CN114213748A - Mica filled polypropylene composite material and preparation method and application thereof - Google Patents
Mica filled polypropylene composite material and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention provides a mica filled polypropylene composite material and a preparation method and application thereof, and relates to the technical field of high polymer materials. The mica filled polypropylene composite material provided by the invention comprises the following components in parts by weight: 65-90 parts of polypropylene resin, 10-30 parts of mica, 0.3-4 parts of maleic anhydride grafted polyethylene wax and 0-1 part of auxiliary agent, wherein the melt index of the polypropylene resin is 0.5-60g/10min at 230 ℃ under the condition of 2.16kg according to ISO 1133-2011. According to the invention, the maleic anhydride grafted polyethylene wax is introduced into the mica filled polypropylene composite material matrix, so that the dispersion effect of mica in polypropylene resin can be improved, and the elongation at break of the composite material is obviously improved; and the toughness of the composite material can be obviously improved under the condition of slightly reducing the rigidity of the composite material, so that the material achieves good rigidity-toughness balance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a mica filled polypropylene composite material and a preparation method and application thereof.
Background
Polypropylene (PP) has the advantages of low density, low price, easy processing, etc., and has been widely used in the industries of automobiles, household electrical appliances, etc., but the disadvantages of poor dimensional stability and low rigidity of polypropylene limit the further application thereof, so mineral fillers need to be added for modification. Common mineral fillers include calcium carbonate, talc, barium sulfate, mica, and the like. Compared with calcium carbonate, talcum powder and barium sulfate, mica has better rigidity and dimensional stability and is applied in practice, but the mica has a lamellar structure, larger diameter-thickness ratio, more surface polar groups and poorer compatibility with PP resin. Even if the coupling agent or the compatilizer is added, the interface bonding force is enhanced, the material rigidity is improved, but the toughness of the PP composite material is always low, and the application range of PP is restricted.
Chinese patent document CN 102532691A discloses a mica modified polypropylene composite material, which is mainly characterized in that a certain amount of polyethylene powder is added into a system to improve the dispersion effect and the material toughening effect of mica powder. Although the addition of the polyethylene powder can improve the toughness of the material to a certain extent, the compatibility between the mica powder and the resin is not obviously improved, and the improvement effect is limited. Chinese patent document CN 105440307A discloses a lubricant and a mica-filled polypropylene composite using the same, which is mainly characterized in that the stacking effect of mica powder is reduced by lubrication, and the warping problem during injection molding is avoided, but the problems of stress concentration and low impact caused by large size of mica cannot be solved.
Disclosure of Invention
The invention mainly aims to provide a mica filled polypropylene composite material, a preparation method and application thereof, and aims to solve the problem that the rigidity and toughness balance of the conventional mica filled polypropylene composite material is difficult to realize.
In order to achieve the purpose, the invention provides a mica filled polypropylene composite material in a first aspect, which comprises the following components in parts by weight: 65-90 parts of polypropylene resin, 10-30 parts of mica, 0.3-4 parts of maleic anhydride grafted polyethylene wax and 0-1 part of auxiliary agent, wherein the melt index of the polypropylene resin is 0.5-60g/10min at 230 ℃ under the condition of 2.16kg according to ISO 1133-2011.
According to the technical scheme, the maleic anhydride grafted polyethylene wax is introduced into the mica filled polypropylene composite material matrix, so that the dispersion effect of mica in polypropylene resin can be improved, and the elongation at break of the composite material is obviously improved; and moreover, the toughness (cantilever beam notch impact strength) of the composite material can be remarkably improved under the condition of slightly reducing the rigidity (flexural modulus) of the composite material, so that the material achieves good rigidity-toughness balance.
It should be noted that the melt index of the polypropylene resin used in the present application is 0.5-60g/10min, when the melt index of the polypropylene resin is higher than 60g/10min, the rigidity and toughness of the prepared mica-filled polypropylene composite material are poor, and the polypropylene resin with the melt index lower than 0.5g/10min is not generally used for preparing injection-molded products.
As a preferred embodiment of the mica-filled polypropylene composite material, the weight part of the maleic anhydride grafted polyethylene wax is 1-2 parts.
