CN109294072B - Polypropylene composition, polypropylene material and application thereof - Google Patents
Polypropylene composition, polypropylene material and application thereof Download PDFInfo
- Publication number
- CN109294072B CN109294072B CN201710616899.3A CN201710616899A CN109294072B CN 109294072 B CN109294072 B CN 109294072B CN 201710616899 A CN201710616899 A CN 201710616899A CN 109294072 B CN109294072 B CN 109294072B
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- polypropylene composition
- parts
- weight
- compatilizer
- 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
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
- C08L23/14—Copolymers of propene
-
- 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
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention belongs to the technical field of polymer processing, and particularly provides a polypropylene composition, a polypropylene material and application thereof. The polypropylene composition comprises, based on the total weight of the polypropylene composition: 60-86 wt% of polypropylene, 8-30 wt% of barium sulfate, 3-10 wt% of compatilizer and 0.01-0.5 wt% of antioxidant; the compatilizer is prepared by melt blending POE, glycidyl methacrylate and polyethylene glycol, wherein the dosage of the glycidyl methacrylate is 1-5 parts by weight and the dosage of the polyethylene glycol is 3-20 parts by weight relative to 100 parts by weight of POE. The polypropylene material provided by the invention overcomes the defects of poor toughness, large molding shrinkage and the like of polypropylene, is suitable for selective laser sintering 3D printing, and has low energy consumption for preparation of the material.
Description
Technical Field
The invention belongs to the technical field of polymer processing, and particularly relates to a polypropylene composition, a polypropylene material prepared from the polypropylene composition, and an application of the polypropylene material.
Background
Selective Laser Sintering (SLS) technology is a rapid prototyping technology, is the most widely used and promising technology in plastic material manufacturing technology, and has recently shown a rapid development trend as a key part of 3D printing technology. The SLS technique is a technique in which a three-dimensional solid is first scanned by a computer, and then material powder previously laid on a table or a part is selectively melted and sintered layer by high-intensity laser irradiation, thereby realizing layer-by-layer molding. The SLS technique has high design flexibility, can produce precise models and prototypes, can form parts with reliable structures that can be used directly, and has short production cycle and simple process, thus being particularly suitable for the development of new products.
The molding materials suitable for the SLS technique are widely available, including polymers, paraffins, metals, ceramics and their composites. However, the properties and properties of the molding material are important factors for the successful sintering of the SLS technology, and directly affect the molding speed, precision, physical and chemical properties and comprehensive properties of the molded part. Despite the wide variety of suitable molding materials, the polymer powder raw materials which can be directly applied to the SLS technology and successfully produce molded products with small dimensional errors, regular surfaces and low porosity are few. In the prior art, the preparation method of the non-metallic material applied to the SLS technology mainly comprises the following steps: the plastic strip raw material is prepared by extrusion blending and the powder raw material is prepared by a crushing method. However, the cryogenic grinding method not only requires special equipment, but also produces rough surface, uneven particle size and irregular shape of the raw powder particles, which is not favorable for forming sintered compact and affects the performance of the compact.
At present, most of SLS technologies in the market use polymer materials, but in the using process, due to shrinkage of the materials and uneven material quality of the materials, a plurality of processing problems are caused, so that the production of high-quality polymer materials is in need of development. The most common selective laser sintering 3D printing materials on the market are ABS and PLA. The ABS has good mechanical property, particularly high toughness, is widely applied to industrial 3D printing, but generates unpleasant gas during printing, is not suitable for environments such as offices and the like, and is opaque; PLA has no unpleasant odor and can be degraded when being printed and melted, but has poor heat resistance and poor mechanical property, and is easy to generate brittle fracture particularly, thereby greatly limiting the use of printed objects.
In addition, polypropylene (PP) has advantages of low density, high strength, heat resistance, good insulation, low price, excellent chemical stability, etc., and thus is one of general-purpose plastics which are widely researched and applied at present, is favored in the fields of home appliances, automobiles, plastic pipes, etc., and has application potential in SLS technology, but has disadvantages of poor impact resistance, poor toughness, large molding shrinkage, etc., and has disadvantages of easy shrinkage of products, deformation and warpage, brittle products, etc., when 3D printing is performed, so that it is limited in 3D printing.
