece；3 D workpiece obtains final products after keeping 30min at 130 DEG C, and 3D prints and uses 3 D-printing Machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives System, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism On；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling spiral shell Female height that can regulate shaping workbench, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw rod Extrusion mechanism is horizontal, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum Including the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system It is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, nozzle number bag Include 8, its generally circular in shape, rectangle, nozzle comprises 650 spray orifices, spray orifice is generally circular in shape, rectangle, and spray orifice exports A diameter of 35 μm, simultaneously nozzle cooling device installed above, cooling device is cross air blasting, and wind-warm syndrome is 15 DEG C, and wind speed is 0.1m/s； Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Embodiment 16

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers 11 lactams and lactone Monomer undecalactone and addition are the auxiliary agent vinylcaprolactam of 0.1wt% and isocyanates and addition is the increasing of 30wt% Mould agent rare earth；The mass ratio of vinylcaprolactam and isocyanates is 1:1；At the catalyst benzene that addition is 1wt% after Rong Rong Base is combined with sodium under the stable compound effect formed and carries out polymerisation at temperature is 300 DEG C, adds in the course of the polymerization process The conductive filler ZnO fragment of 24wt%, it is thus achieved that number-average molecular weight is the subject polymer of 1000, and polymerisation is at Screw Extrusion Completing in machine, screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and measuring pump；Spiral shell Bar is three screw rods, and draw ratio is 48, uniform pitch, and helical angle is 18 °, and spiral groove depth is 1.5mm, and surface roughness is Ra0.8； The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar and temperature sensor are installed Outside screw rod；Then subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece；3 D workpiece exists 160 DEG C keep acquisition final products after 40min, and 3D prints and uses 3 D-printing machine, including the Screw Extrusion set gradually Mechanism, three-dimensional motion mechanism, workbench mechanism and computer control and drive system, and Screw Extrusion mechanism is flat relative to work Platform and profiled member maintain static；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer control with drive system be for The automatically controlling and driving of complete machine；Three-dimensional motion mechanism is made up of X-axis motion, Y-axis motion and Z axis motion； X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes y-axis motor and lead screw guide rails composition； Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis feed screw nut, and Y-axis supports solid Being scheduled on shaping work platform frame, Z axis is vertically fixed on pedestal；Workbench mechanism is by shaping work platform, shaping Workbench bracing frame and leveling nut composition；Shaping work stage+module is on X-axis motion, and having suitably rubs is Number, it is possible to the most fixing ground floor printed material；Shaping work platform frame is connected with described Y-axis motion, with Time affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can regulate the height of shaping workbench Degree, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw Extrusion mechanism is vertical or horizontal, its Including material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes and screw extrusion apparatus The material feed drum being connected, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by conveyance conduit, nozzle, Rotating disk, stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes 10, and it is shaped as three Dihedral, rhombus, nozzle comprises 800 spray orifices, and spray orifice is shaped as cross, in-line, and spray orifice outlet diameter is 25 μm, Nozzle cooling device installed above simultaneously, cooling device is ring blowing or cross air blasting, and wind-warm syndrome is 25 DEG C, and wind speed is 0.1m/s；Cut Only valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Embodiment 17

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by lactam monomers lauric lactam and lactone Monomer dodecalactone and addition are auxiliary agent carbamate and the mixture of carbonic ester of 5wt%, wherein carbamate and carbonic acid The mass ratio of ester is 1:2, and plasticizer phthalic acid dibutyl ester that addition is 36wt% and the mixture of citrate, its The mass ratio 1:3 of middle dibutyl phthalate and citrate；At the catalyst NaOH that addition is 0.9wt% after Rong Rong Enter at temperature is 160 DEG C under acting on the mixture (wherein the mass ratio of NaOH and potassium hydroxide is 2:1) of potassium hydroxide Row polymerisation, adds the conductive filler TiO of 25wt% in the course of the polymerization process₂Powder, it is thus achieved that number-average molecular weight is 10000 Subject polymer, polymerisation completes in screw extruder, screw extruder include screw rod, connect screw rod extruder motor, Heating collar, temperature sensor and measuring pump；Screw rod is single screw rod, and draw ratio is 30, uniform pitch, and helical angle is 14 °, screw channel The degree of depth is 3.5mm, and surface roughness is Ra0.4；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, by vertically Support shaft is fixed；Heating collar and temperature sensor are arranged on outside screw rod；Then subject polymer is printed through fusion sediment 3D, Successively pile up and form 3 D workpiece；3 D workpiece obtains final products after keeping 10min at 150 DEG C, and 3D prints and uses three-dimensional to beat Print machine, controls including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer and drives Dynamic system, Screw Extrusion mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion machine On structure；It is automatically controlling and driving for complete machine that computer controls with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion composition；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis is moved Mechanism includes y-axis motor and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis supports Being fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal； Workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Shaping work stage+module exists On X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform props up Support is connected with described Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down； Leveling nut can regulate the height of shaping workbench, it is ensured that the perpendicularity requirement to shower nozzle discharging opening of the shaping work platform plane； Screw Extrusion mechanism is vertical or horizontal, and it includes material feed drum, screw extrusion apparatus and the shower nozzle being connected with screw extrusion apparatus System；Material feed drum includes the material feed drum being connected with screw extrusion apparatus, and the rounded funnel-form of material feed drum, outside arranges dry heat Device；Nozzle system is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device；Nozzle is installed on conveyance conduit end, Nozzle number includes 6, and it is shaped as rhombus, and nozzle comprises 600 spray orifices, and spray orifice is shaped as Y shape, and spray orifice outlet is straight Footpath is 300 μm, simultaneously nozzle cooling device installed above, and cooling device is ring blowing, and wind-warm syndrome is 15 DEG C, and wind speed is 0.1m/s； Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Embodiment 18

