CN114369348B - 3D printing bio-based copolyester and preparation method thereof - Google Patents
3D printing bio-based copolyester and preparation method thereof Download PDFInfo
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- 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
- C08L67/06—Unsaturated polyesters
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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
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Abstract
The invention belongs to the technical field of C08F299/04 organic high molecular compounds, and particularly relates to a 3D printing bio-based copolyester and a preparation method thereof. The 3D printing bio-based copolyester is prepared from aliphatic polyester, unsaturated polyester and an auxiliary agent; the unsaturated polyester is polypropylene fumarate. The 3D printing bio-based copolyester provided by the invention improves the toughness and tensile strength of printing consumables; through a great deal of research experiments by the applicant, the preparation method for preparing the 3D printing bio-based copolyester is obtained, and the obtained 3D printing bio-based copolyester has good fluency, so that the printing performance is improved, and the problem of nozzle blockage in the printing process is avoided. The 3D printing bio-based copolyester provided by the invention has good biodegradability, can be rapidly decomposed and degraded after being used, avoids damage to the environment, meets the environmental protection requirement, and has great popularization value and use significance.
Description
Technical Field
The invention belongs to the technical field of C08F299/04 organic high molecular compounds, and particularly relates to a 3D printing bio-based copolyester and a preparation method thereof.
Background
As a new technology, 3D printing technology plays a role of traditional Chinese medicine in daily life and industrial production, and with the development of 3D printing technology, consumables for printing also show a state of rapid development.
The patent of 202010021418.6 Chinese invention provides a photo-curable 3D printing polyester oligomer and a preparation method thereof, and discloses a biomedical material which is prepared by aliphatic polyester biodegradable materials for a period of time and has excellent mechanical properties, adjustable degradation speed and good biocompatibility, but the aim is achieved by polylactic acid oligomer in the patent, and polylactic acid has the defects of brittleness and ultraviolet intolerance, and the mechanical properties and photo-curing effect of the material prepared in the patent can influence the application value of the material.
In order to further expand the development of photo-cured 3D printing materials, researchers are still required to optimize the preparation raw materials and the preparation method in order to optimize the development of photo-curing technology and biodegradable materials while guaranteeing the material properties.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a 3D printing bio-based copolyester, wherein the preparation raw materials comprise aliphatic polyester, unsaturated polyester and auxiliary agent;
the unsaturated polyester is polypropylene fumarate.
In the application, the poly propylene fumarate is prepared from experimental matters, and the preparation method of the poly propylene fumarate comprises the following steps:
1) Dimethyl fumarate and 1, 2-propanediol are mixed in a molar ratio of 1:3, adding the mixture into a reaction device, mixing, and then adding zinc chloride and hydroquinone, wherein the molar ratio of the zinc chloride to the hydroquinone is 10:3, mixing and stirring to obtain a mixture A;
2) Deoxidizing the mixture A obtained in the step 1), heating to 90-120 ℃ under the oil bath condition, stabilizing, heating to 120-150 ℃ in a gradient way, and reacting for 10-12 hours;
3) The reaction is carried out for 3 to 10 hours under reduced pressure, and the product is obtained after post treatment.
In some preferred embodiments, the aliphatic polyester is selected from at least one of polybutylene succinate, polycaprolactone, poly (2, 3-butylene/1, 3-propylene/succinic/sebacic/itaconic) ester, poly (lactic/butylene/sebacic/itaconic) ester.
In some preferred embodiments, the aliphatic polyester is polybutylene succinate.
In some preferred embodiments, the weight of the poly propylene fumarate is 80 to 150wt% of the weight of the aliphatic polyester.
Further preferably, the weight of the poly propylene fumarate is 120wt% of the weight of the aliphatic polyester.
During the experiment, the applicant found that the possibility of using poly (propylene fumarate) as a photo-curable 3D printing material can be improved by adding poly (propylene fumarate) in the present system, and that the tensile strength of the prepared material can be improved when the poly (propylene fumarate) is 80-150wt% of the aliphatic polyester, the reason for this phenomenon is presumably due to the fact that: through the interaction of the poly (propylene fumarate) and the aliphatic polyester in the system, a crosslinked network structure can be formed in the system, and the degradation performance of the prepared material can be improved while the migration of active groups in the system can be promoted when the weight of the poly (propylene fumarate) is 80-150wt% of the weight of the aliphatic polyester.
In addition, the applicant found that too little amount of polypropylene fumarate added in the system causes a decrease in the concentration of free radicals, a decrease in the distribution density of crosslinking points, an increase in the probability of chain transfer or chain termination during the reaction, and a decrease in the photocuring effect of the prepared material; however, when the content of the poly (propylene fumarate) is too high, the intermolecular movement frequency in the system is affected, so that the oligomer in the prepared material is increased, and the tensile property of the prepared material is greatly reduced.
In some preferred embodiments, the preparation feed further comprises an aromatic-aliphatic copolymer.
In some preferred embodiments, the aromatic-aliphatic copolymer is polybutylene terephthalate.
In some preferred embodiments, the weight ratio of the aliphatic polyester to the aromatic-aliphatic copolymer is 1: (0.2-1).
In some preferred embodiments, the weight ratio of the aliphatic polyester to the aromatic-aliphatic copolymer is 1:0.4.
in some preferred embodiments, the auxiliary agent is selected from at least one of a modifier, a compatibilizer, a plasticizer, a nucleating agent, a catalyst, and a filler.
In some preferred embodiments, the filler is selected from at least one of nano-silica, graphene oxide, carbon nanotubes, carbon fibers, modified carbon nanotubes.
In some preferred embodiments, the filler is a modified carbon fiber.
In some preferred embodiments, the modified carbon fiber is a surface coating modified carbon fiber.
In some preferred embodiments, the surface coating modified carbon fiber is modified by a coupling agent.
In some preferred embodiments, the coupling agent is selected from at least one of N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, bis- (2- (triethoxysilane) propyl) -tetrasulfide, bis- (2- (triethoxysilane) propyl) -disulfide, γ - (methacryloyloxy) propyl trimethoxysilane, N- β - (aminoethyl) - γ -aminopropyl triethoxysilane.
In some preferred embodiments, the coupling agent is N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane.
N- β - (aminoethyl) - γ -aminopropyl triethoxysilane, CAS:5089-72-5.
In some preferred embodiments, the weight ratio of the coupling agent to the carbon fiber is (0.01-0.5): 1.
further preferably, the weight ratio of the coupling agent to the carbon fiber is 0.35:1.
in the experimental process, the applicant finds that when the coupling agent is used for modifying the carbon fiber, the weight of the coupling agent needs to be particularly controlled, and in the system, the excessive content of the coupling agent can cause self-interaction among the coupling agents, so that a compact siloxane network is generated on the surface of the carbon fiber, and the compatibility is greatly influenced; however, when the amount of the silane coupling agent used is small, the reinforcing effect of the modified carbon fiber is greatly reduced. Therefore, in the system, the amount and type of the coupling agent used for selecting the modified carbon fiber not only affect the strength of intermolecular interaction, but also affect the reinforcing effect of the modified carbon fiber in the system, affect the compatibility of the system, the mechanical properties of the prepared material and the smoothness in the use process, so that the amount and the application type of the coupling agent in the modified carbon fiber need to be strictly controlled in the system.
In some preferred embodiments, the modified carbon fiber is present in an amount of 1 to 10 weight percent based on the weight of the unsaturated polyester.
Further preferably, the weight of the modified carbon fiber is 5wt% of the weight of the unsaturated polyester.
The applicant found through a great deal of creative experimental investigation during the experimental process that the modified carbon fiber added in the system has a great influence on the preparation of the 3D printing copolyester, and the applicant found during the research process that the added modified carbon fiber in the system can change the smoothness during 3D printing and the shrinkage performance of the prepared material, especially the shrinkage rate of the prepared material is only between 0.05 and 0.1 percent when the weight of the modified carbon fiber is 1 to 10 percent of the weight of the unsaturated polyester, and the reason why the phenomenon appears is speculated by the applicant: the carbon fiber modified by N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane has obviously improved polarity of the surface and compatibility between organic matrixes, and when the carbon fiber is used in an aliphatic polyester and unsaturated polyester system, hydrogen bond interaction can be formed between active groups existing on the surface of the N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane and the organic matrixes, and meanwhile, further doping is formed in the aliphatic polyester, the unsaturated polyester and the aromatic-aliphatic copolymer system, migration of active groups or free radicals among molecules is limited, and shrinkage of the polymer during photocuring is avoided.
In some preferred embodiments, the compatibilizing agent is maleic anhydride grafted polypropylene.
The maleic anhydride grafted polypropylene is selected from the system as a compatilizer, so that the stability of the system is greatly influenced, and the applicant finds that the added maleic anhydride grafted polypropylene participates in the preparation of the 3D printing copolyester in the system in the experimental process, so that the stability of a network structure is improved, and the compatibility of the modified carbon fiber is influenced to a certain extent.
In some preferred embodiments, the preparation feedstock further comprises a photoinitiator.
In some preferred embodiments, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.
In some preferred embodiments, the preparation raw materials comprise, in parts by weight: 30-50 parts of aliphatic polyester, 24-75 parts of unsaturated polyester, 12-20 parts of aromatic-aliphatic copolymer, 2-5 parts of filler, 1-3 parts of compatilizer and 0.1-1.5 parts of photoinitiator.
The second aspect of the invention provides a preparation method of a 3D printing bio-based copolyester, which comprises the following steps:
(1) Carrying out melt extrusion on the preparation raw materials at the temperature of 150-190 ℃ of a double-screw extruder to obtain wires;
(2) And (3) irradiating the wire rod obtained in the step (1) with light to obtain the 3D printing bio-based copolyester.
The beneficial effects are that: the 3D printing bio-based copolyester prepared by the invention has the following advantages:
1. the 3D printing bio-based copolyester provided by the invention improves the toughness and tensile strength of printing consumables; through a great deal of research experiments by the applicant, the preparation method for preparing the 3D printing bio-based copolyester is obtained, and the obtained 3D printing bio-based copolyester has good fluency, so that the printing performance is improved, and the problem of nozzle blockage in the printing process is avoided.
2. The 3D printing bio-based copolyester provided by the invention has good biodegradability, can be rapidly decomposed and degraded after being used, avoids damage to the environment, meets the environmental protection requirement, and has great popularization value and use significance;
3. the 3D printing bio-based copolyester prepared by the invention has extremely low shrinkage rate, and the shrinkage rate reaches 0.08%, so that good use effect in the 3D printing process is ensured.
Detailed Description
Examples
Example 1
The 3D printing bio-based copolyester comprises the following preparation raw materials in parts by weight: 40 parts of aliphatic polyester, 48 parts of unsaturated polyester, 16 parts of aromatic-aliphatic copolymer, 2.4 parts of filler, 1.5 parts of compatilizer and 0.8 part of photoinitiator.
The aliphatic polyester is polybutylene succinate with the brand FD92PB purchased from Thailand PTT chemistry;
the unsaturated polyester is polypropylene fumarate;
the preparation method of the polypropylene fumarate comprises the following steps:
1) Dimethyl fumarate and 1, 2-propanediol are mixed in a molar ratio of 1:3, adding the mixture into a reaction device, mixing, and then adding zinc chloride and hydroquinone, wherein the molar ratio of the zinc chloride to the hydroquinone is 10:3, adding 1mol of dimethyl fumarate and 10mol of zinc chloride, mixing and stirring to obtain a mixture A;
2) Deoxidizing the mixture A obtained in the step 1), heating to 100 ℃ under the oil bath condition, stabilizing, heating to 140 ℃ in a gradient way, and reacting for 10 hours;
3) The reaction is carried out for 5 hours under reduced pressure, and the product is obtained after post-treatment.
The aromatic-aliphatic copolymer is polybutylene terephthalate, trade name BM6450XD BK560, available from DuPont, U.S.A.
The filler is modified carbon fiber, the modified carbon fiber is modified carbon fiber by a surface coating method, and the modified carbon fiber by the surface coating method is modified by a coupling agent;
the coupling agent is N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane, CAS:5089-72-5.
The weight ratio of the coupling agent to the carbon fiber is 0.35:1.
the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
A preparation method of a 3D printing bio-based copolyester comprises the following steps:
(1) Carrying out melt extrusion on the preparation raw materials at 160 ℃ of a double-screw extruder to obtain wires;
(2) And (3) irradiating the wire rod obtained in the step (1) with 280 ultraviolet light to obtain the 3D printing bio-based copolyester.
Example 2
The 3D printing bio-based copolyester comprises the following preparation raw materials in parts by weight: 40 parts of aliphatic polyester, 16 parts of aromatic-aliphatic copolymer, 2.4 parts of filler, 1.5 parts of compatilizer and 0.8 part of photoinitiator.
The aliphatic polyester is polybutylene succinate with the brand FD92PB purchased from Thailand PTT chemistry;
the aromatic-aliphatic copolymer is polybutylene terephthalate, trade name BM6450XD BK560, available from DuPont, U.S.A.
The filler is modified carbon fiber, the modified carbon fiber is modified carbon fiber by a surface coating method, and the modified carbon fiber by the surface coating method is modified by a coupling agent;
the coupling agent is N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane, CAS:5089-72-5.
The weight ratio of the coupling agent to the carbon fiber is 0.35:1.
the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
A preparation method of a 3D printing bio-based copolyester comprises the following steps:
(1) Carrying out melt extrusion on the preparation raw materials at 160 ℃ of a double-screw extruder to obtain wires;
(2) And (3) irradiating the wire rod obtained in the step (1) with 280 ultraviolet light to obtain the 3D printing bio-based copolyester.
Example 3
The 3D printing bio-based copolyester comprises the following preparation raw materials in parts by weight: 40 parts of aliphatic polyester, 48 parts of unsaturated polyester, 16 parts of aromatic-aliphatic copolymer, 2.4 parts of filler, 1.5 parts of compatilizer and 0.8 part of photoinitiator.
The aliphatic polyester is polybutylene succinate with the brand FD92PB purchased from Thailand PTT chemistry;
the unsaturated polyester is polypropylene fumarate;
the preparation method of the polypropylene fumarate comprises the following steps:
1) Dimethyl fumarate and 1, 2-propanediol are mixed in a molar ratio of 1:3, adding the mixture into a reaction device, mixing, and then adding zinc chloride and hydroquinone, wherein the molar ratio of the zinc chloride to the hydroquinone is 10:3, adding 1mol of dimethyl fumarate and 10mol of zinc chloride, mixing and stirring to obtain a mixture A;
2) Deoxidizing the mixture A obtained in the step 1), heating to 100 ℃ under the oil bath condition, stabilizing, heating to 140 ℃ in a gradient way, and reacting for 10 hours;
3) The reaction is carried out for 5 hours under reduced pressure, and the product is obtained after post-treatment.
The aromatic-aliphatic copolymer is polybutylene terephthalate, trade name BM6450XD BK560, available from DuPont, U.S.A.
The filler is carbon fiber.
The photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
A preparation method of a 3D printing bio-based copolyester comprises the following steps:
(1) Carrying out melt extrusion on the preparation raw materials at 160 ℃ of a double-screw extruder to obtain wires;
(2) And (3) irradiating the wire rod obtained in the step (1) with 280 ultraviolet light to obtain the 3D printing bio-based copolyester.
Example 4
The 3D printing bio-based copolyester comprises the following preparation raw materials in parts by weight: 40 parts of aliphatic polyester, 20 parts of unsaturated polyester, 16 parts of aromatic-aliphatic copolymer, 2.4 parts of filler, 1.5 parts of compatilizer and 0.8 part of photoinitiator.
The aliphatic polyester is polybutylene succinate with the brand FD92PB purchased from Thailand PTT chemistry;
the unsaturated polyester is polypropylene fumarate;
the preparation method of the polypropylene fumarate comprises the following steps:
1) Dimethyl fumarate and 1, 2-propanediol are mixed in a molar ratio of 1:3, adding the mixture into a reaction device, mixing, and then adding zinc chloride and hydroquinone, wherein the molar ratio of the zinc chloride to the hydroquinone is 10:3, adding 1mol of dimethyl fumarate and 10mol of zinc chloride, mixing and stirring to obtain a mixture A;
2) Deoxidizing the mixture A obtained in the step 1), heating to 100 ℃ under the oil bath condition, stabilizing, heating to 140 ℃ in a gradient way, and reacting for 10 hours;
3) The reaction is carried out for 5 hours under reduced pressure, and the product is obtained after post-treatment.
The aromatic-aliphatic copolymer is polybutylene terephthalate, trade name BM6450XD BK560, available from DuPont, U.S.A.
The filler is modified carbon fiber, the modified carbon fiber is modified carbon fiber by a surface coating method, and the modified carbon fiber by the surface coating method is modified by a coupling agent;
the coupling agent is N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane, CAS:5089-72-5.
The weight ratio of the coupling agent to the carbon fiber is 0.35:1.
the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
A preparation method of a 3D printing bio-based copolyester comprises the following steps:
(1) Carrying out melt extrusion on the preparation raw materials at 160 ℃ of a double-screw extruder to obtain wires;
(2) And (3) irradiating the wire rod obtained in the step (1) with 280 ultraviolet light to obtain the 3D printing bio-based copolyester.
Performance test:
1. shrinkage test: the bio-based copolyesters prepared in examples 1-4 were used for shrinkage testing, with reference to GB/T15585-1995;
2. tensile strength test: the biobased copolyesters prepared in examples 1-4 were used for tensile strength testing, test methods were referred to ASTM D638-10;
| experiment | Shrinkage/% | Tensile Strength-MPa |
| Example 1 | 0.08 | 46 |
| Example 2 | 3.2 | 35 |
| Example 3 | 1.5 | 38 |
| Example 4 | 1.2 | 40 |
The performance test results show that the bio-based copolyester prepared by the invention has extremely low shrinkage and tensile strength, and ensures the use of the bio-based copolyester in the field of 3D printing.
Claims (4)
1. The 3D printing bio-based copolyester is characterized in that the preparation raw materials comprise aliphatic polyester, unsaturated polyester and auxiliary agent; the unsaturated polyester is polypropylene fumarate;
the weight of the poly propylene fumarate is 80-150% of that of the aliphatic polyester;
the auxiliary agent is selected from filling agents;
the filler is modified carbon fiber;
the modified carbon fiber is modified carbon fiber by a surface coating method;
the surface coating method modified carbon fiber is modified by a coupling agent;
the weight ratio of the coupling agent to the carbon fiber is (0.01-0.5): 1, a step of;
the aliphatic polyester is selected from polybutylene succinate;
the preparation raw materials also comprise aromatic-aliphatic copolymer;
the aromatic-aliphatic copolymer is polybutylene terephthalate;
the weight ratio of the aliphatic polyester to the aromatic-aliphatic copolymer is 1: (0.2-1).
2. The 3D printed biobased copolyester of claim 1, wherein said adjuvant further comprises at least one of a modifier, a compatibilizer, a plasticizer, a nucleating agent, a catalyst; the modifier is maleic anhydride grafted polypropylene.
3. The 3D printed biobased copolyester of claim 1, wherein the preparation raw material further comprises a photoinitiator.
4. A process for the preparation of a 3D printed bio-based copolyester according to any one of claims 1 to 3, comprising the steps of:
(1) Carrying out melt extrusion on the preparation raw materials at the temperature of 150-190 ℃ of a double-screw extruder to obtain wires;
(2) Irradiating the wire rod obtained in the step (1) with light to obtain the 3D printing bio-based polyester.
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