CN115466459B - Modified polypropylene fused deposition molding granule and preparation method thereof - Google Patents
Modified polypropylene fused deposition molding granule and preparation method thereof Download PDFInfo
- Publication number
- CN115466459B CN115466459B CN202211084423.7A CN202211084423A CN115466459B CN 115466459 B CN115466459 B CN 115466459B CN 202211084423 A CN202211084423 A CN 202211084423A CN 115466459 B CN115466459 B CN 115466459B
- Authority
- CN
- China
- Prior art keywords
- graphene
- parts
- composite particles
- modified polypropylene
- mos
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 93
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 61
- 230000008021 deposition Effects 0.000 title claims abstract description 40
- 239000008187 granular material Substances 0.000 title claims abstract description 37
- 238000000465 moulding Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 239000011246 composite particle Substances 0.000 claims abstract description 40
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000010146 3D printing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 24
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 19
- 239000008188 pellet Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- LQSJJFOCHVXWNC-UHFFFAOYSA-N C(CC)[Si](OC)(OC)C.NCCNCCN Chemical compound C(CC)[Si](OC)(OC)C.NCCNCCN LQSJJFOCHVXWNC-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000003607 modifier Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
Abstract
The invention discloses a modified polypropylene fused deposition modeling granule and a preparation method thereof, wherein the granule comprises the following raw materials in parts by weight: graphene/MoS 2 6-10 parts of composite particles, 10-60 parts of hyperbranched polysiloxane and 10-1100 parts of polypropylene. The invention uses graphene/MoS 2 The composite particles and hyperbranched polysiloxane are used as modifiers, and the prepared modified polypropylene fused deposition modeling granules have the advantages of high mechanical strength, high impact toughness, strong wear resistance and the like, and have wide application prospects in the field of granule fused deposition modeling. The invention relates to the technical field of preparation of 3D printing materials, and solves the problems of low mechanical strength, large molding shrinkage, low impact toughness, poor creep resistance, poor wear resistance and the like of polypropylene fused deposition molding granules in the prior art.
Description
Technical Field
The invention relates to the technical field of preparation of 3D printing materials, in particular to a modified polypropylene fused deposition modeling granule and a preparation method thereof.
Background
3D printing technology has received much attention since the 80 s of the 20 th century because of its advantages of short cycle, rapid molding, and no need of using a mold; the fused deposition modeling technology is the most widely applied 3D printing technology at present because of the advantages of low equipment investment, environmental protection, simple post-treatment, wide application range and the like. However, the traditional fused deposition modeling technology can only print part of wires with higher hardness, and for some materials with high elasticity and low hardness, the phenomenon that the wires cannot be extruded smoothly easily occurs, and the process of manufacturing the coiled wires increases the working procedures and manufacturing cost, so that the research and development difficulty of the materials is even higher than that of equipment under the general condition.
The 3D printing technology of the granules breaks through the material limitation problem of the traditional fused deposition modeling technology, solves the problems of low universality of consumable materials and difficult material processing, and provides a brand new process category for further popularization and promotion of the fused deposition modeling technology; the polypropylene material has low price, good physical and chemical properties and excellent processing performance, and is expected to be applied to 3D printing technology, so that the cost of the polypropylene material is reduced. However, the existing polypropylene materials in the market have the defects of low mechanical strength, large molding shrinkage, low impact toughness, poor creep resistance, poor wear resistance and the like, meanwhile, polypropylene can undergo solid-liquid-solid 2-time phase transition in the 3D printing process, and when in solidification forming, the problems of edge warping and the like caused by stress strain generated by material shrinkage can be caused, so that the precision and performance of products are affected, and the large-scale application of polypropylene in the 3D printing field is difficult to realize. Therefore, if modified polypropylene fused deposition molding granules with high mechanical strength, high impact toughness and high wear resistance can be developed, the modified polypropylene fused deposition molding granules have extremely high application prospect in the field of 3D printing.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a modified polypropylene fused deposition modeling granule and a preparation method thereof, which are used for solving the problems of low mechanical strength, large modeling shrinkage, low impact toughness, poor creep resistance, poor wear resistance and the like of the polypropylene fused deposition modeling granule in the prior art.
The technical scheme for solving the technical problems is as follows: provides modified polypropylene melt-sinkingThe integrated granules comprise the following raw materials in parts by weight: graphene/MoS 2 6-10 parts of composite particles, 10-60 parts of hyperbranched polysiloxane and 10-1100 parts of polypropylene.
The beneficial effects of the invention are as follows: the invention uses graphene/MoS 2 The composite particles and hyperbranched polysiloxane are used as modifiers, and the hyperbranched polysiloxane has the advantages of low viscosity, high functionality, less chain entanglement, good solubility and the like of the hyperbranched polymer, has the advantages of low free energy and flexible chain length on the surface of the polysiloxane, and can simultaneously play roles of reinforcing, toughening, antifriction and antiwear for polypropylene. MoS is carried out 2 The modified polypropylene fused deposition modeling granules have the advantages of high mechanical strength, high impact toughness, high wear resistance and the like, and have wide application prospects in the field of granule fused deposition modeling.
Wherein, hyperbranched polysiloxane has the structure:
wherein: -r= - (CH 2 ) 3 -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2
Based on the technical scheme, the invention can also be improved as follows:
further, the pellet comprises the following raw materials in parts by weight: graphene/MoS 2 6-10 parts of composite particles, 10-60 parts of hyperbranched polysiloxane and 900-1100 parts of polypropylene.
Further, the pellet comprises the following raw materials in parts by weight: graphene/MoS 2 8 parts of composite particles, 50 parts of hyperbranched polysiloxane and 1000 parts of polypropylene.
Further, graphene/MoS 2 The composite particles are prepared by the following method:
(1) Mixing molybdenum disulfide and graphene oxide, adding hydrazine hydrate, condensing and refluxing for 6-9 hours, and vacuum drying to obtain graphene-loaded molybdenum disulfide composite particles;
(2) Mixing the graphene-supported molybdenum disulfide composite particles prepared in the step (1) with glucose, performing ball milling treatment for 5-10h, and then washing and vacuum drying to obtain graphene/MoS 2 And (3) composite particles.
The beneficial effects of adopting the further technical scheme are as follows: prepared graphene/MoS 2 The composite particles can reach graphene/MoS 2 And the dispersibility is improved.
Further, in the step (1), the mass ratio of the molybdenum disulfide to the graphene oxide is 2-5:1.
further, in the step (2), the mass ratio of the graphene-supported molybdenum disulfide composite particles to glucose is 1:1-10.
Further, in the step (2), the ball material mass ratio of ball milling treatment is 1-5:1.
further, in the step (2), the rotational speed of the ball milling treatment is 300-600rpm.
Further, in the step (2), distilled water is washed 2 to 3 times.
Further, in the step (1) and the step (2), the vacuum drying is performed for 6-12 hours.
Further, hyperbranched polysiloxanes are prepared by the following method: under the protection of nitrogen, 1-tris (hydroxymethyl) ethane and diethylene triaminopropyl methyl-grade dimethoxy silane are mixed and subjected to transesterification polycondensation for 7-11h to prepare hyperbranched polysiloxane.
The beneficial effects of adopting the further technical scheme are as follows: the method for preparing hyperbranched polysiloxane is simple, has low equipment requirement, is environment-friendly, is not easy to generate gel phenomenon, and has stable product.
Further, the temperature is raised to 100-120 ℃ firstly during the transesterification polycondensation reaction, the mixture is stirred until distillate is distilled, and then the temperature is raised to 140-180 ℃ to prepare the hyperbranched polysiloxane.
Further, the temperature rising speed is 10-15 ℃/min when the temperature rises to 100-120 ℃.
Further, when the temperature is raised to 140-180 ℃, the distillate temperature is 55-65 ℃.
Further, the molar ratio of 1, 1-tris (hydroxymethyl) ethane to diethylenetriamine propyl-methyl-grade dimethoxy silane is 4:1-6.
The invention also provides a preparation method of the modified polypropylene fused deposition modeling granule, which comprises the steps of preparing graphene/MoS 2 And (3) carrying out melt mixing on the composite particles, hyperbranched polysiloxane and polypropylene, cooling, and finally granulating to obtain the modified polypropylene melt deposition molding granules.
Further, the melt mixing conditions were: the temperature is 180-200 ℃, the rotating speed is 40-100rmp, and the mixing time is 5-15min.
The invention also provides application of the modified polypropylene fused deposition modeling granules in 3D printing.
The invention has the following beneficial effects:
1. the preparation method of the invention is simple, easy to operate and easy to popularize.
2. The prepared modified polypropylene fused deposition modeling granules have the advantages of high mechanical strength, high impact toughness, strong wear resistance and the like, and have wide application prospect in the field of fused deposition modeling of granules.
Drawings
FIG. 1 is a graph showing the tensile strength of pellets obtained in examples 1, 4-5 and comparative examples 1-3;
FIG. 2 is a graph showing the impact strength test of pellets obtained in examples 1, 4-5 and comparative examples 1-3;
FIG. 3 is a graph showing the abrasion rate of pellets obtained in examples 1, 4-5 and comparative examples 1-3.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the modified polypropylene fused deposition modeling granule comprises the following raw materials in parts by weight: graphene/MoS 2 8 parts of composite particles and hyperbranched polysiloxane50 parts and 1000 parts of polypropylene.
The preparation method of the modified polypropylene fused deposition modeling granule comprises the following steps:
(1) Molybdenum disulfide and graphene oxide are mixed according to a mass ratio of 3:1, mixing, adding hydrazine hydrate, condensing and refluxing for 7 hours, and vacuum drying after the reaction is finished to prepare graphene-loaded molybdenum disulfide composite particles;
(2) And (3) mixing the graphene-loaded molybdenum disulfide composite particles prepared in the step (1) with glucose according to a mass ratio of 1:4, mixing, performing physicochemical treatment in a ball mill for 7h, washing with distilled water for 2 times, and drying in a vacuum drying oven for 7h to obtain graphene/MoS 2 Composite particles; wherein, the ball material mass ratio is 2:1, a step of;
(3) Under the protection of nitrogen, 1-tris (hydroxymethyl) ethane and diethylenetriamine propyl-methyl-grade dimethoxy silane are mixed according to the mole ratio of 4:5.6, mixing, and performing transesterification polycondensation reaction for 8 hours, wherein the temperature is raised to 110 ℃ at a speed of 12 ℃/min, stirring is performed until distillate is distilled, the temperature is raised to 160 ℃ gradually in the reaction process, and the distillation temperature is ensured to be 60 ℃, so that hyperbranched polysiloxane is prepared;
(4) graphene/MoS prepared in the step (2) is subjected to 2 And (3) putting the composite particles, hyperbranched polysiloxane prepared in the step (3) and polypropylene into a double-screw extruder, carrying out melt mixing for 10min at the temperature of 190 ℃ and under the condition of 50rmp, extruding and putting into a stainless steel container for cooling, and finally granulating in a plastic blanking machine to prepare the modified polypropylene melt deposition molding granules.
Example 2:
the modified polypropylene fused deposition modeling granule comprises the following raw materials in parts by weight: graphene/MoS 2 6 parts of composite particles, 10 parts of hyperbranched polysiloxane and 10 parts of polypropylene.
The preparation method of the modified polypropylene fused deposition modeling granule comprises the following steps:
(1) Molybdenum disulfide and graphene oxide are mixed according to a mass ratio of 2:1, mixing, adding hydrazine hydrate, condensing and refluxing for 6 hours, and vacuum drying after the reaction is finished to prepare graphene-loaded molybdenum disulfide composite particles;
(2) And (3) mixing the graphene-loaded molybdenum disulfide composite particles prepared in the step (1) with glucose according to a mass ratio of 1:1, performing physicochemical treatment in a ball mill for 5 hours, washing with distilled water for 2 times, and drying in a vacuum drying oven for 6 hours to obtain graphene/MoS 2 Composite particles; wherein, the ball material mass ratio is 5:1, a step of;
(3) Under the protection of nitrogen, 1-tris (hydroxymethyl) ethane and diethylenetriamine propyl-methyl-grade dimethoxy silane are mixed according to the mole ratio of 4:1, mixing, and performing transesterification polycondensation reaction for 7h, wherein the temperature is raised to 100 ℃ at a speed of 10 ℃/min, stirring is performed until distillate is distilled, the temperature is raised to 140 ℃ gradually in the reaction process, and the distillation temperature is ensured to be 55 ℃, so that hyperbranched polysiloxane is prepared;
(4) graphene/MoS prepared in the step (2) is subjected to 2 Putting the composite particles, hyperbranched polysiloxane prepared in the step (3) and polypropylene into a double-screw extruder, carrying out melt mixing for 15min at 180 ℃ and 40rmp, extruding and putting into a stainless steel container for cooling, and finally granulating in a plastic blanking machine to prepare the modified polypropylene melt deposition molding granules.
Example 3:
the modified polypropylene fused deposition modeling granule comprises the following raw materials in parts by weight: graphene/MoS 2 10 parts of composite particles, 60 parts of hyperbranched polysiloxane and 1100 parts of polypropylene.
The preparation method of the modified polypropylene fused deposition modeling granule comprises the following steps:
(1) Molybdenum disulfide and graphene oxide are mixed according to a mass ratio of 5:1, mixing, adding hydrazine hydrate, condensing and refluxing for 9 hours, and vacuum drying after the reaction is finished to prepare graphene-loaded molybdenum disulfide composite particles;
(2) And (3) mixing the graphene-loaded molybdenum disulfide composite particles prepared in the step (1) with glucose according to a mass ratio of 1:10, performing physicochemical treatment in a ball mill for 10h, washing with distilled water for 3 times, and drying in a vacuum drying oven for 12h to obtain graphene/MoS 2 Composite particles; wherein, the ball material mass ratio is 1:1, a step of;
(3) Under the protection of nitrogen, 1-tris (hydroxymethyl) ethane and diethylenetriamine propyl-methyl-grade dimethoxy silane are mixed according to the mole ratio of 4:6, mixing, and performing transesterification polycondensation reaction for 11h, wherein the temperature is raised to 120 ℃ at a speed of 15 ℃/min, stirring is performed until distillate is distilled, the temperature is gradually raised to 180 ℃ in the reaction process, and the distillation temperature is ensured to be 65 ℃, so that hyperbranched polysiloxane is prepared;
(4) graphene/MoS prepared in the step (2) is subjected to 2 And (3) putting the composite particles, hyperbranched polysiloxane prepared in the step (3) and polypropylene into a double-screw extruder, carrying out melt mixing for 5min at the temperature of 200 ℃ and under the condition of 100rmp, extruding and putting into a stainless steel container for cooling, and finally granulating in a plastic blanking machine to prepare the modified polypropylene melt deposition molding granules.
Example 4:
the modified polypropylene fused deposition modeling granule comprises the following raw materials in parts by weight: graphene/MoS 2 6 parts of composite particles, 50 parts of hyperbranched polysiloxane and 1000 parts of polypropylene.
The preparation method is the same as in example 1.
Example 5:
the modified polypropylene fused deposition modeling granule comprises the following raw materials in parts by weight: graphene/MoS 2 10 parts of composite particles, 50 parts of hyperbranched polysiloxane and 1000 parts of polypropylene.
The preparation method is the same as in example 1.
Comparative example 1:
the modified polypropylene fused deposition modeling granule comprises the following raw materials in parts by weight: graphene/MoS 2 0 part of composite particles, 50 parts of hyperbranched polysiloxane and 1000 parts of polypropylene.
The preparation method is the same as in example 1.
Comparative example 2:
the modified polypropylene fused deposition modeling granule comprises the following raw materials in parts by weight: graphene/MoS 2 2 parts of composite particles, 50 parts of hyperbranched polysiloxane and 1000 parts of polypropylene.
The preparation method is the same as in example 1.
Comparative example 3:
modified polypropylene fused depositionThe molding granules comprise the following raw materials in parts by weight: graphene/MoS 2 4 parts of composite particles, 50 parts of hyperbranched polysiloxane and 1000 parts of polypropylene.
The preparation method is the same as in example 1.
Test examples
1. The pellets prepared in examples 1, 4 to 5 and comparative examples 1 to 3 were subjected to tensile strength, impact strength and abrasion rate tests, and the specific test methods were: see GB 1040-79, GB 2567-2008, GB 3980-83, the results of which are shown in FIGS. 1-3. As can be seen from FIGS. 1-3, the modified polypropylene fused deposition modeling pellets prepared by the invention have higher tensile strength and impact strength, and lower wear rate, while the pellets prepared by the comparative examples have poorer effect.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (5)
1. The modified polypropylene fused deposition modeling granule is characterized by being prepared from the following raw materials in parts by weight: graphene/MoS 2 6-10 parts of composite particles, 10-60 parts of hyperbranched polysiloxane and 10-1100 parts of polypropylene;
the graphene/MoS 2 The composite particles are prepared by the following method:
(1) Mixing molybdenum disulfide and graphene oxide, adding hydrazine hydrate, condensing and refluxing for 6-9 hours, and vacuum drying to obtain graphene-loaded molybdenum disulfide composite particles;
(2) Mixing the graphene-supported molybdenum disulfide composite particles prepared in the step (1) with glucose, performing ball milling treatment for 5-10h, and then washing and vacuum drying to obtain graphene/MoS 2 Composite particles;
in the step (1), the mass ratio of the molybdenum disulfide to the graphene oxide is 2-5:1, a step of;
the hyperbranched polysiloxane is prepared by the following method: under the protection of nitrogen, mixing 1, 1-tris (hydroxymethyl) ethane and diethylenetriamine propyl methyl dimethoxy silane, and carrying out transesterification polycondensation for 7-11h to prepare hyperbranched polysiloxane;
in the step (2), the mass ratio of the graphene-supported molybdenum disulfide composite particles to glucose is 1:1-10;
and during the transesterification polycondensation reaction, firstly heating to 100-120 ℃, stirring until distillate is distilled, and then heating to 140-180 ℃ to prepare the hyperbranched polysiloxane.
2. The modified polypropylene melt deposition modeling pellet of claim 1, wherein the molar ratio of 1, 1-tris (hydroxymethyl) ethane to diethylenetriamine propyl methyl dimethoxy silane is 4:1-6.
3. The process for producing a modified polypropylene melt-deposition modeling pellet as claimed in any one of claims 1 to 2, wherein graphene/MoS is obtained by 2 And (3) carrying out melt mixing on the composite particles, hyperbranched polysiloxane and polypropylene, cooling, and finally granulating to obtain the modified polypropylene melt deposition molding granules.
4. The method for producing a modified polypropylene melt-deposited molded pellet as claimed in claim 3, wherein the melt-mixing conditions are: the temperature is 180-200 ℃, the rotating speed is 40-100rmp, and the mixing time is 5-15min.
5. Use of the modified polypropylene fused deposition modeling pellet of any of claims 1-2 in 3D printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211084423.7A CN115466459B (en) | 2022-09-06 | 2022-09-06 | Modified polypropylene fused deposition molding granule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211084423.7A CN115466459B (en) | 2022-09-06 | 2022-09-06 | Modified polypropylene fused deposition molding granule and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115466459A CN115466459A (en) | 2022-12-13 |
| CN115466459B true CN115466459B (en) | 2024-02-27 |
Family
ID=84370988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211084423.7A Active CN115466459B (en) | 2022-09-06 | 2022-09-06 | Modified polypropylene fused deposition molding granule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115466459B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014210584A1 (en) * | 2013-06-28 | 2014-12-31 | Graphene 3D Lab Inc. | Dispersions for nanoplatelets of graphene-like materials |
| CN105330970A (en) * | 2015-12-03 | 2016-02-17 | 河南工程学院 | Polypropylene transparent material for fused deposition molding and preparation method thereof |
| CN105789595A (en) * | 2016-04-25 | 2016-07-20 | 绍兴文理学院 | Preparation method of graphene/molybdenum disulfide composite material |
| CN106834776A (en) * | 2016-12-16 | 2017-06-13 | 天津大学 | Ni Graphenes heteromers strengthen the preparation method of 6061 alloy-base composite materials |
| CN109648254A (en) * | 2018-10-31 | 2019-04-19 | 慈溪宏康汽车零部件有限公司 | The preparation method of antifriction washer for Automobile drive axle assembly |
| CN110684282A (en) * | 2019-10-30 | 2020-01-14 | 南京聚隆科技股份有限公司 | 3D hollow blow molding micro-foaming polyolefin material and preparation method thereof |
| CN113201266A (en) * | 2021-06-20 | 2021-08-03 | 西北工业大学 | High-performance epoxy bonding type solid self-lubricating coating and preparation and use method thereof |
| CN113683861A (en) * | 2021-08-24 | 2021-11-23 | 江苏中科睿赛污染控制工程有限公司 | High-wear-resistance and high-thermal-conductivity composite material and preparation method and application thereof |
| CN113980394A (en) * | 2021-11-17 | 2022-01-28 | 杭州鑫璐实业有限公司 | MPP (modified Polypropylene) pipe for electric power engineering and production process thereof |
-
2022
- 2022-09-06 CN CN202211084423.7A patent/CN115466459B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014210584A1 (en) * | 2013-06-28 | 2014-12-31 | Graphene 3D Lab Inc. | Dispersions for nanoplatelets of graphene-like materials |
| CN105330970A (en) * | 2015-12-03 | 2016-02-17 | 河南工程学院 | Polypropylene transparent material for fused deposition molding and preparation method thereof |
| CN105789595A (en) * | 2016-04-25 | 2016-07-20 | 绍兴文理学院 | Preparation method of graphene/molybdenum disulfide composite material |
| CN106834776A (en) * | 2016-12-16 | 2017-06-13 | 天津大学 | Ni Graphenes heteromers strengthen the preparation method of 6061 alloy-base composite materials |
| CN109648254A (en) * | 2018-10-31 | 2019-04-19 | 慈溪宏康汽车零部件有限公司 | The preparation method of antifriction washer for Automobile drive axle assembly |
| CN110684282A (en) * | 2019-10-30 | 2020-01-14 | 南京聚隆科技股份有限公司 | 3D hollow blow molding micro-foaming polyolefin material and preparation method thereof |
| CN113201266A (en) * | 2021-06-20 | 2021-08-03 | 西北工业大学 | High-performance epoxy bonding type solid self-lubricating coating and preparation and use method thereof |
| CN113683861A (en) * | 2021-08-24 | 2021-11-23 | 江苏中科睿赛污染控制工程有限公司 | High-wear-resistance and high-thermal-conductivity composite material and preparation method and application thereof |
| CN113980394A (en) * | 2021-11-17 | 2022-01-28 | 杭州鑫璐实业有限公司 | MPP (modified Polypropylene) pipe for electric power engineering and production process thereof |
Non-Patent Citations (2)
| Title |
|---|
| 端氨基超支化聚硅氧烷接枝氧化石墨烯改性环氧胶粘剂的研究;邢继烨等;中国胶粘剂;20200630;第29卷(第6期);7-10 * |
| 谭惠民等.超支化聚合物.北京：化学工业出版社,2005,(第1版),19-20. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115466459A (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101200581B (en) | Natural fiber-reinforced polylatic acid-based resin composition | |
| CN102181140B (en) | Carbon fiber silk waste reinforced polycarbonate composite material and preparation method of the carbon fiber silk waste reinforced polycarbonate composite material | |
| CN109111710B (en) | Heat-resistant PLA-based degradable plastic bottle and preparation method thereof | |
| CN104327358B (en) | The special polyethylene resin composition of massive rotationally moulded products | |
| CN110396286B (en) | Low-price excellent 3D printing consumable and preparation method thereof | |
| WO2006025547A1 (en) | Polyacetal resin composition | |
| CN106543622A (en) | Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness | |
| CN110041705A (en) | A kind of silicone master batch and preparation method thereof of high silicone content | |
| CN106566176A (en) | Application of polyester as a flow promoter in improving glossiness of reinforced ABS composition | |
| CN111253727A (en) | Composite material for preparing high-strength carrier tape | |
| CN104448762A (en) | Polycarbonate alloy material and preparation method thereof | |
| CN113321909A (en) | Heat-resistant polylactic acid composition and preparation method thereof | |
| CN109721958A (en) | A kind of high performance PE T engineering plastics and preparation method thereof | |
| CN115466459B (en) | Modified polypropylene fused deposition molding granule and preparation method thereof | |
| CN104177719B (en) | Special material for cross-flow fan reinforced AS with high heat resistance and preparation method of material | |
| CN109233217A (en) | A kind of injection grade fiberglass reinforced PET micro foaming composite material and preparation method thereof | |
| CN102226004A (en) | Modified poly(lactic acid) and preparation method thereof | |
| CN116675963A (en) | RPET foaming cap peak | |
| CN115850851B (en) | Modified polypropylene composite material and preparation method thereof | |
| CN113563696B (en) | Preparation method of modified polyethylene terephthalate | |
| WO2018129779A1 (en) | Polyolefin thermoplastic elastomer and processing method therefor | |
| CN109504028A (en) | Resin combination and resin-formed body | |
| CN111763313B (en) | Polyamide 56 resin, polyamide 56 resin film, and preparation method and application thereof | |
| CN110028752A (en) | Resin combination and resin-formed body | |
| CN115197549B (en) | Rapid crystallization PET resin of nano attapulgite copolymerized PEG and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |