CN105922577A - Functional fiber-grade 3D printing method based on reactive extrusion - Google Patents

Abstract

The invention relates to a functional fiber-grade 3D printing method based on reactive extrusion. A lactam monomer and/or lactone monomer, an assistant and a plasticizer are fused and have a polymerization reaction under the catalyst effect, a functional agent is added before polymerization or in the polymerization process, and target polymer is obtained; the target polymer is subject to fused deposition 3D printing, and then subject to heat treatment, and a final product is obtained; and according to heat treatment, heat preservation is carried out for 3 min to 60 min at the temperature ranging from 100 DEG C to 180 DEG C. A high-precision high-adapting 3D printer is adopted, the molding precision is high, the efficiency is high, the mechanical property of the product is good, and functional components are good in dispersibility; a technology for directly making the product from the polymeric monomer is adopted, the production flexibility is improved, and meanwhile, the condition that due to crystallization and the large temperature difference of semi-crystalline polymer of nylon, polyester and the like, edge warping is caused, and even printing cannot be carried out is avoided; and the kind of the fused deposition 3D printing material is widened, the quality of the product is improved, and the method has the wide application to the fields of automobile materials, engineering materials, structural parts and the like.

Description

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

Technical field

The invention belongs to 3D printing technique field, relate to a kind of functional fibre-grade 3D based on reactive extrursion Method of printing, special Do not 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 shaping skill The advantages such as art, has volume little, low cost, pollutes low, easy to use.Its ultimate 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), polylactic acid (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 self-cleaning function and preparation method and application ", and (CN104530668A) discloses one The method kind preparing functionalization 3D printed material: this 3D printed material comprises following component: polylactic acid or acrylonitrile-butadiene- The high polymer 70-85 parts such as styrene copolymer；The pigment powder 1-5 part such as titanium white, red, calcium carbonate superfine powder, ultra-fine The inorganic filler 1-5 part such as silicon dioxide and Pulvis Talci, nano functional agent titanium dioxide 0.5-1.5 part, isoprene rubber, thermoplastic poly Ester elastomer binding material 10-20 part.This invention is by by aforementioned component mix homogeneously；Again the material of mix homogeneously is put into list In screw rod plastic extruder, extrusion, cooling and shaping, be dried, traction, coiling, the 3D obtaining having self-cleaning function prints Material.Patent " a kind of flame-proof composite material for 3D printing and preparation method thereof " (CN104479349A) provides one Plant the flame-proof composite material printed for 3D, including the raw material of following weight portion: the nylon resin of 60-95 weight portion；5-40 weight The lubricant of the ABS resin 0.3-2 weight portion of amount part；The compatilizer of 5-20 weight portion；The antioxidant of 0.2-1 weight portion；5-30 The unformed red phosphorus of weight portion, the 3D prepared by the method prints raw material and goods have certain fire resistance.Patent " a kind of electric conductivity 3D prints plastics lines and production method thereof " (CN103788565A), a kind of electric conductivity of this disclosure of the invention 3D prints plastics lines and production method thereof, includes following components according to mass fraction ratio: the ABS of 100 parts, 35-55 part Conductive nano white carbon black, the titanate coupling agent of 0.5-3 part, this invention obtains 3D printing plastic wire and 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 the course of processing, need polymer remelt, and owing to the melting tube of conventional 3D printing is shorter, In order to ensure polymer melt, 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 absorption 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 a kind of functional fibre-grade 3D based on reactive extrursion Method of printing, Be a kind of from monomer directly to the 3D Method of printing of goods.The present invention uses the 3D printer with high-accuracy high-efficiency high-adaptability, With polymer monomer as raw material, adding a certain amount of function ingredients, the 3D through 3D printer molding acquisition with specific function beats Printing product.The method directly to goods from monomer, decreases in conventional 3D printing step and cools down remelted step, reduce into This, it also avoid the second melting process degraded impact on product quality simultaneously, it also avoid material simultaneously and leads owing to water suction waits Degraded in the course of processing caused and hydraulic performance decline；From the direct goods of monomer, machine-shaping temperature can be reduced, it is to avoid due to temperature The problem that difference is excessive and causes the change in size caused because of percent thermal shrinkage；Meanwhile, function ingredients can be realized with monomer making beating uniformly It is blended, or polymerization process adds function ingredients, it is achieved the in-situ polymerization of function ingredients, be blended relative to conventional screw, improve The dispersion effect of function ingredients, it is to avoid the reunion of function ingredients, improves product quality, it is to avoid spray nozzle clogging；And Modulatory character By force, regulation and control production technology can be required according to product quality, it is achieved single line multi-item production, continuous production is good；Simultaneously with having The 3D printer of high-accuracy high-efficiency high-adaptability, improves molding degree of freedom, manufacturing speed and profiled member precision.

