CN103980683B - A kind of 3 D-printing biodegradable polylactic acid material and preparation method thereof - Google Patents
A kind of 3 D-printing biodegradable polylactic acid material and preparation method thereof Download PDFInfo
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- CN103980683B CN103980683B CN201410183478.2A CN201410183478A CN103980683B CN 103980683 B CN103980683 B CN 103980683B CN 201410183478 A CN201410183478 A CN 201410183478A CN 103980683 B CN103980683 B CN 103980683B
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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
- B29B9/12—Making granules characterised by structure or composition
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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
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
-
- 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
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29B9/12—Making granules characterised by structure or composition
- B29B2009/125—Micropellets, microgranules, microparticles
-
- 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
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
-
- 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
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92619—Diameter or circumference
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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Abstract
The present invention relates to a kind of 3 D-printing biodegradable polylactic acid material and its preparation method and application.The material includes the antioxidant of PLA, the fatty poly-ester carbonate of 10-50 weight portions, the organic peroxide of 0.01-1 weight portions, the crosslinking agent of 0.05-1 weight portions, the reinforcing agent of 1-50 weight portions, the compatilizer of 0.3-5 weight portions, the heat stabilizer of 0.1-5 weight portions and the 0.1-1 weight portions of 50-90 weight portions.Biodegradable polylactic acid material of the invention can be used for three-dimensional printing technology, the material meets the use requirement of 3 D-printing, various premium properties with plastics, the preferable transparency can be kept, but also with impact strength higher, toughness and thermal deformation intensity high can be provided, and with good thermal stability and processing stability energy, relatively low cost.
Description
Technical field
The present invention relates to a kind of 3 D-printing material and preparation method thereof, and in particular to a kind of biodegradable polylactic acid material
Material and preparation method thereof.
Background technology
Three-dimensional (3D) printing technique also known as increases material manufacturing technology, actually a kind of emerging technology in rapid shaping field,
It is one kind based on mathematical model file, with powdery metal or plastics etc. can jointing material, by what is successively printed
Mode carrys out the technology of constructed object.General principle is layered manufacturing, successively increases material to generate the technology of 3D solid.Mesh
Before, three-dimensional printing technology is applied primarily to the fields such as product prototype, Making mold and artistic creation, jewelry-making, substitutes
The retrofit technique that these tradition are relied on.In addition, three-dimensional printing technology is gradually applied to medical science, bioengineering, building, clothes
The fields such as dress, aviation, for wide space has been opened up in innovation.
Fused Deposition Modeling (Fused Deposition Modeling, FDM) technical matters is by U.S. Scott Crump
Succeeded in developing in 1988.And the series of products of commercialization are released by Stratasys companies of the U.S..Principle is to utilize thermoplastic poly
Compound material in the molten state, is squeezed out from shower nozzle, and solidification forms the thin layer of contour shape, is further layering final
Form product.It is the increases material manufacturing technology for not using the energy beams such as laser, electron beam.Because its former is simple, use
It is convenient, safeguard simple, material cost performance is high, and product manufacturing cost is relatively low, and forming process is quick and environmentally safe, therefore mesh
Preceding FDM techniques are one of 3D printing technique with the fastest developing speed.The material that FDM is used usually thermoplastic, such as ABS,
PLA (PLA), nylon, polyurethane etc., with thread feed.Wherein PLA is material most popular to people, is also most have
One of biodegradable polymer of future.
It is nontoxic that PLA has, and without pungent smell, melt temperature is relatively low, degradable pollution-free, and cooling meat rate is small,
The advantages of transparent easy dyeing, all meets requirement of the three-dimensional printing technology to polymeric material；But the crystallinity of PLA is smaller,
Ester bond bond energy is small in strand, and the factor being easily broken off causes that the heat distortion temperature of PLA is low, impact strength is low, toughness is bad
Defect, cause the products application scope printed by PLA to be very restricted.
China Patent Publication No. CN103146164A discloses a kind of PLA nano material toughened for rapid shaping
Material and preparation method thereof, the method is to carry out blending extrusion to polyacrylic acid ester microsphere and PLA using double screw extruder
It is modified, although to enhance the toughness of PLA, but not low to the impact strength of PLA and low being modified of heat distortion temperature carries
It is high.China Patent Publication No. CN103087489A discloses a kind of modified polylactic acid material and preparation method thereof, and the method is used poly-
Ether type polyamide elastomer and montmorillonite enhance the tensile strength and elongation at break of PLA, but poly- breast as modifying agent
The impact strength of acid is low and the low defect of heat distortion temperature is improved.It is matrix and other class aliphatic generally with PLA
Although biodegradation material prepared by polyester blend can be tough because PLA is a kind of polymer of linear chain structure with film forming
Property relatively low (referring to CN100999587A), impact resistance is inadequate, it is also difficult to is promoted in 3 D-printing material and used.
China Patent Publication No. CN101643542A has synthesized high score using the carbonic ester of small molecule by ester-interchange method
The fatty poly-ester carbonate of son amount, and can synthesize the makrolon of various backbone structures by adjusting the species of dihydroxylic alcohols,
Such as：Poly- butylene carbonate (PBC), poly- pentylene carbonate (PPMC), the own diester of poly- carbonic acid (PHC) etc., it is achieved thereby that polymer
Structural behaviour it is adjustable.This kind of fatty poly-ester carbonate for preparing has molecular weight high, structure-controllable, can crystallize, tool
Standby good transparent and toughness, and the processing characteristics and thermal stability of material are excellent.The bill of materials is private at present can't
Enough meet the requirement of industrial processes and life application, but toughness and the punching of other polyester materials can be greatly improved with compound use
Hit intensity.
Therefore, it is necessary to develop new poly-lactic acid material to meet the demand of 3 D-printing.
The content of the invention
The present invention provides a kind of lactic acid composite material, comprising：
PLA：50-90 weight portions；
Fatty poly-ester carbonate：10-50 weight portions；
Organic peroxide：0.01-1 weight portions；
Crosslinking agent：0.05-1 weight portions；
Reinforcing agent：1-50 weight portions；
Compatilizer：0.3-5 weight portions；
Heat stabilizer：0.1-5 weight portions；
Antioxidant：0.1-1 weight portions.
In one embodiment, the lactic acid composite material is obtained by by each group lease making melt blending.
The molecular weight of the PLA can be such as 1 × 105~10 × 105, such as 1.5 × 105Or 1.7 × 105.Tool
For body, the PLA can be 2002D for the trade mark of such as Natureworks companies production, molecular weight is 1.5 × 105
Or 4032D, molecular weight are 1.7 × 105PLA.
The number-average molecular weight of the fatty poly-ester carbonate can be such as 4 × 104~15 × 104。
Preferably, the fatty poly-ester carbonate is poly- carbonic acid alkane diol ester, such as poly- carbonic acid C1-12Alkane diol ester, preferably
Selected from poly-carbonic acid 1,2-propylene diester (PPC), poly- carbonic acid 1,3- propylene diesters (PTMC), poly- carbonic acid 1,4- fourths diester (PBC), poly- carbonic acid
One or more in the diester of 1,5- penta (PPMC), the poly- own diester of carbonic acid 1,6- (PHC).
The organic peroxide can be selected from double (tert-butyl peroxide) hexanes of such as 2,5- dimethyl -2,5-
(DHBP), the double butylperoxyisopropyl benzene of 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes, 1,3-, peroxidating
One or more in diisopropylbenzene (DIPB) (DCP), benzoyl peroxide (BPO), dicumyl peroxide.
The crosslinking agent can selected from such as Triallyl isocyanurate, trimethylol-propane trimethacrylate,
One or more in triallyl benzenetricarboxylic acid ester, season amylalcohol tetramethyl acrylate, diallyl phthalate.
The compatilizer can be selected from the Biodegradable aliphatic polyester that such as number-average molecular weight is 1000~10000,
It is selected from polyadipate 1,2- propylene diesters, polyadipate succinic acid -1,2- propylene diesters, poly-succinic 1,2- propylene diesters one
Plant or several.
The reinforcing agent can be such as nano-inorganic substance, be selected from nanoclay, nano silicon, nano-calcium carbonate
One or more in calcium, nanomete talc powder.
