CN114644818B - Modified fully-degradable toughened polylactic acid material for 3D printing and preparation method thereof - Google Patents
Modified fully-degradable toughened polylactic acid material for 3D printing and preparation method thereof Download PDFInfo
- Publication number
- CN114644818B CN114644818B CN202210243977.0A CN202210243977A CN114644818B CN 114644818 B CN114644818 B CN 114644818B CN 202210243977 A CN202210243977 A CN 202210243977A CN 114644818 B CN114644818 B CN 114644818B
- Authority
- CN
- China
- Prior art keywords
- stage
- parts
- composite elastomer
- polylactic acid
- following
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 38
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010146 3D printing Methods 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 42
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- 239000000806 elastomer Substances 0.000 claims abstract description 42
- 239000011159 matrix material Substances 0.000 claims abstract description 42
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 32
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 34
- 239000003963 antioxidant agent Substances 0.000 claims description 26
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 239000002202 Polyethylene glycol Substances 0.000 claims description 25
- 238000004132 cross linking Methods 0.000 claims description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims description 25
- 239000004970 Chain extender Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- -1 alcohol ester Chemical class 0.000 claims description 15
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 13
- 229920005586 poly(adipic acid) Polymers 0.000 claims description 13
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 9
- 229910052623 talc Inorganic materials 0.000 claims description 9
- 235000012222 talc Nutrition 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000109 continuous material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified fully-degradable toughened polylactic acid material for 3D printing and a preparation method thereof, and relates to the field of 3D printing materials, wherein the modified fully-degradable toughened polylactic acid material comprises the following raw materials in parts by weight: 10-90 parts of matrix raw material and 0.1-10 parts of composite elastomer, the invention prepares the composite elastomer by gelatinizing pretreatment on talcum powder, so that a degradable bio-based elastic layer is attached to the surface of the composite elastomer, on one hand, the interfacial adhesion between talcum powder and a polymer matrix can be improved, and on the other hand, the elastic layer can improve the toughness of the material.
Description
Technical Field
The invention relates to the field of 3D printing materials, in particular to a modified fully-degradable toughened polylactic acid material for 3D printing and a preparation method thereof.
Background
3D printing is a rapid prototyping technology, which is a technology for constructing objects by a layer-by-layer printing method by using a powdery metal or plastic or other bondable material based on a digital model file. 3D printing is typically implemented using a digital technology material printer. Often in the fields of mould manufacture, industrial design, etc., are used to manufacture models, and later gradually in the direct manufacture of some products, parts have been printed using this technique. The technology has application in jewelry, footwear, industrial design, construction, engineering and construction automobiles, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.
In the fusion lamination forming technology (FDM) in 3D printing, a three-dimensional product is printed by utilizing the characteristic that engineering plastic wires (such as polylactic acid PLA and the like) can be fused and piled near a melting point. PLA has good mechanical properties and biodegradability so that it has a wide application prospect, but it has a significant disadvantage of being too brittle. In FDM fused deposition rapid prototyping printing application, because of the characteristic of being too fragile, broken materials and unfilled materials can easily appear when printing products and complete products can not be normally printed, continuous materials are required to be manually interfered frequently, and the printed products can easily collide out marks which can not be recovered or are cracked, so that printing requirements can not be well met in many cases, and the application of PLA in the printing field is limited. In order to improve this disadvantage, it is highly desirable to improve the toughness of polylactic acid.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art, and provides a modified fully-degradable toughened polylactic acid material for 3D printing and a preparation method thereof.
The technical scheme of the invention is as follows:
the modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 10-90 parts of matrix raw material and 0.1-10 parts of composite elastomer.
As a preferred embodiment of the present invention, the base material comprises: polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant.
As a preferred embodiment of the present invention, the composite elastomer contains talc.
As a preferred embodiment of the present invention, the talc has a particle size of 1 to 5. Mu.m.
As a preferred embodiment of the present invention, the antioxidant comprises one or more of 2, 6-tert-butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol ester, didodecyl alcohol ester, ditetradecyl alcohol ester and dioctadecyl alcohol ester.
The invention also discloses a preparation method of the modified fully-degradable toughened polylactic acid material for 3D printing, which comprises the steps of adding talcum powder into a bio-based monomer during a crosslinking reaction, and carrying out melt mixing on the composite elastomer obtained after the crosslinking reaction and a matrix raw material, and extruding and molding after the melting.
