CN105330970A - Polypropylene transparent material for fused deposition molding and preparation method thereof - Google Patents

Abstract

The invention discloses a polypropylene transparent material for fused deposition molding and a preparation method thereof. It is made of the following raw materials: 70-99 parts of polypropylene, 0.1-1 part of transparent agent, 1-2 parts of compatibilizer, Lubricant 0.9-3 parts, plasticizer 0.1-5 parts, stabilizer 0.01-0.5 parts. After the transparent agent is added in the present invention, the phenomenon of large-area crystallization during cooling and molding of polypropylene is suppressed, the light transmittance of the polypropylene material is greatly improved, and the polypropylene parts obtained by fusion deposition molding have better toughness and improved mechanical properties. , stronger practicability, and greatly reduced material cost, which is conducive to expanding the application of polypropylene materials in the field of fused deposition molding. The preparation method of the polypropylene transparent material of the present invention is easy to operate, has relatively low requirements on process conditions and production equipment, can realize large-scale promotion and production, has broad market prospects and excellent market benefits.

Description

A kind of polypropylene transparent material for fused deposition molding and preparation method thereof

technical field

The invention belongs to the fields of 3D printing technology and plastic processing, and in particular relates to a polypropylene transparent material for fused deposition molding and a preparation method thereof.

Background technique

3D printing technology, also known as additive manufacturing technology, is a technology based on digital model files and using bondable materials such as powdered metal or plastic to construct objects by layer-by-layer printing. 3D printing technology has been applied in many fields such as information technology, material science, and precision machinery, and it is becoming more and more competitive in today's manufacturing industry, so it is called "manufacturing technology with industrial revolution significance". 3D printing technology breaks through the traditional material deformation molding and removal molding process, and can quickly manufacture three-dimensional solid parts of any complex shape without fixtures or molds, and can effectively reduce the product development cycle. .

As a kind of 3D printing technology, Fused Deposition Molding (Fused Deposition Molding, FDM) is a method of processing thermoplastic filaments through solid-melt-solid two phase transitions. The thermoplastic filament is fed into the nozzle by the wire feeding mechanism, and heated to a molten state in the nozzle. The molten material is extruded from the nozzle, and is selectively coated with the movement of the heating nozzle according to the two-dimensional cross-sectional information given by the computer. After one layer is completed, the nozzle rises to a layer height (or the workbench drops to a layer height), and then the next layer is coated, and so on, finally forming a three-dimensional part.

As one of the five general-purpose resins, polypropylene (PP) has the advantages of low density, high strength, heat resistance, good insulation, stable chemical properties and low price, and has broad application prospects in the field of FDM. However, in the FDM process, PP is prone to large-area crystallization when it is cooled and formed. On the one hand, it leads to poor light transmission, and the printed part is opaque macroscopically. On the other hand, the printed part is easy to shrink and deform, resulting in warping and brittle products Defects, which greatly limit the application of PP in the field of FDM.

Adding inorganic fillers to PP is currently a conventional solution to reduce shrinkage deformation of printed parts and improve molding accuracy. Patent CN201310024331 discloses a PP composite material containing mineral powder filler, which has low shrinkage after printing and good dimensional stability. Patent CN201410717691 relates to thermoplastic materials containing inorganic fillers (including ceramic powder, metal powder, ceramic and metal composite powder). Patent CN201310149323 mentions adding nanocellulose to engineering plastics to improve thermal stability. Although the shrinkage and deformation of the material are weakened after printing and the toughness is improved, the addition of inorganic fillers makes PP more opaque, which cannot meet the requirements for PP light transmission in special occasions. In addition, when the amount of inorganic filler is too large, it is easy to block the nozzle of the FDM printer, and the mechanical properties of the printed part will also be significantly reduced.

Based on the above content, in order to promote the application of PP in the field of FDM, while ensuring that the shrinkage deformation of the material is weakened and the toughness is improved, it is urgent to solve the problem of PP light transmission.