The heat stabilizer can be selected from the one kind in such as calcium stearate, stearic acid, zinc oxide, magnesia, calcium oxide
Or it is several.
The antioxidant can be selected from one or more of such as phosphorous acid lipid and Hinered phenols composite antioxidant.Its
In, the phosphorous acid lipid can selected from Trimethyl phosphite, triphenyl phosphite, phosphorous acid mono-methyl, phosphorous acid monophenyl,
One or more in phosphorous acetoacetic ester etc..The Hinered phenols composite antioxidant is by primary antioxidant 1010 and auxiliary antioxidant
168 compositions.
In one embodiment, the lactic acid composite material is biodegradable.
In embodiments of the invention,
The PLA can be 50,60,70,80 or 90 weight portions；
The fatty poly-ester carbonate can be 10,20,30,40 or 50 weight portions；
The organic peroxide can for 0.01,0.02,0.03,0.04,0.05,0.08,0.1,0.2,0.3,0.4,
0.5th, 0.6,0.7,0.8,0.9 or 1 weight portion；
The crosslinking agent can be 0.05,0.06,0.08,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or 1
Weight portion；
The reinforcing agent can be 1,2,3,4,5,8,10,20,30,40 or 50 weight portions；
The compatilizer can for 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.5,2,2.5,3,3.5,4,4.5 or
5 weight portions；
The heat stabilizer can for 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.5,2,2.5,3,
3.5th, 4,4.5 or 5 weight portion；
The antioxidant：0.1st, 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or 1 weight portion.
The present invention also provides the preparation method of above-mentioned lactic acid composite material, including：
1) by PLA, fatty poly-ester carbonate, organic peroxide, crosslinking agent, compatilizer, reinforcing agent, heat stabilizer
Mix with antioxidant；
2) melt blending post-tensioning is stretched into bar, pelletizing in mixed material being added into such as double screw extruder, obtains grain
Shape hybrid resin is cut into slices；
3) by granular hybrid resin chip drying (such as being vacuum dried) water removal of gained, squeezed with such as single screw extrusion machine
Go out to be processed into filament, obtain the lactic acid composite material.
Wherein, a diameter of such as 0.5mm~5mm of the filament, more preferably preferably 1.0mm~4.0mm, 1.5mm~
3mm, such as 2mm, and the diameter error is within 5%.
The screw slenderness ratio of the double screw extruder is such as 30：1~50：1.
The temperature of the melt blending is preferably 100~300 DEG C, such as 150~190 DEG C.
Described single screw extrusion machine screw diameter is such as 75mm, and draw ratio is such as 20：1~40：1.Wherein extrude
Temperature is such as 170~210 DEG C.
The present invention also provides the printed material comprising above-mentioned lactic acid composite material, preferred three-dimensional printed material.
The present invention also provides above-mentioned lactic acid composite material for preparing printed material, the use of preferred three-dimensional printed material
On the way.
Beneficial effects of the present invention：
1. the pliability of lactic acid composite material of the present invention is good, and impact strength is high, and the transparency is high.
2. the melt strength and heat resistance of lactic acid composite material of the present invention are improved.
3. the processing plasticity of lactic acid composite material of the present invention is improved.
4. the cost of lactic acid composite material of the present invention is reduced.
5. the preparation method of lactic acid composite material of the present invention is simple, can be processed with conventional granulation, wire-drawing equipment, operable
Property it is strong, it is easy to industrialized production simultaneously have good economic benefit.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within appended claims of the present invention and limited
Scope.
Embodiment 1
On the basis of the weight portion of dried PLA.By dried PLA (Natureworks2002D) 800
Gram, 160 grams of poly- butylene carbonate (PBC), 20 grams of polyadipate 1,2- propylene diesters, 3 grams of composite antioxidant, 3 grams of stearic acid and sliding
20 grams of stone flour is premixed 30 minutes in high-speed mixer；After being sufficiently mixed uniformly, cumyl peroxide (DCP) 0.1 is added
Gram, continue after 1 gram of Triallyl isocyanurate to mix 5 minutes, obtain mixed material；By mixed material add to
Draw ratio is 40：In 1 double screw extruder, melt blending is carried out at being 150~190 DEG C in temperature, be drawn into using air-cooled
Bar, pelletizing；The granular hybrid resin section that will be obtained carries out vacuum drying except water process, obtains modified biodegradable
Lactic acid composite material (the weight percentage of moisture<0.6%).
It is 28 that modified biodegradable polylactic acid composite obtained above is added to draw ratio：1 single screw rod
In extruder, the filament of a diameter of 1.5mm is extruded and processed into.Mechanical performance is shown in Table 1.
Embodiment 2
On the basis of the weight portion of dried PLA.By dried PLA (Natureworks4032D) 670
Gram, 150 grams of poly- butylene carbonate (PBC), 100 grams of the own diester of poly- carbonic acid (PHC), 30 grams of poly-succinic 1,2- propane diols, phosphorous
50 grams of 3 grams of triphenyl phosphate ester, 3 grams of calcium stearate and silica, premix 30 minutes in high-speed mixer；It is sufficiently mixed uniform
Afterwards, continue to mix 5 minutes after adding 1 gram of cumyl peroxide (DCP), 0.5 gram of Triallyl isocyanurate, mixed
Material after conjunction；It is 40 that mixed material is added to draw ratio：It is 150~190 in temperature in 1 double screw extruder
Melt blending is carried out at DEG C, bar, pelletizing are drawn into using air-cooled；The graininess hybrid resin section that will be obtained is vacuum dried
Except water process, the biodegradation material (weight percentage of moisture of fatty adoption carbonic ester is obtained<0.6%).
It is 28 that modified biodegradable polylactic acid composite obtained above is added to draw ratio：1 single screw rod
In extruder, the filament of a diameter of 2mm is extruded and processed into.Mechanical performance is shown in Table 1.
Embodiment 3
On the basis of the weight portion of dried PLA.By dried PLA (Natureworks4032D) 640
Gram, 140 grams of poly-carbonic acid 1,2-propylene diester (PPC), 20 grams of polyadipate 1,2- propylene diesters, 3 grams of composite antioxidant, phosphorous acid front three
200 grams of 3 grams of ester and talcum powder are premixed 30 minutes in high-speed mixer；After being sufficiently mixed uniformly, 2,5- dimethyl -2 are added,
Continue to mix 5 minutes after 5- double 1 gram of (tert-butyl peroxide) hexane (DHBP), 1 gram of Triallyl isocyanurates, mixed
Material afterwards；It is 40 that mixed material is added to draw ratio：It it is 150~190 DEG C in temperature in 1 double screw extruder
Under carry out melt blending, be drawn into bar, pelletizing using air-cooled；The granular hybrid resin section that will be obtained is vacuum dried
Except water process, the modified biodegradable polylactic acid composite (weight percentage of moisture is obtained<0.6%).
It is 28 that modified biodegradable polylactic acid composite obtained above is added to draw ratio：1 single screw rod
In extruder, the filament of a diameter of 1.5mm is extruded and processed into.Mechanical performance is shown in Table 1
Embodiment 4
On the basis of the weight portion of dried PLA.By dried PLA (Natureworks4032D) 620
Gram, 300 grams of poly- pentylene carbonate (PPMC), polyadipate succinic acid 1, it is 50 grams of 2- propylene diesters, 3 grams of phosphorous acid mono-methyl, stearic
30 grams of 3 grams of acid and clay, premix 30 minutes in high-speed mixer；After being sufficiently mixed uniformly, 2,5- dimethyl -2,5- are added
Continue to mix 5 minutes after double 0.5 gram of (tert-butyl peroxide) hexanes (DHBP), 3 grams of Triallyl isocyanurate, mixed
Material afterwards；It is 40 that mixed material is added to draw ratio：It it is 150~190 DEG C in temperature in 1 double screw extruder
Under carry out melt blending, be drawn into bar, pelletizing using air-cooled；The graininess hybrid resin section that will be obtained carries out vacuum drying and removes
Water process, obtains the biodegradation material (weight percentage of moisture of fatty adoption carbonic ester<0.6%).
It is 28 that modified biodegradable polylactic acid composite obtained above is added to draw ratio：1 single screw rod
In extruder, the filament of a diameter of 3mm is extruded and processed into.Mechanical performance is shown in Table 1.
Embodiment 5
On the basis of the weight portion of dried PLA.By dried PLA (Natureworks2002D) 560
Gram, 400 grams of poly- butylene carbonate (PBC), 10 grams of poly-succinic 1,2- propylene diesters, 3 grams of composite antioxidant, 3 grams of stearic acid and carbon
30 grams of sour calcium, premixes 30 minutes in high-speed mixer；After being sufficiently mixed uniformly, 2,5- dimethyl -2, the double (peroxides of 5- are added
Change the tert-butyl group) 0.5 gram of hexane (DHBP), continue after 3 grams of trimethylol-propane trimethacrylate to mix 5 minutes, mixed
Material after conjunction；It is 40 that mixed material is added to draw ratio：It is 150~190 in temperature in 1 double screw extruder
Melt blending is carried out at DEG C, bar, pelletizing are drawn into using air-cooled；The graininess hybrid resin section that will be obtained is vacuum dried
Except water process, the biodegradation material (weight percentage of moisture of fatty adoption carbonic ester is obtained<0.6%).
It is 28 that modified biodegradable polylactic acid composite obtained above is added to draw ratio：1 single screw rod
In extruder, the filament of a diameter of 2mm is extruded and processed into.Mechanical performance is shown in Table 1.
Embodiment 6
On the basis of the weight portion of dried PLA.By dried PLA (Natureworks2002D) 300
Gram, 190 grams of poly- butylene carbonate (PBC), 10 grams of poly-succinic 1,2- propylene diesters, 3 grams of composite antioxidant, 3 grams of stearic acid and two
500 grams of silica, premixes 30 minutes in high-speed mixer；After being sufficiently mixed uniformly, 2,5- dimethyl -2 are added, 5- is double
Continue to mix 5 after the gram weight of (tert-butyl peroxide) hexane (DHBP) 0.2 part, 5 grams of trimethylol-propane trimethacrylate
Minute, obtain mixed material；It is 40 that mixed material is added to draw ratio：In 1 double screw extruder, in temperature
To carry out melt blending at 150~190 DEG C, bar, pelletizing are drawn into using air-cooled；The graininess hybrid resin that will be obtained cut into slices into
Row vacuum drying removes water process, obtains the biodegradation material (weight percentage of moisture of fatty adoption carbonic ester<
0.6%).
It is 28 that modified biodegradable polylactic acid composite obtained above is added to draw ratio：1 single screw rod
In extruder, the filament of a diameter of 2mm is extruded and processed into.Mechanical performance is shown in Table 1.
Embodiment 7
On the basis of the weight portion of dried PLA.By dried PLA (Natureworks4032D) 890
Gram, poly- 80 grams of carbonic acid 1,3- propylene diesters (PTMC), 10 grams of polyadipate 1,2- propylene diesters, 3 grams of triphenyl phosphite, stearic acid 3
Gram and 20 grams of silica, in high-speed mixer premix 30 minutes；After being sufficiently mixed uniformly, benzoyl peroxide is added
(BPO) 3 grams, continue after 5 grams of Triallyl isocyanurate to mix 5 minutes, obtain mixed material；By mixed material
It is 40 to add to draw ratio：In 1 double screw extruder, melt blending is carried out at being 150~190 DEG C in temperature, using air-cooled
It is drawn into bar, pelletizing；The graininess hybrid resin section that will be obtained carries out vacuum drying except water process, obtains fatty adoption carbon
Biodegradation material (the weight percentage of moisture of acid esters<0.6%).
It is 28 that modified biodegradable polylactic acid composite obtained above is added to draw ratio：1 single screw rod
In extruder, the filament of a diameter of 3mm is extruded and processed into.Mechanical performance is shown in Table 1.
Comparative example
The trade mark of Natureworks companies of U.S. production is taken for the PLA of 4032D is contrasted, mechanical performance is shown in Table 1.
Embodiment 1~7 and comparative example resin are carried out into impact strength test, the heat of resin according to standard GBT1843-1996
Deformation temperature is tested according to GBT1634.2-2004, and its test result is as shown in table 1.
