CN105885395B - A kind of composition of copolymer nylon 6 for 3D printing and preparation method thereof - Google Patents
A kind of composition of copolymer nylon 6 for 3D printing and preparation method thereof Download PDFInfo
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- CN105885395B CN105885395B CN201610278800.9A CN201610278800A CN105885395B CN 105885395 B CN105885395 B CN 105885395B CN 201610278800 A CN201610278800 A CN 201610278800A CN 105885395 B CN105885395 B CN 105885395B
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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Abstract
The invention discloses a kind of composition of copolymer nylon 6 for 3D printing, it is made up of the composition of following mass fractions：Copolymer nylon 689.4~94.7；The nucleator 0.4~1.2 of nylon 6；The melt processing stabilizers 2~8 of nylon 6；Lubricant 0.2~0.5；Coupling agent 0.3~0.7；Antioxidant 0.6~1.1；Light stabilizer 0.3~0.7.The invention also discloses the preparation method of the above-mentioned composition of copolymer nylon 6 for 3D printing.The composition of copolymer nylon 6 for 3D printing of the present invention, has excellent mechanical property, endurance and melt-processed stability.
Description
Technical field
The present invention relates to high polymer material and its processing and forming field, more particularly to a kind of copolymer nylon for 3D printing
6 compositions and preparation method thereof.
Background technology
China progressively moves towards rich and powerful, and basic change occurs for the life style and dietary structure of people, and mouth disease presents quick-fried
Hairdo increases.Traditional therapy is difficult to be competent at various oral disease therapeutics and health care demand, and mouth disease is with greater need for personalization
Treatment.3D printing technique disclosure satisfy that the demand of personalized treatment, have great potential in oral medical product development.
In August, 2014, IDTechEx companies of the U.S. announce that result of study predicts medical product market 3D printing in 2025
Machine demand market value is up to 6,000,000,000 dollars, and wherein oral medical product market value accounts for 8.67 hundred million dollars.At present, in U.S.'s 3D printing
Technology has been widely used in dental product making, has produced the 3D printer suitable for dental field, such as U.S. in 2015
Once The Perfactory Vida dentistry 3D printers were illustrated in the annual meeting of correction association of state.
China's oral medical product market scale is huge, and it is personalized to be badly in need of the 3D printing with independent intellectual property right and brand
Oral medical product.3D printing dental product relates generally to artificial tooth, orthodontic appliance, retainer, orthognathic surgery guide plate at present.
Wherein, the market demand of 3D printing personalization orthognathic surgery art centering guide and orthodontic retainer is considerable.
Be presently used for the 3D printing material of medical assistance instrument field can be divided into inorganic non-metallic material, metal material and
High polymer material etc..Inorganic non-metallic material typically adhesive powder is melted by the way of laser sintered after with ceramic powders
Etc. being bonded together, also the method for useful chemical precipitation combination binding agent carries out the trial of 3D printing.Metal class product is typically adopted
With selective laser sintering/cladding (SLS) technology, high score subclass product then typically uses fused glass pellet method (FDM).In view of
The limitation of 3D printing equipment and printing technique at present, the leading role of macromolecule 3D printing material is still ABS, PLA and its modified production
Product, print temperature are generally 230~270 DEG C.Also relate to the high performance engineering plastic such as makrolon, nylon, polyether-ether-ketone in the recent period
The 3D printing product of material comes out.But it is with high costs because printing eventually, product stress raisers can not solve, and yield rate is not high
And cause market-oriented application difficult.
The difficulty that engineering plastics are used for 3D printing essentially consists in melting temperature height, secondly to most of engineering plastic resins,
Although special molecular structure assigns its higher intensity, it is negative the problem of be that product is easy to retain residual stress, product sticks up
Song deformation, accurate 3D manufactures can not be realized.By taking nylon material as an example, if carrying out 3D printing production with homopolymerization nylon 6 or nylon66 fiber
Product, because the melt temperature scope of homopolymerization nylon 6, between 220~240 DEG C, the melt temperature scope of homopolymerization nylon66 fiber is 240
Between~260 DEG C, its 3D printing temperature should be arranged on more than 280 DEG C.In general fused glass pellet method (FDM) 3D printer
It can not be competent at, and product preparation is carried out at a temperature of higher than 280 DEG C, nylon 6 or nylon66 fiber melt can be sudden and violent in a long time
Dew in atmosphere, occurs discoloration, degraded, releases peculiar smell etc., products obtained therefrom can not be applied to dental treatment.So also just embody not
Go out the advantage of personalized customization, various troubles, or even the safety of entail dangers to sufferer can be brought when serious to sufferer.