As a preferred scheme of the invention, at least 4 temperature sections are arranged in sequence according to the feeding direction in extrusion molding, and the first stage is as follows: 160-170 ℃, and the second stage: 180-190 ℃, third stage: 190-200 ℃, fourth stage: 190-200 ℃.
As a preferred embodiment of the present invention, the bio-based monomers are polyethylene glycol and sebacic acid.
As a preferable embodiment of the present invention, glycerin is used as the crosslinking agent in the crosslinking reaction.
The beneficial effects of the invention are as follows:
according to the modified fully-degradable toughened polylactic acid material for 3D printing, on one hand, talcum powder with a lamellar structure is added into a high polymer raw material to form composite particles with a core-shell structure, the composite particles are dispersed in a polymer matrix main phase with large occupied amount to form a multiphase structure, and a great amount of silver grains or shearing bands are induced to generate and interact with the shearing bands to absorb punching skills, so that the toughness of the material is improved. On the other hand, the talcum powder is subjected to gelatinization pretreatment, so that the surface of the talcum powder is attached with a degradable bio-based elastic layer, on the one hand, the interfacial adhesion force between the talcum powder and the polymer matrix can be improved, and on the other hand, the elastic layer can stop crack propagation and improve the toughness of the material.
Detailed Description
The following specific examples further illustrate the technical scheme of the present invention.
The chain extender in the following examples was TMP6000 (technical grade).
The particle size of the talc in the examples below was 4. Mu.m.
Example 1
The modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 87 parts of matrix raw material and 3 parts of composite elastomer.
The matrix raw materials comprise: the mass ratio is 7:1:0.1:0.03 of polylactic acid, poly (adipic acid)/butylene terephthalate, a chain extender and an antioxidant.
The antioxidant comprises 2, 6-tertiary butyl-4-methylphenol.
The specific preparation method comprises the following steps: adding talcum powder into the bio-based monomer during the crosslinking reaction, and carrying out melt mixing on the composite elastomer obtained after the crosslinking reaction and the matrix raw material, and extruding and molding after the melt mixing.
Extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 160 ℃, second stage: 185 ℃, third stage: 192 ℃, fourth stage: 195 ℃. The screw speed of the extruder was 115r/min and the feed rate was 5.6r/min.
The preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, simultaneously adding talcum powder accounting for 1% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer (the molecular weight is controlled at 4000 Da), and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the modified polyethylene glycol.
Example 2
The modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 90 parts of matrix raw material and 4 parts of composite elastomer.
The matrix raw materials comprise: the mass ratio is 7:2:0.5:0.04 polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant.
The antioxidant comprises didodecyl alcohol ester.
The specific preparation method comprises the following steps: adding talcum powder into the bio-based monomer during the crosslinking reaction, and carrying out melt mixing on the composite elastomer obtained after the crosslinking reaction and the matrix raw material, and extruding and molding after the melt mixing.
Extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 165 ℃, second stage: 184 ℃, third stage: 190 ℃, fourth stage: 195 ℃. The screw speed of the extruder was 120r/min and the feed rate was 6.5r/min.
The preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, simultaneously adding talcum powder accounting for 1.5% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer (the molecular weight is controlled at 4000 Da), and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the catalyst.
Example 3
The modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 85 parts of matrix raw material and 0.6 part of composite elastomer.
The matrix raw materials comprise: the mass ratio is 9:3:0.7:0.04 polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant.
The antioxidant comprises bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide.
The specific preparation method comprises the following steps: adding talcum powder into the bio-based monomer during the crosslinking reaction, and carrying out melt mixing on the composite elastomer obtained after the crosslinking reaction and the matrix raw material, and extruding and molding after the melt mixing.
Extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 165 ℃, second stage: 186 ℃, third stage: 197 ℃, fourth stage: 198 deg.c. The screw speed of the extruder was 115r/min and the feed rate was 5.5r/min.
The preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, simultaneously adding talcum powder accounting for 1% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer (the molecular weight is controlled at 4000 Da), and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the modified polyethylene glycol.
Example 4
The modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 90 parts of matrix raw material and 0.9 part of composite elastomer.
The matrix raw materials comprise: the mass ratio is 8:3:0.3:0.06 polylactic acid, poly adipic acid/butylene terephthalate, chain extender and antioxidant.
The antioxidant comprises pentaerythritol ester.
The specific preparation method comprises the following steps: adding talcum powder into the bio-based monomer during the crosslinking reaction, and carrying out melt mixing on the composite elastomer obtained after the crosslinking reaction and the matrix raw material, and extruding and molding after the melt mixing.
Extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 170 ℃, a second stage: 190 ℃, third stage: 200 ℃, fourth stage: 200 ℃. The screw speed of the extruder was 126r/min and the feed rate was 7.5r/min.
The preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, simultaneously adding talcum powder accounting for 1% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer (the molecular weight is controlled at 4000 Da), and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the modified polyethylene glycol.
Example 5
The modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 88 parts of matrix raw material and 3 parts of composite elastomer.
The matrix raw materials comprise: the mass ratio is 8:1:0.1:0.03 of polylactic acid, poly (adipic acid)/butylene terephthalate, a chain extender and an antioxidant.
The antioxidant comprises dioctadecyl alcohol ester.
The specific preparation method comprises the following steps: adding talcum powder into the bio-based monomer during the crosslinking reaction, and carrying out melt mixing on the composite elastomer obtained after the crosslinking reaction and the matrix raw material, and extruding and molding after the melt mixing.
Extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 165 ℃, second stage: 186 ℃, third stage: 190 ℃, fourth stage: 190 ℃. The screw speed of the extruder was 115r/min and the feed rate was 7.5r/min.
The preparation method of the composite elastomer comprises the following steps:
under the atmosphere of argon, the sebacic acid and the polyethylene glycol with the molar ratio of 1:1 are polymerized, talcum powder accounting for 1.2 percent of the total mass of the sebacic acid and the polyethylene glycol is added at the same time to obtain a prepolymer (the molecular weight is controlled at 4000 Da), and then the glycerin, the prepolymer and the hexamethylene diisocyanate with the mass ratio of 1:1.5:2.3 are continuously reacted for 2 hours at 130 ℃ to obtain the catalyst.
Comparative example 1 (no composite elastomer)
The modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 88 parts of a base material. The method comprises the following steps: the mass ratio is 8:1:0.1:0.03 of polylactic acid, poly (adipic acid)/butylene terephthalate, a chain extender and an antioxidant.
The antioxidant comprises dioctadecyl alcohol ester.
The specific preparation method comprises the following steps: and (3) melting and mixing the matrix raw materials, and extruding and molding after melting.
Extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 160 ℃, second stage: 180 ℃, third stage: 190 ℃, fourth stage: 190 ℃. The screw speed of the extruder was 115r/min and the feed rate was 7.5r/min.
Comparative example 2 (composite elastomer without talc)
The modified fully-degradable toughened polylactic acid material for 3D printing comprises the following raw materials in parts by weight: 88 parts of matrix raw material and 3 parts of composite elastomer.
The matrix raw materials comprise: the mass ratio is 8:1:0.1:0.03 of polylactic acid, poly (adipic acid)/butylene terephthalate, a chain extender and an antioxidant.
The antioxidant comprises dioctadecyl alcohol ester.
The specific preparation method comprises the following steps: adding talcum powder into the bio-based monomer during the crosslinking reaction, and carrying out melt mixing on the composite elastomer obtained after the crosslinking reaction and the matrix raw material, and extruding and molding after the melt mixing.
Extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 160 ℃, second stage: 180 ℃, third stage: 190 ℃, fourth stage: 190 ℃. The screw speed of the extruder was 115r/min and the feed rate was 7.5r/min.
The preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere to obtain a prepolymer (the molecular weight is controlled at 4000 Da), and then continuously reacting glycerol, the prepolymer and hexamethylene diisocyanate in a mass ratio of 1:1.5:2.3 for 2 hours at 130 ℃ to obtain the catalyst.
The above examples and comparative examples were subjected to tensile properties according to GB/T1040-2006, impact properties according to ISO179, the test values being shown in Table 1:
from the above table, the performance of the examples is better than the comparative examples, probably for the following reasons: analysis of comparative example 1 shows that in the example, the composite elastomer is added, that is, the talcum powder is subjected to gelling pretreatment, so that a layer of degradable bio-based elastic layer is attached to the surface of the talcum powder, on one hand, the interfacial adhesion between the talcum powder and the polymer matrix can be improved, on the other hand, the elastic layer can stop crack propagation, and the toughness of the material is improved; analysis of comparative example 2 shows that in the examples, talcum powder with a lamellar structure is added into a high polymer raw material or an elastic material to form composite particles with a core-shell structure, the composite particles are dispersed in a main phase of a polymer matrix with a large occupied amount to form a multiphase structure, and a great amount of silver grains or shear strips are induced to generate and interact with the shear strips, so that the impact strength is absorbed, and the toughness of the material is improved.
The above additional technical features can be freely combined and superimposed by a person skilled in the art without conflict.
The foregoing is only a preferred embodiment of the present invention, and all technical solutions for achieving the object of the present invention by substantially the same means are included in the scope of the present invention.
Claims (5)
1. The modified fully-degradable toughened polylactic acid material for 3D printing is characterized by comprising the following raw materials in parts by weight: 87 parts of matrix raw material and 3 parts of composite elastomer;
the matrix raw materials comprise: the mass ratio is 7:1:0.1:0.03 polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant;
the antioxidant comprises 2, 6-tertiary butyl-4-methylphenol;
the specific preparation method comprises the following steps: adding talcum powder into a bio-based monomer during a crosslinking reaction, and carrying out melt mixing on the bio-based monomer and a matrix raw material to obtain a composite elastomer after the crosslinking reaction, and carrying out extrusion molding after the melting;
extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 160 ℃, second stage: 185 ℃, third stage: 192 ℃, fourth stage: 195 deg.c;
the screw speed of the extruder is 115r/min, and the feeding speed is 5.6r/min;
the preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, adding talcum powder accounting for 1% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer, controlling the molecular weight to 4000Da, and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the catalyst;
the chain extender adopts TMP6000 and is of industrial grade;
the particle size of the talc was 4. Mu.m.
2. The modified fully-degradable toughened polylactic acid material for 3D printing is characterized by comprising the following raw materials in parts by weight: 90 parts of a matrix raw material and 4 parts of a composite elastomer;
the matrix raw materials comprise: the mass ratio is 7:2:0.5:0.04 polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant;
the antioxidant comprises didodecyl alcohol ester;
the specific preparation method comprises the following steps: adding talcum powder into a bio-based monomer during a crosslinking reaction, and carrying out melt mixing on the bio-based monomer and a matrix raw material to obtain a composite elastomer after the crosslinking reaction, and carrying out extrusion molding after the melting;
extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 165 ℃, second stage: 184 ℃, third stage: 190 ℃, fourth stage: 195 deg.c;
the screw speed of the extruder is 120r/min, and the feeding speed is 6.5r/min;
the preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, adding talcum powder accounting for 1.5% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer, controlling the molecular weight to 4000Da, and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the catalyst;
the chain extender adopts TMP6000 and is of industrial grade;
the particle size of the talc was 4. Mu.m.
3. The modified fully-degradable toughened polylactic acid material for 3D printing is characterized by comprising the following raw materials in parts by weight: 85 parts of matrix raw material and 0.6 part of composite elastomer;
the matrix raw materials comprise: the mass ratio is 9:3:0.7:0.04 polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant;
the antioxidant comprises bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide;
the specific preparation method comprises the following steps: adding talcum powder into a bio-based monomer during a crosslinking reaction, and carrying out melt mixing on the bio-based monomer and a matrix raw material to obtain a composite elastomer after the crosslinking reaction, and carrying out extrusion molding after the melting;
extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 165 ℃, second stage: 186 ℃, third stage: 197 ℃, fourth stage: 198 deg.c; the screw speed of the extruder is 115r/min, and the feeding speed is 5.5r/min;
the preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, adding talcum powder accounting for 1% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer, controlling the molecular weight to 4000Da, and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the catalyst;
the chain extender adopts TMP6000 and is of industrial grade;
the particle size of the talc was 4. Mu.m.
4. The modified fully-degradable toughened polylactic acid material for 3D printing is characterized by comprising the following raw materials in parts by weight: 90 parts of matrix raw material and 0.9 part of composite elastomer;
the matrix raw materials comprise: the mass ratio is 8:3:0.3:0.06 polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant;
the antioxidant comprises pentaerythritol ester;
the specific preparation method comprises the following steps: adding talcum powder into a bio-based monomer during a crosslinking reaction, and carrying out melt mixing on the bio-based monomer and a matrix raw material to obtain a composite elastomer after the crosslinking reaction, and carrying out extrusion molding after the melting;
extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 170 ℃, a second stage: 190 ℃, third stage: 200 ℃, fourth stage: 200 ℃; the screw speed of the extruder is 126r/min, and the feeding speed is 7.5r/min;
the preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, adding talcum powder accounting for 1% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer, controlling the molecular weight to 4000Da, and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the catalyst;
the chain extender adopts TMP6000 and is of industrial grade;
the particle size of the talc was 4. Mu.m.
5. The modified fully-degradable toughened polylactic acid material for 3D printing is characterized by comprising the following raw materials in parts by weight: 88 parts of matrix raw material and 3 parts of composite elastomer;
the matrix raw materials comprise: the mass ratio is 8:1:0.1:0.03 polylactic acid, poly (adipic acid)/butylene terephthalate, chain extender and antioxidant;
the antioxidant comprises dioctadecyl alcohol ester;
the specific preparation method comprises the following steps: adding talcum powder into a bio-based monomer during a crosslinking reaction, and carrying out melt mixing on the bio-based monomer and a matrix raw material to obtain a composite elastomer after the crosslinking reaction, and carrying out extrusion molding after the melting;
extrusion molding is carried out on an extruder, 4 temperature sections are sequentially arranged according to the feeding direction, and the first stage is as follows: 165 ℃, second stage: 186 ℃, third stage: 190 ℃, fourth stage: 190 ℃; the screw speed of the extruder is 115r/min, and the feeding speed is 7.5r/min;
the preparation method of the composite elastomer comprises the following steps:
polymerizing sebacic acid and polyethylene glycol in a molar ratio of 1:1 in an argon atmosphere, adding talcum powder accounting for 1.2% of the total mass of the sebacic acid and the polyethylene glycol to obtain a prepolymer, controlling the molecular weight to 4000Da, and then continuously reacting glycerol and the prepolymer in a mass ratio of 1:1.5:2.3 with hexamethylene diisocyanate at 130 ℃ for 2 hours to obtain the catalyst;
the chain extender adopts TMP6000 and is of industrial grade;
the particle size of the talc was 4. Mu.m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210243977.0A CN114644818B (en) | 2022-03-10 | 2022-03-10 | Modified fully-degradable toughened polylactic acid material for 3D printing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210243977.0A CN114644818B (en) | 2022-03-10 | 2022-03-10 | Modified fully-degradable toughened polylactic acid material for 3D printing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114644818A CN114644818A (en) | 2022-06-21 |
| CN114644818B true CN114644818B (en) | 2023-11-03 |
Family
ID=81993548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210243977.0A Active CN114644818B (en) | 2022-03-10 | 2022-03-10 | Modified fully-degradable toughened polylactic acid material for 3D printing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114644818B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044969A1 (en) * | 1980-07-26 | 1982-02-03 | BASF Aktiengesellschaft | Thermoplastically processable polyurethane elastomers with abrasion resistance, and process for preparing same |
| CN103013070A (en) * | 2012-12-11 | 2013-04-03 | 奇瑞汽车股份有限公司 | Polylactic acid composite material and preparation method thereof |
| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN104672799A (en) * | 2013-12-01 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | Elastomer-coated inorganic rigid granule modified PBT material |
| CN105860468A (en) * | 2016-04-28 | 2016-08-17 | 青岛科技大学 | Biodegradable supertough polylactic acid (PLA) blend material and preparation method thereof |
| CN106633727A (en) * | 2016-12-23 | 2017-05-10 | 浙江海正生物材料股份有限公司 | Polylactic resin composition for blowing transparent heat-resisting bottle |
| WO2018095188A1 (en) * | 2016-11-22 | 2018-05-31 | 金发科技股份有限公司 | Polycarbonate composition and method for preparing same |
| CN109054178A (en) * | 2018-07-20 | 2018-12-21 | 吴伟华 | A kind of talcum powder and preparation method thereof improving toughness |
| US11130259B1 (en) * | 2020-05-20 | 2021-09-28 | Cofco (Jilin) Bio-Chemical Technology Co., Ltd | Device and method for online preparation of modified polylactic acid material with polylactic acid melt |
-
2022
- 2022-03-10 CN CN202210243977.0A patent/CN114644818B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044969A1 (en) * | 1980-07-26 | 1982-02-03 | BASF Aktiengesellschaft | Thermoplastically processable polyurethane elastomers with abrasion resistance, and process for preparing same |
| CN103013070A (en) * | 2012-12-11 | 2013-04-03 | 奇瑞汽车股份有限公司 | Polylactic acid composite material and preparation method thereof |
| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN104672799A (en) * | 2013-12-01 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | Elastomer-coated inorganic rigid granule modified PBT material |
| CN105860468A (en) * | 2016-04-28 | 2016-08-17 | 青岛科技大学 | Biodegradable supertough polylactic acid (PLA) blend material and preparation method thereof |
| WO2018095188A1 (en) * | 2016-11-22 | 2018-05-31 | 金发科技股份有限公司 | Polycarbonate composition and method for preparing same |
| CN106633727A (en) * | 2016-12-23 | 2017-05-10 | 浙江海正生物材料股份有限公司 | Polylactic resin composition for blowing transparent heat-resisting bottle |
| CN109054178A (en) * | 2018-07-20 | 2018-12-21 | 吴伟华 | A kind of talcum powder and preparation method thereof improving toughness |
| US11130259B1 (en) * | 2020-05-20 | 2021-09-28 | Cofco (Jilin) Bio-Chemical Technology Co., Ltd | Device and method for online preparation of modified polylactic acid material with polylactic acid melt |
Non-Patent Citations (3)
| Title |
|---|
| 弹性体共混改性聚乳酸(PLA)高韧性共混物研究进展;赵西坡;胡欢;熊娟;王鑫;余晓磊;彭少贤;;材料导报(S2);全文 * |
| 扩链剂KL-E4370对PLA/PBAT复合材料结构与性能的影响;王冬;蒙钊;丁力;;塑料科技(05);全文 * |
| 结晶行为改善聚乳酸韧性的研究进展;徐敏;刘畅;孙晓敏;赵西坡;彭少贤;;塑料(02);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114644818A (en) | 2022-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104650587A (en) | Modified polyphenylene sulfide resin suitable for 3D printing as well as preparation method and application of modified polyphenylene sulfide resin | |
| CN104031383A (en) | 3D printing modified polyamino acid material and preparation method thereof | |
| EP3733754A1 (en) | Thermoplastic elastomer resin composition | |
| CN114644818B (en) | Modified fully-degradable toughened polylactic acid material for 3D printing and preparation method thereof | |
| CN102504504A (en) | High-impact-resistance heat-resistant polylactic acid alloy material and preparation method thereof | |
| CN112592571A (en) | Medical biodegradable composite sheet material and preparation method thereof | |
| CN108070069A (en) | The high rebound low melting point thermoplastic polyurethane elastomer of soft and preparation method and application | |
| KR101690082B1 (en) | Biodegradable resin composition and biodegradable film prepared therefrom | |
| CN103980690B (en) | A kind of 3D prints modified polyether ketone resin material and preparation method thereof | |
| CN105524448B (en) | A kind of application of polymer processing aids in 3D printing | |
| CN107922533B (en) | Poly (vinyl butyral) -g-polylactide copolymer | |
| CN111269555B (en) | Thermoplastic polyurethane elastomer composition and preparation method thereof | |
| CN111621128A (en) | Preparation method of graphene oxide grafted polycaprolactone, toughening agent and 3D printing consumable | |
| EP0955326A1 (en) | Plasticizer free polyamide,moulded products therefrom and their use | |
| CN108587118B (en) | TPU material with high dimensional stability for tool parts and preparation method thereof | |
| CN109294145B (en) | PS/ASA alloy composition, PS/ASA alloy material and application thereof | |
| CN111890650A (en) | PLA/TPU (polylactic acid/thermoplastic polyurethane) double-component wire for 3D printing and preparation method thereof | |
| CN112538243A (en) | Degradable plastic film and preparation method thereof | |
| JP2000336256A (en) | Resin composition for calendering | |
| CN110172246B (en) | High-compatibility nylon 1012 and nylon 6 alloy and preparation method thereof | |
| CN112795148A (en) | Thermoplastic copolyester composite material and preparation method and application thereof | |
| US20180319928A1 (en) | Controlled glass transition polymeric material and method | |
| JP3324098B2 (en) | Method for producing thermoplastic polyurethane resin and method for producing packings composed of the resin | |
| CN112341793B (en) | Degradable TPU composite film for packaging film and preparation method thereof | |
| KR102243815B1 (en) | A method for processing eco-friendly plastic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |