CN116655895A - 3D printing degradable polyester foaming material and preparation method thereof - Google Patents

3D printing degradable polyester foaming material and preparation method thereof Download PDF

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Publication number
CN116655895A
CN116655895A CN202310459643.1A CN202310459643A CN116655895A CN 116655895 A CN116655895 A CN 116655895A CN 202310459643 A CN202310459643 A CN 202310459643A CN 116655895 A CN116655895 A CN 116655895A
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printing
foaming
acid
polyester
parts
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崔洗金
王威
冉启迪
王松林
朱楷
潘臣玉
靳钰莹
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Zhejiang Hengyi Petrochemical Research Institute Co Ltd
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Zhejiang Hengyi Petrochemical Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to the technical field of polyester synthesis processing, and discloses a 3D printing degradable polyester foaming material and a preparation method thereof, wherein the 3D printing degradable polyester foaming material comprises the following components: 10-100 parts of terephthalic acid; 10-100 parts of adipic acid; 10-50 parts of copolymerized diacid monomer; 10-100 parts of ethylene glycol; 10-50 parts of a comonomer diol; 0.05-0.3 part of tackifier; 0.01-0.1 part of catalyst; 0.01-0.2 part of stabilizer; 0.01-0.2 part of antioxidant. The material has better processability and degradability by adding various dibasic acids and two dihydric alcohols; the viscosity and the melt strength of the material are improved by adding the tackifier, and meanwhile, the degradation performance is not obviously reduced, so that the degradable polyester material synthesized by the invention can be directly used for kettle pressure foaming to obtain a lightweight product with any structure through a 3D printing technology, and the lightweight product does not need subsequent molding processing, is convenient to process and has excellent performance.

Description

3D printing degradable polyester foaming material and preparation method thereof
Technical Field
The invention relates to the technical field of polyester synthesis processing, in particular to a 3D printing degradable polyester foaming material and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is a low cost engineering thermoplastic with good mechanical and thermal properties, such as high modulus of elasticity, relatively high glass transition temperature (Tg) and good solvent resistance, which make it widely used in the fields of fiber weaving, packaging, etc. At present, aromatic polyester foam plastic represented by polyethylene terephthalate (PET) is widely applied in the industrial field and daily life because of its advantages of light weight, strong heat and sound insulation capability, strong shock absorption capability and the like. However, due to its difficulty in degradation, its waste accumulates in large amounts in the natural environment, presenting a great challenge to the global ecosystem. Therefore, the development of degradable polyester foam has become a current research focus. For example, patent CN202210827584.4 blends an aromatic polyester material with a degradable material to obtain a degradable polyester material. The polyester material is compounded with the degradable material, so that the biodegradability of the material is improved, but the material is limited by the performance of the degradable material, the toughness, heat resistance, weather resistance and the like of the composite material are reduced, and the wide use of the material is limited. Therefore, in order to solve the problems, the degradable units are introduced into the polyester chain segments, and the development of the intrinsic degradable polyester material has better application potential.
3D printing, known as additive manufacturing technology (AM), is considered to be an ideal technique for manufacturing products with complex structures from 3D solid models. The method comprises the steps of firstly using computer aided drawing software to construct a solid model, converting the solid model into a corresponding digital model, and finally using a layer-by-layer method to directly manufacture the product. One significant advantage of 3D printing is that workpieces of any complex structure can be manufactured without a mold, and thus are widely used in the fields of medicine, construction, clothing, aerospace, and the like. Currently, polymer materials for 3D printing are increasingly used, and mainly include Polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA), polybutylene succinate (PBS), polycaprolactone (PCL), nylon (PA), and the like. However, with the development of society and the improvement of living standard of people, the requirements of human beings on material varieties and properties are increasing, and various polymers with excellent properties are used in 3D printing.
Because the PET materials in the prior art have low viscosity and poor melt strength, and have poor printability, and are difficult to use in 3D printing, few degradable polyester foam materials are available for Fused Deposition (FDM) molding at present. Therefore, the degradable polyester foaming material with excellent performance and suitable for FDM molding is provided, the problem of increasingly serious environmental pollution is relieved, and the application field of the degradable polyester foaming material is widened based on the unique advantage of 3D printing.