The appearance of copolymer nylon, another quality material is provided for 3D printing selection, its melt temperature scope can reduce
To 180~200 DEG C, crystallinity also has obvious reduction.
Exploitation both has excellent machinability, and and can ensures to realize personalized customization purpose, and then prepares with high-strength
The personalized orthognathic surgery art centering guide of degree and the special composite of copolymer nylon 6 of orthodontic retainer 3D printing are to realize that its 3D is beaten
Print one of key link of oral medical equipment.
The content of the invention
In order to overcome the disadvantages mentioned above of prior art and deficiency, it is an object of the invention to provide a kind of for 3D printing
The composition of copolymer nylon 6, there is excellent mechanical property, endurance and melt-processed stability.
Another object of the present invention is to provide the preparation method of the above-mentioned composition of copolymer nylon 6 for 3D printing.
The purpose of the present invention is achieved through the following technical solutions：
The present invention intends the resin based on copolymer nylon 6, and the addition nucleator of nylon 6 is subtracted with improving the crystal size of nylon 6
Small buckling deformation, addition nano-β-tricalcium phosphate etc. is put down with improving the melt-processed stability of 3D printing silk by rotating Vortex
The mixing of row double screw extruder, can obtain mechanical property more preferably, endurance, the composite wood of melt-processed excellent in stability
Material, the 3D printing for personalized oral cavity medical apparatus such as orthognathic surgery art centering guide, orthodontic retainer are produced, disclosure satisfy that not
With the various customization demands of sufferer.Specifically, composite of the invention includes the composition of following mass parts：
Wherein, the above-mentioned resin of copolymer nylon 6 is the copolymer of caprolactam and polyethers, and its weight average molecular weight is 100,000-
150,000g/mol, caprolactam content is 75~85 (quality) %, and melting temperature is between 180~200 DEG C.
The above-mentioned nucleator of nylon 6 is the sodium ion derivative of ethylene-methacrylic acid copolymer.
The above-mentioned melt processing stabilizers of nylon 6 are bata-tricalcium phosphate, and granularity is 100~300nm.
Above-mentioned lubricant is calcium stearate, zinc stearate or cadmium stearate.
Above-mentioned coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
One or more of gamma-aminopropyl-triethoxy-silane, N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane.
Above-mentioned antioxidant include primary antioxidant N, N'- it is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propionos and auxiliary
Aid anti-oxidants three [2.4- di-tert-butyl-phenyls] phosphite ester；The N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls)
The mass ratio of propiono and three [2.4- di-tert-butyl-phenyls] phosphite esters is 0.2~0.5:0.4~0.6.
Above-mentioned light stabilizer for it is poly- [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- triazines -2,4- [(2,2,
6,6,-tetramethyl-4-piperidyl) imino group] -1,6- oneself two support [(2,2,6,6- tetramethyl -4- piperidyls) imino groups.
The preparation method of the above-mentioned composition of copolymer nylon 6 for 3D printing, it is characterised in that comprise the following steps：
(1) material is premixed：By copolymer nylon 6, the nucleator of nylon 6, the melt processing stabilizers of nylon 6, lubricant, main antioxygen
Agent, auxiliary antioxidant and light stabilizer sequentially add mixer and are pre-mixed, and mixing temperature is 20~50 DEG C, rotating speed 100
~300 revs/min, incorporation time is 1~5 minute；
(2) extruding pelletization：The material of premixing is added into homodromy parallel double screw extruder from feeding machine, melting is squeezed
Go out to be granulated, screw speed is 150~250 revs/min, and feeding machine rotating speed is 10~50 revs/min；Each section of temperature of extruder be
190~230 DEG C.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) present invention selection fusion range resin based on 180~200 DEG C of copolymer nylon 6, can be by 3D printing
Temperature is reduced in the normal range of operation of in general fused glass pellet method (FDM) 3D printer, or lower.