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing of the present invention, by lactam monomers and/or lactone list Under catalyst action, carry out polyreaction after body and auxiliary agent, plasticizer are melted, before polymerization or during add function additive, Obtain subject polymer；Then described subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece；Institute State 3 D workpiece and after heat treatment obtain 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, polyreaction 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, polyreaction can be made to proceed by heat treatment 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:

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, in described lactam monomers is penta In amide, caprolactam, oenantholcatam, spicy inner formyl amine, certain herbaceous plants with big flowers lactams, ten lactams, 11 lactams, lauric lactam More than one；Described internal ester monomer be valerolactone, caprolactone, heptalactone, caprylolactone, certain herbaceous plants with big flowers lactone, ten lactones, in 11 More than one in ester, dodecalactone；Described catalyst is the one in sodium hydroxide, potassium hydroxide, organo-metallic compound Above；Described organo-metallic compound is in the one in methyl, ethyl, propyl group, butyl, phenyl and sodium, potassium, calcium, magnesium A kind of combination formed stable compound；Described auxiliary agent is vinylcaprolactam, isocyanates, carbamate, carbonic acid More than one in ester and sulphonic acid ester；Described plasticizer be dibutyl phthalate, citrate, gallium chloride, lithium chloride, One or more in calcium chloride, clay, rare earth.

Described function additive is that antioxidant, anti ultraviolet agent, anion-generating material, fluorescent material, enhancing implant, carbon are received Mitron or Graphene；Described antioxidant is antioxidant 1010, antioxidant 168 or antioxidant 616；Anti ultraviolet agent is Salicylic acid, benzophenone series benzotriazole system, titanium dioxide, zinc oxide, calcium carbonate, Pulvis Talci or SEED；Anion is sent out Green material is rare ice stone, tourmaline, opal or QICAISHI；Fluorescent material is using the sulfide of alkaline-earth metal, aluminate as sending out Light substrate, with rare earth lanthanide europium, samarium, erbium or neodymium, as activator；Described enhancing implant is that nanoparticle, carbon are received In mitron, Graphene, white carbon black, chopped fiber one or more.Described nanoparticle is montmorillonite, CaCO₃、SiC、SiO₂、 Bentonite, TiO₂、A1₂O₃、ZrO₂, one or more in Cu powder；Described chopped fiber is glass fibre, carbon fiber, virtue One or more in synthetic fibre fiber, polyimide fiber.

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, the temperature of described polyreaction is 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 function additive addition is the 0.01-10wt% of monomer, and the number-average molecular weight of described subject polymer is 1000-20000。

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, described polyreaction is squeezed at screw rod Go out in machine and complete, by controlling extruder temperature, catalyst content, the number-average molecular weight of accuracy controlling polymer；Described screw rod squeezes Go out machine to include screw rod, connect the extruder motor of screw rod, heating collar, temperature sensor and dosing 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.

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, the step that described 3D prints includes:

(1) use CAD or CAM software 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing pump accurate quantification and put down to molding 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.

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, the movement of described shaped platform Speed is 10-10000mm/s；Described dosing pump melt flow is 0.1-3000L/h, and precision is ± 0.1%, so that it is guaranteed that in molding During the accurate control of extrusion capacity, it is ensured that whole mechanism stability in work continuously, simultaneously work as the effect of supercharging, really Protect the smooth extrusion molding of high viscosity thermoplastic.

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, described 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, described Screw Extrusion mechanism maintains static relative to work platforms and profiled member；Described workbench mechanism is installed On three-dimensional motion mechanism；It is automatically controlling and driving for complete machine that described computer controls with drive system.

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, 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.

