CN106280337B - High heat-proof polylactic acid material for rapid shaping - Google Patents
High heat-proof polylactic acid material for rapid shaping Download PDFInfo
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A kind of high heat-proof polylactic acid material for rapid shaping of the invention, includes the component of following mass parts：0.1 ~ 2 part of 100 parts of l-lactic acid resin, 1 ~ 20 part of inorganic filler, 0.01 ~ 5 part of polybasic carboxylic acid metal salt, 0.1 ~ 5 part of amides compound, 0.1 ~ 5 part of plasticizer, 0.1 ~ 1 part of antioxidant and anti-hydrolysis agent；The weight average molecular weight of the l-lactic acid resin is 100000 ~ 400000；The inorganic filler is nano silicon dioxide, talcum powder, calcium sulfate crystal whiskers, one kind in mica or the mixture of at least two formation；The optical purity of the L lactic acid is 95% or more L bodies；The anti-hydrolysis agent is polycarbodiimide compound, single second carbide imine compound according to 10：90~90：The mixture that 10 ratios are formed.The present invention is high, and heat-proof polylactic acid material greatly improves the crystalline rate and crystallinity of poly-lactic acid material, thus the heat resistance of polylactic resin is made to be substantially improved, and dimension card softening shape temperature reduces the phenomenon that polylactic acid is by warpage up to 135.8 DEG C.
Description
Technical field
The present invention relates to 3D printing field of material technology, have and are related to a kind of high heat-proof polylactic acid material for rapid shaping
Material.
Background technology
Increases material manufacturing technology is a kind of emerging technology of rapid shaping field, it is one kind using digital model file as base
Plinth constructs the technology of object by layer-by-layer printing with adhesive materials such as powdery metal or plastics.Substantially former
Reason is layered manufacturing, successively increases material to generate the technology of 3D solid.FDM technology is unique using production rank thermoplastic
Property plastics be consumptive material professional 3D printing technique, this technique do not have to laser, and use is safeguarded simple, and cost is relatively low.Currently, table
Face grade 3D printing equipment is largely manufactured using FDM technology.
FDM technology principle is to utilize thermoplastic, polymeric materials melted by heating, is squeezed out from nozzle, and solidification forms wheel
The thin layer of profile shape, then be layering into and ultimately form product.Therefore the high molecular material of FDM 3D printings needs to have excellent
Processing performance, not only there is lower melting temperature, good mobility and quick solidification rate, it is necessary to have very
It is uneven will not just to there is interiors of products stress distribution in 3D printing shapings in this way for small cooling meat rate and uniform structure
It is different with cooling meat rate, the problems such as causing the properties of product defect printed.
Important component of the 3D printing consumptive material as 3D printing technique, influence prototype shaping speed, precision and physics,
Chemical property directly influences the selection of the secondary application and user of prototype to moulding process equipment.It is common currently on the market
3D printing consumptive material is mainly PLA（Polylactic acid）、 ABS （Acrylonitrile-butadiene-styrene terpolymer）、PETG（Gather to benzene
Naphthalate -1,4 cyclohexane dimethanol ester）Deng, and due to PLA have it is safe and non-toxic, without pungent smell, melting
Many advantages, such as temperature is relatively low, excellent biocompatibility, biodegradability, low-shrinkage, transparent easy dyeing more by
People's likes and pays close attention to；But polylactic acid toughness is poor, lacks the shortcomings of flexible and elasticity, poor heat resistance limits PLA conducts
3D printing consumptive material further uses.
Currently, still having larger demand for high performance 3D printing material in the market.And it is related for FDM 3D printings
Polylactic acid modification data it is less.
China Patent Publication No. CN103146164A discloses a kind of poly- breast nano material toughened for rapid shaping
Sour material and preparation method thereof, this method are that polyacrylic acid ester microsphere and polylactic acid are blended using double screw extruder
It squeezes out and is modified, improve the defect of polylactic acid poor toughness, but the addition of polyacrylic acid ester microsphere causes polylactic acid architecture
It is inhomogenous, processing performance is substantially reduced, and has seriously affected the printing shaping of product.
103665802 A of Chinese patent application publication No. CN disclose a kind of PLA material modification can be used for 3D printing
Method, this method are that inorganic nano material is used to carry out toughening modifying to PLA as toughener, and this method is ground poly- by planetary mills
Lactic acid and inorganic nanometer powder, although can enhance dispersibility of the powder in polylactic acid, processing efficiency is extremely low, is not useable for work
Industry produces.
