CN112812431B - High-performance low-shrinkage polypropylene and preparation method thereof - Google Patents
High-performance low-shrinkage polypropylene and preparation method thereof Download PDFInfo
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- CN112812431B CN112812431B CN202110003092.9A CN202110003092A CN112812431B CN 112812431 B CN112812431 B CN 112812431B CN 202110003092 A CN202110003092 A CN 202110003092A CN 112812431 B CN112812431 B CN 112812431B
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- 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
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
Abstract
The invention provides a high-performance low-shrinkage polypropylene material, which can improve the mechanical property of the polypropylene material, improve the dimensional deformation of the material and ensure the dimensional stability of a product by adding flat glass fibers and glass microspheres into polypropylene. The material has excellent comprehensive mechanical property, can be used for any injection molding part on household appliances, and solves the problems of poor comprehensive mechanical property and weather resistance of polypropylene materials. The dimensional stability of the material can meet the requirements of ABS materials, the material can be produced by using a mold together with the conventional ABS materials, and the problems of assembly and after-sale complaints caused by the shrinkage of parts are solved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to high-performance low-shrinkage polypropylene and a preparation method of the polypropylene.
Background
Polypropylene (PP) is a highly crystalline thermoplastic resin with low density and good chemical resistance, and has wide applications in the household appliance industry. However, in practical engineering applications, compared with Acrylonitrile-Butadiene-Styrene (ABS) copolymer materials, the main problems of PP injection molded products are poor dimensional stability, warpage and size reduction caused by shrinkage deformation, and the mechanical properties of PP materials are significantly lower than those of ABS materials, resulting in limited application of PP materials. At present, the main method for improving the dimensional deformation and the mechanical property of the PP material is to adopt fibers and inorganic fillers for filling modification, but the conventional modification method cannot greatly reduce the dimensional deformation of products.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a high-performance low-shrinkage polypropylene.
The second purpose of the invention is to provide a preparation method of the polypropylene.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to high-performance low-shrinkage polypropylene which comprises the following components in parts by weight:
wherein the melt flow rate of the polypropylene is 15-55g/10min, the test condition is 230 ℃, and the load is 2.16 kg.
Preferably, the flat glass fibers have a length of 0.2 to 2.52mm, preferably 0.5 to 1.5 mm. The cross-sectional width is 35-85 μm and the cross-sectional aspect ratio is 2.5-8.5, preferably 4.0-6.0.
Preferably, the glass beads have a particle size of 15 to 300. mu.m, preferably 150. mu.m and a density of 0.15 to 0.65g/cm3。
Preferably, the auxiliary agent is selected from at least one of toughening agent, nucleating agent, antioxidant and light stabilizer.
The invention also relates to a preparation method of the polypropylene, which comprises the steps of uniformly mixing the components through a high-speed mixer, and then granulating through a double-screw extruder to obtain the high-performance low-shrinkage polypropylene.
Preferably, the mixing time is 8-10 minutes and the extrusion processing temperature is 170-215 ℃.
The invention has the beneficial effects that:
the invention provides a high-performance low-shrinkage polypropylene material, which can improve the mechanical property of the polypropylene material, improve the dimensional deformation of the material and ensure the dimensional stability of a product by adding flat glass fibers and glass microspheres into polypropylene.
The material has excellent comprehensive mechanical property, can be used for any injection molding part on household appliances, and solves the problems of poor comprehensive mechanical property and weather resistance of polypropylene materials. The dimensional stability of the material can meet the requirements of ABS materials, the material can be produced by using a mold together with the conventional ABS materials, and the problems of assembly and after-sale complaints caused by the shrinkage of parts are solved.
Drawings
FIG. 1 is a schematic cross-sectional view of a flat glass fiber of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a high-performance low-shrinkage polypropylene material which comprises the following components in parts by weight:
wherein the melt flow rate of the polypropylene is 15-55g/10min, the test condition is 230 ℃, and the load is 2.16 kg. If the melt flow rate of polypropylene is too low, the dispersibility of the flat glass fibers and glass beads therein is not good, which is not favorable for the uniformity of the material.
The flat glass fibers have a non-circular cross section of a type, as shown in fig. 1, which is approximately rectangular in shape and has a certain ratio of the length to the width of the cross section. Wherein l1Is the cross-sectional width, /)2Is the cross-sectional length. Compared with the glass fiber with a circular cross section, the flat glass fiber is not easy to cause the orientation shrinkage of the plastic melt and enhances the mechanical property of the materialWhile at the same time improving the dimensional stability of the material.
In one embodiment of the invention, the length of the flat glass fibers is 0.2 to 2.52mm, preferably 0.5 to 1.5 mm. The cross-sectional width is 35-85 μm and the cross-sectional aspect ratio is 2.5-8.5, preferably 4.0-6.0. The aspect ratio is too small, the flat characteristic of the glass fiber is not obvious, and the improvement on the dimensional stability of the material is limited; the aspect ratio is too large, so that unidirectional orientation is easily caused in the forming process, and the impact toughness of the product is obviously reduced.
In one embodiment of the present invention, the glass microspheres have a particle size of 15-300. mu.m, preferably 150-200. mu.m, and a density of 0.15-0.65g/cm3. The round hollow glass beads have good fluidity in the die punching process, and more importantly, the glass beads are isotropic, so that the phenomenon that different positions are shrunk inconsistently due to orientation is avoided, and the size stability of a product can be ensured.
In one embodiment of the present invention, the auxiliary agent is selected from at least one of a toughening agent, a nucleating agent, an antioxidant, and a light stabilizer.
Wherein the toughening agent is at least one selected from polypropylene copolymer, Polyethylene (PE), Ethylene Propylene Diene Monomer (EPDM) and Ethylene Propylene Rubber (EPR).
The nucleating agent is organic nucleating agent, such as carboxylic acid metal salt and sorbitol benzyl cross derivative.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is antioxidant 1010 or antioxidant 1076; the auxiliary antioxidant is phosphite antioxidant 168 or antioxidant DLTP.
The light stabilizer is hindered amine light stabilizer, preferably UV 3853 light stabilizer.
The invention also relates to a preparation method of the polypropylene, which comprises the steps of uniformly mixing the components through a high-speed mixer, and then granulating through a double-screw extruder to obtain the high-performance low-shrinkage polypropylene.
In one embodiment of the present invention, the mixing time is 8-10 minutes, the extrusion processing temperature is 170-215 ℃, and preferably, the polypropylene raw material and the auxiliary agent are mixed and then added from the main feeding port, and then the glass fiber and the glass beads are added into the screw extruder from the side feeding port of the extruder.
Experimental example 1
Pouring the polypropylene and other auxiliary materials into a high-speed mixer to be mixed for 8-10 minutes, and then granulating by a double-screw extruder, wherein the extrusion processing temperature is 170-215 ℃. The proportions of the components of the examples and comparative examples are shown in Table 1. The copolymerized polypropylene is a size stabilizer, and the addition of the copolymerized polypropylene can reduce crystallization and size change.
The manufacturer of polypropylene in the raw materials is in the era of Taoism, and the brand is PP-Y35. The flat glass fibers of examples 1-1 to 1-4 had a length of 1.0 to 1.5mm, a cross-sectional width of 40 to 50 μm, and a cross-sectional aspect ratio of 4.5 to 6.5. The glass beads have a particle size of 100-200 μm and a density of 0.45-0.55g/cm3. The glass fibers of comparative examples 1 to 3 had a cross-sectional diameter equal to the cross-sectional width of the flat glass fiber of example 1. The glass flakes in comparative examples 1-4 were sieved with a 2500-. The ABS resin manufacturers of comparative examples 1 to 11 were LG in Korea and the brand ABS-121H.
TABLE 1
Test example 1
And transferring the polypropylene particles prepared in the examples and the comparative examples into an injection molding machine, and performing injection molding at 180-230 ℃ to obtain a sample strip. And (3) carrying out a tensile strength test on the spline according to the national standard GB/T1040-. The test results are shown in Table 2.
TABLE 2
The test results in Table 2 show that the test results of examples 1-1 to 1-4 are similar to those of comparative examples 1-11, and that the polypropylene modified material obtained by the present invention can achieve the mechanical properties, heat resistance and dimensional deformation of ABS material. The shrinkage of the materials is obviously higher than that of ABS materials, and the materials cannot be used for replacing ABS materials in practical production application.
Experimental example 2
The aspect ratio of the cross section of the flat glass fiber was changed based on example 1-1, and the specific arrangement is shown in Table 3, and other raw materials and preparation methods were the same as those of example 1-1.
TABLE 3
| Examples/comparative examples | Aspect ratio of flat glass fiber cross-section |
| Examples 1 to 1 | 4.5-6.5 |
| Example 2-1 | 1.5-3.5 |
| Examples 2 to 2 | 2.5-4.5 |
| Examples 2 to 3 | 6.5-8.5 |
| Examples 2 to 4 | 2.5-8.5 (all types have) |
Test example 2
The same test method as in test example 1 was used, and the test results are shown in Table 4.
TABLE 4
The results of the tests in Table 4 show that the polypropylene modified material system has no large change in the comprehensive mechanical and thermal properties in the specified size range of the flat glass fiber, and has shrinkage in the range of 0.3-0.6%, but has better improvement in dimensional deformation in the preferred size range. Therefore, the flat glass fiber within the limited size range can meet the size requirement of thin-wall injection molding of household electrical appliances, and can replace ABS materials for application.
Experimental example 3
The particle size and density of the glass beads were varied based on example 1-1, the specific arrangement is shown in Table 5, and the other raw materials and preparation method were the same as in example 1-1.
TABLE 5
Test example 3
The same test method as in test example 1 was used, and the test results are shown in Table 6.
TABLE 6
The test results in table 6 show that the glass bead sizes are best in the optimum range for improved dimensional distortion. When the size of the glass bead is smaller, the shrinkage rate of the material is increased; larger sizes result in increased material density.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. The high-performance low-shrinkage polypropylene is characterized by comprising the following components in parts by weight:
the aspect ratio of the cross section of the flat glass fiber is 4.5-6.5, the length of the flat glass fiber is 0.2-2.52mm, and the width of the cross section is 35-85 μm;
the glass beads have a particle size of 100-200 μm and a density of 0.45-0.55g/cm3。
2. The polypropylene of claim 1, wherein the polypropylene in the composition has a melt flow rate of 15 to 55g/10min, and the test conditions are 230 ℃ and a load of 2.16 kg.
3. The polypropylene according to claim 1, wherein the auxiliary agent is at least one selected from the group consisting of a toughening agent, a nucleating agent, an antioxidant, and a light stabilizer.
4. The polypropylene of claim 3, wherein the toughening agent is selected from at least one of co-polypropylene, polyethylene PE, ethylene propylene diene monomer, and ethylene propylene rubber.
5. The method for preparing polypropylene according to any one of claims 1 to 4, wherein the method comprises uniformly mixing the components by a high-speed mixer and then granulating by a twin-screw extruder to obtain the high-performance low-shrinkage polypropylene.
6. The method as claimed in claim 5, wherein the mixing time is 8-10 minutes and the extrusion processing temperature is 170-215 ℃.
7. The method of claim 5, wherein the polypropylene raw material and the auxiliary agent are mixed and then fed from a main feeding port, and then the glass fiber and the glass bead are fed into the screw extruder from a side feeding port of the extruder.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118437A (en) * | 2017-05-18 | 2017-09-01 | 中广核俊尔新材料有限公司 | Lower shrinkage, Long Glass Fiber Reinforced PP Composite of low warpage and its preparation method and application |
| CN109438899A (en) * | 2018-09-26 | 2019-03-08 | 雷诺丽特塑料科技（北京）有限公司 | A kind of 3D printing polypropylene material of lower shrinkage high tenacity and preparation method thereof |
| CN110804282A (en) * | 2019-11-14 | 2020-02-18 | 福建华塑新材料有限公司 | Modified flat glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN111138755A (en) * | 2019-12-25 | 2020-05-12 | 江苏金发科技新材料有限公司 | Low-density low-dielectric polypropylene composite material and preparation method thereof |
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- 2021-01-04 CN CN202110003092.9A patent/CN112812431B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118437A (en) * | 2017-05-18 | 2017-09-01 | 中广核俊尔新材料有限公司 | Lower shrinkage, Long Glass Fiber Reinforced PP Composite of low warpage and its preparation method and application |
| CN109438899A (en) * | 2018-09-26 | 2019-03-08 | 雷诺丽特塑料科技（北京）有限公司 | A kind of 3D printing polypropylene material of lower shrinkage high tenacity and preparation method thereof |
| CN110804282A (en) * | 2019-11-14 | 2020-02-18 | 福建华塑新材料有限公司 | Modified flat glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN111138755A (en) * | 2019-12-25 | 2020-05-12 | 江苏金发科技新材料有限公司 | Low-density low-dielectric polypropylene composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 圆玻纤和扁平玻纤复配增强PA6及其性能研究;许鸿基等;《广东化工》;20191231;第46卷(第5期);第71-73页 * |
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