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, described workbench mechanism is by becoming Type work platforms, shaping work platform frame and leveling nut composition；Described shaping work stage+module is in described X-axis fortune On motivation structure, there is suitable coefficient of friction, it is possible to the most fixing ground floor printed material；Described 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 and move along a straight line up and down；Institute State leveling nut and can regulate the height of molding work platforms, it is ensured that the perpendicularity of shower nozzle discharging opening is wanted by shaping work platform plane Ask.

A kind of functional fibre-grade as above 3D based on reactive extrursion Method of printing, described Screw Extrusion mechanism is vertical Formula or horizontal, it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Described feed Cylinder 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 spray Head system is made up of conveyance conduit, nozzle, rotating disk, stop valve and chiller；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 chiller installed above, and chiller is ring blowing or side-blown Wind, pathogenic wind-warm is 15-25 DEG C, and wind speed is 0.01-0.1m/s；Described stop valve is installed on above the chiller 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 dosing 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 dosing pump, it is achieved molding 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 dosing 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 rate of cooling 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 the simultaneously multiple profiled member of molding, such that it is able to be effectively improved molding Efficiency, meets the requirement of batch molding.

(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 motility of production, reduce Properties of product dependencies 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 ambient 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, and molding is 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers valerolactam and internal ester monomer Valerolactone and addition are the auxiliary agent vinylcaprolactam of 0.1wt% and plasticizer phthalic acid two that addition is 10wt% Butyl ester；Under the catalyst sodium hydroxide effect that addition is 0.01wt%, at temperature is 150 DEG C, polyreaction is carried out after Rong Rong, Add the function additive antioxidant 1010 of 0.01wt% before polymerization, 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 dosing 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, 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 3min 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 work platforms 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 molding work platforms, it is ensured that the shaping work platform plane perpendicularity requirement to shower nozzle discharging opening；Screw extruder Structure is vertical, 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 chiller are constituted；Nozzle is installed on conveyance conduit end, nozzle number one, its Generally circular in shape, nozzle comprises 1 spray orifice, spray orifice is generally circular in shape, and spray orifice outlet diameter is 10 μm, simultaneously on nozzle Chiller is installed by side, and chiller is ring blowing, and pathogenic wind-warm is 15 DEG C, and wind speed is 0.01m/s；Stop valve is installed on shower nozzle Above chiller；

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 molding；

(2) subject polymer is fed forward, and is controlled by dosing pump accurate quantification and put down to molding 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 Molding, 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers caprolactam and internal ester monomer Caprolactone and addition are the auxiliary agent isocyanates of 5wt% and plasticizer citrate that addition is 40wt%；Adding after Rong Rong Dosage be 1wt% catalyst potassium hydroxide effect under at temperature is 300 DEG C, carry out polyreaction, in polymerization process, Add the function additive anti ultraviolet agent salicylic acid of 10wt%, it is thus achieved that number-average molecular weight is the subject polymer of 20000, polyreaction Screw extruder completes, screw extruder include screw rod, connect the extruder motor of screw rod, heating collar, temperature sensor and Dosing 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, and surface is thick Rugosity 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 Degree 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 Work platforms 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 molding work platforms 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 chiller 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, chiller is cross air blasting, and pathogenic wind-warm is 25 DEG C, and wind speed is 0.1m/s；Stop valve is installed on above the chiller of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAM software 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 molding；