Disclosure of Invention
The invention aims to overcome the problems of PET materials in the prior art, and provides a 3D printing degradable polyester foaming material and a preparation method thereof, and the material has better processability and degradability by adding various dibasic acids and two dibasic alcohols; the viscosity and the melt strength of the material are improved by adding the adhesion promoter, and the degradation performance is not obviously reduced, so that the degradable polyester material synthesized by the invention can be directly used for kettle pressure foaming to obtain lightweight products with any structures through a 3D printing technology, is free from subsequent molding processing, is convenient to process, has excellent performance, is extremely environment-friendly, and can be applied to the fields of biomedicine, packaging and transportation, automotive interiors, furniture building materials and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the 3D printing degradable polyester foaming material comprises the following components in parts by weight:
10-100 parts of terephthalic acid;
10-100 parts of adipic acid;
10-50 parts of copolymerized diacid monomer;
10-100 parts of ethylene glycol;
10-50 parts of a comonomer diol;
0.05-0.3 part of tackifier;
0.01-0.1 part of catalyst;
0.01-0.2 part of stabilizer;
0.01-0.2 part of antioxidant;
the adhesion promoter is one or more selected from pentaerythritol, dimethylolpropionic acid, glycerol, triglycidyl isocyanurate, pyromellitic dianhydride, dicumyl peroxide and trimethylolpropane trimethacrylate.
Firstly, the strength of the material is improved by adding the aromatic diacid terephthalic acid, the degradability of the material is improved by adding the aliphatic diacid adipic acid, the regularity of a polyester chain is destroyed by adding the copolymerized diacid monomer and the copolymerized diol monomer, the crystallization capacity, the melting point and the processing temperature of the polyester material are reduced, and the degradability of the material is further improved. Secondly, the invention also adds the adhesion promoter, and the adhesion promoter can react with diacid monomers in the system to form a small amount of branched structures, thereby inhibiting the movement of molecular chains to achieve the adhesion promoting effect; the viscosity and the melt strength of the material are improved by adding a proper amount of tackifier, so that the printability of the material is improved.
It is worth noting that the addition amount of the aromatic diacid and the aliphatic diacid needs to be controlled within a proper range, and the material degradation performance is poor when the aromatic diacid is too much, and the material strength is poor when the aliphatic diacid is too much. Meanwhile, the research of the invention shows that the excessive addition of the comonomer can easily cause the formation of new crystallization areas, so that the addition of the comonomer needs to be controlled within a proper range. In addition, the amount of the tackifier needs to be controlled within a reasonable range, the tackifier cannot achieve the tackifying effect when the amount of the tackifier is too small, and more crosslinking branched structures can be formed when the amount of the tackifier is too large, so that the degradability of the material is reduced. According to the invention, through adjusting the types and the contents of the components, the finally obtained polyester material has high strength, is degradable, can be printed in 3D and has good low-temperature foaming effect; the 3D printing technology can be directly used for kettle pressure foaming to obtain lightweight products with any structures, subsequent molding processing is not needed, the processing is convenient, the performance is excellent, the environment is protected, and the method can be applied to the fields of biomedicine, packaging and transportation, automotive interiors, furniture building materials and the like.
Preferably, the copolymerized diacid monomer is selected from one or more of succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.
Preferably, the comonomer diol monomer is selected from one or more of propylene glycol, butylene glycol, pentylene glycol, neopentyl glycol, hexylene glycol, 2, 4-tetramethyl-1, 3-cyclobutanediol and 1, 4-cyclohexanedimethanol.
Preferably, the catalyst is selected from one or more of ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, tetraisopropyl titanate and Yitaikang.
Preferably, the stabilizer is selected from one of phosphoric acid, trimethyl phosphate, triphenyl phosphate, triethyl phosphorylacetate and triphenyl phosphite.
Preferably, the antioxidant is selected from one of antioxidant 1010, antioxidant 1076 and antioxidant 565.
