CN109486142A - A kind of polylactic acid-polycaprolactone composite material and preparation method thereof for 3D printing - Google Patents
A kind of polylactic acid-polycaprolactone composite material and preparation method thereof for 3D printing Download PDFInfo
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- CN109486142A CN109486142A CN201811595994.0A CN201811595994A CN109486142A CN 109486142 A CN109486142 A CN 109486142A CN 201811595994 A CN201811595994 A CN 201811595994A CN 109486142 A CN109486142 A CN 109486142A
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- polycaprolactone
- polylactic acid
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- composite material
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
Polylactic acid-polycaprolactone composite material and preparation method thereof that the invention discloses a kind of for 3D printing, it is raw materials used by weight are as follows: 70-80 parts of polylactic acid (PLA), 10-20 parts of polycaprolactone (PCL), silicon ball -5-10 parts of polycaprolactone, 1-5 parts of crosslinking agent, 1-5 parts of inorganic filler, 0.2-1 parts of heat stabilizer, 0.1-0.5 parts of lubricant.The present invention feature weaker for PLA material toughness and plasticity, is added polycaprolactone and silicon ball-polycaprolactone, significantly improves its toughness and intensity, gained composite material exhibits go out superior mechanical property, have widened the type of 3D printing material.
Description
Technical field
The invention belongs to 3D printing technical field of material, and in particular to a kind of polylactic acid-for 3D printing gathers oneself
Lactone composition and preparation method thereof.
Background technique
3D printing (3D printing), also referred to as increasing material manufacturing or rapid shaping technique have developed nearly 40 years.Make
For the important carrier and approach for pushing the global third time industrial revolution, the deep extensive concern and research by all circles of 3D printing technique.
Its crucial technical advantage is the labyrinth product that different materials are quickly manufactured using digitlization means.Compared to traditional skill
Art, 3D printing can save the time, not need mold, manufacturing process energy conservation and be suitble to personalized customization.Currently, 3D printing is
It is gradually widely used in multiple manufacturing related fieldss, such as medical instrument, space flight and aviation, life science, function
Energy material, building, machinery, chemical industry and Art Design etc..
The material category that can be used for 3D printing is various, includes plastics, metal and high molecular material etc..Wherein, polylactic acid
And polycaprolactone is two kinds of most commonly seen high molecular materials for 3D printing.Polylactic acid and polycaprolactone are asepsis environment-protectings
Degradable environment-friendly material.The generation having no irritating odor during 3D printing.Also, above two material by
Applied in food packaging and medical material.In conclusion the two is the good material for 3D printing.
However, there is the problems such as rigidity is low with toughness, and melt strength is low, difficult forming in polylactic acid.Currently, for its presence
The shortcomings that, patent CN 106832830A is added to the block copolymer of polylactic acid-polycarbonate in polylactic acid to improve its phase
Answer performance.However polycarbonate and polylactic acid compatibility are poor, it is difficult to reach ideal effect.Patent CN 104356619A is poly-
Polyacrylate is added in lactic acid to improve the toughness of material, still, polyacrylate can not degrade, and destroy it in biology
The application in the fields such as medicine.
Summary of the invention
For the deficiency of current material, the present invention provides a kind of polylactic acid for 3D printing-polycaprolactone composite woods
Material and preparation method thereof.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of polylactic acid-polycaprolactone composite material for 3D printing, it is raw materials used by weight are as follows: polylactic acid
(PLA) 70-80 parts, 10-20 parts of polycaprolactone, silicon ball -5-10 parts of polycaprolactone, 1-5 parts of crosslinking agent, 1-5 parts of inorganic filler, heat
0.2-1 parts of stabilizer, 0.1-0.5 parts of lubricant.
Wherein, the molecular weight of polylactic acid used is between 10-20 ten thousand.
The molecular weight of polycaprolactone used is between 1-5 ten thousand.
Silicon ball-polycaprolactone used is the SiO that surface grafting has polycaprolactone2Nanosphere (SiO2- g-PCL), wherein
SiO2The diameter of nanosphere is 100-200nm, and the molecular weight for the polycaprolactone being grafted thereon is between 5000-10000.It is prepared
Method are as follows: in SiO2The toluene solution of caprolactone monomer and octoate catalyst stannous is added in nanosphere, then in stirring bar
It is passed through nitrogen after vacuumizing under part, repetition vacuumizes-step 3 time of inflated with nitrogen, to eliminate the air in system, then system is added
Heat reacts 1-3 h to 190 DEG C, washes away unreacted monomer through methanol, collects sediment to get the silicon ball-polycaprolactone；Its
In, SiO2The dosage of nanosphere is the 0.5wt%-2.5wt% of caprolactone monomer, the molar ratio of caprolactone monomer and stannous octoate
For 10:1.
Crosslinking agent used is benzoyl peroxide, 2,4- dichlorobenzoperoxide, two (tertiary fourth of 2,5- dimethyl -2,5-
Base peroxidating) hexane, any one or a few in acrylic acid 4- hydroxybutyl.