Through a large number of experiments, the inventor finds that when the addition amount of the maleic anhydride grafted polyethylene wax in the mica filled polypropylene composite material system is 1-2 parts by weight, the prepared mica filled polypropylene composite material can show better rigidity and toughness levels.
In a preferred embodiment of the mica-filled polypropylene composite material of the present invention, the mica is sericite, the mesh number is 40 to 500 meshes, and the aspect ratio is 70 to 90.
Through a large number of experiments, the inventor finds that when the maleic anhydride grafted polyethylene wax is matched with mica with a lower mesh number (40-500 meshes), the prepared mica filled polypropylene composite material has better rigidity and toughness than the mica filled polypropylene composite material prepared by matching the maleic anhydride grafted polyethylene wax with mica with a higher mesh number (more than 500 meshes).
As a preferred embodiment of the mica-filled polypropylene composite of the present invention, the adjuvant comprises an antioxidant; the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
In a second aspect, the present invention further provides a preparation method of the mica-filled polypropylene composite material, including the following steps: adding polypropylene resin, mica, maleic anhydride grafted polyethylene wax and an auxiliary agent into a high-speed mixer, uniformly mixing, transferring into a double-screw extruder, extruding at the temperature of 200-220 ℃, controlling the current ratio at 70-80%, and extruding and granulating to obtain the mica filled polypropylene composite material.
In a third aspect, the invention also provides an application of the mica filled polypropylene composite material in the preparation of injection molding products. The injection products comprise parts with high requirements on material rigidity and toughness, such as automobile plastic parts, household appliance plastic parts and the like, such as parts of a dishwasher base and a sweeper water tank.
Compared with the prior art, the invention has the beneficial effects that:
according to the technical scheme, the maleic anhydride grafted polyethylene wax is introduced into the mica filled polypropylene composite material matrix, so that the dispersion effect of mica in polypropylene resin can be improved, and the elongation at break of the composite material is obviously improved; and the toughness of the composite material can be obviously improved under the condition of slightly reducing the rigidity of the composite material, so that the material achieves good rigidity-toughness balance.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The examples of the invention and the comparative examples used the following raw materials:
polypropylene 1: melt index 28g/10min (ISO 1133-2011) under the trademark PP EP548R, available from Mediterranean shell;
polypropylene 2: the melt index is 60g/10min (ISO 1133-2011), the mark is PP BX3900 and the product is purchased from SK chemistry;
polypropylene 3: the melt index is 100g/10min (ISO 1133-2011), the mark is PP K7100, and the product is purchased from China petrochemical;
maleic anhydride grafted polyethylene wax: the trade mark is K6105, purchased from Ou Ying chemical Co., Ltd, Guangzhou;
ethylene-octene copolymer: POE ENGAGE 8842, available from Dow chemical;
maleic anhydride grafted polyethylene: under the designation MC218, from Nile energy;
mica 1: 40 mesh, AY-03N, available from Jiangmen Jingda mica materials Co.Ltd;
mica 2: 325 mesh, and the mark is mica powder-P-325 mesh, purchased from Jiangmen Jingda mica materials GmbH;
mica 3: 500 meshes, HYC500, available from Jiangmen Jingda mica materials Co.Ltd;
mica 4: 600 mesh, brand W-600, purchased from Cistanchis county Huajingmiao mica, Inc.;
mica 5: 1250 mesh, the trade mark is W-1250, purchased from Huajingmica GmbH, Lingshou county;
antioxidant: antioxidant 1010, commercially available;
antioxidant 168, commercially available;
wherein, the antioxidant 1010 and the antioxidant 168 are added according to the proportion of 1: 1.
The preparation method of the mica filled polypropylene composite material in the embodiment and the comparative example comprises the following steps: adding polypropylene resin, mica, maleic anhydride grafted polyethylene wax and an auxiliary agent into a high-speed mixer, uniformly mixing, transferring into a double-screw extruder, extruding at the temperature of 200-220 ℃, controlling the current ratio at 70-80%, and extruding and granulating to obtain the mica filled polypropylene composite material.
Relevant performance test standards or methods in the examples and comparative examples of the invention are as follows:
dispersing effect of mica
The mica dispersion effect is related to the elongation at break of the material, and the higher the elongation at break of the material is, the better the dispersion effect of the mica in the polypropylene resin is reflected. Elongation at break: testing according to the national standard GB/T1040-2018;
secondly, toughness of the material
Notched izod impact strength: testing according to the national standard GB/T1843-2008 to obtain a type A notch;
third, material rigidity
1. Bending strength: testing according to the national standard GB/T9341-2008;
2. flexural modulus: testing according to the national standard GB/T9341-2008.
TABLE 1 raw material composition (in parts by weight) and Performance test results for examples 1-7 and comparative examples 1-6
As shown in Table 1, the addition amount of the maleic anhydride grafted polyethylene wax in examples 1-7 is 0.3-4 parts compared with that in comparative examples 1-2, and the rigidity and toughness of the mica filled polypropylene composite material prepared by the maleic anhydride grafted polyethylene wax are good.
In examples 1, 4 to 6 and comparative examples 1 to 2, the amount of mica added was 20 parts by weight, except that polypropylene and maleic anhydride-grafted polyethylene wax were added in different amounts. Comparative example 1 does not contain any maleic anhydride grafted polyethylene wax and the corresponding mica filled polypropylene composite has higher rigidity but lower toughness. With the increasing amount of the maleic anhydride grafted polyethylene wax, the toughness of the corresponding mica-filled polypropylene composite material was gradually improved, and at the same time, the rigidity was gradually reduced, and the rigidity and toughness of the corresponding mica-filled polypropylene composite materials in examples 1 and 4 to 6 were good. The addition amounts of the maleic anhydride grafted polyethylene wax in examples 4 to 5 are 1 and 2 parts by weight, respectively, and the rigidity and toughness of the corresponding mica filled polypropylene composite material are better than those in examples 1 and 6, which shows that the addition amount of the maleic anhydride grafted polyethylene wax in the mica filled polypropylene composite material system of the invention is best 1 to 2 parts by weight. It is noted that the general criteria for a material having good stiffness and toughness balance at an addition level of 20 parts by weight mica are: the impact strength of a cantilever beam notch is more than 9MPa, the bending strength is more than 26MPa, and the bending modulus is more than 1800 MPa. In contrast to comparative example 2, the maleic anhydride grafted polyethylene wax is added excessively, and the corresponding mica filled polypropylene composite material has improved toughness, but the rigidity slides down to a significant degree, so that the requirement of rigidity and toughness balance cannot be met.
In examples 4, 7 and 6, the melt indexes of the polypropylene are different, the toughness of the material is gradually reduced along with the increase of the melt index of the polypropylene, in comparative example 6, the polypropylene with the melt index of 100g/10min is adopted, the rigidity and the toughness of the prepared mica filled polypropylene composite material are lower than those of the mica filled polypropylene composite material corresponding to examples 4 and 7, and the elongation at break of the mica filled polypropylene composite material prepared in comparative example 6 is obviously reduced, which shows that the dispersion effect of the mica in comparative example 6 is poor.
Compared with the examples 2-4, the addition amount of the polypropylene and the mica in the comparative example 3 is not in the claimed range, the rigidity of the corresponding mica filled polypropylene composite material is higher, but the toughness and the elongation at break are obviously reduced;
in comparative examples 4 and 5, ethylene-octene copolymer and maleic anhydride grafted polyethylene are respectively adopted to replace maleic anhydride grafted polyethylene wax in example 4, and the corresponding mica filled polypropylene composite material has a small amount of improved toughness and a large reduction of rigidity; or the toughness is reduced, the rigidity is improved, and the effect is completely opposite to that of maleic anhydride grafted polyethylene wax.
TABLE 2 composition of the raw materials (in parts by weight) and performance test results for examples 4, 8-11
In table 2, only the mesh number of mica was adjusted, and the other components were kept the same, and it was found from the experimental results that as the mesh number of mica was increased, the elongation at break of the mica-filled polypropylene composite material was gradually increased, and the toughness of the composite material was also gradually increased, but at the same time, the flexural strength and flexural modulus of the composite material were gradually decreased, and in example 10, the flexural strength and flexural modulus of the mica-filled polypropylene composite material corresponding to that of example 9 were significantly decreased, and the balance of rigidity and toughness of the composite material was deteriorated, using mica of 600 meshes. Therefore, in the invention, when the maleic anhydride grafted polyethylene wax is matched with mica with a lower mesh number (40-500 meshes), the prepared mica filled polypropylene composite material has better rigidity and toughness than a mica filled polypropylene composite material prepared by matching the maleic anhydride grafted polyethylene wax with mica with a higher mesh number (more than 500 meshes).
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The mica filled polypropylene composite material is characterized by comprising the following components in parts by weight: 65-90 parts of polypropylene resin, 10-30 parts of mica, 0.3-4 parts of maleic anhydride grafted polyethylene wax and 0-1 part of auxiliary agent, wherein the melt index of the polypropylene resin is 0.5-60g/10min at 230 ℃ under the condition of 2.16kg according to ISO 1133-2011.
2. The mica-filled polypropylene composite of claim 1, wherein the maleic anhydride-grafted polyethylene wax is present in an amount of from 1 to 2 parts by weight.
3. The mica-filled polypropylene composite of claim 1, wherein the mica is sericite having a mesh size of 40 to 500 mesh.
4. The mica-filled polypropylene composite of claim 1, wherein the adjuvant comprises an antioxidant.
5. The mica-filled polypropylene composite of claim 4, wherein the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
6. A method of preparing a mica-filled polypropylene composite as claimed in any one of claims 1 to 5 comprising the steps of: adding polypropylene resin, mica, maleic anhydride grafted polyethylene wax and an auxiliary agent into a high-speed mixer, uniformly mixing, transferring into a double-screw extruder, extruding at the temperature of 200-220 ℃, controlling the current ratio at 70-80%, and extruding and granulating to obtain the mica filled polypropylene composite material.
7. Use of a mica-filled polypropylene composite as claimed in any one of claims 1 to 5 in the manufacture of an injection moulded product.
8. The use of claim 7, wherein the injection molded product comprises at least one of automotive plastic parts and household appliance plastic parts.
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| CN202111352575.6A CN114213748A (en) | 2021-11-16 | 2021-11-16 | Mica filled polypropylene composite material and preparation method and application thereof |
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Citations (6)
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|---|---|---|---|---|
| CA1221186A (en) * | 1984-04-04 | 1987-04-28 | University Of Toronto Innovations Foundation (The) | Reinforced resin composites |
| JPH0959448A (en) * | 1995-08-25 | 1997-03-04 | Tonen Corp | Mica-reinforced polypropylene resin compostion |
| WO2002051930A1 (en) * | 2000-12-22 | 2002-07-04 | Samsung General Chemicals Co., Ltd. | Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties |
| CN102093636A (en) * | 2011-01-13 | 2011-06-15 | 贵州大学 | High-performance polypropylene compound material and preparation method thereof |
| CN103554666A (en) * | 2013-10-29 | 2014-02-05 | 上海骏齐新材料科技有限公司 | Mica-reinforced polypropylene composite material and preparation method thereof |
| CN108219276A (en) * | 2018-01-12 | 2018-06-29 | 广东羽龙科技有限公司 | A kind of high tenacity heat superconducting flame-retardant polypropylene composite material and preparation process and purposes |
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2021
- 2021-11-16 CN CN202111352575.6A patent/CN114213748A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1221186A (en) * | 1984-04-04 | 1987-04-28 | University Of Toronto Innovations Foundation (The) | Reinforced resin composites |
| JPH0959448A (en) * | 1995-08-25 | 1997-03-04 | Tonen Corp | Mica-reinforced polypropylene resin compostion |
| WO2002051930A1 (en) * | 2000-12-22 | 2002-07-04 | Samsung General Chemicals Co., Ltd. | Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties |
| CN102093636A (en) * | 2011-01-13 | 2011-06-15 | 贵州大学 | High-performance polypropylene compound material and preparation method thereof |
| CN103554666A (en) * | 2013-10-29 | 2014-02-05 | 上海骏齐新材料科技有限公司 | Mica-reinforced polypropylene composite material and preparation method thereof |
| CN108219276A (en) * | 2018-01-12 | 2018-06-29 | 广东羽龙科技有限公司 | A kind of high tenacity heat superconducting flame-retardant polypropylene composite material and preparation process and purposes |
Non-Patent Citations (1)
| Title |
|---|
| 童筱莉等: "PEW-g-MAH的制备及其对PP/Talc的改性", 《现代塑料加工应用》, vol. 17, no. 4, pages 4 - 7 * |
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