The material property of the embodiment of table 1. and comparative example
Claims (15)
1. a kind of lactic acid composite material, comprising：
PLA：60-90 weight portions；
Fatty poly-ester carbonate：10-40 weight portions；
Organic peroxide：0.01-1 weight portions；
Crosslinking agent：0.05-1 weight portions；
Reinforcing agent：1-50 weight portions；
Compatilizer：1-5 weight portions；
Heat stabilizer：0.1-5 weight portions；
Antioxidant：0.1-1 weight portions,
Wherein, the lactic acid composite material is obtained by by each group lease making melt blending；
The compatilizer is selected from the following Biodegradable aliphatic polyester of one or more：Polyadipate 1,2- propylene diesters,
Polyadipate succinic acid -1,2- propylene diesters, poly-succinic 1,2- propylene diesters；
The reinforcing agent is nano-inorganic substance；
The fatty poly-ester carbonate is selected from poly-carbonic acid 1,2-propylene diester, poly- carbonic acid 1,3- propylene diesters, poly- butylene carbonate, poly- carbon
One or more in sour penta diester, the own diester of poly- carbonic acid.
2. the material described in claim 1, wherein the molecular weight of the PLA is 1 × 105~10 × 105；The aliphatic poly
The number-average molecular weight of carbonic ester is 4 × 104~15 × 104。
3. the material described in claim 2, wherein the molecular weight of the PLA is 1.5 × 105~1.7 × 105。
4. the material described in any one of claim 1-3, wherein：
The organic peroxide is selected from double (tert-butyl peroxide) hexanes of 2,5- dimethyl -2,5-, the double (t-butyl peroxies of 1,1-
Base) -3,3,5- trimethyl-cyclohexanes, the double butylperoxyisopropyl benzene of 1,3-, cumyl peroxide, benzoyl peroxide, two
One or more in cumyl peroxide；
The crosslinking agent is selected from Triallyl isocyanurate, trimethylol-propane trimethacrylate, triallyl benzene three
One or more in acid esters, season amylalcohol tetramethyl acrylate, diallyl phthalate；
The compatilizer is selected from the Biodegradable aliphatic polyester that number-average molecular weight is 1000~10000；
The heat stabilizer is selected from one or more in calcium stearate, stearic acid, zinc oxide, magnesia, calcium oxide；
The antioxidant is selected from one or more in phosphorous acid lipid and Hinered phenols composite antioxidant.
5. the material described in claim 4, wherein the reinforcing agent be selected from nanoclay, nano silicon, nano-calcium carbonate,
One or more in nanomete talc powder.
6. the preparation method of material described in any one of claim 1-5, including：
1) by PLA, fatty poly-ester carbonate, organic peroxide, crosslinking agent, compatilizer, reinforcing agent, heat stabilizer and anti-
Oxygen agent mixes；
2) melt blending post-tensioning is stretched into bar, pelletizing in mixed material being added into double screw extruder, obtains granular compound tree
Fat is cut into slices；
3) the granular hybrid resin chip drying of gained is removed water, is processed into filament, obtain the lactic acid composite material.
7. the preparation method described in claim 6, wherein step 3) in, the drying is vacuum drying, and is squeezed with single screw rod
Go out machine and be extruded and processed into filament.
8. the method described in claim 7, wherein a diameter of 0.5mm~5mm of the filament, and the diameter error exists
Within 5%.
9. the method described in claim 8, wherein a diameter of 1.0mm~4.0mm of the filament.
10. the method described in claim 8, wherein a diameter of 1.5mm~3mm of the filament.
Method described in 11. claims 8, wherein a diameter of 2mm of the filament.
Method described in 12. claim any one of 6-11, wherein：
The screw slenderness ratio of the double screw extruder is 30：1~50：1；
The temperature of the melt blending is 100~300 DEG C；
Described single screw extrusion machine screw diameter is 75mm, and draw ratio is 20：1~40：1, wherein extrusion temperature be 170~
210℃。
Method described in 13. claims 12, wherein the temperature of the melt blending is 150~190 DEG C.
The 14. 3 D-printing materials comprising material described in claim any one of 1-5.
Material described in 15. claim any one of 1-5 is used to prepare the purposes of 3 D-printing material.
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