CN113584630A - Pearlescent 3D printing material and preparation method thereof - Google Patents
Pearlescent 3D printing material and preparation method thereof Download PDFInfo
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- CN113584630A CN113584630A CN202111027981.5A CN202111027981A CN113584630A CN 113584630 A CN113584630 A CN 113584630A CN 202111027981 A CN202111027981 A CN 202111027981A CN 113584630 A CN113584630 A CN 113584630A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The application discloses a pearlescent 3D printing material and a preparation method thereof, the pearlescent 3D printing material comprises a mixture of PLA and a second additive, and the refractive index of the second additive is not lower than 1.57; the second additive is amorphous or polyester copolymer with melting point lower than 190 ℃; the intrinsic viscosity of the polyester copolymer is 0.5-0.75, the glass transition temperature of the polyester copolymer is 55-85 ℃, the difference between the glass transition temperature of the polyester copolymer and the glass transition temperature of PLA is not more than 20 ℃, and the weight average molecular weight of the PLA is 1.0 x 105‑2.0*105. The mixture is not added with a phase solvent, an antioxidant, white oil and other auxiliary agents. The application also discloses a method for preparing the printing material.
Description
Technical Field
The invention relates to the field of 3D printing, in particular to a pearlescent 3D printing material and a preparation method thereof.
Background
The FDM type 3D printing method by the wire melt extrusion stack molding has become the mainstream 3D printing molding method because of its simple operation and low price of equipment material. However, the texture existing in the wire printing process can cause the roughness of the surface of the printed product, and the wire printed product with the pearly luster effect has less texture on the surface of the product and smoother surface due to the pearly luster effect of the surface. The pearly luster effect of a product printed by the pearly luster wire obtained by the conventional method of adding the pearly luster powder is weaker, and the mechanical property of the product printed by adding too much pearly luster powder is influenced. The pearly luster effect of the material can be realized through the difference of the light transmission and the refractive index of the material and the limited mixing uniformity, and in the pearly luster material, when visible light enters into the alternating layers formed by different material sheets, the phenomena of refraction, scattering, reflection, light splitting, interference and the like occur to the light, so that sparkling and glittering like pearls are generated. Therefore, the higher the transparency of the material is, the larger the refractive index difference is, and the more obvious the pearl effect is. Meanwhile, the material mixing needs to keep limited uniformity, the uniformity is too good, several materials are completely compatible together, and the pearlescent effect is not obvious. Patent CN106633723A provides a 3D prints wire rod with pearl effect, and the printing material that this patent provided need use twin-screw extruder to carry out the granulation earlier when preparing, and rethread screw extruder extrudes the wire rod, and twin-screw extruder is because shearing mixing ability is stronger, causes the material to mix too evenly easily and leads to pearl effect worse. At the same time, the cost of extruding the product through two screws is also higher.
The main factor that PLA can be widely used in 3D printing is that PLA crystallization speed is slower, and its cooling design temperature is decided by glass transition temperature, and PLA's glass transition temperature is about 65 ℃, and under this temperature, PLA cooling rate is moderate, and the shaping shrinkage factor is lower, prints the difficult limit that sticks up, prints bonding strength higher. Meanwhile, because PLA is hard, the printing precision is high when the suspended part is printed. Therefore, when the blending material used by the PLA pearlescent material is selected, the material with higher transparency, the glass transition temperature close to that of the PLA and harder material needs to be selected, and meanwhile, the processing temperature of the material is close to that of the PLA, and the difference between the refractive index of the material and the PLA is larger.
Disclosure of Invention
Aiming at the problems, the invention provides a pearlescent 3D printing material and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a pearlescent 3D printing material comprises a mixture of PLA and a second additive, wherein the refractive index of the second additive is not lower than 1.57; the second additive is amorphous or polyester copolymer with melting point lower than 190 ℃; the intrinsic viscosity of the polyester copolymer is 0.5 to 0.75, and the glass transition temperature of the polyester copolymer isIs 55-85 deg.C, has a difference of no more than 20 deg.C with PLA glass transition temperature, and has a weight average molecular weight of 1.0 x 105-2.0*105. The mixture is not added with a phase solvent, an antioxidant, white oil and other auxiliary agents.