(2) nucleator of nylon 6 that the present invention is added can effectively improve the crystallization rate of nylon 6, hence it is evident that reduce Buddhist nun
The crystal size of dragon 6, prevents oversized spherocrystal from producing, and reduces the possibility for producing internal stress to greatest extent, disappears substantially
Except the buckling deformation of product, the printing precision of 3D printing product can be more reliably ensured.
(3) present invention addition calcium stearate and nano-β-tricalcium phosphate can assign nylon 6 as melt processing stabilizers
With good melt-processed stability, the 3D printing silk of size uniformity can be obtained, has further ensured 3D printing product
Precision.
(4) antiaging system with antioxidant, auxiliary antioxidant and light stabilizer structure that the present invention is added also can
Effectively ensure that the nylon 6 of fusion sediment occurs without obvious discoloration or degraded at the right time, will not also produce peculiar smell
Gas.
(5) present invention is by the mixing of homodromy parallel double screw extruder, can obtain mechanical property more preferably, it is resistance to tired
The composite of labor, melt-processed excellent in stability, for personalized oral cavity medical apparatus such as orthognathic surgery art centering guide, correction
The 3D printing production of retainer, disclosure satisfy that the various customization demands of different sufferers.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
In embodiments of the invention, for copolymer nylon 6 from caprolactam-copolyether of oneself synthesis, its is heavy respectively
Son amount is 100,000-150,000g/mol, and caprolactam content is 75~85 (quality) %, and melting temperature is at 180~200 DEG C
Between；The nucleator of nylon 6 is the sodium ion derivative of ethylene-methacrylic acid copolymer, is produced for du pont company, optional
The trade mark is Surlyn8920, Surlyn8940, preferably Surlyn8920；The melt processing stabilizers preferred size of nylon 6 be 100~
300nm bata-tricalcium phosphate；Lubricant is calcium stearate, zinc stearate, preferably cadmium stearate, calcium stearate；Coupling agent is purchased from
Nanjing is through Tian Wei Chemical Co., Ltd.s gamma-aminopropyl-triethoxy-silane, trade name KH550；Antioxidant 1098, auxiliary antioxidant
168th, light stabilizer 944 is Ciba's production.
The mechanical property of the composition of copolymer nylon 6 for 3D printing of embodiments of the invention is entered using national standard
Row test.Fatigue performance is then carried out on the MARS III torque rheometers of Thermo Fisher companies using pattern of rocking
The fatigue experiment of 300000 times, experimental temperature are 36 DEG C (approximate Human Oral Cavity temperature), and it is 300,000 times to rock number, and set of frequency is
10Hz, strain are arranged to 0.1%.Phenomena such as whether batten occurs damaged and stress whitening investigated.
Embodiment 1
Each raw material is weighed according to following proportioning：It is 89.4 parts to be copolymerized PA6 mass fractions, and Surlyn8920 mass fractions are
0.4 part, nano-β-tricalcium phosphate mass fraction is 8 parts, and calcium stearate mass fraction is 0.2 part, coupling agent KH550 mass fractions
For 0.7 part, the mass fraction of antioxidant 1098 is 0.4 part, and irgasfos 168 mass fraction is 0.6 part, the mass parts of light stabilizer 944
Number is 0.3 part.Will copolymerization PA6, Surlyn8920, nano-β-tricalcium phosphate, calcium stearate, coupling agent KH550, antioxidant
1098th, irgasfos 168 and light stabilizer 944 etc. sequentially add mixer and are pre-mixed, and mixing temperature is 35 DEG C, and rotating speed is
150 revs/min, incorporation time is 4 minutes.The material of premixing is added into homodromy parallel twin-screw extrusion from feeding machine
Machine, melting extrusion are granulated, and screw speed is 180 revs/min, and feeding machine rotating speed is 30 revs/min.Each section of temperature of extruder be
190~230 DEG C.Tie rod crosses water pelletizing.
The performance of the copolymerization PA6 compositions for 3D printing is tested, test result is shown in Table 1.