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by valerolactam that mass ratio is 1:1, in oneself Acid amides and addition are auxiliary agent vinylcaprolactam and the mixing that plasticizer is clay and rare earth of addition 35wt% of 5wt% Thing, wherein the mass ratio 4:3 of clay and rare earth；In temperature under the catalyst NaOH effect that addition is 0.01wt% after Rong Rong Degree is to carry out polymerisation at 300 DEG C, adds conductive filler conductive carbon black and the mixing of stainless steel wire of 14wt% before polymerization Thing, wherein the mass ratio 1:2 of conductive black and stainless steel wire, it is thus achieved that number-average molecular weight is the subject polymer of 20000, polymerization Reaction completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, TEMP Device and measuring pump；Screw rod is single screw rod, and draw ratio is 12, uniform pitch, and helical angle is 16 °, and spiral groove depth is 1.5mm, table Surface roughness is Ra0.8；The extruder motor connecting screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar It is arranged on outside screw rod with temperature sensor；Then subject polymer is printed through fusion sediment 3D, successively pile up and form three-dimensional Workpiece；3 D workpiece obtains final products after keeping 60min at 100 DEG C, and 3D prints and uses 3 D-printing machine, including depending on The Screw Extrusion mechanism of secondary setting, three-dimensional motion mechanism, workbench mechanism and computer control and drive system, Screw Extrusion Mechanism maintains static relative to workbench and profiled member；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer controls It is automatically controlling and driving for complete machine with drive system；Three-dimensional motion mechanism by X-axis motion, Y-axis motion and Z axis motion forms；X-axis motion includes X-axis motor and lead screw guide rails composition；Y-axis motion includes Y-axis electricity Machine and lead screw guide rails composition；Z axis motion includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis leading screw On nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal；Workbench mechanism by Shaping work platform, shaping work platform frame and leveling nut composition；Shaping work stage+module on X-axis motion, There is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Shaping work platform frame and described Y-axis Motion is connected, the most affixed with Z axis moving slide block, it is possible to do with Z axis and move along a straight line up and down；Leveling nut can regulate The height of shaping work platform, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw Extrusion mechanism is Vertical or horizontal, it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum bag Including the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by Conveyance conduit, nozzle, rotating disk, stop valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes One, it is generally circular in shape, and nozzle comprises 1 spray orifice, and spray orifice is generally circular in shape, and spray orifice outlet diameter is 500 μm, simultaneously Nozzle cooling device installed above, cooling device is ring blowing, and wind-warm syndrome is 15 DEG C, and wind speed is 0.01m/s；Stop valve is installed on Above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Embodiment 19

The 3D Method of printing of a kind of fibre-grade conductive articles based on reactive extrursion, by valerolactam that mass ratio is 1:1, in oneself Acid amides and addition are auxiliary agent vinylcaprolactam and the mixing that plasticizer is clay and rare earth of addition 36wt% of 5wt% Thing, wherein the mass ratio 4:3 of clay and rare earth；In temperature under the catalyst NaOH effect that addition is 0.01wt% after Rong Rong Degree is to carry out polymerisation at 300 DEG C, adds conductive filler silver and the mixture of nickel of 18wt%, wherein silver and nickel before polymerization Mass ratio 1:5, it is thus achieved that number-average molecular weight is the subject polymer of 20000, and polymerisation completes in screw extruder, spiral shell Bar extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and measuring pump；Screw rod is single screw rod, Draw ratio is 12, uniform pitch, and helical angle is 16 °, and spiral groove depth is 1.5mm, and surface roughness is Ra0.8；Connect screw rod Extruder motor be fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar and temperature sensor are arranged on outside screw rod Face；Then subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece；3 D workpiece is 100 DEG C of holdings Obtaining final products after 60min, 3D prints and uses 3 D-printing machine, including the Screw Extrusion mechanism set gradually, three-dimensional Motion, workbench mechanism and computer control and drive system, and Screw Extrusion mechanism is relative to workbench and profiled member Maintain static；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer controls and drive system is automatic for complete machine Control and drive；Three-dimensional motion mechanism is made up of X-axis motion, Y-axis motion and Z axis motion；X-axis is moved Mechanism includes X-axis motor and lead screw guide rails composition；Y-axis motion includes y-axis motor and lead screw guide rails composition；Z axis moves Mechanism includes Z axis motor and lead screw guide rails composition；X-axis is supported and fixed on Y-axis feed screw nut, and Y-axis is supported and fixed on shaping On workbench bracing frame, Z axis is vertically fixed on pedestal；Workbench mechanism is by shaping work platform, shaping work platform Bracing frame and leveling nut composition；Shaping work stage+module, on X-axis motion, has suitable coefficient of friction, it is possible to The most fixing ground floor printed material；Shaping work platform frame and described Y-axis motion are connected, simultaneously and Z axis Moving slide block is affixed, it is possible to do moving along a straight line up and down with Z axis；Leveling nut can regulate the height of shaping workbench, it is ensured that The perpendicularity requirement to shower nozzle discharging opening of the shaping work platform plane；Screw Extrusion mechanism is vertical or horizontal, and it includes feed Cylinder, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes the confession being connected with screw extrusion apparatus Barrel, the rounded funnel-form of material feed drum, outside arranges drying heater；Nozzle system by conveyance conduit, nozzle, rotating disk, cut Only valve and cooling device are constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes one, and it is generally circular in shape, nozzle On comprise 1 spray orifice, spray orifice is generally circular in shape, and spray orifice outlet diameter is 500 μm, and nozzle cooling device installed above, cold simultaneously Radiator cooler is ring blowing, and wind-warm syndrome is 15 DEG C, and wind speed is 0.01m/s；Stop valve is installed on above the cooling device of shower nozzle；

The step that concrete 3D prints includes:

Claims

1. a 3D Method of printing for fibre-grade conductive articles based on reactive extrursion, is characterized in that: by lactam monomers and/or interior Under catalyst action, carry out polymerisation after ester monomer and auxiliary agent, plasticizer are melted, before polymerization or during add conduction Filler, it is thus achieved that subject polymer；Then described subject polymer is printed through fusion sediment 3D, successively pile up formation three Dimension workpiece；Described 3 D workpiece after heat treatment obtains final products；

Described plasticizer is dibutyl phthalate, citrate, gallium chloride, lithium chloride, calcium chloride, clay, dilute One or more in soil；

Described heat treatment refers to keep 3-60min at 100-180 DEG C.

The 3D Method of printing of a kind of fibre-grade the most according to claim 1 conductive articles based on reactive extrursion, it is characterised in that Described lactam monomers be valerolactam, caprolactam, oenantholcatam, spicy inner formyl amine, certain herbaceous plants with big flowers lactams, ten lactams, ten More than one in one lactams, lauric lactam；Described internal ester monomer be valerolactone, caprolactone, heptalactone, caprylolactone, More than one in certain herbaceous plants with big flowers lactone, ten lactones, undecalactone, dodecalactone；Described catalyst be NaOH, potassium hydroxide, More than one in organo-metallic compound；Described organo-metallic compound is in methyl, ethyl, propyl group, butyl, phenyl A kind of with sodium, potassium, calcium, magnesium in the stable compound that formed of a kind of combination；Described auxiliary agent be vinylcaprolactam, More than one in isocyanates, carbamate, carbonic ester and sulphonic acid ester；Described conductive filler is described conductive fill Agent is conductive carbon black, metal fragment or powder, stainless steel wire, carbon fiber, graphite fibre, copper fiber, aluminizes in glass One or more；Described metal fragment or powder are copper, nickel, silver, CuI, SnO₂、SnO₂/Sb、SnO₂/In、CuS、 CuCl、ZnO、TiO₂In one or more.

