CN111171541A - Modified PC/ABS composition for 3D printing and preparation method thereof - Google Patents
Modified PC/ABS composition for 3D printing and preparation method thereof Download PDFInfo
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- CN111171541A CN111171541A CN201811234950.5A CN201811234950A CN111171541A CN 111171541 A CN111171541 A CN 111171541A CN 201811234950 A CN201811234950 A CN 201811234950A CN 111171541 A CN111171541 A CN 111171541A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a modified PC/ABS composition for 3D printing and a preparation method thereof, and mainly solves the problem that the PC/ABS alloy in the prior art has large warpage during 3D printing. The modified PC/ABS composition comprises the following components: 1 to 99 parts by mass of PC, 1 to 99 parts by mass of ABS and 0.1 to 50 parts by mass of aliphatic aromatic copolyester, thereby better solving the problem and being applicable to the industrial production of modified polycarbonate/acrylonitrile-butadiene-styrene copolymer materials for 3D printing.
Description
Technical Field
The invention belongs to the field of 3D printing materials, and particularly relates to a modified PC/ABS material for 3D printing and a preparation method thereof.
Technical Field
The principle is that firstly, a digitalized three-dimensional model is obtained through computer modeling or direct scanning of a prototype, then, software is used for cutting the model into two-dimensional section data according to a certain coordinate axis, and a 3D printer is used for printing layer by layer and stacking the section data to form an entity. Through the recent 30 years of development, 3D printing technology has been considered as one of the core technologies that may change the way laboratory and industrial production. The additive manufacturing technology can save materials, shorten the research and development period and reduce the cost, and has great potential application in the aspects of mold manufacturing, product design, medical treatment, education, aerospace and the like.
At present, a 3D printing molding method mainly includes: fused Deposition Modeling (FDM), Stereolithography (SLA), and Selective Laser Sintering (SLS), among others. The FDM technology does not need laser, is simple in use and maintenance, low in cost and widely applied. The technical principle is that a thermoplastic polymer is heated and melted, then extruded out through a spray head, cooled and solidified to form a thin layer with an outline shape, and then overlapped and stacked layer by layer to finally form a product. Therefore, the thermoplastic polymer for FDM3D printing is required to have excellent fluidity and fast curing rate, and the FDM3D printing consumables commonly used in the market at present are mainly ABS (acrylonitrile-butadiene-styrene terpolymer) and PLA (polylactic acid), and in addition, a small amount of PC (polycarbonate), TPU (thermoplastic polyurethane), PA (nylon), and the like.
The ABS resin is one of five synthetic resins, is formed by ternary polymerization of acrylonitrile, butadiene and styrene, and has the comprehensive properties of high chemical stability, oil resistance and surface hardness of polyacrylonitrile, toughness and cold resistance of polybutadiene, good dielectric property, gloss, processability and the like of polystyrene. In addition, ABS resin is easy to coat and color, can be subjected to secondary processing such as surface metal spraying, electroplating, welding, hot pressing, bonding and the like, and is widely applied to the industrial fields of machinery, automobiles, electronic appliances, instruments, textile, buildings and the like.
Polycarbonates are high molecular polymers containing carbonate groups in the molecular chain, and are classified into various types, such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester group. Among them, aromatic polycarbonates are excellent in mechanical properties and are widely used in the fields of glass assembly industry, automobile industry, electronic and electric appliance industry, and the like.
The PC/ABS alloy is a mixture of polycarbonate and acrylonitrile-butadiene-styrene copolymer. The composite material combines the excellent characteristics of the two materials (such as formability of ABS and mechanical property, impact strength, temperature resistance, ultraviolet resistance and the like of PC), improves the fluidity compared with PC, improves the processing performance, and reduces the sensitivity of products to stress, thereby being widely applied to high-strength and high-heat-resistant parts such as automobile interior and exterior decorations, automobile lamps and the like. However, when the PC/ABS alloy is used for 3D printing consumables, the shrinkage rate of each dimension after cooling is relatively large, the PC/ABS alloy is easily separated from a printing bottom plate, warping and even falling occur, and the quality and precision of a printed product are affected. The shrinkage of PC/ABS alloy is usually reduced by adding inorganic components (such as CN104830040A, CN104559023A and CN106893247A), but the PC/ABS alloy is expensive in raw materials (such as multi-wall carbon nano tubes) or complicated in preparation process, has a great influence on product dyeing and the like, and is not beneficial to industrial production and application. CN107033571A discloses the introduction of a compatibilizer in PC/ABS to achieve better mechanical properties, however it does not address the problem of warpage.
