CN108467544B - High-strength, high-rigidity and transparent modified polypropylene composite material and preparation method thereof - Google Patents
High-strength, high-rigidity and transparent modified polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength, high-rigidity and transparent modified polypropylene composite material and a preparation method thereof. The composite material comprises polypropylene, fluorophlogopite, a compatilizer, an antioxidant, a nucleating agent, a lubricant, optional zinc oxide whiskers and optional nano zinc oxide. The fluorophlogopite is added through side feeding, and the obtained composite material has extremely high mechanical property, and can realize low filling and high performance of the composite material. The polypropylene composite material is enhanced and simultaneously shows the characteristic of transparency. Further, by compounding the zinc oxide whiskers and the fluorophlogopite, reinforcing and filling of blank areas of a matrix generated by bridging between flaky mica by small-size zinc oxide whiskers is realized, the nanometer advantages of nanometer zinc oxide in polymer reinforcement are combined, the synergistic reinforcement of micro and nanometer fillers with different scales in different scale spaces in the matrix material is fully utilized, and the low filling and high performance of the polypropylene material are effectively realized.
Description
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and particularly relates to a high-strength, high-rigidity and transparent modified polypropylene composite material and a preparation method thereof.
Background
The polypropylene plastic is a thermoplastic resin prepared by polymerizing propylene, is usually colorless and semitransparent, odorless and nontoxic, can be sterilized by steam, is corrosion-resistant, has better mechanical property and transparency than polyethylene, and is a general plastic with excellent comprehensive performance. Most importantly, the polypropylene material can be modified by means of blending, reinforcing, filling and the like, so that the engineering and high performance of the general plastic of the polypropylene material are realized, and the requirements of the polypropylene material in the application fields of household appliances, automobile interior and exterior trimming parts, body building, office supplies, sanitary wares and the like are met.
The glass fiber reinforced polypropylene material has the advantages of high mechanical property strength, good heat resistance, stable size and the like, the strength and modulus of the glass fiber reinforced polypropylene can be comparable to those of engineering plastics, and the glass fiber reinforced polypropylene material can replace steel and engineering plastics by plastics in practical application, and meets the use requirements of high-strength structural parts in the fields of automobiles, household appliances and the like. However, since the glass fiber has a high length-diameter ratio, the glass fiber is easily oriented in the molding process to cause anisotropy in material strength and shrinkage, so that in a thin product part, the glass fiber orientation easily causes warping of the product, and the application of the glass fiber reinforced polypropylene in mechanical parts with high requirements on dimensional precision and flatness is limited. Moreover, the floating fibers in the glass fiber reinforced composite material can seriously affect the appearance property of the material. The existing filling modified polypropylene composite materials of other inorganic materials such as calcium carbonate, talcum powder and the like generally have the following defects: the mechanical strength and rigidity indexes are insufficient, the modified composite material is usually opaque and milky, the original transparent property of a base material is sacrificed, the appearance performance of the material is influenced, and the like, so that the application range of the polypropylene is limited to a great extent. Therefore, the development of high-strength, excellent-appearance, isotropic, high-performance modified polypropylene composites is increasingly becoming a market-competitive product.
Mica is a sheet structure, has a large diameter-thickness ratio and is a typical two-dimensional reinforcing material, so that the mica-filled polyolefin has the characteristics of high strength and rigidity, good dimensional stability, good insulating property and the like.
Chinese patent CN102093636A discloses a mica modified polypropylene composite material, and the result shows that mica effectively improves the mechanical properties of polypropylene. The disadvantages are that: the addition amount of mica in the composite material is very high (up to 56 wt%), which is much higher than the content of resin matrix (30%), so that the mica agglomeration is serious, the characteristics of the two-dimensional mica reinforced material are not fully exerted, and the development trend of light weight of the current composite material is not met. Moreover, when the filling amount is larger, the material processing difficulty is also increased. In addition, the compatilizer (maleic anhydride grafted polypropylene) added into the composite material is higher in proportion, so that the investment of material cost is increased on one hand, and the TVOC and the ageing resistance of the material are not facilitated on the other hand.
