CN115466459A - Modified polypropylene fused deposition molding granule and preparation method thereof - Google Patents
Modified polypropylene fused deposition molding granule and preparation method thereof Download PDFInfo
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- CN115466459A CN115466459A CN202211084423.7A CN202211084423A CN115466459A CN 115466459 A CN115466459 A CN 115466459A CN 202211084423 A CN202211084423 A CN 202211084423A CN 115466459 A CN115466459 A CN 115466459A
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- -1 polypropylene Polymers 0.000 title claims abstract description 100
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 68
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 68
- 230000008021 deposition Effects 0.000 title claims abstract description 51
- 239000008187 granular material Substances 0.000 title claims abstract description 30
- 238000000465 moulding Methods 0.000 title claims abstract description 25
- 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 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 48
- 239000011246 composite particle Substances 0.000 claims abstract description 38
- 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
- 239000008188 pellet Substances 0.000 claims description 22
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 19
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 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
- 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
- 125000004185 ester group Chemical group 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 238000006068 polycondensation 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
- QIHWDPWTUZQBNX-UHFFFAOYSA-N 3-(methoxy-methyl-penta-1,4-dien-3-yloxysilyl)propane-1,1,1-triamine Chemical compound C(=C)C(O[Si](OC)(C)CCC(N)(N)N)C=C QIHWDPWTUZQBNX-UHFFFAOYSA-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
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- ZDWRDFHIVPNKBD-UHFFFAOYSA-N ethene (methoxy-methyl-propylsilyl)oxymethanetriamine Chemical compound NC(O[Si](OC)(C)CCC)(N)N.C=C.C=C ZDWRDFHIVPNKBD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance 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
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000007788 liquid 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
- 238000012827 research and development Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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 molding 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 the 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 a preparation technology of a 3D printing materialThe technical field solves the problems that the polypropylene fused deposition molding granules in the prior art have the defects of low mechanical strength, large molding shrinkage, low impact toughness, poor creep resistance, poor wear resistance and the like.
Description
Technical Field
The invention relates to the technical field of preparation of 3D printing materials, in particular to modified polypropylene fused deposition molding granules and a preparation method thereof.
Background
Since the 80 s of the 20 th century, the 3D printing technology has attracted much attention because of its advantages of rapid molding in a short cycle and no need for a mold; the fused deposition modeling technology is a 3D printing technology which is most widely applied at present due to the advantages of low equipment investment, environmental friendliness, simple post-treatment, wide application range and the like. However, the conventional fused deposition modeling technology can only print a part of wires with high hardness, the materials with high elasticity and low hardness are easily extruded out, the process and the manufacturing cost of the coiled wires are increased in the process of manufacturing the coiled wires, and the research and development difficulty of the materials is even higher than that of equipment under common conditions.
The 3D printing technology of the granular materials breaks through the material limitation problem of the traditional fused deposition modeling technology, solves the problems of low consumable universality 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 is expected to be applied to the 3D printing technology due to low price, good physical and chemical properties and excellent processing performance, and the cost is reduced. However, the polypropylene materials on the market at present have the defects of low mechanical strength, large molding shrinkage, low impact toughness, poor creep resistance, poor wear resistance and the like, and meanwhile, the polypropylene can undergo 2-time phase change from solid to liquid to solid in the 3D printing process, and when the polypropylene is solidified and formed, the stress strain generated by material shrinkage can cause edge warping and the like, so that the precision and the performance of products are influenced, and the large-scale application of the polypropylene in the 3D printing field is difficult to realize. Therefore, if a modified polypropylene fused deposition molding granule with high mechanical strength, high impact toughness and strong wear resistance can be developed, the modified polypropylene fused deposition molding granule has a very high application prospect in the field of 3D printing.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a modified polypropylene fused deposition modeling pellet and a preparation method thereof, so as to solve 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 pellet in the prior art.
The technical scheme for solving the technical problems is as follows: the modified polypropylene fused deposition molding 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 10-1100 parts of polypropylene.