Contents of the invention

The purpose of the present invention is to provide a polypropylene transparent material for fused deposition molding to overcome the opaque defects of existing polypropylene materials for fused deposition molding due to crystallization and inorganic fillers. The addition of a transparent agent can avoid the occurrence of large-area crystallization. Improve the light transmittance of polypropylene materials, while improving the light transmittance of polypropylene materials, enhance the toughness of polypropylene materials, reduce the shrinkage and deformation of printed parts, and expand the application of polypropylene materials in the field of fused deposition molding.

Another object of the present invention is to provide a method for preparing a polypropylene transparent material for fused deposition molding, which has a simple process and low cost, and can quickly produce a polypropylene transparent material that meets the requirements of fused deposition molding.

To achieve the above object, the present invention adopts the following technical solutions:

A polypropylene transparent material for fused deposition molding, which is made of the following raw materials in parts by weight: 90-99 parts of polypropylene, 0.1-1 part of transparent agent, 1-2 parts of compatibilizer, and 0.9 parts of lubricant -3 parts, plasticizer 0.1-5 parts, stabilizer 0.01-0.5 parts.

The polypropylene is at least one of polymers obtained by the polymerization of propylene alone or polymers obtained by the copolymerization of propylene and other olefins.

Described transparent agent is sorbitol derivative, and its general chemical structure formula is , where the group R is , , , one or a combination of them.

The compatibilizer is maleic anhydride grafted polypropylene.

The lubricant is one or a combination of polyolefin, stearylamide lubricant or polyethylene glycol.

The plasticizer is one or more of dioctyl phthalate, epoxidized soybean oil, and glycerin.

The stabilizer is one or a mixture of hindered phenol macromolecular antioxidants, phosphorous acid antioxidants or alkyl ester antioxidants.

A preparation method of polypropylene transparent material for fused deposition molding, the steps are as follows:

(1) Mixing of reagents and raw materials: first put polypropylene into the mixer, then add transparent agent, lubricant and plasticizer, and stir until the surface of the particles is liquid and bright, that is, stir evenly. After the mixing is completed, add anti Oxidizing agent carries out follow-up mixing, continues to mix 2 minutes, finally obtains mixed raw material;

(2) Heating extrusion: Add the mixed raw materials into the twin-screw extruder, and keep the feeding speed uniform and smooth to ensure that there is no blockage during the extrusion process, and the filament is stable and smooth;

(3) Rolling wire: by installing a die at the exit of the extruder, the diameter of the wire is limited to 1.75±0.05mm, and finally the wire is collected and shaped by a disc device.

In the twin-screw extrusion process in the step (2), the temperature in the first stage is 210°C, the temperature in the second stage is 240°C, and the temperature in the third stage is 210°C.

By means of the above-mentioned technical scheme, the advantages and beneficial effects that the present invention has are:

1. After adding the transparent agent in the present invention, the phenomenon of large-area crystallization during cooling and molding of polypropylene is suppressed, and the light transmittance of the polypropylene material is greatly improved.

2. The transparent agent can endow the polypropylene parts obtained by FDM with better toughness, improved mechanical properties and stronger practicability.

3. Adding a small amount of transparent agent can achieve the effect of improving light transmittance and toughness, and the cost of materials is greatly reduced, which is conducive to expanding the application of polypropylene materials in the field of FDM.

4. The preparation method of the polypropylene transparent material of the present invention is easy to operate, requires relatively low process conditions and production equipment, can realize large-scale promotion and production, has broad market prospects, and excellent market benefits.

detailed description

The features, benefits and advantages of the present invention will become apparent to those skilled in the art from reading the disclosure of this specification.

All formulation and testing herein took place at a 25°C environment unless otherwise specified.

Herein "comprises", "comprising", "comprising", "containing", "having" or other variations thereof are intended to cover non-closed inclusions and no distinction is made between these terms. The term "comprising" means that other steps and ingredients can be added which do not affect the end result. The term "comprising" also includes the terms "consisting of" and "consisting essentially of". The compositions and methods/processes of the present invention may comprise, consist of and consist essentially of the essential elements and limitations described herein and any additional or optional ingredients, components, steps or limitations described herein .

Without further elaboration, it is believed that one skilled in the art, using the preceding description, can utilize the present invention to its fullest extent. The following examples are intended to further describe and demonstrate specific embodiments within the scope of the present invention. Therefore, the examples should be understood only to illustrate the present invention in more detail, but not to limit the content of the present invention in any way.

The following examples further illustrate preferred embodiments within the scope of the present invention. These examples are illustrative only and do not limit the scope of the invention, since many changes may be made in the invention without departing from its spirit and scope.

Example 1

The polypropylene transparent material for fused deposition molding of this embodiment is made of the following raw materials: polypropylene 99g, transparent agent 0.1g, compatibilizer 1g, lubricant 1g, plasticizer 0.9g, stabilizer 0.2 g.

The polypropylene is a polymer obtained by polymerizing propylene alone. The polypropylene material used is produced by Sinopec Yangzi Petrochemical Co., Ltd., the brand is M02-V, and the transparent agent is tris(3,4,5-dimethyl Dibenzylidene) sorbitol, compatibilizer is maleic anhydride grafted polypropylene, lubricant is polyolefin, plasticizer is dioctyl phthalate, stabilizer is hindered phenol macromolecular antioxidant .

The preparation method of the polypropylene transparent material for fused deposition molding in this embodiment, the steps are as follows:

(1) Mixing of reagents and raw materials: first put polypropylene into the mixer, then add transparent agent, lubricant and plasticizer, and stir until the surface of the particles is liquid and bright, that is, stir evenly. After the mixing is completed, add anti Oxidizing agent carries out follow-up mixing, continues to mix 2 minutes, finally obtains mixed raw material;

(2) Heated extrusion: Add the mixed raw materials into the twin-screw extruder, keep the feeding speed uniform and smooth, ensure that there will be no blockage during the extrusion process, the filament will be stable and smooth, and the temperature in the first stage of the twin-screw extrusion process 210°C, the temperature of the second stage is 240°C, and the temperature of the third stage is 210°C;

(3) Rolling wire: by installing a die at the exit of the extruder, the diameter of the wire is limited to 1.75±0.05mm, and finally the wire is collected and shaped by a disc device.

Example 2

The polypropylene transparent material for fused deposition molding of this embodiment is made of the following raw materials: polypropylene 99g, transparent agent 0.1g, compatibilizer 1g, lubricant 1g, plasticizer 0.9g, stabilizer 0.2 g;

The polypropylene is a polymer obtained by copolymerization of propylene and other olefins, the transparent agent is a sorbitol derivative, and its general chemical structure is , where the group R is The compatibilizer is maleic anhydride grafted polypropylene; the lubricant is a mixture of polyolefin and stearamide lubricant; the plasticizer is a mixture of dioctyl phthalate and epoxy soybean oil; stabilizer It is a mixture of antioxidant 1010 and four [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester.

The preparation method of the polypropylene transparent material for fused deposition molding in this embodiment is the same as that in Embodiment 1.

Example 3

The polypropylene transparent material for fused deposition molding of the present embodiment is made of the following raw materials: polypropylene 95g, transparent agent 0.5g, compatibilizer 1.5g, lubricant 3g, plasticizer 0.1g, stabilizer 0.01g.

Wherein the polypropylene is a blend of a polymer obtained by the independent polymerization of propylene and a polymer obtained by copolymerization of propylene and other olefins; the transparent agent is a sorbitol derivative, and its general chemical structure is , where one group R is , another group R is The compatibilizer is maleic anhydride grafted polypropylene; the lubricant is a stearamide lubricant; the plasticizer is epoxy soybean oil; the stabilizer is an alkyl ester antioxidant.

The preparation method of the polypropylene transparent material for fused deposition molding in this embodiment is the same as that in Embodiment 1.

Example 4

The polypropylene transparent material for fused deposition molding of this embodiment is made of the following raw materials in parts by weight: 98g of polypropylene, 0.8g of transparent agent, 2g of compatibilizer, 0.9g of lubricant, and 5g of plasticizer , Stabilizer 0.5g.

Among them, polypropylene is a polymer obtained by polymerizing propylene alone; the transparent agent is a sorbitol derivative, and its general chemical structure is , where one group R is , another group R is The compatibilizer is maleic anhydride grafted polypropylene; the lubricant is polyethylene glycol; the plasticizer is a mixture of epoxidized soybean oil and glycerin; the stabilizer is phosphorous acid antioxidant and alkyl ester antioxidant. Oxygen mixture.

The preparation method of the polypropylene transparent material for fused deposition molding in this embodiment is the same as that in Embodiment 1.

Example 5

The polypropylene transparent material for fused deposition molding of this embodiment is made of the following raw materials: 90g of polypropylene, 1g of transparent agent, 1g of compatibilizer, 1g of lubricant, 0.9g of plasticizer, and 0.2g of stabilizer .

Among them, polypropylene is a polymer obtained by copolymerization of propylene and other olefins; the transparent agent is a sorbitol derivative, and its general chemical structure is , where the group R is The compatibilizer is maleic anhydride grafted polypropylene; the lubricant is a mixture of polyolefin and polyethylene glycol; the plasticizer is epoxy soybean oil; the stabilizer is antioxidant 1010, four [β-(3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester.

The preparation method of the polypropylene transparent material for fused deposition molding in this embodiment is the same as that in Embodiment 1.

Table 1 Embodiment 1-5 and comparative example 1 material formula (weight/g)

Test methods for mechanical properties of polypropylene transparent materials for fused deposition modeling

The fused deposition modeling machine MEM-320A (data processing software Auroral 1.8) produced by Beijing Yinhua was used to print the prepared polypropylene transparent material for fused deposition modeling as sample strips for mechanical performance testing. The specific printing conditions of the fused deposition modeling machine MEM-320A are: the thickness of the forming layer is 0.175mm, the scanning speed is 40cm ³ /h, the temperature of the nozzle is 210°C, the temperature of the forming chamber is 70°C, and other parameters such as the scanning line width are adopted System default parameters for molding.

The tensile performance test is carried out in accordance with GB/T1040, and the printed sample sample size is 150×10×4mm, and the tensile speed is 50mm/min; the bending performance test is carried out in accordance with GB/T9341, and the printed sample sample size is 80 ×10×4mm, the bending speed is 2mm/min, the span is 64mm; the Charpy impact strength is tested according to GB/T1043, the size of the printed sample spline is 80×6×4mm, and the notch depth is three times the thickness of the sample one-third.

The comprehensive mechanical performance test of the material is judged by the values of tensile strength, elongation at break, flexural modulus and impact strength obtained from the test.

Table 2 Example 1-5 and comparative example 1 sample mechanical property test result

Table 2 is the test results of the mechanical properties of the samples of Examples 1-5 and Comparative Example 1. As can be seen from Table 2, compared with Comparative Example 1, after adding the transparent agent in polypropylene, along with the increase of the transparent agent content, the tensile strength, elongation at break, bending strength and notched impact strength of the polypropylene transparent material All have significantly improved, more practical.

Test method for light transmission of polypropylene transparent materials for fused deposition modeling

The light transmittance test of the polypropylene material is carried out according to GB/T2410-2008, the size of the printed sample is 50×50×1mm, and the light transmittance of the sample is measured with a haze meter. Adjust the zero knob of the haze meter so that the indication of the galvanometer is zero when the integrating sphere is in the dark, and when the light is unobstructed, adjust the indication of the galvanometer to 100, which is recorded as T1, and then place the sample perpendicular to the light path, The indication of the galvanometer of the recording instrument is T2, and the light transmittance T of the sample is calculated according to the following formula:

T=(T2/T1)×100

The calculation result is accurate to 0.1%.

The materials of Comparative Example 1 and Examples 1-3 were printed as samples of 50×50×1 mm, and the light transmittance of the samples was tested according to the above light transmittance test method. Table 3 is the test results of the light transmittance of the materials of Comparative Example 1 and Examples 1-5. In the comparative example, because there is no transparent agent added, the light transmittance of the polypropylene material is very poor, only 25.6%. The addition of a transparent agent can significantly improve the light transmittance of the polypropylene material. When the content of the transparent agent in Example 1 is 0.2 parts, the light transmittance of the polypropylene material is significantly increased to 58.9%. Continue to increase the content of the transparent agent, and the light transmittance of the polypropylene material also increases. When the content of the transparent agent in Example 3 is 1 part, the light transmittance of the polypropylene material can be increased to 76.1%, which can meet the requirements for the transparent polypropylene material in the application.

Table 3 embodiment 1-5 and comparative example 1 sample light transmittance test result

The present invention unexpectedly finds that after adding a transparent agent, the phenomenon of large-area crystallization during cooling and molding of polypropylene is suppressed, the light transmittance of the polypropylene material is greatly improved, and the polypropylene parts obtained by fusion deposition molding have better toughness and mechanical properties. Improved performance and enhanced usability. The polypropylene transparent material of the present invention can achieve the effect of improving light transmittance and toughness by adding a small amount of transparent agent, and the cost of the material is greatly reduced, which is beneficial to expanding the application of the polypropylene material in the field of fusion deposition molding. The preparation method of the polypropylene transparent material of the present invention is easy to operate, has relatively low requirements on process conditions and production equipment, can realize large-scale promotion and production, has broad market prospects and excellent market benefits.

Dimensions and numerical values disclosed herein are not to be construed as strict limitations to the precise values stated. Unless stated otherwise, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

All documents cited in the Summary of the Invention are, in relevant part, incorporated herein by reference. Citation of any document should not be construed as an admission that it is prior art with respect to the present invention.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other modifications and changes can be made without departing from the spirit and scope of the invention. These modifications and variations are all within the protection scope of the present invention.

Claims (9)

1. a fused glass pellet polypropylene transparent material, is characterized in that it is made up of the raw material of following portions by weight: polypropylene 90-99 part, transparent base 0.1-1 part, compatilizer 1-2 part, lubricant 0.9-3 part, softening agent 0.1-5 part, stablizer 0.01-0.5 part.

2. polypropylene transparent material according to claim 1, is characterized in that: described polypropylene is at least one that propylene is polymerized separately in the polymkeric substance that the polymkeric substance or propylene that obtain and other alpha-olefinic copolymerization obtain.

3. polypropylene transparent material according to claim 1, is characterized in that: described transparent base is glucitols derivative, and its chemical structure of general formula is , wherein radicals R is , , or in one or its combination.

4. polypropylene transparent material according to claim 1, is characterized in that: described compatilizer is maleic anhydride graft type polypropylene.

5. polypropylene transparent material according to claim 1, is characterized in that: described lubricant is the mixing of one or more in polyolefine, stearylamide series lubricant agent or polyoxyethylene glycol.

6. polypropylene transparent material according to claim 1, is characterized in that: described softening agent is the mixing of one or more in dioctyl phthalate (DOP), epoxy soybean oil, glycerine.

7. polypropylene transparent material according to claim 1, is characterized in that: described stablizer is the mixing of one or more in Hinered phenols macromole type oxidation inhibitor, phosphorous acid kind antioxidant or alkane ester kind antioxidant.

8. the preparation method of arbitrary described fused glass pellet polypropylene transparent material in claim 1-7, is characterized in that step is as follows:

(1) reagent mixes with starting material: first in stirrer, put into polypropylene, add transparent base, lubricant and softening agent again, stir until all general liquid light of particle surface, namely stir, to be mixed complete after, add antioxidant again and carry out follow-up mixing, continue mixing 2 minutes, finally obtain mixing raw material;

(2) add hot-extrudable: joined by mixing raw material in twin screw extruder, feed rate keeps evenly smooth, ensures not produce blocking in extrusion, and wire vent is stable smooth;

(3) curled hair: by installing a mouthful mould additional in the outlet of forcing machine, the diameter limiting wire vent, at 1.75 ± 0.05mm, collects shaping silk material finally by device for disc wrapping wire.

9. the preparation method of polypropylene transparent material according to claim 8, is characterized in that: first paragraph temperature 210 ° of C, second segment temperature 240 ° of C in the middle twin screw extrusion of described step (2), the 3rd section of temperature 210 ° of C.