The 3D Method of printing of a kind of fibre-grade the most according to claim 1 conductive articles based on reactive extrursion, it is characterised in that The temperature of described polymerisation is 150-300 DEG C, and catalyst loading is 0.01-1wt%, and additive dosage is 0.1-5wt%, Described plasticizer addition is 10-40wt%, and described conductive filler addition is the 0.01-30wt% of monomer, described target The number-average molecular weight of polymer is 1000-20000.

The 3D Method of printing of a kind of fibre-grade the most according to claim 1 conductive articles based on reactive extrursion, it is characterised in that Described polymerisation completes in screw extruder, and described screw extruder includes screw rod, the extruder motor connecting screw rod, adds Gas ket, temperature sensor and measuring pump；Described screw rod is the one in single screw rod, twin-screw, three screw rods, and draw ratio is 12-48, uniform pitch, helical angle is 14-18 °, and spiral groove depth is 1.5-3.5mm, and surface roughness is Ra0.4-0.8；Institute The extruder motor stating connection screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Described heating collar and temperature pass Sensor is arranged on outside screw rod.

The 3D Method of printing of a kind of fibre-grade the most according to claim 1 conductive articles based on reactive extrursion, it is characterised in that The step that described 3D prints includes:

(2) described subject polymer is fed forward, and is controlled by measuring pump accurate quantification and by nozzle system extrusion to becoming Type platform, shaped platform makees X-Y plane motion under computer system control；When the temperature of the polymer of extrusion is less than solid Change and start curing molding after temperature, become the cross section of profiled member a layer thickness, terminate the deposition material of a layer solidify rapidly and with Adjacent material molding bonded, shaped platform, at the height of Z axis Move Up One Layer, carries out the deposition of next layer, the most successively Pile up and form 3 D workpiece.

The 3D Method of printing of a kind of fibre-grade the most according to claim 5 conductive articles based on reactive extrursion, it is characterised in that The translational speed of described shaped platform is 10-10000mm/s；Described measuring pump melt flow is 0.1-3000L/h, precision For ± 0.1%.

The 3D Method of printing of a kind of fibre-grade the most according to claim 1 conductive articles based on reactive extrursion, it is characterised in that Described 3D prints and uses 3 D-printing machine, including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, work Platform mechanism and computer control and drive system, and described Screw Extrusion mechanism is fixing relative to workbench and profiled member not Dynamic；Described workbench mechanism is arranged on three-dimensional motion mechanism；It is for complete machine that described computer controls with drive system Automatically control and drive.

The 3D Method of printing of a kind of fibre-grade the most according to claim 7 conductive articles based on reactive extrursion, it is characterised in that Described three-dimensional motion mechanism is made up of X-axis motion, Y-axis motion and Z axis motion；Described X-axis is moved Mechanism includes X-axis motor and lead screw guide rails composition；Described Y-axis motion includes y-axis motor and lead screw guide rails composition； Described Z axis motion includes Z axis motor and lead screw guide rails composition；Described X-axis is supported and fixed on Y-axis feed screw nut, Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal.

The 3D Method of printing of a kind of fibre-grade the most according to claim 7 conductive articles based on reactive extrursion, it is characterised in that Described workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Described shaping work Stage+module, on described X-axis motion, has suitable coefficient of friction, it is possible to the most fixing ground floor prints Material；Described shaping work platform frame is connected with described Y-axis motion, the most affixed with Z axis moving slide block, Can do with Z axis and move along a straight line up and down；Described leveling nut can regulate the height of shaping workbench, it is ensured that shaping work The platform plane perpendicularity requirement to shower nozzle discharging opening.

The 3D Method of printing of a kind of fibre-grade the most according to claim 7 conductive articles based on reactive extrursion, its feature exists In, described Screw Extrusion mechanism is vertical or horizontal, and it includes material feed drum, screw extrusion apparatus and and screw extrusion apparatus The nozzle system being connected；Described material feed drum includes the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, Outside arranges drying heater；Described nozzle system is made up of conveyance conduit, nozzle, rotating disk, stop valve and cooling device； Described nozzle is installed on conveyance conduit end, and nozzle number at least includes one, it is generally circular in shape, rectangle, triangle, One or more in rhombus, nozzle comprises 1-1000 spray orifice, spray orifice is generally circular in shape, rectangle, triangle, water chestnut One or more in shape, cross, in-line, Y shape, spray orifice outlet diameter is 10-500 μm, simultaneously above nozzle Installing cooling device, cooling device is ring blowing or cross air blasting, and wind-warm syndrome is 15-25 DEG C, and wind speed is 0.01-0.1m/s；Described Stop valve is installed on above the cooling device of shower nozzle.