The invention also provides a preparation method of the 3D printing degradable polyester foaming material, which comprises the following steps:
(1) Esterification reaction: adding terephthalic acid, adipic acid, a copolymerized diacid monomer, ethylene glycol and a copolymerized diacid monomer into a polymerization reaction kettle in proportion, adding a catalyst at the same time, stirring and mixing uniformly, introducing inert gas until the pressure reaches 80-150kPa, gradually heating the temperature in the kettle to 200-230 ℃ for esterification reaction until the temperature at the top of the esterification tower begins to drop, and ending the esterification reaction until the water yield reaches more than 95% of the theoretical water yield to obtain an esterification liquid;
(2) Polycondensation reaction: adding a stabilizer, an antioxidant and a tackifier into the esterified liquid in the step (1), stirring and mixing uniformly, slowly heating the system to 230-290 ℃, vacuumizing, pre-condensing for 30-90min under low vacuum, slowly vacuumizing to below 80Pa, and performing high-vacuum polycondensation for 60-150min; after the polycondensation reaction is finished, a discharge hole is opened, and the polyester wire with the diameter of 1.7-1.8mm for fused deposition modeling is obtained through cold water traction;
(3) 3D printing: filling the prepared polyester wire into a printer for printing to obtain a 3D printing polyester material;
(4) Foaming: placing the 3D printing polyester material into a high-pressure foaming kettle, filling a foaming agent, and heating until the foaming agent reaches a supercritical state; and (3) rapidly decompressing to normal pressure after maintaining the pressure for a period of time, cooling the foaming kettle, and taking out to obtain the 3D printing degradable polyester foaming material.
Preferably, in the step (3), the polyester wire is placed in a vacuum oven at 55-65 ℃ for drying for 6-12 hours to remove water before 3D printing; the 3D printing parameters in step (3) are: the printing temperature is 150-260 ℃, the printing speed is 20-40mm/s, the filling degree is 100%, and the layer thickness is 0.1-0.2mm.
In the 3D printing process, the key step is the reasonable selection of printing temperature and printing speed. Too low a printing temperature is easy to cause nozzle blockage, and too high a printing temperature can cause the material to flow too fast, so that the printing and forming are not easy. Meanwhile, 3D printing is a process combining printing speed and melt outflow speed, and the two processes must be properly matched to meet the printing requirement. If the printing speed is faster than the melt outflow speed, the material is not filled enough, and broken lines are easily caused; if the printing speed is slower than the melt outflow speed, fuse wires are easily accumulated on the extrusion head, and uneven distribution of materials is caused. Therefore, the present invention performs strict control of printing parameters in order to obtain a product excellent in printing quality.
Preferably, in the step (4), the 3D printing polyester material is placed in a vacuum oven at 55-65 ℃ to be dried for 6-24 hours to remove moisture before foaming; the foaming agent in the step (4) is one or two of carbon dioxide, nitrogen and alkane, the foaming temperature is 60-200 ℃, the foaming pressure is 10-30MPa, the pressure maintaining time is 5-150min, the pressure releasing time is 0-5s, and the cooling time is 0-30min.
In the foaming process, the pressure maintaining time and the pressure relief mode are critical to the quality of the final foam. The pressure maintaining time is too short, so that the foaming agent is not easy to fully swell in the material, and the excessive melting and adhesion of the material are easily caused due to the too long pressure maintaining time. In addition, improper pressure relief can easily lead to uneven foaming, ultimately resulting in poor foam quality. The invention can control the foaming process to obtain the polyester foaming material with excellent performance.
Therefore, the invention has the following beneficial effects:
(1) The degradable polyester material prepared by the invention adopts an in-situ polymerization process, and has better processability and degradability by adding various dibasic acids and two dihydric alcohols, and the process is simple and the operation is convenient;
(2) The viscosity and the melt strength of the degradable polyester material are improved by adding the adhesion promoter, the degradable polyester material can be directly used for kettle pressure foaming to obtain any structural product by a 3D printing technology, subsequent molding processing is not needed, and the processing is convenient; compared with the prior bead foam molding, the process is simplified, and the energy consumption is reduced;
(3) Compared with the conventional polyester foam material, the degradable polyester foam material prepared by the invention can be slowly degraded under natural conditions, and has small influence on an ecological system; compared with the traditional degradable foam material, the foam material obtained by the invention has the advantages of excellent strength, good weather resistance and lower processing cost, is beneficial to industrial production, and can be applied to the fields of biomedicine, packaging and transportation, automobile interior trim, furniture building materials and the like.