The invention has the beneficial effects that: the invention uses graphene/MoS 2 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 surface free energy and long flexible chain length of the polysiloxane, and can simultaneously play roles of strengthening and toughening, reducing friction and resisting wear for the polypropylene. Mixing MoS 2 The modified polypropylene fused deposition modeling aggregate is compounded with graphene, a synergistic effect can be achieved, the friction performance can be optimized due to the similarity of the structure and the morphology, the prepared modified polypropylene fused deposition modeling aggregate has the advantages of high mechanical strength, high impact toughness, strong wear resistance and the like, and the modified polypropylene fused deposition modeling aggregate has a wide application prospect in the field of aggregate fused deposition modeling.
Wherein, the structure of the hyperbranched polysiloxane is as follows:
wherein: -R = - (CH) 2 ) 3 -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2
On the basis of the technical scheme, the invention can be further improved as follows:
further, the 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 900-1100 parts of polypropylene.
Further, the granules comprise 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 6-9h, and performing vacuum drying to obtain graphene-loaded molybdenum disulfide composite particles;
(2) Mixing the graphene molybdenum disulfide-loaded composite particles prepared in the step (1) with glucose, carrying out ball milling for 5-10h, washing and vacuum drying to obtain graphene/MoS 2 Composite particles.
The beneficial effect of adopting the further technical scheme is as follows: prepared graphene/MoS 2 The composite particles can reach graphene/MoS 2 The best composite effect and the improved dispersibility.
Further, in the step (1), the mass ratio of molybdenum disulfide to graphene oxide is 2-5:1.
further, in the step (2), the mass ratio of the graphene-loaded molybdenum disulfide composite particles to glucose is 1:1-10.
Further, in the step (2), the mass ratio of ball materials subjected to ball milling treatment is 1-5:1.
further, in the step (2), the rotation 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), vacuum drying is carried out for 6-12h.
Further, the hyperbranched polysiloxane is prepared by the following method: under the protection of nitrogen, 1-tri (hydroxymethyl) ethane and diethylene triamino propyl methyl dimethoxy silane are mixed for ester exchange polycondensation reaction for 7-11h to prepare the hyperbranched polysiloxane.
The beneficial effects of adopting the further technical scheme are as follows: the method for preparing the hyperbranched polysiloxane is simple, low in equipment requirement, green and environment-friendly, not easy to cause a gel phenomenon, and stable in product.
Further, during ester exchange polycondensation, the temperature is raised to 100-120 ℃, the mixture is stirred until distillate is distilled off, and then the temperature is raised to 140-180 ℃ to prepare the hyperbranched polysiloxane.
Further, the heating speed is 10-15 ℃/min when the temperature is raised to 100-120 ℃.
Further, when the temperature is raised to 140-180 ℃, the temperature of distillate is 55-65 ℃.
Further, the molar ratio of 1, 1-tris (hydroxymethyl) ethane to divinyltriaminopropylmethyldimethoxysilane was 4:1-6.
The invention also provides a preparation method of the modified polypropylene fused deposition molding granules, which is to mix the graphene/MoS 2 And melting and mixing the composite particles, the hyperbranched polysiloxane and the polypropylene, cooling, and finally granulating to obtain the modified polypropylene fused deposition molding granules.
Further, the melt mixing conditions were: the temperature is 180-200 ℃, the rotating speed is 40-100rmp, and the material mixing time is 5-15min.
The invention also provides application of the modified polypropylene fused deposition modeling granule in 3D printing.
The invention has the following beneficial effects:
1. the preparation method is simple, easy to operate and easy to popularize.
2. The prepared modified polypropylene fused deposition modeling granular material has the advantages of high mechanical strength, high impact toughness, strong wear resistance and the like, and has wide application prospect in the field of granular material fused deposition modeling.
Drawings
FIG. 1 is a graph showing tensile strength measurements of pellets prepared in examples 1, 4 to 5 and comparative examples 1 to 3;
FIG. 2 is a graph showing the impact strength test of pellets obtained in examples 1, 4 to 5 and comparative examples 1 to 3;
FIG. 3 is a graph showing wear rate measurements of pellets prepared in examples 1, 4 to 5 and comparative examples 1 to 3.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
the modified polypropylene fused deposition molding 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.