The method is to obtain the printing material with the pearly luster effect, for the unidirectional index of the pearly luster effect, the larger the difference value of the refractive indexes of the two materials is, the mixing uniformity of the two materials is limited, and the stronger the pearly luster effect of a product printed by the finally prepared printing material is, so the preparation method adopts a single-screw extruder to melt, mix and extrude for molding at one time after the PLA and the second additive are mixed together, and because the mixing capability of the single-screw extruder to the materials is general, the mixing uniformity of the materials is better controlled, and the better pearly luster effect is more easily obtained. In order to not change the printing process conditions of the original PLA to a large extent, a formula system which takes PLA as a main material and takes a second additive as an auxiliary material is selected, the refractive index of PET polyester reaches about 1.58 and better transparency are combined, meanwhile, the PET and the PLA both belong to polyester materials, the solubility parameter difference is small, and the moisture content difference of the two materials is small and is about 0.2%. The lower moisture content is beneficial to the difficulty of generating bubbles in the subsequent printing process. But the melting point of PET is as high as about 260 ℃, the processing temperature is about 260-275 ℃, the difference with the PLA processing temperature is large, therefore, the method adopts a mode of adding other monomers in the polymerization process of PET to reduce the melting point of the PET, obtains amorphous or low-melting-point polyester copolymer with the fluidity close to that of PLA, and then uses the amorphous or low-melting-point polyester copolymer as a second additive to carry out primary extrusion molding with the PLA through a single-screw extruder, because the solubility parameters and the fluidity of the two materials are basically close to each other, the thermodynamic compatibility of the two materials is ensured to be free from problems, meanwhile, the limited material mixing capability of the single-screw extruder ensures the limited mixing uniformity of the two materials, and since the refractive index of PLA is 1.44, while the refractive index of the second additive used in the present application is not less than 1.57, therefore, the difference value of the refractive indexes of the two materials is as high as 0.13, so that the product printed by the material prepared by the method has stronger pearl effect.
And only PLA and the second additive are contained in the whole mixture, the mixture does not contain a compatilizer, an antioxidant and white oil, the compatilizer is added to enable the two materials to be mixed more uniformly, the more uniform the two materials are mixed, the weaker the pearly luster effect of a product sheet printed by the finally obtained material is, and the antioxidant and the white oil are not added, the color and luster difference can be weakened due to the two materials, so that the pearly luster effect is poor, the antioxidant and the white oil are not added, the refractive index difference between the PLA and the second additive is larger, and the pearly luster effect of the product obtained by the finally prepared material in the printing process is more obvious.
In summary, according to the scheme, the PLA and the second additive are mixed under the condition that the phase solvent, the antioxidant and the white oil are not added, and the mixture is extruded by the screw extruder only once, so that the two materials are combined and incompletely compatible, and the obtained product has a stronger pearlescent effect. Meanwhile, even if the antioxidant is not added, the prepared printing material still has good ageing resistance, so that the printing material has long service life.
Optionally, the blend of PLA and the second blend is free of phase solvents, antioxidants, and white oil.
Optionally, the mixture further comprises a color master batch or a toner.
Optionally, the weight average molecular weight of the PLA is 1.6 x 105-2.0*105(ii) a The intrinsic viscosity of the polyester copolymer is 0.6 to 0.7.
Optionally, the second additive is melted with PLA at a temperature of 190 ℃ to 235 ℃.
Optionally, the mass of the second additive accounts for 10-30% of the mass of the whole mixture.
Preferably, the mass of the second additive accounts for 15-25% of the mass of the whole mixture.
The preparation method for preparing the pearlescent 3D printing material comprises the following steps:
in a first step, a polyester copolymer is prepared which is amorphous or has a melting point below 190 ℃
Secondly, uniformly mixing PLA and the polyester copolymer according to a certain proportion by a high-speed mixer, and then drying in a dehumidifying drying machine at the drying temperature of 55-70 ℃ for 4-6 hours, wherein the moisture content of the dried particle blend is within 300ppm
Thirdly, the dried blend directly enters a single-screw extruder to be melted and extruded at the temperature of between 190 and 235 ℃ to form the monofilament required by 3D printing, and the rotating speed of the screw is between 450 and 700rpm
Fourthly, the monofilaments sequentially pass through a constant-temperature water tank at 40-60 ℃, a cooling water tank at 20-30 ℃, a blow-drying machine, a traction machine and a wire storage rack, and finally enter a winding machine for winding to obtain the PLA composite wire with a bright surface and a specified diameter size.
The screw length-diameter ratio of the selected single-screw extruder is not higher than 33 to 1.
The prepared PLA pearl monofilament has the diameter of about 1.75mm or 2.85mm and the diameter error is within +/-0.05 mm.
The chosen amorphous or polyester copolymer with a melting point lower than 190 ℃ comprises the following steps:
terephthalic acid, ethylene glycol, a copolymerization dibasic acid monomer and a titanium catalyst are added into an esterification kettle according to a certain proportion, and the content of the titanium catalyst in the polymer is about 0.1-0.2 percent. The esterification is carried out at the temperature of 230 ℃ and 250 ℃, and when the water yield reaches 95 percent of the theoretical water yield, the esterified substance is moved into the polycondensation kettle.
When the dihydric alcohol is used for copolymerization, the copolymerized dihydric alcohol is added into the polycondensation kettle in a monomer or polymer mode and is pre-condensed for 2-3 hours at the temperature of 235-.
After the pre-polycondensation is finished, the vacuum is further increased to high vacuum, the final polycondensation reaction is carried out at the vacuum degree of 100-plus-300 Pa and the temperature of 235-plus-255 ℃, and when the stirring current is increased to the stage, the materials are discharged in time, pulled into strips and granulated
The comonomer comprises one or more of isophthalic acid, adipic acid, sebacic acid, 1, 4-butanediol and 1, 4-cyclohexanedimethanol.
Preferred comonomers are isophthalic acid, adipic acid.
The invention has the beneficial effects that: by mixing the PLA and the additive under the condition that a phase solvent, an antioxidant and white oil are not added and extruding the mixture by a screw extruder only once after mixing, the two materials are combined but not completely compatible, and the finally obtained product has a stronger pearlescent effect.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to examples.
Example 1
(1) Preparation of isophthalic acid modified PET second additive
Adding terephthalic acid, isophthalic acid, ethylene glycol and a titanium catalyst into an esterification kettle, wherein the molar ratio of the terephthalic acid to the isophthalic acid is 1 to 1, the molar ratio of the alkyd is 1.15 to 1, the content of the titanium catalyst is 0.12%, the esterification temperature is 240 ℃, when the water yield reaches 95% of the theoretical water yield, the esterified product is moved into a polycondensation kettle, pre-shrinking is carried out for 120min under the vacuum conditions of 245 ℃ and 2000Pa, and then the esterified product enters a final shrinking stage, the final shrinking temperature is 235 ℃, the vacuum degree is 200Pa, when the stirring current starts to rise to a plateau stage, the esterified product is discharged, and an amorphous polyester copolymer is obtained, wherein the glass transition temperature of the copolymer is 75 ℃, the copolymer basically has no melting point, the refractive index of the material is 1.58, and the viscosity is 0.68.
(2) PLA in the form of pellets (weight average molecular weight 1.8X 10)5) And dry-mixing the dried granular m-phthalic acid modified polyester copolymer with a polymerized granular m-phthalic acid modified polyester copolymer in a high-speed mixer according to a ratio of 4 to 1, drying in a dehumidification dryer, wherein the drying temperature is 65 ℃, the drying time is 5 hours, the dried water content is 200ppm, the dried granular mixture enters a single-screw extruder with the length-diameter ratio of 32 to 1 to be melted, blended and extruded into monofilaments, the extrusion temperature is 230 ℃, the rotation speed of the screw is 460rpm, the monofilaments are obtained by passing a melt through a discharge die head of 3.0mm, the monofilaments pass through a constant-temperature water tank of 45 ℃ and a cooling water tank of 25 ℃ in sequence, pass through a blow-drying machine, a traction machine and a wire storage rack, and finally enter a winding machine to be wound, so that the PLA composite wire rod with the bright surface and the diameter of 1.75mm is obtained. The monofilament wires are printed by a 3D printer at 210 ℃ to obtain a product with bright surface and excellent pearly luster effect.
Example 2
(1) Preparation of butanediol modified PET second additive
Adding terephthalic acid, ethylene glycol and a titanium catalyst into an esterification kettle, wherein the molar ratio of alkyd is 1.15 to 1, the content of the titanium catalyst is 0.14 percent, the esterification temperature is 245 ℃, when the water yield reaches 95 percent of the theoretical water yield, an esterified product is moved into a polycondensation kettle, PBT resin with the viscosity of 0.7 is added, the molar ratio of the PBT to the terephthalic acid of the early-stage PET esterified product is 2 to 1, the PBT is preshrinked for 130min under the vacuum condition of 247 ℃ and 3000Pa and then enters a final shrinkage stage, the final shrinkage temperature is 230 ℃, the vacuum degree is 150Pa, when the stirring current starts to rise to a plateau stage, an amorphous polyester copolymer and an amorphous PET/PBT copolymer are obtained, the glass transition temperature of the copolymer is 64 ℃, the melting point is basically not existed, the refractive index of the material is 1.58, and the viscosity is 0.65.
(2) PLA in the form of pellets (weight average molecular weight 1.6X 10)5) And dry-mixing the granular butanediol modified polyester copolymer obtained by polymerization with a high-speed mixer according to the proportion of 3: 1, drying the mixture in a dehumidification dryer, wherein the drying temperature is 58 ℃, the drying time is 6 hours, the dried moisture content is 240ppm, the dried granular mixture enters a single-screw extruder with the length-diameter ratio of 30: 1 to be melted, blended and extruded into monofilaments, the extrusion temperature is 225 ℃, the rotating speed of the screw is 500rpm, the monofilaments are obtained by passing a melt through a discharge die head of 2.8mm, the monofilaments pass through a constant-temperature water tank of 42 ℃ and a cooling water tank of 25 ℃ in sequence, pass through a blow-drying machine, a traction machine and a wire storage frame, and finally enter a winding machine to be wound, so that the PLA composite wire rod with the bright surface and the diameter of 1.75mm is obtained. The monofilament wire is printed by a 3D printer at 205 ℃ to obtain a product with bright surface and excellent pearly luster effect.
Example 3
(1) Second additive for preparing m-phthalic acid and adipic acid two-monomer modified PET
Adding terephthalic acid, isophthalic acid, adipic acid, ethylene glycol and a titanium catalyst into an esterification kettle, wherein the molar ratio of the terephthalic acid to the isophthalic acid to the adipic acid is 7: 2: 1, the molar ratio of the alcohol to the acid is 1.2 to 1, the content of the titanium catalyst is 0.15 percent, the esterification temperature is 235 ℃, when the water yield reaches 95 percent of the theoretical water yield, the esterified product is moved into a polycondensation kettle, is preshrinked for 125min under the vacuum condition of 240 ℃ and 1800Pa and then enters a final shrinkage stage, the final shrinkage temperature is 235 ℃, the vacuum degree is 120Pa, when the stirring current starts to rise to a plateau period, the product is discharged, and the amorphous polyester copolymer is obtained, wherein the glass transition temperature of the copolymer is 70 ℃, the melting point is 185 ℃, the refractive index of the material is 1.57, and the viscosity is 0.62.
(2) PLA in the form of pellets (weight average molecular weight 1.2X 10)5) And dry-mixing the granular isophthalic acid and adipic acid monomer modified polyester copolymer obtained by polymerization in a high-speed mixer according to a ratio of 5: 1, drying in a dehumidification dryer at a drying temperature of 60 ℃ for 5 hours, wherein the dried water content is 220ppm, melting and blending the dried granular mixture in a single-screw extruder with a length-diameter ratio of 28: 1 to extrude monofilaments, wherein the extrusion temperature is 220 ℃, the rotation speed of the screw is 550rpm, the monofilaments are obtained by passing a melt through a 3.0mm discharge die head, passing the monofilaments through a 40 ℃ constant-temperature water tank and a 25 ℃ cooling water tank in sequence, passing through a blow-drying machine, a traction machine and a wire storage rack, and finally passing through a winding machine to be wound to obtain the PLA composite wire with a bright surface and a diameter of 1.75 mm. The monofilament wire is printed by a 3D printer at 195 ℃ to obtain a product with bright surface and excellent pearl effect.
Example 4
(1) Preparation of second additive of 1, 4-cyclohexanedimethanol modified PET
Adding terephthalic acid, ethylene glycol and a titanium catalyst into an esterification kettle, wherein the molar ratio of the alkyd is 1.12 to 1, the content of the titanium catalyst is 0.18 percent, the esterification temperature is 245 ℃, when the water yield reaches 95 percent of the theoretical water yield, transferring the esterified substance into a polycondensation kettle, adding 1, 4-cyclohexanedimethanol, and the molar ratio of the 1, 4-cyclohexanedimethanol to the ethylene glycol of the earlier-stage PET esterified substance is 5 to 1; pre-shrinking for 140min at 250 ℃ and 2500Pa under vacuum conditions, then entering a final shrinking stage, wherein the final shrinking temperature is 240 ℃, the vacuum degree is 100Pa, discharging when the stirring current starts to rise to a plateau period, and obtaining an amorphous polyester copolymer, wherein the glass transition temperature of the copolymer is 80 ℃, the melting point of the copolymer is 188 ℃, the refractive index of the material is 1.59, and the viscosity of the material is 0.60.
(2) PLA in the form of pellets (weight-average molecular weight 1.4X 10)5) And dry-mixing the dry-mixed material and the granular 1, 4-cyclohexanedimethanol modified polyester copolymer obtained by polymerization in a high-speed mixer according to the proportion of 6: 1, drying the dry-mixed material in a dehumidification dryer, wherein the drying temperature is 7 ℃, the drying time is 4 hours, the moisture content after drying is 260ppm, the dried granular mixture enters a single-screw extruder with the length-diameter ratio of 30: 1 to be melted, blended and extruded into monofilaments, the extrusion temperature is 215 ℃, the rotation speed of the screw is 600rpm, the monofilaments are obtained by passing a melt through a discharge die head of 2.5mm, the monofilaments pass through a constant-temperature water tank of 55 ℃ and a cooling water tank of 30 ℃ in sequence, pass through a blow-dryer, a tractor and a wire storage rack, and finally enter a winding machine to be wound, so that the PLA composite wire with the bright surface and the diameter of 2.85mm is obtained. The monofilament wire is printed by a 3D printer at 200 ℃ to obtain a product with bright surface and excellent pearly luster effect.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, which is defined by the claims and their equivalents, and can be directly or indirectly applied to other related fields of technology.
Claims (10)
1. The pearlescent 3D printing material is characterized by comprising a mixture of PLA and a second additive, wherein the refractive index of the second additive is not lower than 1.57; the second additive is amorphous or polyester copolymer with the melting point lower than 190 ℃; the intrinsic viscosity of the polyester copolymer is 0.5-0.75, the glass transition temperature of the polyester copolymer is 55-85 ℃, the difference between the glass transition temperature of the polyester copolymer and the glass transition temperature of PLA is not more than 20 ℃, and the weight average molecular weight of the PLA is 1.0 x 105-2.0*105。
2. The pearlescent 3D printing material of claim 1, wherein the compound further comprises a color masterbatch or toner.
3. The bead of claim 1Optical 3D printing material, characterized in that the weight average molecular weight of the PLA is 1.6 x 105-2.0*105(ii) a The intrinsic viscosity of the polyester copolymer is 0.6 to 0.7.
4. The method for preparing the pearlescent 3D printing material according to claim 1, wherein the mass of the second additive accounts for 10-30% of the mass of the whole mixture.
5. The method for preparing a pearlescent 3D printing material according to claim 1, characterized in that the second additive is melted with PLA at a temperature of 190 ℃ to 235 ℃.
6. The method for preparing a pearlescent 3D printing material according to claim 1, wherein the mixture does not contain a phase solvent, an antioxidant and white oil.
7. A method for preparing the pearlescent 3D printing material according to any one of claims 1 to 6, characterized by comprising the steps of,
preparing amorphous polyester copolymer with melting point lower than 190 ℃;
dry-mixing PLA and a polyester copolymer to form a blend, and drying the blend by dehumidification and drying;
and (3) feeding the dried copolymer into a single-screw extruder for melt extrusion to form monofilaments required by 3D printing.
8. The method of claim 7, wherein the preparing the polyester-free copolymer comprises the steps of,
s1: adding terephthalic acid, ethylene glycol, a copolymerization dibasic acid monomer and a titanium catalyst into an esterification kettle according to a certain proportion for esterification, and when the water yield reaches 95 percent of the theoretical water yield, transferring the esterified substance into a polycondensation kettle;
s2: when dihydric alcohol is used for copolymerization, copolymerized dihydric alcohol is added into a polycondensation kettle in a monomer or polymer mode and preshrinked for 2-3 hours under the vacuum degree of 1000-3000 Pa;
s3: after the pre-polycondensation is finished, the vacuum is further pulled to high vacuum, the final polycondensation reaction is carried out under the vacuum degree of 100-300Pa, and when the stirring current is increased to the stage, the materials are discharged, pulled into strips and granulated to obtain the amorphous or low-melting-point polyester copolymer.
9. The method according to claim 8, wherein the comonomer comprises one or more of isophthalic acid, adipic acid, sebacic acid, 1, 4-butanediol, and 1, 4-cyclohexanedimethanol.
10. The method of claim 7, wherein the monofilament is produced to have a diameter of about 1.75mm or 2.85mm with a diameter tolerance of ± 0.05 mm.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168617A (en) * | 2006-10-26 | 2008-04-30 | 中国石化仪征化纤股份有限公司 | Plasticizing and modifying method for polylactic acid |
| CN105400165A (en) * | 2015-12-11 | 2016-03-16 | 中国科学院宁波材料技术与工程研究所 | Bio-based polyester modified polylactic resin, preparation method and processing forming method |
| CN106459597A (en) * | 2014-05-29 | 2017-02-22 | 宝洁公司 | Glossy article |
| CN106633723A (en) * | 2016-11-22 | 2017-05-10 | 福建师范大学 | 3D printing wire rod with pearl effect and preparation method thereof |
| CN108070225A (en) * | 2016-11-17 | 2018-05-25 | 普立万聚合体（上海）有限公司 | Polyester article with simulation metal or pearlescent appearance |
| CN111100307A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Thermochromic low-melting-point polyester master batch and preparation method thereof |
| CN112852128A (en) * | 2019-11-12 | 2021-05-28 | 中国石油化工股份有限公司 | Composition for 3D printing, 3D printed product and preparation method thereof |
| CN112852127A (en) * | 2019-11-12 | 2021-05-28 | 中国石油化工股份有限公司 | Composition for 3D printing, 3D printed product and preparation method thereof |
-
2021
- 2021-09-02 CN CN202111027981.5A patent/CN113584630A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168617A (en) * | 2006-10-26 | 2008-04-30 | 中国石化仪征化纤股份有限公司 | Plasticizing and modifying method for polylactic acid |
| CN106459597A (en) * | 2014-05-29 | 2017-02-22 | 宝洁公司 | Glossy article |
| CN105400165A (en) * | 2015-12-11 | 2016-03-16 | 中国科学院宁波材料技术与工程研究所 | Bio-based polyester modified polylactic resin, preparation method and processing forming method |
| CN108070225A (en) * | 2016-11-17 | 2018-05-25 | 普立万聚合体（上海）有限公司 | Polyester article with simulation metal or pearlescent appearance |
| CN106633723A (en) * | 2016-11-22 | 2017-05-10 | 福建师范大学 | 3D printing wire rod with pearl effect and preparation method thereof |
| CN111100307A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Thermochromic low-melting-point polyester master batch and preparation method thereof |
| CN112852128A (en) * | 2019-11-12 | 2021-05-28 | 中国石油化工股份有限公司 | Composition for 3D printing, 3D printed product and preparation method thereof |
| CN112852127A (en) * | 2019-11-12 | 2021-05-28 | 中国石油化工股份有限公司 | Composition for 3D printing, 3D printed product and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 上海市教育委员会组编: "《高分子材料成型加工》", 31 May 2000, 中国轻工业出版社 * |
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