Drawings
Fig. 1 is a diagram of a 3D printing model structure used in an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
General examples
The preparation method of the 3D printing degradable polyester foaming material comprises the following steps:
(1) Esterification reaction: adding 10-100 parts of terephthalic acid, 10-100 parts of adipic acid, 10-50 parts of copolymerized diacid monomer, 10-100 parts of glycol and 10-50 parts of copolymerized glycol monomer into a 2.5L polymerization reaction kettle in proportion, adding 0.01-0.1 part of catalyst, stirring for 15-30min at a stirring speed of 40r/min to uniformly mix, introducing inert gas until the pressure reaches 80-150kPa, gradually heating the temperature in the kettle to 200-230 ℃ for esterification reaction until the temperature at the top of the esterification tower begins to drop, the outflow water reaches more than 95% of the theoretical water yield, and ending the esterification reaction to obtain an esterification liquid; the copolymerized diacid monomer is selected from one or more of succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and hexadecanedioic acid; the comonomer diol monomer is selected from one or more of propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, 2, 4-tetramethyl-1, 3-cyclobutanediol and 1, 4-cyclohexanedimethanol; the catalyst is one or more selected from ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, tetraisopropyl titanate and Yitaikang;
(2) Polycondensation reaction: adding 0.05-0.3 part of adhesion promoter, 0.01-0.2 part of stabilizer and 0.01-0.2 part of antioxidant into the esterified liquid in the step (1), and stirring for 15-30min at normal pressure at a stirring speed of 40r/min to uniformly mix the materials; then slowly heating the system to 230-290 ℃, vacuumizing, pre-condensing for 30-90min under low vacuum, slowly vacuumizing to below 80Pa, increasing the rotating speed to 60r/min, performing high-vacuum polycondensation reaction for 60-150min, when the stirring torque reaches a preset value, finishing the polycondensation reaction, opening a discharge hole, and drawing by cold water to obtain the FDM polyester wire with the diameter of 1.7-1.8 mm; the adhesion promoter is one or more selected from pentaerythritol, dimethylolpropionic acid, glycerol, triglycidyl isocyanurate, pyromellitic dianhydride, dicumyl peroxide and trimethylolpropane trimethacrylate; the stabilizer is selected from one of phosphoric acid, trimethyl phosphate, triphenyl phosphate, triethyl phosphoryl acetate and triphenyl phosphite; the antioxidant is selected from one of antioxidant 1010, antioxidant 1076 and antioxidant 565;
(3) 3D printing: designing a model structure to be printed by using CAD software, storing the file into an STL format, and slicing by slicing software; then the slice file is led into an FDM printer, the printing temperature is set to be 150-260 ℃, the printing speed is 20-40mm/s, the filling degree is 100%, and the layer thickness is 0.1-0.2mm; drying the prepared polyester wire in a vacuum oven at 55-65 ℃ for 6-12 hours to remove water, then loading the dried polyester wire into a printer for printing, and starting the printer to prepare the 3D printing polyester material;
(4) Foaming: drying the 3D printing polyester material in a vacuum oven at 55-65 ℃ for 6-24 hours to remove water, then placing the polyester material in a high-pressure foaming kettle, filling a foaming agent, and heating to a target temperature of 60-200 ℃ and a target pressure of 10-30MPa; and (3) rapidly decompressing the sample to normal pressure for 0-5s after the pressure is maintained for 5-150min, cooling the foaming kettle for 0-30min, and taking out to obtain the 3D printing degradable polyester foaming material.