Inorganic filler used is any one or a few in graphene aerogel, hydroxyapatite or lime stone.
Heat stabilizer used is any one in phosphorous acid esters, epoxidized soybean oil or calcium zinc stabilizer.
It is with lubricator odium stearate, arbitrary a kind of in paraffin.
The preparation method of the polylactic acid-polycaprolactone composite material includes the following steps:
(1) polylactic acid, polycaprolactone, silicon ball-polycaprolactone, crosslinking agent, inorganic filler, heat stabilizer, lubrication are weighed in proportion
Agent is sufficiently mixed uniformly after it is sufficiently dried and is blended with high mixer；
(2) cooling by mixture double screw extruder melting extrusion obtained by step (1)；The operation temperature of double screw extruder
Control is between 150-180 DEG C；
(3) step (2) resulting materials are squeezed out through single screw extrusion machine, obtains the composite material for 3D printing.
The beneficial effects of the present invention are:
(1) present invention is added to a kind of Inorganic-Organic Hybrid Material in polylactic acid-polycaprolactone compound --- and silicon ball-is poly-
Caprolactone.In the material, the toughness of polylactic acid and polycaprolactone is can be improved in its own to silicon ball, and gathers oneself with multi-arm structure
Lactone provides higher crosslink density, and the interaction between polymer molecular chain can be improved, to be conducive to improve multiple
The toughness and intensity of condensation material entirety.
(2) new material provided by the invention has preferable mechanical property, can better meet the actual demand of 3D printing.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The preparation of silicon ball-polycaprolactone: 1.14g SiO is added in the flask of 500mL2Nanosphere (diameter 100-
200nm), 114g(1mol) caprolactone monomer, toluene of 1 mL containing 0.04 g(0.1mmol) octoate catalyst stannous is added later
Solution.It is passed through nitrogen after vacuumizing under agitation, repetition vacuumizes-and the step 3 time of inflated with nitrogen to be to eliminate the sky in system
Gas；Reaction system is heated to 190 DEG C, 1-3h is reacted, is cooled to room temperature later, washes away unreacted monomer using methanol, is collected
Sediment to get arrive silicon ball-polycaprolactone.
Embodiment 1
80 parts by weight of polylactic acid (molecular weight 100,000), 10 parts by weight of polycaprolactone (molecular weight 10,000), silicon ball-are weighed respectively gathers oneself
It is 5 parts by weight of lactone (silicon ball diameter 100nm, polycaprolactone molecular weight 5000), 2 parts by weight of crosslinking agent benzoyl peroxide, inorganic
2 parts by weight of filler hydroxyapatite, 0.5 parts by weight of heat stabilizer diphosphorous acid pentaerythrite diisodecyl ester, lubricant stearic acid
0.5 parts by weight of sodium are sufficiently mixed uniformly by above-mentioned material sufficiently drying and after blending with high mixer, then use double screw extruder
It is cooling in 150 DEG C of melting extrusions, then resulting materials are added in single screw extrusion machine and are squeezed out, it is prepared for 3D printing
Silk material.
Embodiment 2
75 parts by weight of polylactic acid (molecular weight 200,000), 15 parts by weight of polycaprolactone (molecular weight 30,000), silicon ball-are weighed respectively gathers oneself
It is 5 parts by weight of lactone (silicon ball diameter 100nm, polycaprolactone molecular weight 5000), 2 parts by weight of crosslinking agent benzoyl peroxide, inorganic
2 parts by weight of filler hydroxyapatite, 0.5 parts by weight of heat stabilizer diphosphorous acid pentaerythrite diisodecyl ester, lubricant stearic acid
0.5 parts by weight of sodium are sufficiently mixed uniformly by above-mentioned material sufficiently drying and after blending with high mixer, then use double screw extruder
It is cooling in 150 DEG C of melting extrusions, then resulting materials are added in single screw extrusion machine and are squeezed out, it is prepared for 3D printing
Silk material.
Embodiment 3
70 parts by weight of polylactic acid (molecular weight 200,000), 20 parts by weight of polycaprolactone (molecular weight 50,000), silicon ball-are weighed respectively gathers oneself
10 parts by weight of lactone (silicon ball diameter 200nm, polycaprolactone molecular weight 10000), 3 parts by weight of crosslinking agent benzoyl peroxide, nothing
1 parts by weight of machine filler graphene aerogel, 0.8 parts by weight of heat stabilizer pentaerythritol bis-phosphite, lubricant stearic acid sodium
0.2 parts by weight are sufficiently mixed uniformly by above-mentioned material sufficiently drying and after blending with high mixer, are then existed with double screw extruder
180 DEG C of melting extrusions, it is cooling, then resulting materials are added in single screw extrusion machine and are squeezed out, it is prepared for 3D printing
Silk material.
Comparative example
70 parts by weight of polylactic acid (molecular weight 200,000), 20 parts by weight of polycaprolactone (molecular weight 50,000), crosslinking agent peroxide are weighed respectively
Change 3 parts by weight of benzoyl, 1 parts by weight of inorganic filler graphene aerogel, 0.8 weight of heat stabilizer pentaerythritol bis-phosphite
Part, 0.2 parts by weight of lubricant stearic acid sodium are sufficiently mixed uniformly, so by above-mentioned material sufficiently drying and after blending with high mixer
Afterwards with double screw extruder in 180 DEG C of melting extrusions, cooling, then resulting materials are added in single screw extrusion machine and are squeezed out, made
It is standby to obtain the silk material for 3D printing.
The Mechanics Performance Testing situation of 1 different materials of table
Seen from table 1, with simple polylactic acid and compared with composite material made from silicon ball-polycaprolactone is not added, system of the present invention
Standby polylactic acid-polycaprolactone composite material hardness, toughness, intensity are preferable, it was demonstrated that it is with better mechanical property.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (10)
1. a kind of polylactic acid-polycaprolactone composite material for 3D printing, it is characterised in that: it is raw materials used by weight
Are as follows: 70-80 parts of polylactic acid, 10-20 parts of polycaprolactone, silicon ball -5-10 parts of polycaprolactone, 1-5 parts of crosslinking agent, inorganic filler 1-5
Part, 0.2-1 parts of heat stabilizer, 0.1-0.5 parts of lubricant.
2. polylactic acid-polycaprolactone composite material according to claim 1 for 3D printing, it is characterised in that: used
The molecular weight of polylactic acid is between 10-20 ten thousand.
3. polylactic acid-polycaprolactone composite material according to claim 1 for 3D printing, it is characterised in that: used
The molecular weight of polycaprolactone is between 1-5 ten thousand.
4. polylactic acid-polycaprolactone composite material according to claim 1 for 3D printing, it is characterised in that: used
Silicon ball-polycaprolactone is the SiO that surface grafting has polycaprolactone2Nanosphere, wherein SiO2The diameter of nanosphere is 100-
200nm, the molecular weight for the polycaprolactone being grafted thereon is between 5000-10000.
5. polylactic acid-polycaprolactone composite material according to claim 1 for 3D printing, it is characterised in that: used
Crosslinking agent be benzoyl peroxide, 2,4- dichlorobenzoperoxide, 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) oneself
Any one or a few in alkane, acrylic acid 4- hydroxybutyl.
6. polylactic acid-polycaprolactone composite material according to claim 1 for 3D printing, it is characterised in that: used
Inorganic filler is any one or a few in graphene aerogel, hydroxyapatite or lime stone.
7. polylactic acid-polycaprolactone composite material according to claim 1 for 3D printing, it is characterised in that: used
Heat stabilizer is any one in phosphite ester, epoxidized soybean oil or calcium zinc stabilizer.
8. polylactic acid-polycaprolactone composite material according to claim 1 for 3D printing, it is characterised in that: used
Lubricant is odium stearate, arbitrary a kind of in paraffin.
9. a kind of preparation method of polylactic acid-polycaprolactone composite material as described in claim 1, it is characterised in that: including
Following steps:
(1) polylactic acid, polycaprolactone, silicon ball-polycaprolactone, crosslinking agent, inorganic filler, heat stabilizer, lubrication are weighed in proportion
Agent is sufficiently mixed uniformly after it is sufficiently dried and is blended with high mixer；
(2) cooling by mixture double screw extruder melting extrusion obtained by step (1)；
(3) step (2) resulting materials are squeezed out through single screw extrusion machine, obtains the composite material for 3D printing.
10. the preparation method of polylactic acid-polycaprolactone composite material according to claim 9, it is characterised in that: twin-screw
The operation temperature of extruder controls between 150-180 DEG C.
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| CN201811595994.0A CN109486142B (en) | 2018-12-26 | 2018-12-26 | Polylactic acid-polycaprolactone composite material for 3D printing and preparation method thereof |
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Cited By (5)
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| CN109908359A (en) * | 2019-04-21 | 2019-06-21 | 西北工业大学 | A kind of drug continuous controlled-release administrating system and preparation method thereof stage by stage |
| CN110051887A (en) * | 2019-03-27 | 2019-07-26 | 王小健 | A kind of bone rehabilitation protector low temperature 3D printing material and preparation method thereof |
| CN111068104A (en) * | 2019-11-27 | 2020-04-28 | 东南大学 | Absorbable polymer material with antibacterial function and preparation and application thereof |
| CN111378262A (en) * | 2020-04-16 | 2020-07-07 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN112920581A (en) * | 2021-04-01 | 2021-06-08 | 青岛科技大学 | Biodegradable nano composite material for 3D printing |
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| CN111068104A (en) * | 2019-11-27 | 2020-04-28 | 东南大学 | Absorbable polymer material with antibacterial function and preparation and application thereof |
| CN111378262A (en) * | 2020-04-16 | 2020-07-07 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN111378262B (en) * | 2020-04-16 | 2023-03-21 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN112920581A (en) * | 2021-04-01 | 2021-06-08 | 青岛科技大学 | Biodegradable nano composite material for 3D printing |
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