The preparation process of fused deposition formed modified polypropylene granule includes the following steps:
(1) Molybdenum disulfide and graphene oxide are mixed according to the mass ratio of 3:1, mixing, adding hydrazine hydrate, condensing and refluxing for 7 hours, and performing vacuum drying after the reaction is finished to obtain graphene-loaded molybdenum disulfide composite particles;
(2) Mixing the graphene molybdenum disulfide-loaded composite particles prepared in the step (1) and glucose according to a mass ratio of 1:4, mixing, performing physical and chemical treatment in a ball mill for 7 hours, then washing with distilled water for 2 times, and drying in a vacuum drying oven for 7 hours to obtain the graphene/MoS 2 Composite particles; wherein, the ball material mass ratio is 2:1;
(3) Under the protection of nitrogen, 1-tri (hydroxymethyl) ethane and divinyltriaminopropylmethyl dimethoxysilane are mixed according to a molar ratio of 4:5.6, carrying out ester exchange polycondensation reaction for 8h, wherein the temperature is raised to 110 ℃ at the speed of 12 ℃/min, stirring is carried out until distillate is distilled, the temperature is gradually raised to 160 ℃ in the reaction process, and the distillation temperature is ensured to be 60 ℃ to prepare hyperbranched polysiloxane;
(4) Preparing the graphene/MoS prepared in the step (2) 2 And (3) putting the composite particles, the hyperbranched polysiloxane prepared in the step (3) and the polypropylene into a double-screw extruder, melting and mixing for 10min at 190 ℃ and 50rmp, then extruding, putting into a stainless steel container for cooling, and finally granulating in a plastic cutter to prepare the modified polypropylene fused deposition molding granules.
Example 2:
the modified polypropylene fused deposition molding pellet 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 process of fused deposition formed granule of modified polypropylene includes the following steps:
(1) Molybdenum disulfide and graphene oxide are mixed according to the mass ratio of 2:1, mixing, adding hydrazine hydrate, condensing and refluxing for 6 hours, and performing vacuum drying after the reaction is finished to obtain graphene-loaded molybdenum disulfide composite particles;
(2) Mixing the graphene molybdenum disulfide-loaded composite particles prepared in the step (1) with glucose according to a mass ratio of 1:1, mixing, performing physical and chemical treatment in a ball mill for 5 hours, then 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 mass ratio of the ball material is 5:1;
(3) Under the protection of nitrogen, 1-tri (hydroxymethyl) ethane and divinyltriaminopropylmethyl dimethoxysilane are mixed according to a molar ratio of 4:1, carrying out ester exchange polycondensation reaction for 7h, wherein the temperature is increased to 100 ℃ at the speed of 10 ℃/min, stirring is carried out until distillate is distilled out, the temperature is gradually increased to 140 ℃ in the reaction process, and the distillation temperature is ensured to be 55 ℃, so as to prepare hyperbranched polysiloxane;
(4) Preparing the graphene/MoS prepared in the step (2) 2 And (3) putting the composite particles, the hyperbranched polysiloxane prepared in the step (3) and the polypropylene into a double-screw extruder, melting and mixing for 15min at 180 ℃ and 40rmp, then extruding, putting into a stainless steel container for cooling, and finally granulating in a plastic cutting machine to prepare the modified polypropylene fused deposition molding granules.
Example 3:
the modified polypropylene fused deposition molding 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 process of fused deposition formed modified polypropylene granule includes the following steps:
(1) Molybdenum disulfide and graphene oxide are mixed according to the mass ratio of 5:1, mixing, adding hydrazine hydrate, condensing and refluxing for 9 hours, and performing vacuum drying after the reaction is finished to obtain graphene-loaded molybdenum disulfide composite particles;
(2) Mixing the graphene molybdenum disulfide-loaded composite particles prepared in the step (1) with glucose according to a mass ratio of 1:10, mixing, performing physical and chemical treatment in a ball mill for 10 hours, then washing with distilled water for 3 times, and drying in a vacuum drying oven for 12 hours to obtain graphene/MoS 2 Composite particles; wherein the mass ratio of the ball material is 1:1;
(3) Under the protection of nitrogen, 1-tri (hydroxymethyl) ethane and divinyltriaminopropylmethyl dimethoxysilane are mixed according to a molar ratio of 4:6, mixing, and carrying out ester exchange polycondensation reaction for 11h, wherein the temperature is raised to 120 ℃ at a speed of 15 ℃/min, stirring is carried out 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 as to prepare hyperbranched polysiloxane;
(4) Preparing the graphene/MoS prepared in the step (2) 2 And (4) putting the composite particles, the hyperbranched polysiloxane prepared in the step (3) and the polypropylene into a double-screw extruder, melting and mixing for 5min at 200 ℃ and 100rmp, then extruding, putting into a stainless steel container for cooling, and finally granulating in a plastic cutter to prepare the modified polypropylene melt deposition molding granules.
Example 4:
the modified polypropylene fused deposition molding pellet 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 example 1.
Example 5:
the modified polypropylene fused deposition molding pellet 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 that of example 1.
Comparative example 1:
a modified polypropylene fused deposition modeling granule comprises the following componentsThe weight parts of the raw materials are as follows: 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 that of example 1.
Comparative example 2:
the modified polypropylene fused deposition molding 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 example 1.
Comparative example 3:
the modified polypropylene fused deposition molding granule comprises 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 example 1.
Test examples
1. The pellets obtained in examples 1, 4 to 5 and comparative examples 1 to 3 were subjected to tensile strength, impact strength and wear rate tests by the following specific test methods: see GB 1040-79, GB 2567-2008, GB 3980-83, the results are shown in FIGS. 1-3. As can be seen from FIGS. 1 to 3, the modified polypropylene fused deposition modeling pellets obtained by the present invention have higher tensile strength and impact strength, and lower wear rate, while the pellets obtained by the comparative example have a poor effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. The modified polypropylene fused deposition molding granule is characterized by comprising 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.
2. The modified polypropylene fused deposition modeling pellet of claim 1, wherein the graphene/MoS is 2 CompoundingThe particles were prepared by the following method:
(1) Mixing molybdenum disulfide and graphene oxide, adding hydrazine hydrate, condensing and refluxing for 6-9h, and performing vacuum drying to obtain graphene-loaded molybdenum disulfide composite particles;
(2) Mixing the graphene molybdenum disulfide-loaded composite particles prepared in the step (1) with glucose, performing ball milling treatment for 5-10h, and then washing and vacuum drying to prepare graphene/MoS 2 Composite particles.
3. The modified polypropylene fused deposition modeling pellet as claimed in claim 2, wherein in step (1), the mass ratio of molybdenum disulfide to graphene oxide is 2-5:1.
4. the modified polypropylene fused deposition modeling pellet as claimed in claim 2, wherein in step (2), the mass ratio of the graphene-molybdenum disulfide-loaded composite particles to glucose is 1:1-10.
5. The modified polypropylene fused deposition modeling pellet of claim 1, wherein the hyperbranched polysiloxane is prepared by the following method: under the protection of nitrogen, 1-tri (hydroxymethyl) ethane and diethylene triamino propyl methyl dimethoxy silane are mixed for ester exchange polycondensation reaction for 7-11h to prepare the hyperbranched polysiloxane.
6. The modified polypropylene fused deposition modeling pellet as claimed in claim 5, wherein the hyperbranched polysiloxane is prepared by heating to 100-120 ℃ during ester exchange polycondensation reaction, stirring until distillate is distilled off, and then heating to 140-180 ℃.
7. The modified polypropylene fused deposition modeling pellet of claim 5, wherein the molar ratio of 1, 1-tris (hydroxymethyl) ethane to divinyltriaminopropylmethyldimethoxysilane is 4:1-6.
8. According to the rightThe method for preparing a modified polypropylene fused deposition modeling pellet as claimed in any one of claims 1 to 7, wherein the graphene/MoS is prepared 2 And melting and mixing the composite particles, the hyperbranched polysiloxane and the polypropylene, cooling, and finally granulating to obtain the modified polypropylene melt deposition molding granules.
9. The method for preparing a modified polypropylene fused deposition modeling pellet as claimed in claim 8, wherein the melt mixing conditions are: the temperature is 180-200 ℃, the rotating speed is 40-100rmp, and the mixing time is 5-15min.
10. Use of the modified polypropylene fused deposition modeling pellet of claim 1 for 3D printing.
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