(2) subject polymer is fed forward, and is controlled by dosing pump accurate quantification and put down to molding 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, Dosing 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers oenantholcatam and internal ester monomer Heptalactone and addition are the auxiliary agent carbamate of 0.5wt% and plasticizer gallium chloride that addition is 15wt%；Adding after Rong Rong Dosage be the catalyst methyl of 0.08wt% be combined with sodium formed stable compound effect under gather at temperature is 250 DEG C Close reaction, in polymerization process, add the function additive anion-generating material rare ice stone of 0.9wt%, it is thus achieved that the equal molecule of number Amount is the subject polymer of 10000, and polyreaction completes in screw extruder, and screw extruder includes screw rod, connects screw rod Extruder motor, heating collar, temperature sensor and dosing pump；Screw rod is three screw rods, and draw ratio is 45, uniform pitch, helical angle Being 16 °, spiral groove depth is 1.8mm, and surface roughness is Ra0.6；The extruder motor connecting screw rod is fixedly mounted on screw rod Right side, is fixed by vertical support shaft；Heating collar and temperature sensor are arranged on outside screw rod；Then by subject polymer through melted Deposition 3D prints, and successively piles up and forms 3 D workpiece；3 D workpiece obtains final products, 3D after keeping 10min at 120 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 work platforms 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 work platforms 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 Y-axis motion, the most affixed with Z axis moving slide block, it is possible to do the most straight with Z axis Line moves；Leveling nut can regulate the height of molding work platforms, it is ensured that shower nozzle discharging opening is hung down by shaping work platform plane Directly spend requirement；Screw Extrusion mechanism is vertical, and it includes material feed drum, screw extrusion apparatus and the spray being connected with screw extrusion apparatus Head system；Material feed drum includes the material feed drum being connected with screw extrusion apparatus, the rounded funnel-form of material feed drum, and outside arranges to be dried and adds Hot device；Nozzle system is made up of conveyance conduit, nozzle, rotating disk, stop valve and chiller；Nozzle is installed on conveyance conduit end End, nozzle number includes 3, and it is shaped as triangle, and nozzle comprises 800 spray orifices, and spray orifice is shaped as triangle, spray A diameter of 100 μm of hole exits, nozzle chiller installed above simultaneously, chiller is ring blowing, and pathogenic wind-warm is 20 DEG C, wind Speed is 0.05m/s；Stop valve is installed on above the chiller 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing 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, Dosing 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers spicy inner formyl amine and internal ester monomer Caprylolactone and addition are the auxiliary agent carbonic ester of 2wt% and plasticizer lithium chloride that addition is 20wt%；After Rong Rong at addition it is The ethyl of 0.07wt% is combined with potassium under the stable compound effect formed and carries out polyreaction at temperature is 200 DEG C, anti-in polymerization During Ying, adding the function additive fluorescent material of 2.5wt%, wherein the sulfide of alkaline-earth metal is as luminous host, Rare Earth Lanthanum Series elements europium is as activator, it is thus achieved that number-average molecular weight is the subject polymer of 1000, and polyreaction completes in screw extruder, Screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and dosing pump；Screw rod is single screw rod, Draw ratio is 15, uniform pitch, and helical angle is 16 °, and spiral groove depth is 1.8mm, and surface roughness is Ra0.6；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 work platforms 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 molding On work platforms 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 molding work platforms, 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 material feed drum, screw rod Extrusion device and the nozzle system being connected with screw extrusion apparatus；Material feed drum includes the material feed drum being connected with screw extrusion apparatus, supplies The rounded funnel-form of barrel, outside arranges drying heater；Nozzle system is by conveyance conduit, nozzle, rotating disk, stop valve and cold Radiator cooler is constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes one, and it is shaped as rhombus, and nozzle comprises 500 Individual spray orifice, spray orifice is shaped as rhombus, and spray orifice outlet diameter is 50 μm, simultaneously nozzle chiller installed above, chiller Drying for ring, pathogenic wind-warm is 19 DEG C, and wind speed is 0.02m/s；Stop valve is installed on above the chiller 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing 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, dosing 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers certain herbaceous plants with big flowers lactams and internal ester monomer 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%；At addition after Rong Rong Be combined under the stable compound effect formed with calcium for the propyl group of 0.3wt% and at temperature is 160 DEG C, carry out polyreaction, in polymerization In course of reaction, the function additive adding 3wt% strengthens implant nanoparticle montmorillonite, it is thus achieved that number-average molecular weight is 1000 Subject polymer, polyreaction completes in screw extruder, screw extruder include screw rod, connect screw rod extruder motor, Heating collar, temperature sensor and dosing pump；Screw rod is single screw rod, and draw ratio is 32, uniform pitch, and helical angle is 16 °, screw channel The degree of 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, 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 12min at 110 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 work platforms 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 molding work platforms, 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 chiller；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 chiller installed above, chiller is cross air blasting, and pathogenic wind-warm is 22 DEG C, and wind speed is 0.09m/s；Cut-off Valve is installed on above the chiller of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAD or CAM software 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 molding；