The invention discloses a composition and a preparation method of a modified PC/ABS composition for 3D printing, which effectively reduces the warping degree of a printed product by introducing organic components, and is beneficial to subsequent dyeing and other applications due to light material color.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems that in the prior art, PC/ABS printed products have high warping degree, and meanwhile, the materials have dark colors and are not beneficial to subsequent dyeing and other applications.
The second technical problem to be solved by the invention is to provide a preparation method of the modified PC/ABS composition for 3D printing, which corresponds to the first technical problem.
The third technical problem to be solved by the present invention is to provide a 3D printing line made of a material containing the modified PC/ABS composition described above for solving one of the technical problems.
The fourth technical problem to be solved by the present invention is to provide a method for manufacturing a 3D printing line corresponding to the third technical problem.
The fifth technical problem to be solved by the present invention is to provide an application method of 3D printing line corresponding to the third technical problem.
In order to solve one of the above technical problems, the invention adopts the technical scheme that: a modified PC/ABS composition comprises the following components in parts by mass:
(1)1 to 99 of a PC resin;
(2)1 to 99 of an ABS resin;
(3)0.1 to 50 of an aliphatic aromatic copolyester.
In the above technical scheme, the PC resin is selected from the group consisting of melt polycondensation of bisphenol a and diphenyl carbonate or direct esterification of bisphenol a and phosgene.
In the above technical scheme, the ABS resin is selected from any one of bulk continuous polymerization or emulsion polymerization.
In the technical scheme, the ABS resin is selected from a mixture of bulk continuous polymerization and emulsion polymerization, and the mixture comprises the following components in parts by mass: 0-99 parts of bulk continuous polymerization ABS resin and 0-99 parts of emulsion ABS resin.
in the above-mentioned technical means, the aliphatic aromatic copolyester is preferably a copolyester obtained by condensing an α, ω -aliphatic diacid or a derivative thereof, which is an α, ω -aliphatic diacid having 2 to 22 main chain carbon atoms and includes oxalic acid, 1, 3-malonic acid, succinic acid (1, 4-succinic acid), glutamic acid (1, 5-glutaric acid), adipic acid (1, 6-adipic acid), 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, and a dibasic acid having up to 22 carbon atoms, and an aromatic diacid or a derivative thereof, which includes anhydrides, esters, acid halides and the like corresponding to the above-mentioned diacids, with at least one aliphatic diol.
In the above embodiment, the aromatic diacid is preferably at least one of terephthalic acid, dimethyl terephthalate, 1, 4-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 4, 4 '-diphenyletherdicarboxylic acid, 4, 3' -diphenyletherdicarboxylic acid, 4, 4 '-diphenylthioether dicarboxylic acid, 4, 3' -diphenylthioether dicarboxylic acid, 4, 4 '-diphenylsulfone dicarboxylic acid, 4, 3' -diphenylsulfone dicarboxylic acid, 4, 4 '-benzophenonedicarboxylic acid, and 4, 3' -benzophenonedicarboxylic acid. The derivatives of the aromatic diacids include anhydrides, esters, acid halides, etc. corresponding to the diacids described above.
In the technical scheme, the aliphatic and aromatic diacid is preferably aliphatic and aromatic diacid containing substituent groups; the substituent is preferably straight-chain alkyl, branched-chain alkyl, cyclic alkyl or alkyl with an unsaturated structure; and dibasic acids with other substituents such as cyclohexyl.
In the above technical solution, the aliphatic diol includes ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 2-heptanediol, 1, 3-heptanediol, 1, 4-heptanediol, 1, 5-heptanediol, 1, 6-heptanediol, 1, 7-heptanediol, 1, 2-octanediol, 1, 3-octanediol, 1, 4-octanediol, 1, 5-octanediol, 1, 6-octanediol, 1, 7-octanediol, 1, 8-octanediol, 1, 2-nonanediol, 1, 3-nonanediol, 1, 4-nonanediol, 1, 5-nonanediol, 1, 6-nonanediol, 1, 7-nonanediol, 1, 8-nonanediol, 1, 9-nonanediol, 1, 2-decanediol, 1, 3-decanediol, 1, 4-decanediol, 1, 5-decanediol, 1, 6-decanediol, 1, 7-decanediol, 1, 8-decanediol, 1, 9-decanediol, 1, 10-decanediol up to a diol having a carbon number of 24, and a diol having other substituents such as cyclohexyl.
In the above technical solution, the aliphatic aromatic copolyester preferably comprises poly (ethylene terephthalate-co-oxalate), poly (ethylene terephthalate-co-malonate), poly (ethylene terephthalate-co-succinate), poly (ethylene terephthalate-co-glutarate), poly (ethylene terephthalate-co-adipate), poly (ethylene terephthalate-co-suberate), poly (propylene terephthalate-co-oxalate), poly (propylene terephthalate-co-malonate), poly (propylene terephthalate-co-succinate), poly (propylene terephthalate-co-glutarate), poly (propylene terephthalate-co-adipate), poly (propylene terephthalate-co-suberate), poly (ethylene terephthalate-co-adipate), poly (ethylene terephthalate-co-suberate), poly (ethylene terephthalate-co-adipate), poly (ethylene terephthalate-co-, Polytrimethylene terephthalate-co-sebacate, polybutylene terephthalate-co-oxalate, polybutylene terephthalate-co-malonate, polybutylene terephthalate-co-succinate, polybutylene terephthalate-co-glutarate, polybutylene terephthalate-co-adipate, polybutylene terephthalate-co-suberate, polybutylene terephthalate-co-adipate, polyhexamethylene terephthalate-co-oxalate, polyhexamethylene terephthalate-co-malonate, poly (co-ethylene terephthalate-co-butylene succinate), poly (co-ethylene glutarate), poly (co-ethylene adipate), poly (co-ethylene suberate), and the like.
In the technical scheme, the modified PC/ABS composition for 3D printing comprises 1 to 99 parts by mass of ABS, 1 to 99 parts by mass of PC and 0.1 to 50 parts by mass of aliphatic aromatic copolyester.
In the above technical solution, the modified PC/ABS composition for 3D printing preferably further comprises the components: (4)0.1-20 parts of functional improvement auxiliary agent; the functional improvement auxiliary agent is at least one selected from a compatilizer, an inorganic filler, an antioxidant, a lubricant, a colorant and a chain extender.
The aliphatic aromatic copolyester of the present invention can be prepared by polymerizing the above-mentioned various diacids and diols. The catalyst for polymerization includes compounds containing metallic tin, antimony, titanium, etc. Aliphatic aromatic copolyesters include chain-extended polyesters, and a variety of compounds or polymers reactive with carboxyl or hydroxyl groups can be used as chain extenders, including, for example, isocyanates containing two or more functional groups such as hexamethylene diisocyanate (HMDI). Suitable chain extenders include compounds containing multiple epoxy functional groups, such as those produced by BASF
ADR-4368C,
ADR-4368CS and the like.
The aliphatic aromatic copolyesters of the invention include linear and branched polyesters. The synthesis of branched polyesters one or more branching agents are added during the synthesis. The branching agent is generally a polybasic acid having two or more carboxyl groups, a polyhydric alcohol or a polyhydroxy acid having two or more hydroxyl groups, or the like. Suitable branching agents include glycerol, trimethylolethane, trimethylolpropane, 1,2, 4-butanetriol, pentaerythritol, 1,2, 6-hexanetriol, sorbitol, 1,2, 3-benzenetricarboxylic acid (hemimellitic acid), 1,2, 4-benzenetricarboxylic acid (trimelitic acid), 1,3, 5-benzenetricarboxylic acid (trimesic acid), anhydrides, and the like.
In order to solve the second technical problem, the invention adopts the technical scheme that: a method for preparing the modified PC/ABS composition in any technical scheme for solving the technical problems adopts continuous melt blending extrusion, and the modified PC/ABS composition is obtained by melt blending and extruding the required amount of PC, the required amount of ABS, the required amount of aliphatic aromatic copolyester and optional additives.
In the above technical scheme, the melt blending method of the modified PC/ABS composition for 3D printing is preferably a twin-screw continuous extrusion method.
In the above technical scheme, the melt blending method of the modified PC/ABS composition for 3D printing preferably comprises the steps of uniformly mixing the PC, the ABS and the aliphatic aromatic copolyester according to a required proportion, and then continuously extruding and granulating to prepare the modified PC/ABS composition.
In the above technical scheme, the melt blending method of the modified PC/ABS composition for 3D printing preferably includes adding PC, ABS and aliphatic aromatic copolyester to a twin-screw extruder in respective amounts for extrusion granulation.
In the above technical scheme, the screw rotation speed of the melt blending method of the modified PC/ABS composition for 3D printing is preferably 50rpm to 1500rpm.
In the above technical scheme, the temperature of the melt blending method of the modified PC/ABS composition for 3D printing is preferably 160 ℃ to 260 ℃.
In order to solve the third technical problem, the invention adopts the technical scheme that: A3D printing line comprising the modified PC/ABS composition according to any of the preceding claims for solving one of the above-mentioned problems.
In order to solve the fourth technical problem, the invention adopts the technical scheme that: A3D printing line preparation method comprises the following steps: and (2) granulating the modified PC/ABS composition in any one of the technical schemes for solving the technical problems, melting and extruding by a screw extruder, cooling and carrying out orientation drafting to obtain the 3D printing line.
In the above technical scheme, the method for cooling and granulating the composition melt, and simultaneously performing drawing and winding on the composition melt through melt extrusion to form a thread is preferably a single-screw extrusion method, wherein the composition particles are melt extruded through a single-screw extruder, and are cooled through two sections of water baths with different temperatures and simultaneously drawn and wound to form a 3D printing line.
In order to solve the technical problems, the invention adopts the technical scheme that: use of a 3D printing line according to any of the three preceding solutions to the technical problem.
In the above technical solution, the application is not particularly limited, for example, the 3D printing line of the present invention may be used in Fused Deposition Modeling (FDM) to prepare a 3D printed product.
The materials and preparation methods used in the present invention are briefly described below:
PC resin
The PC resin in the present invention is a high molecular polymer containing carbonate groups in the molecular chain, and is generally obtained by melt polycondensation of bisphenol A and diphenyl carbonate or direct esterification of bisphenol A and phosgene.
ABS resin
The ABS resin in the invention is a graft copolymer of acrylonitrile, 1, 3-butadiene and styrene, and is generally a mixture of a graft copolymer containing butadiene and an acrylonitrile-styrene copolymer, wherein the acrylonitrile accounts for 15% -35%, the butadiene accounts for 5% -30% and the styrene accounts for 40% -60%. It is generally used in industry to mix acrylonitrile-styrene copolymer with polybutadiene and then copolymerize them, or to add acrylonitrile and styrene monomer to polybutadiene latex for graft copolymerization.
3. Aliphatic aromatic copolyester
the aliphatic aromatic copolyester alpha, omega-aliphatic diacid or a derivative thereof and the copolyester formed by condensing aromatic diacid or a derivative thereof with at least one aliphatic diol comprise but are not limited to polyethylene terephthalate-co-oxalate, polyethylene terephthalate-co-malonate, polyethylene terephthalate-co-succinate, polyethylene terephthalate-co-glutarate, polyethylene terephthalate-co-adipate, polyethylene terephthalate-co-suberate, polypropylene terephthalate-co-oxalate, polypropylene terephthalate-co-malonate, polypropylene terephthalate-co-succinate, polypropylene terephthalate-co-glutarate, polypropylene terephthalate-co-adipate, polypropylene terephthalate-co-suberate, polypropylene terephthalate-co-sebacate, polyethylene terephthalate-co-oxalate, polybutylene terephthalate-co-malonate, polyethylene terephthalate-co-succinate (PBAT), polyethylene terephthalate-co-glutarate, polypropylene terephthalate-co-sebacate, polyethylene terephthalate-co-adipate, polyethylene terephthalate-adipate, polyethylene terephthalate-co-adipate, polyethylene terephthalate-adipate, polyethylene terephthalate-co-adipate co-adipate, polyethylene terephthalate, co-adipate, co-adipate, and the like.
4. Functional improvement aid
The function improvement auxiliary in the present invention comprises a compatibilizer, an inorganic filler, an antioxidant, a lubricant, a colorant, a chain extender, and a transesterification inhibitor, preferably at least one of them.
The compatibilizer includes copolymers containing maleic acid and derivatives thereof such as styrene-maleic anhydride copolymers, styrene-maleic anhydride-acrylonitrile copolymers, styrene-maleic acid, styrene-maleimide copolymers, and ABS-maleic anhydride graft copolymers, and copolymers containing methacrylic acid esters, acrylic acid esters, and derivatives thereof such as ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-glycidyl methacrylate, and styrene-acrylonitrile-glycidyl methacrylate.
The inorganic filler comprises inorganic materials such as calcium carbonate, talc, kaolin, attapulgite, silicon dioxide, carbon black, titanium dioxide, glass beads, glass powder, glass fiber, zirconia, alumina, magnesia, iron oxide, boron nitride, silicon carbide, carbon fiber, aluminum powder, copper powder and the like.
The antioxidant includes hindered phenols, phosphites and other compounds.
The lubricant includes pentaerythritol stearate, wax-based lubricant, and the like.
The colorant comprises yellow 6G, orange GS, etc.
The chain extender comprises isocyanate compounds, epoxy compounds, carbodiimide compounds and the like.
The ester exchange inhibitor comprises diisooctyl phosphate, zinc sulfate, diethyl sulfate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, triphenyl phosphite, etc.