Example 1:
the preparation method of the 3D printing degradable polyester foaming material comprises the following steps:
(1) Esterification reaction: adding 60 parts of terephthalic acid, 20 parts of adipic acid, 20 parts of suberic acid, 75 parts of ethylene glycol and 25 parts of 1, 4-cyclohexanediol into a 2.5L polymerization reaction kettle in proportion, adding 0.05 part of catalyst ethylene glycol antimony, stirring for 15min at a stirring speed of 40r/min to uniformly mix the materials, introducing inert gas until the pressure reaches 100kPa, gradually heating the temperature in the kettle to 230 ℃ for esterification reaction until the temperature at the top of the esterification kettle begins to drop, and the outflow water reaches more than 95% of the theoretical water yield, and ending the esterification reaction to obtain an esterification liquid;
(2) Polycondensation reaction: adding 0.2 part of pentaerythritol, 0.01 part of triphenyl phosphite serving as a stabilizer and 0.01 part of antioxidant 1010 into the esterified liquid in the step (1), and stirring for 15min at normal pressure at a stirring speed of 40r/min to uniformly mix the materials; then slowly heating the system to 260 ℃, vacuumizing, pre-condensing for 60min under low vacuum, slowly vacuumizing to below 80Pa, slowly heating the system to 280 ℃, increasing the rotating speed to 60r/min, performing high-vacuum polycondensation reaction for 60-150min, when the stirring torque reaches a preset value, finishing the polycondensation reaction, opening a discharge hole, and drawing by cold water to obtain the FDM polyester wire with the diameter of 1.75 mm;
(3) 3D printing: designing a model structure to be printed by using CAD software, storing a file into an STL format as shown in figure 1, and slicing by slicing software; then the slice file is led into an FDM printer, the printing temperature is set to be 180 ℃, the printing speed is 20mm/s, the filling degree is 100%, and the layer thickness is 0.2mm; drying the prepared polyester wire in a vacuum oven at 60 ℃ for 8 hours to remove water, then loading the polyester wire into a printer for printing, and starting the printer to prepare a 3D printing polyester material;
(4) Foaming: drying the 3D printing polyester material in a vacuum oven at 60 ℃ for 12 hours to remove water, then placing the polyester material in a high-pressure foaming kettle, filling carbon dioxide, and heating to a target temperature of 140 ℃ and a target pressure of 15MPa; and (3) rapidly decompressing the sample to normal pressure for 2 seconds after the sample is maintained for 15 minutes, cooling the kettle to be foamed for 5 minutes, and taking out to obtain the 3D printing degradable polyester foaming material.
Example 2:
the difference from example 1 is that in step (1) no 1, 4-cyclohexanediol is added, replaced by an equivalent amount of neopentyl glycol; the remaining components and preparation methods were the same as in example 1.
The differences between the components added in the preparation of the 3D printing degradable polyester foam materials in examples 3 to 7 and comparative examples 1 to 6 and example 1 are shown in table 1; the remaining components and preparation methods were the same as in example 1.
Table 1: the component usage amounts in examples and comparative examples.
The properties of the degradable polyester foam materials prepared in the above examples and comparative examples were tested, and the test results are shown in table 2; the test method is as follows:
(1) Intrinsic Viscosity (IV): the polyester sample was dissolved in phenol: measuring the intrinsic viscosity of a sample at room temperature by adopting an Ubbelohde viscometer in a mixed solvent with the mass ratio of tetrachloroethane of 3:2;
(2) Melting Point (T) g ) And glass transition temperature (T) m ): scanning the sample by using a differential scanning calorimeter, and performing temperature rise and fall circulation for 3 times at the temperature of between 40 ℃ below zero and 280 ℃ below zero, so as to determine the melting point and the glass transition temperature of the polymer;
(3) Testing the interlayer adhesion force of the printing spline: performing a tensile test on a directly printed and molded tensile I-dumbbell type sample by referring to a standard DB34/T3563-2019 additive manufacturing Fused Deposition Modeling (FDM) part performance test method to obtain a printed spline tensile strength and elongation at break;
(4) Printing spline light transmittance test: the method is tested by adopting an A-method haze meter method according to the standard GB/T2410-2008 'determination of light transmittance and haze of transparent plastics';
(5) Foam density: cutting 3 small blocks from a sample by using a knife, measuring the foam volume by using a drainage method, measuring the foam mass by using an analytical balance, and obtaining the foam density by calculating and averaging;
(6) Foam enzyme degradability: the prepared polyester sample was placed in a citric acid buffer solution of Aspergillus niger (aspergillus niger) enzyme, ph=4.0, the buffer solution was replaced every 2 days and the residual mass of the sample was measured;
(7) Foam water degradability: the prepared polyester sample was placed in an aqueous solution at ph=13, and the residual mass of the sample was measured every 2 days.
Table 2: and (5) testing the performance of the degradable polyester foaming material.
It can be seen from examples 1,3, 4 and comparative examples 1-2 that the introduction of terephthalic acid increases the rigidity of the molecular chains, and the glass transition temperature, intrinsic viscosity, interlayer adhesion of printed splines and foam density of the material are all improved, but the degradation performance of the material is reduced. As can be seen by comparing example 1 with comparative examples 1-2, the material degradation performance is greatly reduced when the aliphatic diacid is missing, wherein the loss of suberic acid has a greater effect on the material degradation performance than the loss of adipic acid. As can be seen from comparing examples 1,3 and 4, as the terephthalic acid content increases, the rigidity of the chain increases, and the movement of the molecular chain requires more energy, so that the mobility of the chain becomes weaker, which is manifested in a gradual rise in the glass transition temperature Tg. However, as the benzene ring content is gradually increased, the non-degradable chain segments are gradually increased, and the degradation performance of the non-degradable chain segments is gradually weakened through an enzyme degradation experiment and a water degradation experiment.
As can be seen from comparison of example 1 and comparative example 3, the melting point of the material appeared at the other diol comonomer content of 0%, because the aliphatic molecular chain polymerized by the formulation was well-arranged, and it was very easy to repeatedly fold and discharge into the crystal lattice to form platelets, while with the introduction of 25% of 1, 4-cyclohexanediol, the existence of the cyclic structure inhibited the formation of the crystal region, and thus the melting point disappeared, the foaming temperature was lowered, and the foaming magnification increased. Meanwhile, as can be seen from comparison of examples 1 and examples 5 to 6, the glass transition temperature of the material gradually decreases with the increase of the content of 1, 4-cyclohexanediol, and further, it is demonstrated that 1, 4-cyclohexanediol can inhibit the ordered arrangement of molecular chains of the material, thereby effectively lowering the melting point and the foaming temperature, and at the same time, the introduction of the ring structure can increase the rigidity of the molecular chains, which is manifested as an increase in tensile strength and elongation at break, but has less influence on the degradation performance of the material.
As can be seen from comparing example 1 with comparative example 4, the addition of a small amount of tackifier helps to increase the intrinsic viscosity and melt strength of the material, improve the printability and foamability of the material, and manifest as an improvement in the mechanical properties of the printed bars and an improvement in the final foaming magnification. As can be seen from comparison of examples 1, 7 and comparative example 5, when the amount of the tackifier is within the range defined by the present invention, the increase in the amount of the tackifier is advantageous for improving the foamability of the material, but when the amount of the tackifier is too large, the foamability of the material is lowered and the degradability is lowered due to the generation of more crosslinked branched structures beyond the range of the present invention.
As can be seen from example 1 and comparative example 6, the addition of a small amount of stabilizer and antioxidant is advantageous for the polycondensation reaction, and the polyester material added with the stabilizer has a higher intrinsic viscosity and a higher foaming ratio. Meanwhile, through an enzyme degradation experiment and a water degradation experiment, the effect of the small amount of stabilizer addition on the degradation performance of the polyester material is less. It can be seen from examples 1 and 2 that the polymeric materials obtained by the reaction of the different co-diol monomers have different characteristics, and that the polyester molecules obtained using 1, 4-cyclohexanedimethanol have a more random structure than the polyester molecules obtained using neopentyl glycol, and thus have a lower glass transition temperature, a lower foaming temperature, a higher foaming ratio and better degradation properties.
As can be seen from the data in table 1, the polyester materials have different chain structures using different raw materials and proportions, and thus exhibit different intrinsic viscosity, melting point, glass transition temperature, mechanical strength, light transmittance, foam density and degradation characteristics. The strength of the polyester material is improved by adding the aromatic diacid, the degradability of the polyester material is improved by adding the aliphatic diacid, the crystallization capacity and the processing temperature of the polyester material are reduced by adding the comonomer, the melt strength and the printability of the material are improved by adding the tackifier, and finally, the obtained polyester material has high strength, is degradable and good in low-temperature foaming effect, can be used for obtaining any structural product through 3D printing and kettle-pressure foaming, does not need subsequent molding processing, is convenient to process, and has wide application prospects.