(2) subject polymer is fed forward, and is controlled by dosing pump accurate quantification and put down to molding 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, Dosing 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers ten lactams and internal ester monomer Ten lactones and addition are the auxiliary agent vinylcaprolactam of 4wt% and plasticizer clay that addition is 23wt%；After Rong Rong Addition be the catalyst butyl of 0.2wt% be combined with magnesium formed stable compound effect under be polymerized at temperature is 160 DEG C Reaction, in polymerization process, adds the function additive CNT of 5wt%, it is thus achieved that number-average molecular weight is the target of 1200 Polymer, polyreaction completes in screw extruder, and screw extruder includes screw rod, connects the extruder motor of screw rod, heating Circle, temperature sensor and dosing 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 work platforms 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 molding work platforms, 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 chiller；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 chiller installed above, chiller is cross air blasting, and pathogenic wind-warm is 15 DEG C, and wind speed is 0.1m/s； Stop valve is installed on above the chiller of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAM software 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing 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, Dosing 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers 11 lactams and lactone list Body undecalactone and addition are the auxiliary agent vinylcaprolactam of 0.1wt% and isocyanates and addition is the plasticising of 30wt% Agent rare earth；The mass ratio of vinylcaprolactam and isocyanates is 1:1；At the catalyst phenyl that addition is 1wt% after Rong Rong Be combined with sodium under the stable compound effect formed at temperature is 300 DEG C, carries out polyreaction, in polymerization process, add Add the function additive Graphene of 6wt%, it is thus achieved that number-average molecular weight is the subject polymer of 1000, and polyreaction is at screw extruder In complete, screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and dosing pump；Screw rod Being three screw rods, 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, molding Work platforms 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 molding work platforms 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 chiller 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 chiller installed above simultaneously, chiller is ring blowing or cross air blasting, and pathogenic wind-warm is 25 DEG C, and wind speed is 0.1m/s；Cut Only valve is installed on above the chiller 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing 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, Dosing 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by lactam monomers lauric lactam and lactone list Body dodecalactone and addition are auxiliary agent carbamate and the mixture of carbonic ester of 5wt%, wherein carbamate and carbonic ester Mass ratio be 1:2, and the plasticizer that addition is 36wt% is dibutyl phthalate and the mixture of citrate, its The mass ratio 1:3 of middle dibutyl phthalate and citrate；At the catalyst sodium hydroxide 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 sodium hydroxide and potassium hydroxide is 2:1) of potassium hydroxide Row polyreaction, adds the function additive antioxidant 168 of 7wt% before polyreaction, it is thus achieved that number-average molecular weight is 10000 Subject polymer, polyreaction completes in screw extruder, screw extruder include screw rod, connect screw rod extruder motor, Heating collar, temperature sensor and dosing 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 work platforms 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 molding work platforms, 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 chiller；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 chiller installed above, and chiller is ring blowing, and pathogenic wind-warm is 15 DEG C, and wind speed is 0.1m/s； Stop valve is installed on above the chiller of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAM software 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing 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, dosing 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