5. Method for preparing modified PC/ABS composition for 3D printing
The method for preparing the PC/ABS composition comprises the steps of uniformly mixing the required amount of PC, the required amount of ABS, the required amount of aliphatic aromatic copolyester and the optional required amount of functional modification auxiliary agent in a molten state in a continuous process, and extruding and granulating. The continuous melting preparation method of the invention uniformly mixes PC particles, ABS particles and aliphatic aromatic copolyester particles according to a certain proportion, and then adds the mixture into a feeding port of a double-screw extruder according to a certain feeding rate by using a feeding machine. The feeder can be a weight loss feeder or a volume feeder. The other embodiment is that a plurality of feeders are adopted to respectively meter and add the PC particles, the ABS particles, the aliphatic aromatic copolyester particles and the optional functional modification auxiliary agent on a double-screw extruder according to a certain feeding proportion for reaction and extrusion, and extruded sample bars are cut into particles through a water tank or underwater to prepare the composition particles. The extrudate can also be air cooled by an anhydrous process and then pelletized.
Extrusion temperatures suitable for the present invention are preferably from 140 ℃ to those having low thermal decomposition temperatures for PC, ABS and aliphatic aromatic copolyesters, more preferably from 160 ℃ to 240 ℃. The rotation speed of the extruder is preferably 50rpm to 1500rpm, more preferably 100rpm to 800 rpm.
Melt blending devices suitable for use in the present invention include a variety of mixers, Farrel continuous mixers, Banbury mixers, single screw extruders, twin screw extruders, multiple screw extruders (more than two screws), reciprocating single screw extruders such as Buss Ko-kneaders (Buss Ko-kneaders), and the like. Preferred processes are continuous melt blending extrusion processes including twin screw extrusion processes. Continuous twin-screw extruders suitable for use in the present invention include twin-screw extruders of different designs, such as the ZSK Mcc18 co-rotating parallel twin-screw extruder manufactured by Coperion, Germany, and the like.
6. Method for preparing PC/ABS composition 3D printing line
The invention discloses a method for 3D printing line of PC/ABS composition, which is characterized in that the composition consists of 1 to 99 parts by mass of PC, 1 to 99 parts by mass of ABS, 0.01 to 0 to 50 parts by mass of aliphatic aromatic copolyester and optionally 0.1 to 20 parts by mass of functional improvement auxiliary agent. The composition is prepared by the continuous melt extrusion blending process described above. In the method, the composition is melted and extruded in a screw extruder, and is cooled and simultaneously drafted and rolled into threads.
The invention discloses a method for 3D printing of a PC/ABS composition, which is a single-screw extrusion method. In this process, the pre-prepared composition is fed into a single-screw extruder which is generally divided into three stages in terms of effective length, the first stage being a conveying section in which the composition is preheated and extruded; the second section is a compression section, the depth of the thread groove is reduced from large to small, and the melt temperature reaches the degree of plasticizing and melting the composition; the third section is a metering section, and the composition melt is conveyed to a 3D printing line die according to a certain melt flow under the rotation of a screw rod. The die is provided with one or more circular small holes, and the circular holes can be selected to have different diameters according to the requirements of a printer, and the diameter is generally 1.75mm or 3.00 mm. And cooling and drafting the extruded printing line, and rolling after detection. There are various methods of cooling, including water cooling or air cooling.
The extrusion temperature of the 3D printed line of the composition is from 100 ℃ to 260 ℃, preferably from 180 ℃ to 240 ℃. The number of revolutions of the single-screw extruder is 10 to 200rpm, preferably 25 to 100 rpm.
The invention relates to a method for preparing a film, in particular to a double-screw extrusion film-forming method. The process is different from the single screw extruder method, the feeding rate of the composition is completed by one feeder, the feeder suitable for the invention comprises a weight loss type feeder or a volume type feeder, the tail end of the double screw extruder is provided with a cast film die or a blown film die, and the film led out from the die is further formed.
By adopting the technical scheme of the invention, the warping problem of the PC in the printing process is solved, and the curvature of the 3D printing product made of the polycarbonate modified material is less than 0.5m-1The color is lighter, and a better technical effect is achieved. The invention carries out performance measurement according to the following method:
melt index (MFR) determination method: measured according to ISO 1133 standard by using a Lloyd Davenport MFI-10/230 melt index meter, the cylinder temperature is 220 ℃, the weight load is 10.0kg, the diameter of a die is 2.095mm, the length is 8mm, the preheating time is 4min, samples are automatically cut at set time intervals, 5 times of averaging is carried out, and the measurement result is expressed by grams per 10 minutes (g/10 min).
The curvature measuring method comprises the following steps: according to a thickness of 150X 15.0X 4.0mm3Dimensions the bars were printed on a 3D printer and placed on a horizontal surface. And (3) regarding the warped sample strip as a section of circular arc, and converting the radius of the circular arc by measuring the tilting height of the two ends of the sample strip compared with the horizontal plane, wherein the radius of the circular arc is the curvature.
Detailed Description
The present invention is specifically described by the following examples. It should be noted that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention, and that those skilled in the art can make modifications and adaptations of the present invention.
Comparative example 1
Weighing the following raw materials in proportion: 70 parts of PC (brand: SABIC HF1130), 30 parts of ABS (brand: Gaoqiao petrochemical 8434), 3 parts of styrene-maleic anhydride copolymer (Shanghai Wen SMA), 0.8 part of antioxidant 1010 and 0.8 part of white oil. ABS, PC, SMA, antioxidant 1010 and white oil are mixed uniformly, the mixture is fed through a hopper at the first section of a double-screw extruder, the mixture is melted and extruded, a brace is cooled in a water bath and then cut into particles, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 23.0g/10min at 220 ℃ under 10.0 kg.
Comparative example 2
Weighing the following raw materials in proportion: 70 parts of PC (brand: SABIC HF1130), 30 parts of ABS (brand: Gaoqiao petrochemical 8391), 3 parts of styrene-maleic anhydride copolymer (Shanghai Wen SMA), 0.8 part of antioxidant 1010 and 0.8 part of white oil. ABS, PC, SMA, antioxidant 1010 and white oil are mixed uniformly, the mixture is fed through a hopper at the first section of a double-screw extruder, the mixture is melted and extruded, a brace is cooled in a water bath and then cut into particles, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 23.9g/10min at 220 ℃ under 10.0 kg.
[ example 1 ]
Weighing the following raw materials in proportion: 8 parts of ABS (trademark: Gaoqiao petrochemical 8434), 72 parts of PC (trademark: SABIC HF1130) and 72 parts of aliphatic aromatic copolyester PBAT (BASF C1200)) 20 parts by weight of ester exchange inhibitor Na2HPO45 parts of antioxidant, 1010 parts of antioxidant and 0.8 part of white oil. Mixing ABS, PC, PBAT and ester exchange inhibitor Na2HPO4The antioxidant 1010 and the white oil are uniformly mixed, the mixture is fed through a hopper at the first section of a double-screw extruder, the mixture is melted and extruded, the bracing piece is cut into granules after being cooled in water bath, the rotating speed of the screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 23.7g/10min at 220 ℃ under 10.0 kg.
[ example 2 ]
Weighing the following raw materials in proportion: 8 parts of ABS (trademark: Gaoqiao petrochemical 8391), 72 parts of PC (trademark: SABIC HF1130), 20 parts of aliphatic aromatic copolyester PBAT BASF C1200, and an ester exchange inhibitor Na2HPO45 parts of antioxidant, 1010 parts of antioxidant and 0.8 part of white oil. The components are uniformly mixed, the materials are fed through a hopper at the first section of a double-screw extruder, the materials are melted and extruded, the bracing piece is cut into particles after being cooled by water bath, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 45.2g/10min at 220 ℃ under 10.0 kg.
[ example 3 ]
Weighing the following raw materials in proportion: 8 parts of ABS (Qimei PA758), 72 parts of PC (SABIC HF1130), 20 parts of aliphatic aromatic copolyester PBAT (BASF C1200), and an ester exchange inhibitor Na2HPO45 parts of antioxidant, 1010 parts of antioxidant and 0.8 part of white oil. The components are uniformly mixed, the materials are fed through a hopper at the first section of a double-screw extruder, the materials are melted and extruded, the bracing piece is cut into particles after being cooled by water bath, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 48.8g/10min at 220 ℃ under 10.0 kg.
[ example 4 ]
Weighing the following raw materials in proportion: 24 parts of ABS (high petrochemical 8391), 56 parts of PC (SABICHF1130), 20 parts of aliphatic aromatic copolyester PBAT (BASF C1200), and an ester exchange inhibitor Na2HPO45 parts of antioxidant, 1010 parts of antioxidant and 0.8 part of white oil. The components are uniformly mixed, the materials are fed through a hopper at the first section of a double-screw extruder, the materials are melted and extruded, the bracing piece is cut into particles after being cooled by water bath, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 50.5g/10min at 220 ℃ under 10.0 kg.
[ example 5 ]
Weighing the following raw materials in proportion: 24 parts of ABS (Qimei PA758), 56 parts of PC (SABIC HF1130), 20 parts of aliphatic aromatic copolyester PBAT (BASF C1200), and an ester exchange inhibitor Na2HPO45 parts of antioxidant, 1010 parts of antioxidant and 0.8 part of white oil. The components are uniformly mixed, the materials are fed through a hopper at the first section of a double-screw extruder, the materials are melted and extruded, the bracing piece is cut into particles after being cooled by water bath, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The melt index of the particles at 220 ℃ under 10.0kg was 54.4g/10 min.
[ example 6 ]
Weighing the following raw materials in proportion: 90 parts of ABS (high-bridged petrochemical 8434), 8 parts of PC (SABICHF1130), 2 parts of aliphatic aromatic copolyester PBAT (BASF C1200), 0.8 part of antioxidant 1010 and 0.8 part of white oil. Feeding the components in a first section of a double-screw extruder through a hopper, carrying out melt extrusion, drawing strips, cooling in water bath, and then cutting into granules, wherein the rotating speed of a screw is 120r/min, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 25.8g/10min at 220 ℃ under 10.0 kg.
[ example 7 ]
Weighing the following raw materials in proportion: 80 parts of ABS (high-bridged petrochemical 8434), 16 parts of PC (SABICHF1130), 4 parts of aliphatic aromatic copolyester PBAT (BASF C1200), 0.8 part of antioxidant 1010 and 0.8 part of white oil. The components are uniformly mixed, the materials are fed through a hopper at the first section of a double-screw extruder, the materials are melted and extruded, the bracing piece is cut into particles after being cooled by water bath, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The melt index of the pellets at 220 ℃ under 10.0kg was 31.5g/10 min.
[ example 8 ]
Weighing the following raw materials in proportion: 70 parts of ABS (high-bridged petrochemical 8434), 24 parts of PC (SABICHF1130), 6 parts of aliphatic aromatic copolyester PBAT (BASF C1200), 0.8 part of antioxidant 1010 and 0.8 part of white oil. The components are uniformly mixed, the materials are fed through a hopper at the first section of a double-screw extruder, the materials are melted and extruded, the bracing piece is cut into particles after being cooled by water bath, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 35.1g/10min at 220 ℃ under 10.0 kg.
[ example 9 ]
Weighing the following raw materials in proportion: 60 parts of ABS (high-bridged petrochemical 8434), 32 parts of PC (SABICHF1130), 8 parts of aliphatic aromatic copolyester PBAT (BASF C1200), 0.8 part of antioxidant 1010 and 0.8 part of white oil. ABS, the blend of comparative example 1, antioxidant 1010 and white oil are mixed uniformly, the mixture is fed through a hopper at the first section of a double-screw extruder, the mixture is melted and extruded, the brace is cooled in water bath and then cut into particles, the rotating speed of a screw is 120rpm, the feeding speed is 10kg/h, and the temperature of each section of the extruder is 200-230 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby. The pellets had a melt index of 43.3g/10min at 220 ℃ under 10.0 kg.
[ example 10 ]
The blend particles of examples 1-9 were fed from a hopper at the first stage of a single screw extruder, melt extruded, and drawn into strands cooled in two water baths of different temperatures, and simultaneously drawn to test the diameter of the strand, and then wound into strands, the screw speed was 20rpm, the temperature of each stage of the extruder was 200-230 ℃, and the drawing speed was adjusted in real time according to the test diameter of the strand to ensure the diameter of the strand to be about 1.75mm or 3.00 mm.
[ example 11 ]
The wire rod obtained in example 10 was subjected to 3D printing on a MakerBot Replicator 2X 3D printer. When a sample strip product is printed, the sample strip parameters and the printing parameters are as follows, the size of the sample strip is a cuboid of 150mm multiplied by 15.0mm multiplied by 4.0mm, the printing parameters are the resolution (resolution) standard, the extrusion speed of a nozzle is 120mm/s, the moving speed is 150mm/s, the filling rate of the sample strip is 100%, the height of each layer is 200 mu m, the temperature of the nozzle is 240 ℃, and the temperature of a bottom plate is 40 ℃. The specimens were considered to have an arc length, the modified materials of examples 1 to 9 had low warpage, and the specimens obtained from the samples of examples 1 and 3 had curvatures of 0.66m, respectively-1And 0.42m-1。
Comparative example 3
The blend particles in the comparative examples 1-2 are fed by a hopper at the first section of a single screw extruder, melted and extruded, the bracing piece is cooled by two sections of water baths with different temperatures, and simultaneously, the bracing piece is coiled into a wire after the wire diameter is qualified through a drawing test, the rotating speed of the screw is 20rpm, the temperature of each section of the extruder is 200-230 ℃, and the drawing speed is adjusted in real time according to the wire diameter to be tested so as to ensure that the wire diameter is about 1.75mm or 3.00 mm.
Comparative example 4
The wire rod obtained in comparative example 3 was 3D printed on a MakerBot Replicator 2X 3D printer. When a sample strip product is printed, the sample strip parameters and the printing parameters are as follows, the size of the sample strip is a cuboid with the size of 150mm multiplied by 15.0mm multiplied by 4.0mm, the printing parameters are that the resolution (resolution) is standard, the extrusion speed of a nozzle is 120mm/s, the moving speed is 150mm/s, the filling rate of the sample strip is 100 percent, the height of each layer is 200 mu m, and the temperature of the nozzle is 100 percentThe temperature was 240 ℃ and the temperature of the soleplate was 40 ℃. The specimens were considered to have an arc length and the modified materials of comparative examples 1 and 2 were severely warped, and the specimen obtained as in comparative examples 1 and 2 had a curvature of 1.5m-1And 1.4m-1The curvatures thereof were 2.3 times and 3.3 times as large as those of example 1 and example 3 in example 11, respectively.
Claims (10)
1. A modified PC/ABS composition comprises the following components in parts by mass:
(1)1 to 99 parts of a PC resin;
(2)1 to 99 parts of an ABS resin;
(3)0.1 to 50 parts of aliphatic aromatic copolyester.
2. The modified PC/ABS composition of claim 1, wherein the PC resin is selected from the group consisting of bisphenol A melt-condensed with diphenyl carbonate or bisphenol A directly esterified with phosgene.
3. The modified PC/ABS composition of claim 1, wherein the ABS resin is selected from one or a mixture of two or more of ABS resins obtained by bulk continuous polymerization or emulsion polymerization, and the mixture comprises, by mass, 0 to 99 parts of bulk continuous polymerization ABS resin and 0 to 99 parts of emulsion ABS resin.
4. the modified PC/ABS composition of claim 1, wherein the aliphatic aromatic copolyester is a copolyester of an α, ω -aliphatic diacid or a derivative thereof and an aromatic diacid or a derivative thereof condensed with at least one aliphatic diol.
5. The modified PC/ABS composition according to claim 1, characterized in that the composition further comprises the components: (4)0.1-20 parts of functional improvement auxiliary agent; the functional improvement auxiliary agent is one or more than two of compatilizer, inorganic filler, antioxidant, lubricant, colorant and chain extender.
6. the modified PC/ABS composition according to claim 4, wherein the α, ω -aliphatic diacid is a substituted or unsubstituted α, ω -aliphatic diacid having 2 to 22 main chain carbon atoms and derivatives thereof, such as preferably oxalic acid, 1, 3-malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid up to a carbon number of 22, and derivatives thereof include at least one of the corresponding acid anhydrides, esters, acid halides of the above diacids, and aromatic diacids, preferably terephthalic acid, dimethyl terephthalate, 1, 4-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 4, 4 '-diphenyl ether, 4, 3' -naphthalenedicarboxylic acid, 4, 4 '-thiobisulphide, 4, 3' -diphenylsulfone, 4, 4 '-diphenylsulfone, 4, 3, 4, 4' -naphthalenedicarboxylic acid, 1,3 '-decanedioic acid, 1,4, 3' -pentanediol, 1, 5-decanediol, 1,4, 3 '-pentanediol, 1, 4-decanediol, 3-decanediol, 4, 3' -sebacic acid, 1, 4-decanediol, 3-decanediol, 4, 3-decanediol, 1, 4-decanediol, 3-decanediol, 6-1, 5-decanediol, 3-1, 3-1, 5-heptanediol, 1, 4-decanediol, 1, 3-1, 3-decanediol, 1, 4-1, 3-1, 4-1, 5-1, 3-decanediol, 1, 5-1, 1-decanediol, 3-1, 4-1, 3-1, 3-1-decanediol, 3-1, 1-1, 6-1, 3-1, 1-heptanediol, 1-1, 3-1, 3-1-heptanediol, 3-1.
7. A method for preparing the modified PC/ABS composition as claimed in any one of claims 1 to 6, wherein the modified PC/ABS composition is obtained by carrying out continuous melt blending and extrusion on the required amount of PC, the required amount of ABS, the required amount of aliphatic aromatic copolyester and any optional functional improvement auxiliary agent.
8. A3D printing line comprising the modified PC/ABS composition of any of claims 1 to 6.
9. A3D printing line preparation method comprises the following steps: the modified PC/ABS composition of any of claims 1 to 6, which is pelletized, melt extruded by a screw extruder, cooled and oriented drawn to obtain the 3D printing line.
10. Use of the 3D printing line according to claim 9.
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