Chinese patents CN103554666A, CN106009285A and CN103772816A disclose mica reinforced polypropylene composite materials and preparation methods thereof, wherein mica, polypropylene and auxiliaries are uniformly mixed and stirred in a plastic cylinder or a high-speed mixer, and are extruded and blended through a main feeding port, and in the blending process, the large sheet structure of the mica is damaged due to high-strength shearing of materials in a melting section, the diameter-thickness ratio is greatly reduced, and the mechanical property of the mica/polypropylene composite material obtained by the method is improved in a small range, so that the performance indexes of the modified polypropylene composite material and the engineering plastic are far away.
In addition, most of the patents for preparing mica modified polypropylene composite materials adopt natural mica powder such as sericite (CN101580613B and CN102532691B) or wet white mica powder (CN104419059A), on one hand, the diameter-thickness ratio and the lamella thickness of the physically ground mica powder are not uniform, and on the other hand, natural mineral sources contain more Fe2O3(3.0% -6.0%) and TiO2(0.6-0.9%) and other metal impurities not only affect the whiteness of the mica powder, but also can cause degradation of polymer materials and affect the properties of ageing resistance, transparency and the like.
At present, no polypropylene composite material with high strength, high rigidity and transparent property exists in the prior art.
Disclosure of Invention
The invention aims to solve the technical problems of high mica adding amount, unobtrusive mechanical property of the composite material and poor appearance of the material in the mica/polypropylene composite material in the prior art, and provides a transparent modified polypropylene composite material with high strength and rigidity and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the polypropylene composite material comprises the following components in parts by weight: 60-90 parts of polypropylene, 10-40 parts of fluorophlogopite, 1-5 parts of compatilizer, 0.4-0.7 part of antioxidant, 0.2-0.5 part of nucleating agent and 0.2-0.5 part of lubricant. Preferably, 70-80 parts of polypropylene, 20-30 parts of fluorophlogopite, 3-5 parts of compatilizer, 0.4-0.6 part of antioxidant, 0.3-0.4 part of nucleating agent and 0.3-0.4 part of lubricant.
Preferably, the polypropylene composite material comprises the following components in parts by weight: 60-90 parts of polypropylene, 10-40 parts of fluorophlogopite, 3-8 parts of zinc oxide whisker, 1-5 parts of compatilizer, 0.4-0.7 part of antioxidant, 0.2-0.5 part of nucleating agent and 0.2-0.5 part of lubricant. Preferably, 70-80 parts of polypropylene, 20-25 parts of fluorophlogopite, 3-5 parts of zinc oxide whisker, 3-5 parts of compatilizer, 0.4-0.6 part of antioxidant, 0.3-0.4 part of nucleating agent and 0.3-0.4 part of lubricant.
More preferably, the polypropylene composite material of the present invention comprises the following components by weight: 60-90 parts of polypropylene, 10-40 parts of fluorophlogopite, 3-8 parts of zinc oxide whisker, 0.5-1.0 part of nano zinc oxide, 1-5 parts of compatilizer, 0.4-0.7 part of antioxidant, 0.2-0.5 part of nucleating agent and 0.2-0.5 part of lubricant. Preferably, 70-80 parts of polypropylene, 20-25 parts of fluorophlogopite, 3-5 parts of zinc oxide whisker, 0.8-1.0 part of nano zinc oxide, 3-5 parts of compatilizer, 0.4-0.6 part of antioxidant, 0.3-0.4 part of nucleating agent and 0.3-0.4 part of lubricant.
The polypropylene is one of homo-polypropylene and/or random copolymerization polypropylene, and the melt flow rate is 10-60g/10min (230 ℃, 2.16 kg).
The chemical structural formula of the fluorophlogopite is KMg3(AlSi3O10)F2The average particle size of the mica is 20-80 μm, the length-diameter ratio is not less than 60, and the whiteness is 94-96.
Fe in fluorophlogopite of the invention2O3Not more than 0.25 wt%, and TiO2≤0.1wt％。
The zinc oxide whisker has a three-dimensional four-needle structure, and the length of a needle body of the zinc oxide whisker is 1-10 mu m.
The nano zinc oxide is fibrous whisker with the grain diameter of about 20-100 nm.
The compatilizer is one or more of maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene, glycidyl acrylate grafted polypropylene and butyl methacrylate grafted polypropylene.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant comprises one or more of hindered phenol and hindered amine antioxidants; the auxiliary antioxidant comprises one or more of thioesters and phosphite antioxidants.
Preferably, the mass ratio of the main antioxidant to the auxiliary antioxidant is 0.5-1: 1.
the main antioxidant is preferably one or more of N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (antioxidant 1098), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine (antioxidant 1024) and tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol (antioxidant 1010).
The auxiliary antioxidant is preferably one or more of tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626) and dioctadecyl thiodipropionate.
The nucleating agent is an organic transparent nucleating agent for polypropylene, and preferably one or more of aromatic acid metal soaps, dibenzylidene sorbitols and organic phosphates.
The lubricant comprises one or more of liquid paraffin, stearate, butyl stearate and ethylene bis-hard amide.
The preparation of the polypropylene composite according to the present invention may be carried out in equipment known in the art, preferably a twin-screw extruder.
The invention also provides a method for preparing the polypropylene composite material, which comprises the following steps: according to the proportion, polypropylene, a compatilizer, an antioxidant, a nucleating agent and a lubricant are uniformly mixed in a high-speed mixer, then the mixture is added into a double-screw extruder through a main feeding port, fluorophlogopite is added into the double-screw extruder through a lateral feeding port of the double-screw extruder at the same time, and the mixture is subjected to melt extrusion granulation, water cooling and granulation to obtain the flaky mica modified polypropylene composite material; to reduce shear failure of fluorophlogopite, it was added at a side feed port located downstream.
When the polypropylene composite material contains zinc oxide whiskers, the method for preparing the polypropylene composite material comprises the following steps: uniformly mixing polypropylene, a compatilizer, an antioxidant, a nucleating agent and a lubricant in a high-speed mixer according to a ratio, adding the mixture into a double-screw extruder through a main feeding port, simultaneously adding fluorophlogopite into a rear lateral feeding port of the double-screw extruder, adding zinc oxide whiskers into the mixture through the main feeding port and/or the lateral feeding port, performing melt extrusion granulation, and performing water cooling and granulation to obtain a flaky mica modified polypropylene composite material; preferably, the zinc oxide whiskers and the fluorophlogopite are respectively added through a front lateral feeding port and a rear lateral feeding port of the extruder.
When the polypropylene composite material contains zinc oxide whiskers and nano zinc oxide, in order to better disperse the nano zinc oxide, the polypropylene composite material adopts a form of nano zinc oxide master batches (a mixture of the nano zinc oxide and polypropylene). The method for preparing the polypropylene composite material comprises the following steps: according to the proportion, polypropylene, nano zinc oxide master batches, a compatilizer, an antioxidant, a nucleating agent and a lubricant are uniformly mixed in a high-speed mixer, then the mixture is added into a double-screw extruder through a main feeding port, meanwhile, zinc oxide whiskers and fluorophlogopite are respectively added into the extruder through a front-mounted lateral feeding port and a rear-mounted lateral feeding port, and the mixture is subjected to melt extrusion granulation, water cooling and grain cutting to obtain the flaky mica modified polypropylene composite material.
The temperature of the double-screw extruder is 170-230 ℃, the rotating speed is 150-300 rpm, the length-diameter ratio (L/D) of the double-screw extruder is 35-50, and a front lateral feeding port and a rear lateral feeding port are respectively arranged behind a main feeding port of the double-screw extruder; preferably, the forward side feed port is located 1/3 screw length after the main feed port and the aft side feed port is located 2/3 screw length after the main feed port.
Compared with the prior art, the invention has the following beneficial effects: the mica reinforced polypropylene composite material prepared by adjusting the component proportions and the processing technology has the following advantages:
(1) the invention adds the fluorophlogopite with low impurity and high purity in a side feeding mode, and improves the compatibility between the polypropylene and the mica based on the formula optimization, the composite material prepared by the invention has extremely high mechanical property, compared with the existing similar formula materials such as natural sericite and the like, the composite material can realize low filling and high performance, and the obtained composite material has the characteristics of high strength and high rigidity.
(2) The modified composite material obtained by the invention has the characteristics of high strength, high rigidity and transparency, the light transmittance of the composite material is between 44% and 52%, the transparent characteristic is similar to that of a resin matrix, and the requirement of material visualization is met. The improvement of the transparency of the product by adding mica with a specific structure is not related to the application of polypropylene modification at present. This is very different from other inorganic materials such as calcium carbonate, talc, etc., which all sacrifice the transparent properties of the modified material and give an opaque milky appearance.
(3) According to the invention, the zinc oxide whiskers and the mica are compounded according to a certain proportion, and the regulation and control of the processing technology are based, so that the zinc oxide whiskers with smaller sizes can well reinforce and fill a blank area of a matrix generated by bridging between flaky mica in the process of coating the mica by a polypropylene matrix, the complementary synergistic reinforcing effect of two fillers is fully exerted, and the tensile strength, the bending strength and the bending modulus of the composite material are enhanced.
(4) According to the invention, based on the cooperative reinforcement of zinc oxide and mica, the size advantage of nano zinc oxide in polymer reinforcement is combined with that of the conventional micron-sized filler, so that fluorophlogopite, zinc oxide whiskers and nano zinc oxide can fully utilize the cooperative reinforcement effect of micron and nano fillers with different sizes and shapes in different size spaces in a matrix material, the mica filling amount is reduced, the composite material still has excellent mechanical properties (tensile strength, bending strength and bending modulus), and the low filling and high performance of the polypropylene material are effectively realized.
(5) The modified polypropylene composite material obtained by the invention has excellent effects on mechanical property and appearance property, can meet the manufacturing requirements in the fields of high rigidity and high rigidity, and is particularly suitable for the automobile industry and the aerospace industry.
Detailed Description
The invention is further described in the following with reference to examples, but the scope of protection of the invention is not limited to the examples only, but also includes any other known variations within the scope of the claims of the invention.
A double-screw extruder: cobolon (Nanjing) machinery, Inc., model CTE35 PLUS.
Polypropylene: homo-polypropylene, tianjin Zhongsha petrochemical 6012;
mica, wakame mica ltd, model synthetic mica fluorophlogopite HC800 and wet process muscovite W800;
antioxidant: turbo-Baker Switzerland, model 1010 and 168, 626;
a compatilizer: maleic anhydride grafted polypropylene, jiangsu kosher compatibilizer, inc, model 9801;
nucleating agent: sorbitol derivative Millad3988, Milliken, USA;
lubricant: calcium stearate;
zinc oxide whisker, Haozi nanotechnology (Shanghai) Ltd., three-dimensional four-needle structure, with the length of the needle body being 3.0 μm;
the nano zinc oxide is fibrous whisker with the grain diameter of about 40 nm.
Example 1
1) Weighing 90 parts by weight of polypropylene, 1 part by weight of maleic anhydride grafted polypropylene, 0.3 part by weight of antioxidant 1010, 0.4 part by weight of antioxidant 168, 0.5 part by weight of nucleating agent and 0.3 part by weight of lubricant, mixing for 2-3 minutes in a high-speed mixer, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 10 parts of mica (HC800) into a rear lateral feed (eighth section), and performing melt extrusion at the temperature of 180 ℃ and the rotating speed of 150 revolutions per minute to obtain a strip-shaped primary material;
3) and cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in table 1.
Example 2
1) Mixing 80 parts of polypropylene, 3 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.4 part of antioxidant 168, 0.4 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 20 parts of mica (HC800) into a rear lateral feed (eighth section), and performing melt extrusion at the temperature of 200 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material;
3) cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, cutting the plastic particles into plastic particles by the granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in table 1.
Example 3
1) Mixing 70 parts of polypropylene, 5 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.3 part of antioxidant 168, 0.3 part of nucleating agent and 0.5 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 30 parts of mica (HC800) into a rear lateral feed (eighth section), and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 200 revolutions per minute to obtain a strip-shaped primary material;
3) cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, cutting the plastic particles into plastic particles by the granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in table 1.
Example 4
1) Mixing 60 parts of polypropylene, 7 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.2 part of nucleating agent and 0.3 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 40 parts of mica (HC800) into a rear lateral feed (eighth section), and performing melt extrusion at the temperature of 220 ℃ and the rotating speed of 300 revolutions per minute to obtain a strip-shaped primary material;
3) cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, cutting the plastic particles into plastic particles by the granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in table 1.
Comparative example 1
1) Mixing 70 parts of polypropylene, 5 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.3 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 30 parts of another wet mica W800 into a rear lateral feed (eighth section), and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material;
3) cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, cutting the plastic particles into plastic particles by the granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in table 1.
TABLE 1 sample Performance test results
| Performance of | PP resin | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Density (g/cm)3，ISO 1183) | 0.86 | 0.95 | 1.03 | 1.13 | 1.21 | 1.12 |
| MFI(g/10min,230℃，2.16kg) | 11.3 | 9.6 | 7.8 | 6.1 | 5.3 | 7.4 |
| Tensile Strength (MPa, ISO 527-2) | 38 | 43.4 | 46.5 | 56.8 | 45.7 | 44.2 |
| Modulus of elasticity (MPa, ISO 527-2) | 2358 | 3897 | 5045 | 6226 | 7058 | 4240 |
| Elongation at Break (%, ISO 527-2) | 40 | 16 | 10 | 3.2 | 3.8 | 12 |
| Flexural strength (MPa, ISO178) | 60.4 | 64.5 | 68.3 | 73.8 | 74.7 | 62.6 |
| Flexural modulus (MPa, ISO178) | 2032 | 3696 | 4705 | 5815 | 6230 | 3791 |
| Light transmittance (%, 1mm) | 56％ | 52％ | 48％ | 48％ | 36％ | 12％ |
As can be seen from table 1: compared with polypropylene pure resin, the modified polypropylene composite material is obtained by adding the flaky fluorophlogopite into the polypropylene, the tensile strength, the elastic modulus, the bending strength and the bending modulus of the material are greatly improved along with the increase of the mica content, particularly the elastic modulus and the bending modulus, and the rigidity and the strength of the modified material are greatly improved. The prepared modified material has excellent mechanical property, the tensile strength of a sample strip is as high as 56.8MPa, and the increase amplitude is about 49 percent compared with PP; the bending strength can reach 73.8MPa, and the increase amplitude is about 22 percent; the flexural modulus reaches 5815MPa, and the increase amplitude is about 186%. The prepared material has high strength and rigidity, and can replace engineering plastics with higher cost, thereby achieving the purpose of reducing the cost. The prepared composite material has extremely high mechanical property, and can realize low filling and high performance of the composite material compared with the existing similar formula materials such as natural wet mica and the like.
In comparative example 1, the wet mica (W800) modified polypropylene composite exhibited an opaque dark gray color, and the tensile strength and flexural strength, and flexural modulus rise of the modified composite were comparable to that of only 10 parts fluorophlogopite modified composite (example 1).
The modified polypropylene composite material still keeps the transparent property after being filled and modified by mica with different parts, has higher light transmittance, is more beneficial to regulating and controlling the apparent property of the material, and meets the requirements on the appearance of the material in different application fields. The wet laid mica (W800) modified polypropylene composite of comparative example 1 exhibited an opaque dark gray color with a light transmission of only 12%.
Example 5
1) Mixing 70 parts of polypropylene, 5 parts of zinc oxide whisker, 5 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 626, 0.3 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 25 parts of mica (HC800) into a lateral feed inlet (eighth section), and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material;
3) and cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in Table 2.
Example 6
1) Mixing 70 parts of polypropylene, 5 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 626, 0.3 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 5 parts of zinc oxide whiskers and 25 parts of mica (HC800) into a front lateral feed inlet (fifth section), and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 180 revolutions per minute to obtain a strip-shaped primary material;
3) and cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in Table 2.
Example 7
1) Mixing 70 parts of polypropylene, 5 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 626, 0.3 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, arranging a lateral feed inlet (eighth section), simultaneously adding 25 parts of mica (HC800) and 5 parts of zinc oxide whiskers, and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 180 revolutions per minute to obtain a strip-shaped primary material;
3) and cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in Table 2.
Example 8
1) Mixing 70 parts of polypropylene, 5 parts of maleic anhydride grafted polypropylene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 626, 0.3 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and stirring and mixing uniformly;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 8 parts of zinc oxide whiskers into a front lateral feed inlet (fifth section) and 22 parts of mica (HC800) into a rear lateral feed inlet (eighth section), and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 180 revolutions per minute to obtain a strip-shaped primary material;
3) and cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in Table 2.
Example 9
1) Firstly, preparing nano zinc oxide and polypropylene into master batches with the content of 50 wt% by a screw extruder, then mixing 69.5 parts of polypropylene, 5 parts of maleic anhydride grafted polypropylene, 1 part of nano zinc oxide polypropylene master batches, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 626, 0.2 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and uniformly stirring and mixing;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 4 parts of zinc oxide whiskers into a front lateral feed inlet (fifth section) and 24 parts of mica (HC800) into a rear lateral feed inlet (eighth section), and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 180 revolutions per minute to obtain a strip-shaped primary material;
3) and cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in Table 2.
Example 10
1) Firstly, preparing master batches with the content of 50 wt% of nano zinc oxide from nano zinc oxide and polypropylene through a screw extruder, then mixing 69 parts of polypropylene, 5 parts of maleic anhydride grafted polypropylene, 2 parts of nano zinc oxide polypropylene master batches, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 626, 0.2 part of nucleating agent and 0.4 part of lubricant in a high-speed mixer for 2-3 minutes, and uniformly stirring and mixing;
2) taking out the raw materials uniformly mixed in the step 1), pouring the raw materials into a feed inlet of a double-screw extruder, adding 3 parts of zinc oxide whiskers and 23 parts of mica (HC800) into a front lateral feed inlet (fifth section), and performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 180 revolutions per minute to obtain a strip-shaped primary material;
3) and cooling the primary material obtained in the step 2) in a water tank and air, cutting the primary material into plastic particles by a granulator, performing injection molding to obtain sample strips, and performing mechanical property test respectively, wherein the results are shown in Table 2.
TABLE 2 sample Performance test results
| Performance of | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 |
| Density (g/cm)3，ISO 1183) | 1.13 | 1.13 | 1.13 | 1.14 | 1.11 | 1.10 |
| MFI(g/10min,230℃，2.16kg) | 5.9 | 5.6 | 6.4 | 5.4 | 5.5 | 5.2 |
| Tensile Strength (MPa, ISO 527-2) | 54.8 | 62.5 | 52.3 | 60.5 | 63.9 | 65.6 |
| Modulus of elasticity (MPa, ISO 527-2) | 6254 | 6670 | 6060 | 6430 | 6874 | 7054 |
| Elongation at Break (%, ISO 527-2) | 3.0 | 2.8 | 3.4 | 3.2 | 3.0 | 2.6 |
| Flexural strength (MPa, ISO178) | 74.4 | 80.4 | 72.2 | 76.6 | 82.3 | 84.4 |
| Flexural modulus (MPa, ISO178) | 5610 | 6260 | 5626 | 6074 | 6521 | 6650 |
| Light transmittance (%, 1mm) | 44％ | 49％ | 46％ | 44％ | 47％ | 52％ |
The invention further optimizes the preparation process of the composite material and improves the performance of the composite material by compounding the zinc oxide whiskers and the mica according to a certain proportion and regulating and controlling the feeding process as in example 5, example 6 and example 7. It was found by comparison that, the zinc oxide whiskers are uniformly dispersed in the polypropylene matrix through the front side feeding port in advance (example 6), on one hand, the damage caused by high shear of the melting section when the whiskers are added by the main feeding mode is avoided (example 5), and on the other hand, the intercalation of the large-flake mica blocking whiskers is not uniformly dispersed when the mica and the whiskers are simultaneously introduced in example 7. In the process of coating mica with polypropylene matrix, zinc oxide whiskers with smaller sizes are well reinforced and filled in the blank area of the matrix generated by bridging between flaky mica by the processing mode of example 6, so that the complementary synergistic reinforcing effect of the two fillers is fully exerted, and the tensile strength, the bending strength and the bending modulus of the composite material are further improved as shown in table 2.
The invention further combines the unique quantum size effect, surface effect, synergistic effect and other nano composite advantages of nano zinc oxide in polymer reinforcement compared with the conventional micron-sized material while the zinc oxide whisker and mica are synergistically reinforced, introduces the nano zinc oxide in the form of master batch through the main feeding, fully utilizes the spatial synergistic reinforcement effect of micron and nano fillers with different sizes and shapes in the matrix material, further improves the tensile strength and rigidity of the composite material while reducing the filling amount of the mica, and effectively realizes the low filling and high performance of the polypropylene material (example 9 and example 10).
Although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A polypropylene composite characterized by: the coating comprises the following components in parts by weight: 60-90 parts of polypropylene, 10-40 parts of fluorophlogopite, 3-8 parts of zinc oxide whisker, 0.5-1.0 part of nano zinc oxide, 1-5 parts of compatilizer, 0.4-0.7 part of antioxidant, 0.2-0.5 part of nucleating agent and 0.2-0.5 part of lubricant; the chemical structural formula of the fluorophlogopite is KMg3(AlSi3O10)F2The average grain diameter is 20-80 μm, the length-diameter ratio is more than or equal to 60, and the whiteness is 94-96; the zinc oxide whisker is of a three-dimensional four-needle structure, and the length of a needle body of the zinc oxide whisker is 1-3 mu m; the nano zinc oxide is fibrous whisker with the grain diameter of 20-100 nm.
2. The polypropylene composite according to claim 1, wherein: the coating comprises the following components in parts by weight: 70-80 parts of polypropylene, 20-25 parts of fluorophlogopite, 3-5 parts of zinc oxide whisker, 0.8-1.0 part of nano zinc oxide, 3-5 parts of compatilizer, 0.4-0.6 part of antioxidant, 0.3-0.4 part of nucleating agent and 0.3-0.4 part of lubricant.
3. The polypropylene composite according to claim 1, wherein: the polypropylene is selected from homo-polypropylene and/or random co-polypropylene, and the melt flow rate is 10-60g/10min at 230 ℃ and under 2.16kg pressure.
4. The polypropylene composite according to claim 1, wherein: fe in the fluorophlogopite2O3Not more than 0.25 wt%, and TiO2≤0.1wt％。
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