A kind of functional fibre-grade 3D based on reactive extrursion Method of printing, by the valerolactam that mass ratio is 1:1, own interior acyl Amine and addition are the auxiliary agent vinylcaprolactam of 5wt% and the plasticizer that addition is 35wt% is clay and the mixing of rare earth Thing, wherein the mass ratio 4:3 of clay and rare earth；In temperature under the catalyst sodium hydroxide effect that addition is 0.01wt% after Rong Rong Degree is to carry out polyreaction at 300 DEG C, adds 8wt% function additive anti ultraviolet agent benzophenone series benzo in polymerization process Triazole system, it is thus achieved that number-average molecular weight is the subject polymer of 20000, and polyreaction completes in screw extruder, Screw Extrusion Machine includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and dosing pump；Screw rod is single screw rod, draw ratio Being 12, uniform pitch, helical angle is 14 °, and spiral groove depth is 1.5mm, and surface roughness is Ra0.8；Connect the extrusion of screw rod Motor is fixedly mounted on the right side of screw rod, vertical support shaft fix；Heating collar and temperature sensor are arranged on outside screw rod；So After by subject polymer through fusion sediment 3D print, successively pile up formed 3 D workpiece；3 D workpiece keeps 60min at 100 DEG C Rear acquisition final products, 3D prints and uses 3 D-printing machine, including the Screw Extrusion mechanism set gradually, three-dimensional motion machine Structure, workbench mechanism and computer control and drive system, and Screw Extrusion mechanism is fixing relative to work platforms and profiled member not Dynamic；Workbench mechanism is arranged on three-dimensional motion mechanism；Computer control with drive system be for complete machine automatically control with Drive；Three-dimensional motion mechanism is made up of X-axis motion, Y-axis motion and Z axis motion；X-axis motion bag Include 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 bag Include 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 work and puts down On platform bracing frame, Z axis is vertically fixed on pedestal；Workbench mechanism is by shaping work platform, shaping work platform frame Form with leveling nut；Shaping work stage+module, on X-axis motion, has suitable coefficient of friction, it is possible to well Fixing ground floor printed material；Shaping work platform frame is connected with described Y-axis motion, simultaneously sliding with Z axis motion 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 molding work platforms, it is ensured that molding work Make the platform plane perpendicularity requirement to shower nozzle discharging opening；Screw Extrusion mechanism is vertical or horizontal, and it includes material feed drum, spiral shell Bar extrusion device and the nozzle system being connected with screw extrusion apparatus；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 by conveyance conduit, nozzle, rotating disk, stop valve and Chiller is constituted；Nozzle is installed on conveyance conduit end, and nozzle number includes one, and it is generally circular in shape, and nozzle comprises 1 spray orifice, spray orifice is generally circular in shape, and spray orifice outlet diameter is 500 μm, simultaneously nozzle chiller installed above, chiller Drying for ring, pathogenic wind-warm is 15 DEG C, and wind speed is 0.01m/s；Stop valve is installed on above the chiller of shower nozzle；

The step that concrete 3D prints includes:

(1) use CAM software 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing 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, Dosing 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 preparation process of polymer and print procedure such as embodiment 1, difference is that described function additive is antioxidant 616, Obtaining number-average molecular weight is the subject polymer of 10000.

Embodiment 11

The preparation process of polymer and print procedure such as embodiment 2, difference is that described function additive is anti ultraviolet agent dioxy Change titanium, it is thus achieved that number-average molecular weight is the subject polymer of 15000.

Embodiment 12

The preparation process of polymer and print procedure such as embodiment 3, difference is that described function additive is anion generation material Material tourmaline, it is thus achieved that number-average molecular weight is the subject polymer of 13000.

Embodiment 13

The preparation process of polymer and print procedure such as embodiment 4, difference is that described function additive is fluorescent material, with Aluminate is as luminous host, and rare earth lanthanide samarium, as activator, it is thus achieved that number-average molecular weight is the target polymerization of 16000 Thing.

Embodiment 14

The preparation process of polymer and print procedure such as embodiment 5, difference is that described function additive implant is nanoparticle Sub-TiO₂, it is thus achieved that number-average molecular weight is the subject polymer of 18000.

Embodiment 15

The preparation process of polymer and print procedure such as embodiment 6, difference is that described function additive strengthens implant for receiving Rice corpuscles SiC, it is thus achieved that number-average molecular weight is the subject polymer of 19000.

Embodiment 16

The preparation process of polymer and print procedure such as embodiment 7, it is short that difference is that described function additive strengthens implant Fiber aramid fiber, it is thus achieved that number-average molecular weight is the subject polymer of 11000.

Claims (10)

1. functional fibre-grade 3D based on reactive extrursion Method of printing, is characterized in that: by lactam monomers and/or lactone Under catalyst action, carry out polyreaction after monomer and auxiliary agent, plasticizer are melted, before polymerization or during add function and help Agent, it is thus achieved that subject polymer；Then described subject polymer is printed through fusion sediment 3D, successively pile up and form three-dimensional work Part；Described 3 D workpiece after heat treatment obtains final products；

Described plasticizer is dibutyl phthalate, citrate, gallium chloride, lithium chloride, calcium chloride, clay, dilute More than one in soil；

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

A kind of functional fibre-grade the most according to claim 1 3D based on reactive extrursion Method of printing, 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, More than one in 11 lactams, lauric lactam；Described internal ester monomer is valerolactone, caprolactone, heptalactone, pungent More than one in lactone, certain herbaceous plants with big flowers lactone, ten lactones, undecalactone, dodecalactone；Described catalyst be sodium hydroxide, More than one in potassium hydroxide, organo-metallic compound；Described organo-metallic compound be methyl, ethyl, propyl group, The stable compound that a kind of combination in a kind of and sodium in butyl, phenyl, potassium, calcium, magnesium is formed；Described auxiliary agent is second More than one in acyl caprolactam, isocyanates, carbamate, carbonic ester and sulphonic acid ester；Described plasticizer is One or more in dibutyl phthalate, citrate, gallium chloride, lithium chloride, calcium chloride, clay, rare earth； Described function additive is that antioxidant, anti ultraviolet agent, anion-generating material, fluorescent material, enhancing implant, carbon are received Mitron or Graphene；Described antioxidant is antioxidant 1010, antioxidant 168 or antioxidant 616；Uvioresistant Agent is salicylic acid, benzophenone series benzotriazole system, titanium dioxide, zinc oxide, calcium carbonate, Pulvis Talci or SEED；Negative Ion generating material is rare ice stone, tourmaline, opal or QICAISHI；Fluorescent material is with the sulfide of alkaline-earth metal, aluminum Hydrochlorate is as luminous host, with rare earth lanthanide europium, samarium, erbium or neodymium, as activator；Described enhancing implant is In nanoparticle, CNT, Graphene, white carbon black, chopped fiber one or more；Described nanoparticle be montmorillonite, CaCO₃、SiC、SiO₂, bentonite, TiO₂、A1₂O₃、ZrO₂, one or more in Cu powder；Described chopped fiber For one or more in glass fibre, carbon fiber, aramid fiber, polyimide fiber.

A kind of functional fibre-grade the most according to claim 1 3D based on reactive extrursion Method of printing, it is characterised in that The temperature of described polyreaction 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 function additive addition is the 0.01-10wt% of monomer, and described target is gathered The number-average molecular weight of compound is 1000-20000.

A kind of functional fibre-grade the most according to claim 1 3D based on reactive extrursion Method of printing, it is characterised in that Described polyreaction completes in screw extruder, described screw extruder include screw rod, connect screw rod extruder motor, Heating collar, temperature sensor and dosing pump；Described screw rod is the one in single screw rod, twin screw, three screw rods, draw ratio For 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； The extruder motor of described connection screw rod is fixedly mounted on the right side of screw rod, vertical support shaft fix；Described heating collar and temperature Degree sensor is arranged on outside screw rod.

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

(1) use CAD or CAM software 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 molding；

(2) described subject polymer is fed forward, and is controlled by dosing pump accurate quantification and extruded to shaped platform by nozzle system, 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, terminate the deposition material of a layer solidify rapidly and with material around 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.

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

A kind of functional fibre-grade the most according to claim 1 3D based on reactive extrursion Method of printing, 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 fixed relative to work platforms and profiled member Motionless；Described workbench mechanism is arranged on three-dimensional motion mechanism；Described computer control with drive system be for The automatically controlling and driving of complete machine.

A kind of functional fibre-grade the most according to claim 7 3D based on reactive extrursion Method of printing, 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.

A kind of functional fibre-grade the most according to claim 7 3D based on reactive extrursion Method of printing, it is characterised in that Described workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Described molding work Make stage+module on described X-axis motion, there is suitable coefficient of friction, it is possible to the most fixing ground floor is beaten Printed material material；Described shaping work platform frame is connected with described Y-axis motion, simultaneously solid with Z axis moving slide block Connect, it is possible to do moving along a straight line up and down with Z axis；Described leveling nut can regulate the height of molding work platforms, it is ensured that becomes The perpendicularity requirement to shower nozzle discharging opening of the type work platforms plane.

A kind of functional fibre-grade the most according to claim 7 3D based on reactive extrursion Method of printing, it is characterised in that Described Screw Extrusion mechanism is vertical or horizontal, it include material feed drum, screw extrusion apparatus and with screw extrusion apparatus phase Nozzle system even；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 chiller； 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, Pedicellus et Pericarpium Trapae One or more in shape, cross, in-line, Y shape, spray orifice outlet diameter is 10-500 μm, simultaneously above nozzle Installing chiller, chiller is ring blowing or cross air blasting, and pathogenic wind-warm is 15-25 DEG C, and wind speed is 0.01-0.1m/s；Described Stop valve is installed on above the chiller of shower nozzle.