In decades of plastic material development, low cost and high performance become the main development direction of plastic materials, and the specific gravity of filling composite materials is getting larger and larger. The requirement for SLS rapid molding polypropylene materials is higher and higher, and the main direction of research is to solve the problems of easy aging, large shrinkage and the like of the materials. The commonly used inorganic fillers comprise calcium carbonate, mica, wollastonite and the like, the added fillers can effectively improve the shrinkage rate of the material and prolong the service life of the material, but the toughness of the material is obviously reduced, and the phase separation of two-phase materials brings serious defects to the performance of a product, so that how to prepare the qualified selective laser sintering 3D printing filling polypropylene material is the key point of material research.
At present, there is a need to develop a filled polypropylene composite material with high strength, high toughness and low shrinkage for selective laser sintering 3D printing to overcome the limitations of 3D printing materials.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a polypropylene composition, a polypropylene material prepared from the polypropylene composition, and applications of the polypropylene material.
According to a first aspect of the present invention, there is provided a polypropylene composition comprising, based on the total weight of the polypropylene composition: 60-86 wt% of polypropylene, 8-30 wt% of barium sulfate, 3-10 wt% of compatilizer and 0.01-0.5 wt% of antioxidant;
the compatilizer is prepared by melt blending POE, glycidyl methacrylate and polyethylene glycol, wherein the dosage of the glycidyl methacrylate is 1-5 parts by weight and the dosage of the polyethylene glycol is 3-20 parts by weight relative to 100 parts by weight of POE.
According to a second aspect of the present invention, there is provided a polypropylene material obtained by melt blending and molding the above-mentioned polypropylene composition.
According to a third aspect of the present invention, the present invention provides the use of the above-described polypropylene material for selective laser sintering 3D printing.
In the polypropylene composition, the compatilizer can improve the processing performance of the polypropylene material and can obtain the polypropylene material with excellent mechanical property. Specifically, the compatilizer can accelerate the crystallization speed of polypropylene, improve the molding speed, refine the spherulite size, improve the compatibility among materials and reduce the energy consumption in the production process of the materials; the polypropylene material has tensile strength of more than or equal to 28MPa, elongation of more than or equal to 4 percent, bending strength of more than or equal to 32MPa, bending modulus of more than or equal to 1.5MPa, and impact strength of a notch of a simply supported beam: not less than 6.3kJ/m2(23℃)、≥3.5kJ/m2The polypropylene material with the mechanical property parameters can be used as a selective laser sintering 3D printing material, overcomes the defects of large shrinkage rate, low toughness and the like of polypropylene, reduces the preparation energy consumption of the material and reduces the cost.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given with reference to the accompanying embodiments, which are given by way of illustration only and are not intended to limit the invention.
According to a first aspect of the present invention, there is provided a polypropylene composition comprising, based on the total weight of the polypropylene composition: 60-86 wt% of polypropylene, 8-30 wt% of barium sulfate, 3-10 wt% of compatilizer and 0.01-0.5 wt% of antioxidant;
the compatilizer is prepared by melt blending POE, Glycidyl Methacrylate (GMA) and polyethylene glycol, wherein the using amount of the glycidyl methacrylate is 1-5 parts by weight and the using amount of the polyethylene glycol is 3-20 parts by weight relative to 100 parts by weight of the POE.
Preferably, the amount of GMA is 1 to 3 parts by weight and the amount of polyethylene glycol is 10 to 20 parts by weight, based on 100 parts by weight of POE.
The number average molecular weight of the polyethylene glycol can be 4000-8000, and is preferably 6000.
According to the invention, the compatilizer can be prepared by adopting a method which comprises the following steps:
1) mixing POE, GMA and polyethylene glycol to obtain a mixed material;
2) reacting and extruding the mixed material in melt blending equipment to obtain a molten material;
3) and cooling, granulating and drying the molten material to obtain the compatilizer.
In the preparation process of the compatilizer, the temperature of the melt blending reaction can be the conventional blending temperature used in POE processing, as long as the complete melting of the matrix resin can be ensured and the matrix resin is not decomposed. Preferably, the temperature of the melt blending reaction is 210-230 ℃.
In the present invention, the polypropylene may be a random copolymer polypropylene, and the comonomer is ethylene. Preferably, the melt flow index of the polypropylene at 230 ℃ under a load of 2.16kg is 20-40 g/10 min. Additionally, the polypropylene is commercially available, for example under the designation 7726, 9020.
In the invention, barium sulfate is used as a filler, and has good thermal stability, dimensional stability and aging resistance, low product shrinkage and low linear expansion coefficient. The barium sulfate may be a technical grade product. The particle size of the barium sulfate can be 15-25 μm, and is preferably 20 μm.
In the invention, the antioxidant is added to prevent or delay the oxidative degradation reaction of the polypropylene material, thereby prolonging the service life of the polypropylene material, and particularly when the dosage is in the range, the polypropylene material with stable property and longer service cycle can be obtained. The antioxidant may be selected from hindered phenolic antioxidants and/or phosphite antioxidants.
Specifically, examples of the hindered phenol type macromolecular antioxidant may include, but are not limited to: 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide and pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010).
Examples of the phosphorous-based antioxidant may include, but are not limited to: tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), tetrakis- (2, 4-di-tert-butylphenyl) -4, 4 '-biphenylbisphosphite (P-EPQ), octaethylpentaerythritol tetraphosphite, 2' -ethylenebis (4, 6-di-tert-butylphenyl) fluorophosphite.
Preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite. Further, the weight ratio of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] to tris [2, 4-di-tert-butylphenyl ] phosphite may be 0.8 to 1.2: 1.
In addition, other common additives (such as nucleating agent) can be included in the polypropylene composition according to the processing and application requirements of the polypropylene composition, and the amount of the additives can be selected conventionally. Such as: the polypropylene composition can also comprise 0.1-0.5 wt% of a nucleating agent.
According to a second aspect of the present invention, there is provided a polypropylene material obtained by melt blending and molding the above-mentioned polypropylene composition.
The specific preparation method of the polypropylene material can comprise the following steps:
1) uniformly mixing all components contained in the polypropylene composition to obtain a mixed material;
2) reacting and extruding the mixed material in melt blending equipment to obtain a molten material;
3) and cooling, granulating and drying the molten material to obtain the polypropylene material.
In the present invention, the materials can be mixed by using various mixing devices in the prior art, such as a stirrer, a kneader, etc. The material mixing equipment is preferably a high-speed stirrer, and the specific use method can be as follows: and (3) dry-mixing the materials to be mixed in a high-speed stirrer for 1-3 minutes to obtain uniform mixed materials.
In the process for producing a polypropylene material according to the present invention, the melt blending temperature is a blending temperature generally used in polypropylene processing, as long as complete melting of the matrix resin is ensured without decomposition thereof. Preferably, the temperature of the melt blending is 225 to 250 ℃.
In the invention, the melt blending equipment used in the preparation of the compatilizer and the polypropylene material can be general blending equipment in the rubber and plastic processing industry, such as: twin screw extruders, single screw extruders, roll mills, internal mixers or BUSS mixing units, etc. Preferably, a double-screw extruder is selected for melt blending extrusion granulation. The rotating speed of the screw during extrusion can be 150-360 rpm.
The polypropylene material with any shape, such as a cylindrical material with a circular cross section and a diameter of 1.75 +/-0.2 mm, can be prepared by adopting the method.
The preparation method of the polypropylene material has simple steps and easy operation, and can obtain the polypropylene material with the shape, the character and the like which are particularly suitable for selective laser sintering 3D printing.
According to a third aspect of the present invention, the present invention provides the use of the above-described polypropylene material for selective laser sintering 3D printing.
The present invention will be described in detail below with reference to examples.
In the following examples and comparative examples:
PP: number 7726, Zhongpetrochemical Yanshan.
Barium sulfate: technical grade, particle size 20 μm.
POE: number 7367, du pont, usa.
GMA: guangzhou Runbang chemical Co., Ltd.
Polyethylene glycol: the trade mark PEG 6000.
The torque values were observed on-line through the twin-screw extruder.
Determination of tensile Properties Standard: ISO 527: 1993.
measurement criteria for flexural Properties: ISO 178; 1993.
the determination standard of the impact strength of the simply supported beam is as follows: ISO 179: 1993.
example 1
This example illustrates the polypropylene composition and polypropylene material of the present invention.
The composition of the polypropylene composition is as follows, based on the total weight of the polypropylene composition: 70 parts of polypropylene, 30 parts of barium sulfate, 5 parts of compatilizer and 0.32 part of antioxidant (the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1: 1).
Based on the total weight of the compatilizer, the compatilizer is prepared by melting and blending 100 parts of POE, 3 parts of GMA and 15 parts of polyethylene glycol. Specifically, adding POE, GMA and polyethylene glycol into a high-speed stirrer, stirring for 3 minutes at normal temperature to uniformly mix the materials, injecting the mixed materials into a reactive double-screw extruder through a liquid metering pump, melting and blending at 210-230 ℃ with the screw rotating speed of 300rpm, and extruding and granulating to obtain the compatilizer.
The polypropylene material is prepared by melt extrusion and molding of the polypropylene composition. Specifically, adding polypropylene, barium sulfate, a compatilizer and a stabilizer into a high-speed stirrer, stirring for 3 minutes at normal temperature to uniformly mix the materials, carrying out melt blending on the mixed materials in a reactive double-screw extruder at the melt blending temperature of 225-250 ℃ and the screw rotation speed of 300rpm, and carrying out extrusion granulation to obtain the polypropylene material.
Examples 2 to 3
A polypropylene material was prepared by referring to the method of example 1, except that the polypropylene composition of example 2 was 80 parts polypropylene and 20 parts barium sulfate, and the polypropylene composition of example 3 was 90 parts polypropylene and 10 parts barium sulfate.
Examples 4 to 6
Examples 4 to 6 the polypropylene materials were prepared by the methods 1 to 3, respectively, except that the polypropylene composition contained 7 parts of the compatibilizer.
Examples 7 to 9
Examples 7 to 9 Polypropylene materials were prepared according to methods 1 to 3, respectively, except that 10 parts of a compatibilizer was used in the polypropylene composition.
Comparative example 1
The polypropylene material of this comparative example was prepared in the same manner as in example 1, except that the polypropylene composition did not contain barium sulfate and a compatibilizer.
Comparative examples 2 to 4
The preparation methods of the polypropylene materials in comparative examples 2 to 4 are the same as those in examples 1 to 3, respectively, except that the polypropylene composition does not contain a compatibilizer.
Comparative example 5
The polypropylene material of this comparative example was prepared in the same manner as in example 3, except that the polypropylene composition contained 10 parts of polyethylene glycol and no compatibilizer.
Comparative example 6
The polypropylene material of this comparative example was prepared by the same procedure as in example 9, except that the compatibilizer in the polypropylene composition was prepared by melt blending 100 parts POE and 3 parts GMA.
The torque values of the polypropylene materials obtained in each of the examples and comparative examples were measured, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the addition of the compatibilizer can reduce the torque value of the polypropylene material, and as the weight fraction of the compatibilizer increases (from 5 to 10 weight fractions), the torque value of the polypropylene material decreases to a greater extent, and this change rule applies even if the contents of polypropylene and calcium sulfate in the polypropylene material are changed. In addition, the reduction of the torsion value of the polypropylene material can be realized by independently adding polyethylene glycol, but the compatilizer prepared from POE and GMA cannot play a role in reducing the torsion value, and the torque value generated by extrusion pressure is larger on the contrary because the POE material and the GMA generate a crosslinking reaction in the twin-screw extrusion process. Along with the increase of the filling amount of the material, the load of equipment is increased, the working efficiency is restricted in the actual production process, and the compatilizer disclosed by the invention can reduce the torsion value of the polypropylene material, so that the processing energy consumption of the polypropylene material is reduced, the production efficiency of the material is improved, and the production cost of the material is reduced.
The polypropylene materials of the respective examples and comparative examples were measured for their physical and mechanical properties, and the results are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, the addition of the compatibilizer improves the overall performance of the polypropylene material, improves the impact strength and toughness of the material, and also improves the tensile strength and flexural strength of the material, as compared to a polypropylene material that does not contain a compatibilizer, and also improves the toughness of the material as the addition of the compatibilizer increases, it is expected that the increase in the bonding area between the components of the composition is promoted by the increase in the compatibilizer, which increases the toughness of the material.
In addition, although the energy consumption problem in the material processing process can be effectively solved by adding the polyethylene glycol, the physical and mechanical properties of the material are obviously reduced because the polypropylene and the filling material added into the polyethylene glycol are subjected to more severe phase separation, and the quality of the material cannot be guaranteed; in addition, the polypropylene material prepared by the compatilizer without polyethylene glycol has lower tensile strength, bending strength and the like.
The compatilizer plays a role in determining the physical and mechanical properties of the composite material in the melting process of the components of the composition, and the compatilizer is utilized to make up for the defects of the polypropylene material in the rapid sintering process, so that the material part of the invention has more stable size and more excellent performance, and the development of the polypropylene composite material of the invention widens a new direction for the development of the polypropylene material.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (8)
1. A polypropylene composition, characterized in that the polypropylene composition consists of, based on the total weight of the polypropylene composition: 60-86 wt% of polypropylene, 8-30 wt% of barium sulfate, 3-10 wt% of compatilizer and 0.01-0.5 wt% of antioxidant;
the compatilizer is prepared by melt blending POE, glycidyl methacrylate and polyethylene glycol, wherein the using amount of the glycidyl methacrylate is 1-5 parts by weight, the using amount of the polyethylene glycol is 3-20 parts by weight and the number average molecular weight of the polyethylene glycol is 4000-8000 relative to 100 parts by weight of POE.
2. The polypropylene composition according to claim 1, wherein the polypropylene has a melt flow index of 20 to 40g/10min at 230 ℃ under a 2.16kg load.
3. The polypropylene composition according to claim 1, wherein the antioxidant is selected from hindered phenolic antioxidants and/or phosphite antioxidants.
4. The polypropylene composition according to claim 3, wherein the antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite.
5. The polypropylene composition according to claim 1, wherein the melt blending reaction temperature is from 210 to 230 ℃.
6. A polypropylene material obtained by melt-blending and molding the polypropylene composition according to any one of claims 1 to 5.
7. The polypropylene material according to claim 6, wherein the melt blending temperature is 225 to 250 ℃.
8. Use of the polypropylene material according to claim 6 or 7 for selective laser sintering 3D printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710616899.3A CN109294072B (en) | 2017-07-25 | 2017-07-25 | Polypropylene composition, polypropylene material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710616899.3A CN109294072B (en) | 2017-07-25 | 2017-07-25 | Polypropylene composition, polypropylene material and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109294072A CN109294072A (en) | 2019-02-01 |
| CN109294072B true CN109294072B (en) | 2021-11-19 |
Family
ID=65167950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710616899.3A Active CN109294072B (en) | 2017-07-25 | 2017-07-25 | Polypropylene composition, polypropylene material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109294072B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532687A (en) * | 2010-12-21 | 2012-07-04 | 上海日之升新技术发展有限公司 | Composite material with low shrinkage rate and preparation method thereof |
| 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 |
| CN105440613A (en) * | 2015-11-05 | 2016-03-30 | 张晓军 | PLA 3D printing material and product thereof |
| CN105906940A (en) * | 2016-05-27 | 2016-08-31 | 中山大学惠州研究院 | Marble or wood 3D printing plastic and preparation method thereof |
| CN106633363A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Polypropylene composition for 3D printing, and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100233146A1 (en) * | 2002-09-09 | 2010-09-16 | Reactive Surfaces, Ltd. | Coatings and Surface Treatments Having Active Enzymes and Peptides |
| US8530577B2 (en) * | 2008-06-30 | 2013-09-10 | Fina Technology, Inc. | Compatibilized polypropylene heterophasic copolymer and polylactic acid blends for injection molding applications |
-
2017
- 2017-07-25 CN CN201710616899.3A patent/CN109294072B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532687A (en) * | 2010-12-21 | 2012-07-04 | 上海日之升新技术发展有限公司 | Composite material with low shrinkage rate and preparation method thereof |
| CN106633363A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Polypropylene composition for 3D printing, and preparation method thereof |
| CN105440613A (en) * | 2015-11-05 | 2016-03-30 | 张晓军 | PLA 3D printing material and product thereof |
| 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 |
| CN105906940A (en) * | 2016-05-27 | 2016-08-31 | 中山大学惠州研究院 | Marble or wood 3D printing plastic and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Effect of interfacial structure on crystallization behavior of polypropylene/polyolefin elastomer/barium sulfate ternary composites;Wu, Hong et al.;《JOURNAL OF MACROMOLECULAR SCIENCE PART B-PHYSICS》;TAYLOR & FRANCIS INC, 530 WALNUT STREET, STE 850, PHILADELPHIA, PA 19106 USA;20070308;第46卷(第2期);第329-339页 * |
| MAPP－g－PEG 增容聚丙烯木塑复合材料的研究;赵秀琴 等;《湖北农业科学》;20130405;第52卷(第7期);第1641-1643页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109294072A (en) | 2019-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107099077B (en) | Method for preparing conductive resin composition | |
| KR101309738B1 (en) | Polymer/conductive filler composite with high electrical conductivity and the preparation method thereof | |
| US20200248014A1 (en) | Thermally conductive polymer based filament | |
| CN104031316A (en) | Ultra-low density polypropylene composite material capable of being used for 3D printing and preparation method thereof. | |
| JP6527010B2 (en) | Thermally conductive resin molding and method for producing the same | |
| JP2006097006A (en) | Method for producing electrically conductive resin composition and application thereof | |
| CN101418121B (en) | Low melting point nylon 6 and preparation method thereof | |
| CN107974025B (en) | Non-filling low-shrinkage polypropylene composite material and preparation method thereof | |
| CN114539750A (en) | Copolymerization toughening modification material for 3D printing PLA and preparation method thereof | |
| CN102532706B (en) | Preparation method of polypropylene composite material with high strength and high toughness | |
| CN109294072B (en) | Polypropylene composition, polypropylene material and application thereof | |
| CN109294145B (en) | PS/ASA alloy composition, PS/ASA alloy material and application thereof | |
| CN114395242B (en) | High-heat-conductivity POK composite material and preparation method and application thereof | |
| JP2021011563A (en) | Resin composition and molded article | |
| KR101812884B1 (en) | Polylactic acid composition of filament for improving printing speed | |
| JP7073115B2 (en) | pellet | |
| CN111187456B (en) | High-density polyethylene composition, preparation method thereof, 3D printing material and application thereof | |
| CN112063169A (en) | Bio-based PA56/ABS alloy and preparation method thereof | |
| CN112708260A (en) | Nylon 6 composite material, preparation method and application | |
| JP5916532B2 (en) | Polyphenylene sulfide resin / polyamide 46 resin composite material | |
| EP3620489B1 (en) | Electrically conductive resin composition and preparation method thereof | |
| EP3626778B1 (en) | Electrically conductive resin composition and preparation method thereof | |
| CN107304293B (en) | Formed product of polyphenylene sulfide resin composition containing weld line | |
| KR20200120703A (en) | Polyamide composition for liquid assisted injection molding applications | |
| CN109280317B (en) | Fiber-exposed metal fiber acrylonitrile-butadiene-styrene/polycarbonate alloy material 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 |