From the data of examples 1 to 7 and comparative examples 1 to 6, it is understood that the above-described requirements can be satisfied in all respects only in the scope of the claims of the present invention, resulting in an optimized 3D printing degradable polyester foam. And the corresponding negative effects are brought to the change of the proportion and the replacement/addition of the raw materials. The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (9)

1. The 3D printing degradable polyester foaming material is characterized by comprising the following components in parts by weight:
10-100 parts of terephthalic acid;
10-100 parts of adipic acid;
10-50 parts of copolymerized diacid monomer;
10-100 parts of ethylene glycol;
10-50 parts of a comonomer diol;
0.05-0.3 part of tackifier;
0.01-0.1 part of catalyst;
0.01-0.2 part of stabilizer;
0.01-0.2 part of antioxidant;
the adhesion promoter is one or more selected from pentaerythritol, dimethylolpropionic acid, glycerol, triglycidyl isocyanurate, pyromellitic dianhydride, dicumyl peroxide and trimethylolpropane trimethacrylate.
2. The 3D printing degradable polyester foam material according to claim 1 wherein the copolymerized diacid monomer is selected from one or more of succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.
3. The 3D printing degradable polyester foam material according to claim 1 wherein the comonomer glycol monomer is selected from one or more of propylene glycol, butylene glycol, pentylene glycol, neopentyl glycol, hexylene glycol, 2, 4-tetramethyl-1, 3-cyclobutanediol and 1, 4-cyclohexanedimethanol.
4. The 3D printing degradable polyester foaming material according to claim 1, wherein the catalyst is one or more selected from ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, tetraisopropyl titanate and Yitaikang.
5. The 3D printing degradable polyester foam material according to claim 1 wherein the stabilizer is selected from one of phosphoric acid, trimethyl phosphate, triphenyl phosphate, triethyl phosphorylacetate and triphenyl phosphite.
6. The 3D printed degradable polyester foam material of claim 1, wherein the antioxidant is selected from one of antioxidant 1010, antioxidant 1076, and antioxidant 565.
7. A method for preparing the 3D printing degradable polyester foam material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) Esterification reaction: adding terephthalic acid, adipic acid, a copolymerized diacid monomer, ethylene glycol and a copolymerized diacid monomer into a polymerization reaction kettle in proportion, adding a catalyst at the same time, stirring and mixing uniformly, introducing inert gas until the pressure reaches 80-150kPa, gradually heating the temperature in the kettle to 200-230 ℃ for esterification reaction until the temperature at the top of the esterification tower begins to drop, and ending the esterification reaction until the water yield reaches more than 95% of the theoretical water yield to obtain an esterification liquid;
(2) Polycondensation reaction: adding a stabilizer, an antioxidant and a tackifier into the esterified liquid in the step (1), stirring and mixing uniformly, slowly heating the system to 230-290 ℃, vacuumizing, pre-condensing for 30-90min under low vacuum, slowly vacuumizing to below 80Pa, and performing high-vacuum polycondensation for 60-150min; after the polycondensation reaction is finished, a discharge hole is opened, and the polyester wire with the diameter of 1.7-1.8mm for fused deposition modeling is obtained through cold water traction;
(3) 3D printing: filling the prepared polyester wire into a printer for printing to obtain a 3D printing polyester material;
(4) Foaming: placing the 3D printing polyester material into a high-pressure foaming kettle, filling a foaming agent, and heating until the foaming agent reaches a supercritical state; and (3) rapidly decompressing to normal pressure after maintaining the pressure for a period of time, cooling the foaming kettle, and taking out to obtain the 3D printing degradable polyester foaming material.
8. The preparation method of claim 7, wherein in the step (3), the polyester wire is dried in a vacuum oven at 55-65 ℃ for 6-12 hours to remove water before 3D printing;
the 3D printing parameters in step (3) are: the printing temperature is 150-260 ℃, the printing speed is 20-40mm/s, the filling degree is 100%, and the layer thickness is 0.1-0.2mm.
9. The method according to claim 7, wherein in the step (4), the 3D printing polyester material is dried in a vacuum oven at 55-65 ℃ for 6-24 hours to remove moisture before foaming;
the foaming agent in the step (4) is one or two of carbon dioxide, nitrogen and alkane, the foaming temperature is 60-200 ℃, the foaming pressure is 10-30MPa, the pressure maintaining time is 5-150min, the pressure releasing time is 0-5s, and the cooling time is 0-30min.
CN202310459643.1A 2023-04-26 2023-04-26 3D printing degradable polyester foaming material and preparation method thereof Pending CN116655895A (en)

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