Embodiment 2
Each raw material is weighed according to following proportioning：It is 91.9 parts to be copolymerized PA6 mass fractions, and Surlyn8920 mass fractions are
0.8 part, nano-β-tricalcium phosphate mass fraction is 5 parts, and calcium stearate mass fraction is 0.3 part, coupling agent KH550 mass fractions
For 0.5 part, the mass fraction of antioxidant 1098 is 0.5 part, and irgasfos 168 mass fraction is 0.5 part, the mass parts of light stabilizer 944
Number is 0.5 part.Will copolymerization PA6, Surlyn8920, nano-β-tricalcium phosphate, calcium stearate, coupling agent KH550, antioxidant
1098th, irgasfos 168 and light stabilizer 944 etc. sequentially add mixer and are pre-mixed, and mixing temperature is 30 DEG C, and rotating speed is
200 revs/min, incorporation time is 3 minutes.The material of premixing is added into homodromy parallel twin-screw extrusion from feeding machine
Machine, melting extrusion are granulated, and screw speed is 200 revs/min, and feeding machine rotating speed is 40 revs/min.Each section of temperature of extruder be
190~230 DEG C.Tie rod crosses water pelletizing.
The performance of the copolymerization PA6 compositions for 3D printing is tested, test result is shown in Table 1.
Embodiment 3
Each raw material is weighed according to following proportioning：It is 94.7 parts to be copolymerized PA6 mass fractions, and Surlyn8920 mass fractions are
1.2 parts, nano-β-tricalcium phosphate mass fraction is 2 parts, and calcium stearate mass fraction is 0.5 part, coupling agent KH550 mass fractions
For 0.3 part, the mass fraction of antioxidant 1098 is 0.2 part, and irgasfos 168 mass fraction is 0.4 part, the mass parts of light stabilizer 944
Number is 0.7 part.Will copolymerization PA6, Surlyn8920, nano-β-tricalcium phosphate, calcium stearate, coupling agent KH550, antioxidant
1098th, irgasfos 168 and light stabilizer 944 etc. sequentially add mixer and are pre-mixed, and mixing temperature is 40 DEG C, and rotating speed is
300 revs/min, incorporation time is 5 minutes.The material of premixing is added into homodromy parallel twin-screw extrusion from feeding machine
Machine, melting extrusion are granulated, and screw speed is 220 revs/min, and feeding machine rotating speed is 50 revs/min.Each section of temperature of extruder be
190~230 DEG C.Tie rod crosses water pelletizing.
The performance of the copolymerization PA6 compositions for 3D printing is tested, test result is shown in Table 1.
Comparative example 1
Each raw material is weighed according to following proportioning：It is 97.5 parts to be copolymerized PA6 mass fractions, and Surlyn8920 mass fractions are
1.0 parts, the mass fraction of antioxidant 1098 is 0.5 part, and irgasfos 168 mass fraction is 0.5 part, the mass fraction of light stabilizer 944
For 0.5 part.Copolymerization PA6, Surlyn8920, antioxidant 1098, irgasfos 168 and light stabilizer 944 etc. are sequentially added into mixing
Machine is pre-mixed, and mixing temperature is 30 DEG C, and rotating speed is 200 revs/min, and incorporation time is 3 minutes.By the material of premixing from
Feeding machine adds homodromy parallel double screw extruder, and melting extrusion is granulated, and screw speed is 200 revs/min, and feeding machine turns
Speed is 30 revs/min.Each section of temperature of extruder is 190~230 DEG C.Tie rod crosses water pelletizing.
The performance of the copolymerization PA6 compositions for 3D printing is tested, test result is shown in Table 1.
Comparative example 2
Each raw material is weighed according to following proportioning：It is 97.5 parts to be copolymerized PA6 mass fractions, and Surlyn8920 mass fractions are
1.0 parts, the mass fraction of antioxidant 1098 is 0.5 part, and irgasfos 168 mass fraction is 0.5 part, the mass fraction of light stabilizer 944
For 0.5 part.Copolymerization PA6, Surlyn8920, antioxidant 1098, irgasfos 168 and light stabilizer 944 etc. are sequentially added into mixing
Machine is pre-mixed, and mixing temperature is 30 DEG C, and rotating speed is 200 revs/min, and incorporation time is 3 minutes.By the material of premixing from
Feeding machine adds homodromy parallel double screw extruder, and melting extrusion is granulated, and screw speed is 200 revs/min, and feeding machine turns
Speed is 30 revs/min.Each section of temperature of extruder is 190~230 DEG C.Tie rod crosses water pelletizing.
The performance of the copolymerization PA6 compositions for 3D printing is tested, test result is shown in Table 1.
Comparative example 3
Each raw material is weighed according to following proportioning：It is 93.2 parts to be copolymerized PA6 mass fractions, nano-β-tricalcium phosphate mass parts
Number is 5 parts, and calcium stearate mass fraction is 0.3 part, and the mass fraction of antioxidant 1098 is 0.5 part, and irgasfos 168 mass fraction is
0.5 part, the mass fraction of light stabilizer 944 is 0.5 part.Will copolymerization PA6, nano-β-tricalcium phosphate, calcium stearate, antioxidant
1098th, irgasfos 168 and light stabilizer 944 etc. sequentially add mixer and are pre-mixed, and mixing temperature is 30 DEG C, and rotating speed is
200 revs/min, incorporation time is 3 minutes.The material of premixing is added into homodromy parallel twin-screw extrusion from feeding machine
Machine, melting extrusion are granulated, and screw speed is 200 revs/min, and feeding machine rotating speed is 30 revs/min.Each section of temperature of extruder be
190~230 DEG C.Tie rod crosses water pelletizing.
The performance of the copolymerization PA6 compositions for 3D printing is tested, test result is shown in Table 1.
Table 1 is used for the composition of copolymer nylon 6 proportioning and performance of 3D printing
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of composition of copolymer nylon 6 for 3D printing, it is characterised in that be made up of the composition of following mass fractions：
The copolymer nylon 6 is the copolymer of caprolactam and polyethers, and its weight average molecular weight is 100,000-150,000g/mol,
Caprolactam content is 75~85wt%, and melting temperature is between 180~200 DEG C；The nucleator of nylon 6 is ethene-methyl
The sodium ion derivative of acrylic copolymer；The melt processing stabilizers of nylon 6 are bata-tricalcium phosphate.
2. copolymer nylon 6 composition according to claim 1 for 3D printing, it is characterised in that the lubricant is
Calcium stearate, zinc stearate or cadmium stearate.
3. copolymer nylon 6 composition according to claim 1 for 3D printing, it is characterised in that the coupling agent is
Gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy silicon
One or more of alkane, N- cyclohexyl-γ-aminopropyltriethoxy dimethoxysilane.
4. copolymer nylon 6 composition according to claim 1 for 3D printing, it is characterised in that the antioxidant packages
Include N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and three (2,4- di-tert-butyl-phenyls) phosphorous
Acid esters；The N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and three (2,4- di-tert-butyls
Base) mass ratio of phosphite ester is (0.2~0.5):(0.4~0.6).
5. copolymer nylon 6 composition according to claim 1 for 3D printing, it is characterised in that the light stabilizer
For poly- { [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- triazines -2,4- [(2,2,6,6,-tetramethyl-4-piperidyl)
Imino group] -1,6- oneself two support [(2,2,6,6- tetramethyl -4- piperidyls) imino group].
6. copolymer nylon 6 composition according to claim 1 for 3D printing, it is characterised in that the β-tricresyl phosphate
Calcium granularity is 100~300nm.
7. the preparation method of the composition of copolymer nylon 6 for 3D printing described in claim 1, it is characterised in that including with
Lower step：
(1) material is premixed：By the copolymer nylon 6, nucleator of nylon 6, the melt processing stabilizers of nylon 6, lubricant, coupling agent, anti-
Oxygen agent and light stabilizer sequentially add mixer and are pre-mixed, and mixing temperature is 20~50 DEG C, and rotating speed is 100~300 revs/min
Clock, incorporation time are 1~5 minute；
(2) extruding pelletization：The material of premixing is added into homodromy parallel double screw extruder from feeding machine, melting extrusion is made
Grain, screw speed are 150~250 revs/min, and feeding machine rotating speed is 10~50 revs/min；Each section of temperature of extruder be 190~
230℃。
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| US20210238414A1 (en) * | 2018-10-24 | 2021-08-05 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing |
| CN109705570B (en) * | 2018-12-19 | 2021-09-07 | 青岛科凯达橡塑有限公司 | Special thermoplastic composite material suitable for 3D printing and preparation method thereof |
| CN115873400B (en) * | 2021-09-30 | 2024-04-02 | 上海金发科技发展有限公司 | PA6 composition and preparation method and application thereof |
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| CN104448805A (en) * | 2014-12-18 | 2015-03-25 | 陈梓煜 | High-strength nylon-based composite material for 3D printing and preparation method of high-strength nylon-based composite material for 3D printing |
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