Invention content
The object of the present invention is to provide a kind of high heat-proof polylactic acid material for rapid shaping, the high heat-proof polylactic acid materials
Material reaches 59MPa or more according to Standards for Testing Materials tensile strength, bending strength reaches 98MPa or more and dimension card softening shape temperature
115 DEG C, tensile strength, bending strength and heat resistance are improved, and the heat resistance of material improves particularly evident, PLA consumptions
The practicability and the scope of application of material greatly promote.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of resistance to hot polymerization of height for rapid shaping
Lactate material includes the component of following mass parts：
100 parts of l-lactic acid resin,
1 ~ 20 part of inorganic filler,
0.01 ~ 5 part of polybasic carboxylic acid metal salt,
0.1 ~ 5 part of amides compound,
0.1 ~ 5 part of plasticizer,
0.1 ~ 1 part of antioxidant,
0.1 ~ 2 part of anti-hydrolysis agent；
The weight average molecular weight of the l-lactic acid resin is 100000 ~ 400000；
The polybasic carboxylic acid metal salt meets one kind in following two structures：
Formula（1）：
Formula（2）：
Formula（1）Middle m=1 ~ 6 indicate that the carboxylic acid main chain methylene quantity of aromatic series polyacid, n=2 ~ 6 indicate n polynary carboxylics
Acid groups are connected to form aromatic series polyacid by covalent bond and phenyl ring, and aromatic series polyacid can be to phenylenediacetic Acid, three second of equal benzene
Sour, equal benzene tetraacethyl, six acetic acid of benzene, to benzene dipropionic acid, three propionic acid of equal benzene, four propionic acid of benzene, six propionic acid of benzene, to two butyric acid of benzene,
Three butyric acid of benzene, four butyric acid of benzene, six butyric acid of benzene, to two valeric acid of benzene, three valeric acid of equal benzene, four valeric acid of equal benzene, six valeric acid of benzene, to benzene two
Sour, equal benzene three acid, equal benzene four acid, benzene six acid, to two enanthic acid of benzene, three enanthic acid of equal benzene, four enanthic acid of equal benzene, six enanthic acid of benzene,
To one kind in two octanoic acid of benzene, three octanoic acid of equal benzene, equal four octanoic acid of benzene, six octanoic acid of benzene etc.；N=2 ~ 6 indicate n polybasic carboxylic acid base
Group is connected by covalent bond with phenyl ring；X indicate metal ion, X indicate metal ion, selected from Li, Na, K, Mg, Ca, Ba, B,
At least one of Al, Zn, Fe；
Formula（2）Middle m=0 ~ 6 indicate the main chain methylene quantity of the carboxylic acid group of pentamethylene polyacid；N=2 ~ 5 indicate n
Polybasic carboxylic acid group is connected by covalent bond with pentamethylene；X indicate metal ion, selected from Li, Na, K, Mg, Ca, Ba, B,
At least one of Al, Zn, Fe；
The amides compound is ethylenebisstearamide, ethylenebisoleoamide, oleamide, erucic amide, tristearin
At least one of amide, ethylenebis lauramide；
The anti-hydrolysis agent is polycarbodiimide compound, single second carbide imine compound, the acrylic acid with epoxy group
At least one of copolymer；
The inorganic filler is nano silicon dioxide, talcum powder, calcium sulfate crystal whiskers, one kind in mica or at least two shapes
At mixture；
The optical purity of the Pfansteihl is 95% or more L bodies；The anti-hydrolysis agent is polycarbodiimide compound, list
Carbodiimide compound is according to 10：90~90：The mixture that 10 ratios are formed.
The further improved technical solution of above-mentioned technical proposal is as follows：
In said program, the weight average molecular weight of the l-lactic acid resin is 100000 ~ 400000.
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art：
1. the present invention is used for the high heat-proof polylactic acid material of rapid shaping, the polylactic acid of specific physico-chemical parameter is used
Resin, the polybasic carboxylic acid metal salt of specific physico-chemical parameter and other auxiliary combinations use, and greatly improve poly-lactic acid material
Crystalline rate and crystallinity, thus the heat resistance of polylactic resin is made to be substantially improved, dimension card softening shape temperature is up to 135.8
DEG C, thus the phenomenon that polylactic acid is by warpage is reduced, greatly improve the practicability and the scope of application of PLA resin.
2. the present invention is used for the high heat-proof polylactic acid material of rapid shaping, mechanical performance is also improved, and material stretches
Intensity reaches 63MPa or more, bending strength reaches 110MPa or more, has changed simultaneously the brittleness of PLA itself, uses the present invention's
The durability of article is considerably beyond conventional PLA material made of the printing of high-intensity high heat-resistance polylactic acid consumptive material, and can also hold
Pressure by bigger and abrasion.
Specific implementation mode
Following embodiment and comparative example further describe the present invention, and however, the present invention is not limited to these examples：
Embodiment：By the polylactic acid of 100 mass parts, the nucleating agent of 0.01~5 mass parts, 0.1~2 mass parts water repellent agent,
0.1 ~ 5 mass parts nucleation-accelerant, 0.1 ~ 5 part of mass parts plasticizer, 0.1 ~ 20 mass parts filler, 0.1 ~ 1 mass parts it is anti-oxidant
Agent after evenly mixing, melt blending extruding pelletization under the conditions of 180~205 DEG C.Modified polylactic acid material derived above is dried
It is added in FDM 3D printing consumptive material extruders after dry, 180-210 DEG C of extrusion temperature, control water temperature, extrusion capacity and pulling speed,
It is respectively 1.75 ± 0.03mm to control consumptive material diameter.The print temperature for controlling 3D printer is 200-210 DEG C, hott bed temperature 30-
90℃.Control 3D printer printing meets 1B types sample as defined in GB/T 1040.2-2006.It is stretched according to Standards for Testing Materials
Intensity, bending strength and vicat softening temperature.
Tensile strength is evaluated：It is carried out according to GB/T 1040-2006, rate of extension 10mm/min；
Bending strength is evaluated：It is carried out according to GB/T 9341-2008, test rate 2mm/min；
Evaluation of Heat Tolerance：It is carried out according to GB/T 1633-2000,10N, 120 DEG C/min conditions is selected to be tested.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Synthesis example 1：Synthesis to phenylmalonate calcium
By 11.11 grams（0.05mol）To phenylmalonate（4251-21-2）It is added to mechanical agitation stick with 250ml water
Round-bottomed flask in, be heated to 80 DEG C, and stir 30 minutes, it made fully to dissolve.By 3.70 grams（0.05mol）2 powder of Ca (OH)
End is dissolved in 500ml water, and solution temperature is 100 DEG C.2 aqueous solutions of Ca (OH) are added to in phenylmalonate solution, and are stirred
Mix 45 minutes to not having White Flocculus or precipitation generate.Reactant is filtered, wash, dry, pulverize after obtain pair
Phenylmalonate calcium.Obtain product 12.01g, yield 92.3%.
Synthesis example 2：Synthesis to benzene ethanedioic acid zinc
Benzene ethanedioic acid zinc is synthesized, by 19.4 grams（0.1mol）To benzene ethanedioic acid（7325-46-4）It is added to 250ml water
In round-bottomed flask with mechanical agitation stick, 80 DEG C is heated to, and stir 30 minutes, it is made fully to dissolve.Then it will contain 8g
The aqueous solution 200mL of (0.2mol) NaOH is added in round-bottomed flask, is stirred 5 minutes.13.6g (0.1mol) chlorination will be contained
The aqueous solution 200mL of zinc is added in round-bottomed flask, is heated to 80 DEG C and is stirred 40 minutes, constantly has during the reaction white
Color precipitation generate, reaction product is filtered, is washed, is dried, grind after obtain 19.3 grams of white powder, yield is
75.0%。
Synthesis example 3：1,2- pentamethylene dioctyl phthalate calcium
By 7.91 grams（0.05mol）To 1,2- pentamethylene dioctyl phthalate（1461-97-8）It is added to machinery with 250ml water
In the round-bottomed flask of stirring rod, 80 DEG C is heated to, and stir 30 minutes, it is made fully to dissolve.By 3.70 grams（0.05mol）Ca
(OH) 2 powder is dissolved in 500ml water, and solution temperature is 100 DEG C.2 aqueous solutions of Ca (OH) are added to 1,2- pentamethylene diformazans
In acid solution, and stir 45 minutes to not having White Flocculus or precipitation generate.Reactant is filtered, washs, dry,
1,2- pentamethylene dioctyl phthalate calcium is obtained after crushing.Obtain 8.9 grams of product, yield 86.4%.
Embodiment 1
The polylactic acid that 100 parts are dried（4043D, Nature Works）, 0.4 part to phenylmalonate calcium crystallization nucleating agent,
This obtains phenylmalonate calcium by synthesis example 1,0.5 part of ethylenebisstearamide, 1 part of tributyl 2-acetylcitrate plasticising
Agent, 1 part of 5000 mesh talcum powder, 0.1 part of polycarbodiimide compound, 0.2 part of single second carbide imine compound, 0.2 part of antioxygen
Agent 1010 and 168 compositions are uniformly mixed, melt blending extruding pelletization under the conditions of 180~205 DEG C.By poly- breast derived above
Sour modified material dries 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature in moisture eliminating drying box.Later by drying
Resin combination is added in FDM 3D printing consumptive material extruders, 180-210 DEG C of extrusion temperature.It controls water temperature, extrusion capacity and leads
Draw rate, control consumptive material diameter is respectively 1.75 ± 0.03mm, obtains modified FDM 3D printing consumptive materials.Control 3D printer is beaten
It is 200-210 DEG C to print temperature, 80 DEG C of hott bed temperature.Control 3D printer printing meets 1B types as defined in GB/T 1040.2-2006
Sample.According to Standards for Testing Materials tensile strength 61.7MPa, 123.2 DEG C of bending strength 101.2MPa and Wei Ka softening shape temperature.
Embodiment 2
By 100 parts（Parts by weight）The polylactic acid (6400D, Nature Works) of drying, 0.4 part to phenylmalonate calcium knot
Brilliant nucleating agent, 1 part of tributyl 2-acetylcitrate plasticizer, 0.5 part of ethylenebisstearamide, 1 part of 5000 mesh talcum powder, 0.1
Part polycarbodiimide compound, 0.2 part of single second carbide imine compound, 0.2 part of antioxidant 1010 and the mixing of 168 compositions are equal
It is even, melt blending extruding pelletization under the conditions of 180~205 DEG C.By modified polylactic acid material derived above in moisture eliminating drying box
Middle drying 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature.The resin combination of drying is added to FDM 3D later
In printing consumables extruder, 180-210 DEG C of extrusion temperature.Control water temperature, extrusion capacity and pulling speed, control consumptive material diameter difference
For 1.75 ± 0.03mm, modified FDM 3D printing consumptive materials are obtained.The print temperature for controlling 3D printer is 200-210 DEG C, hott bed
80 DEG C of temperature.Control 3D printer printing meets 1B types sample as defined in GB/T 1040.2-2006.According to Standards for Testing Materials
Tensile strength 63.3MPa, 125.6 DEG C of bending strength 103.5MPa and Wei Ka softening shape temperature.
Embodiment 3
By 100 parts（Parts by weight）The polylactic acid (6400D, Nature Works) of drying, 0.4 part to phenylmalonate calcium knot
Brilliant nucleating agent, 2 parts of tributyl 2-acetylcitrate plasticizer, 2 parts of ethylenebisstearamides, 10 part of 5000 mesh talcum powder, 0.1
Part polycarbodiimide compound, 0.2 part of single second carbide imine compound, 0.2 part of antioxidant 1010 and the mixing of 168 compositions are equal
It is even, melt blending extruding pelletization under the conditions of 180~205 DEG C.By modified polylactic acid material derived above in moisture eliminating drying box
Middle drying 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature.The resin combination of drying is added to FDM 3D later
In printing consumables extruder, 180-210 DEG C of extrusion temperature.Control water temperature, extrusion capacity and pulling speed, control consumptive material diameter difference
For 1.75 ± 0.03mm, modified FDM 3D printing consumptive materials are obtained.The print temperature for controlling 3D printer is 200-210 DEG C, hott bed
80 DEG C of temperature.Control 3D printer printing meets 1B types sample as defined in GB/T 1040.2-2006.According to Standards for Testing Materials
Tensile strength 65.3MPa, 135.8 DEG C of bending strength 110.2MPa and Wei Ka softening shape temperature.
Embodiment 4
By 100 parts（Parts by weight）The polylactic acid (6400D, Nature Works) of drying, 0.4 part to benzene ethanedioic acid zinc knot
Brilliant nucleating agent, 2 parts of tributyl 2-acetylcitrate plasticizer, 0.5 part of ethylenebisstearamide, 10 part of 5000 mesh talcum powder,
0.1 part of polycarbodiimide compound, 0.2 part of single second carbide imine compound, 0.2 part of antioxidant 1010 and 168 compositions are mixed
Close uniform, melt blending extruding pelletization under the conditions of 180~205 DEG C.Modified polylactic acid material derived above is dry in dehumidifying
4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature are dried in dry case.The resin combination of drying is added to FDM later
In 3D printing consumptive material extruder, 180-210 DEG C of extrusion temperature.Control water temperature, extrusion capacity and pulling speed, control consumptive material diameter point
Not Wei 1.75 ± 0.03mm, obtain modified FDM 3D printing consumptive materials.The print temperature for controlling 3D printer is 200-210 DEG C, heat
80 DEG C of bed tempertaure.Control 3D printer printing meets 1B types sample as defined in GB/T 1040.2-2006.According to standard testing material
Expect tensile strength 59.2MPa, 119.4 DEG C of bending strength 98.3MPa and Wei Ka softening shape temperature.
Embodiment 5
By 100 parts（Parts by weight）The polylactic acid (6400D, Nature Works) of drying, 0.4 part of 1,2- pentamethylene diformazan
Sour calcium crystallization nucleating agent, 2 parts of tributyl 2-acetylcitrate plasticizer, 0.5 part of ethylenebisstearamide, 8 part of 5000 mesh talcum
Powder, 2 parts of calcium sulfate crystal whiskers, 0.1 part of polycarbodiimide compound, 0.2 part of single second carbide imine compound, 0.2 part of antioxidant
1010 and 168 compositions are uniformly mixed, melt blending extruding pelletization under the conditions of 180~205 DEG C.By polylactic acid derived above
Modified material dries 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature in moisture eliminating drying box.Later by the tree of drying
Oil/fat composition is added in FDM 3D printing consumptive material extruders, 180-210 DEG C of extrusion temperature.Control water temperature, extrusion capacity and traction
Rate, control consumptive material diameter is respectively 1.75 ± 0.03mm, obtains modified FDM 3D printing consumptive materials.Control the printing of 3D printer
Temperature is 200-210 DEG C, 80 DEG C of hott bed temperature.Control 3D printer printing meets 1B types as defined in GB/T 1040.2-2006 and tries
Sample.According to Standards for Testing Materials tensile strength 59.0MPa, bending strength 102.3MPa and 121.0 DEG C of vicat softening temperature.
Comparative example 1
The polylactic acid (4043D, Nature Works) that 100 parts are dried, 1 part of tributyl 2-acetylcitrate plasticizer,
0.5 part of ethylenebisstearamide, 1 part of 5000 mesh talcum powder, 0.1 part of polycarbodiimide compound, 0.2 part of single carbonization two
Group with imine moiety, 0.2 part of antioxidant 1010 and 168 compositions are uniformly mixed, and melt blending squeezes out under the conditions of 180~205 DEG C
It is granulated.Modified polylactic acid material derived above is dried into 4h, 85 DEG C of moisture eliminating drying box temperature, dew point temperature in moisture eliminating drying box
- 40 DEG C of degree.The resin combination of drying is added in FDM 3D printing consumptive material extruders later, 180-210 DEG C of extrusion temperature.
Water temperature, extrusion capacity and pulling speed are controlled, control consumptive material diameter is respectively 1.75 ± 0.03mm, obtains modified FDM 3D printings consumption
Material.The print temperature for controlling 3D printer is 200-210 DEG C, 30 DEG C of hott bed temperature.Control 3D printer printing meets GB/T
1040.2-2006 defined 1B types sample.According to Standards for Testing Materials tensile strength 59.9MPa, bending strength 96.3MPa and dimension
63.2 DEG C of card softening temperature.
Comparative example 2
The polylactic acid (4043D, Nature Works) that 100 parts are dried, 1 part of tributyl 2-acetylcitrate plasticizer,
0.1 part of polycarbodiimide compound, 0.2 part of single second carbide imine compound, 0.2 part of antioxidant 1010 and 168 compositions are mixed
Close uniform, melt blending extruding pelletization under the conditions of 180~205 DEG C.Modified polylactic acid material derived above is dry in dehumidifying
4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature are dried in dry case.The resin combination of drying is added to FDM later
In 3D printing consumptive material extruder, 180-210 DEG C of extrusion temperature.Control water temperature, extrusion capacity and pulling speed, control consumptive material diameter point
Not Wei 1.75 ± 0.03mm, obtain modified FDM 3D printing consumptive materials.The print temperature for controlling 3D printer is 200-210 DEG C, heat
30 DEG C of bed tempertaure.Control 59.8 DEG C of 3D printer 54.1MPa, bending strength 87.1MPa and vicat softening temperature.
High-intensity high heat-resistance poly-lactic acid material using the present invention, material are can be seen that from embodiment, comparative example and reference example
Tensile strength, bending strength and the heat resistance of material are improved, and the heat resistance of material improves particularly evident, PLA consumptive materials
Practicability and the scope of application greatly promote.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (2)
1. a kind of high heat-proof polylactic acid material for rapid shaping, it is characterised in that：Include the component of following mass parts：
100 parts of l-lactic acid resin,
1 ~ 20 part of inorganic filler,
0.01 ~ 5 part of polybasic carboxylic acid metal salt,
0.1 ~ 5 part of amides compound,
0.1 ~ 5 part of plasticizer
0.1 ~ 1 part of antioxidant,
0.1 ~ 2 part of anti-hydrolysis agent；
The polybasic carboxylic acid metal salt meets one kind in following two structures：
Formula（1）：
Formula（2）：
Formula（1）Middle m=1 ~ 6 indicate the carboxylic acid main chain methylene quantity of aromatic series polyacid, and n=2 ~ 6 indicate n polybasic carboxylic acid base
Group is connected to form aromatic series polyacid by covalent bond and phenyl ring, and aromatic series polyacid is to phenylenediacetic Acid, equal benzene triacetic acid, equal benzene four
Acetic acid, six acetic acid of benzene, to benzene dipropionic acid, three propionic acid of equal benzene, four propionic acid of benzene, six propionic acid of benzene, to two butyric acid of benzene, three butyric acid of equal benzene,
Four butyric acid of benzene, six butyric acid of benzene, to two valeric acid of benzene, three valeric acid of equal benzene, four valeric acid of equal benzene, six valeric acid of benzene, to two caproic acid of benzene, equal benzene three
Caproic acid, four caproic acid of equal benzene, six caproic acid of benzene, to one kind in two enanthic acid of benzene, three enanthic acid of equal benzene, four enanthic acid of equal benzene, six enanthic acid of benzene； X
Indicate that metal ion, metal therein are selected from least one of Li, Na, K, Mg, Ca, Ba, Al, Zn, Fe；
Formula（2）Middle m=0 ~ 6 indicate the main chain methylene quantity of the carboxylic acid group of pentamethylene polyacid；N=2 ~ 5 indicate that n is a polynary
Carboxylic acid group is connected by covalent bond with pentamethylene；X indicate metal ion, metal therein be selected from Li, Na, K, Mg, Ca,
At least one of Ba, Al, Zn, Fe；
The amides compound be ethylenebisstearamide, ethylenebisoleoamide, oleamide, erucic amide, stearmide,
At least one of ethylenebis lauramide；
The inorganic filler is nano silicon dioxide, talcum powder, calcium sulfate crystal whiskers, one kind in mica or at least two formation
Mixture；
The l-lactic acid resin is obtained by Pfansteihl dehydrating polycondensation, and the optical purity of the Pfansteihl is 95% or more；It is described
Anti-hydrolysis agent is polycarbodiimide compound, single second carbide imine compound according to 10：90~90：The mixing that 10 ratios are formed
Object.
2. the high heat-proof polylactic acid material according to claim 1 for rapid shaping, it is characterised in that：It is described left-handed poly-
The weight average molecular weight of lactic acid resin is 100000 ~ 400000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610761569.9A CN106280337B (en) | 2015-03-18 | 2015-03-18 | High heat-proof polylactic acid material for rapid shaping |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510118872.2A CN104987680B (en) | 2015-03-18 | 2015-03-18 | High-intensity high heat-resistance poly-lactic acid material for 3D printing |
| CN201610761569.9A CN106280337B (en) | 2015-03-18 | 2015-03-18 | High heat-proof polylactic acid material for rapid shaping |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510118872.2A Division CN104987680B (en) | 2015-03-18 | 2015-03-18 | High-intensity high heat-resistance poly-lactic acid material for 3D printing |
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| CN105385124B (en) * | 2015-11-30 | 2017-04-26 | 浙江工业大学 | Carbon fiber reinforced polylactic acid 3D printing material and preparation method thereof |
| CN106893277A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of inorganics filled biodegradable 3D printing consumptive material and preparation method thereof |
| CN106674933A (en) * | 2016-11-30 | 2017-05-17 | 中广核三角洲（苏州）新材料研发有限公司 | Degradable insulating wire cable material with heat resistance and durability |
| CN106674932A (en) * | 2016-11-30 | 2017-05-17 | 中广核三角洲（苏州）新材料研发有限公司 | Thermal resistant degradable insulating material for wire cables |
| US20200070404A1 (en) * | 2017-03-02 | 2020-03-05 | Bond High Performance 3D Technology B.V. | Object made by additive manufacturing and method to produce said object |
| JP7110233B2 (en) * | 2017-04-25 | 2022-08-01 | ビーエーエスエフ ソシエタス・ヨーロピア | Compositions used in 3D printing systems, their applications |
| CN107936502A (en) * | 2017-11-03 | 2018-04-20 | 金发科技股份有限公司 | A kind of polylactic acid 3D printing material and wire rod prepared therefrom |
| CN110157167A (en) * | 2018-02-08 | 2019-08-23 | 肇庆益晟商贸有限公司 | A kind of low temperature 3D printing material and its preparation method and application |
| CN114381101B (en) * | 2021-12-31 | 2023-07-14 | 中广核高新核材科技（苏州）有限公司 | Cold-molded heat-resistant semi-permeable biodegradable plastic and preparation method thereof |
| CN115960447A (en) * | 2022-12-30 | 2023-04-14 | 中广核高新核材科技（苏州）有限公司 | High-toughness crystalline heat-resistant biodegradable desorption tube material and preparation method thereof |
| CN116162337A (en) * | 2023-01-17 | 2023-05-26 | 金发科技股份有限公司 | Aging-resistant polylactic acid material, preparation method thereof and tableware |
| CN116102858A (en) * | 2023-01-17 | 2023-05-12 | 金发科技股份有限公司 | Modified polylactic acid material, preparation method thereof and tableware |
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| US3962368A (en) * | 1971-05-17 | 1976-06-08 | Hoechst Aktiengesellschaft | Linear polyester molding composition containing cross-linked linear polyester as a nucleating agent |
| DE2124336C3 (en) * | 1971-05-17 | 1986-07-31 | Hoechst Ag, 6230 Frankfurt | Thermoplastic polyester molding compounds |
| JP2003231799A (en) * | 2002-02-08 | 2003-08-19 | Toyota Motor Corp | Polylactic acid resin composition, molding and method for producing the same |
| JP2010150365A (en) * | 2008-12-25 | 2010-07-08 | Takemoto Oil & Fat Co Ltd | Crystal nucleus agent for polylactic acid resin, and polylactic acid resin composition |
| TWI488859B (en) * | 2009-09-09 | 2015-06-21 | Nissan Chemical Ind Ltd | Method for producing metal phosphonate and thermoplastic resin composition containing metal phosphonate |
| CN103113727B (en) * | 2013-01-31 | 2015-09-23 | 金发科技股份有限公司 | A kind of completely biological degradation polylactic acid matrix material and its preparation method and application |
| CN103467950B (en) * | 2013-09-29 | 2015-09-02 | 成都新柯力化工科技有限公司 | A kind of 3D prints modified polylactic acid material and preparation method thereof |
| CN103880627B (en) * | 2014-04-11 | 2016-08-31 | 南京工业大学 | A kind of nucleating agent in polylactic acid production and its preparation method and application |
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| CN106280337A (en) | 2017-01-04 |
| CN104987680A (en) | 2015-10-21 |
| CN104987680B (en) | 2017-03-01 |
| CN106243655B (en) | 2018-12-25 |
| CN106317814A (en) | 2017-01-11 |
| CN106317814B (en) | 2018-06-19 |
| CN106243655A (en) | 2016-12-21 |
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