CN111393749A - Polypropylene composite material and preparation method thereof - Google Patents
Polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a polypropylene composite material and a preparation method thereof. The preparation method of the polypropylene composite material provided by the invention comprises the following steps: providing deactivated molecular sieve powder, wherein the chemical composition of the deactivated molecular sieve powder comprises aluminum oxide and silicon oxide; modifying the inactivated molecular sieve powder by using a coupling agent to obtain a modified molecular sieve; and mixing the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent, and sequentially carrying out melt blending and injection molding on the obtained mixed material to obtain the polypropylene composite material. Test knotThe result shows that the density of the polypropylene composite material prepared by the preparation method is as low as 0.902g/cm3The density is low; the tensile strength reaches 40.8MPa, the bending strength reaches 49MPa, the bending modulus reaches 1290MPa, and the impact strength reaches 40.8KJ/m2And the mechanical property is excellent.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a polypropylene composite material and a preparation method thereof.
Background
The method for carrying out composite modification on polypropylene (PP) is a conventional method for improving mechanical properties such as flexural modulus, tensile strength and the like of polypropylene at present. Fillers commonly used to reinforce and modify PP include talc, mica, wollastonite, glass fibers, and whiskers. It has been reported that 20 wt.% talc filled polypropylene can achieve a flexural modulus of 2000MPa, but at a higher density (about 1.04 g/cm)3) The product has larger mass; the density of the 10 wt.% talc-filled polypropylene was about 0.97g/cm3However, the flexural modulus and tensile strength are low, and thus, it is seen that talc powder filling cannot satisfy both low density and high performance of polypropylene. The glass fiber reinforced polypropylene has good mechanical property, but the density of the prepared material is 1.5g/cm3～2.0g/cm3(＞1.0g/cm3) And the density is high, so that the requirement of lightweight composite materials is difficult to meet. Therefore, the existing modified polypropylene material cannot meet the requirements of low density and high mechanical property at the same time.
Deactivated molecular sieve catalysts in the Methanol To Propylene (MTP) industry are generally only stockpiled or directly discarded as industrial solid wastes, and resource recycling is difficult to realize.
At present, no report is available for recycling deactivated molecular sieve catalysts in the Methanol To Propylene (MTP) industry to obtain modified polypropylene materials with low density and high mechanical properties.
Disclosure of Invention
In view of the above, the invention aims to provide a polypropylene composite material, which has the advantages of low density, high flexural modulus and high tensile strength, and realizes the recycling of solid wastes; the invention also provides a preparation method of the polypropylene composite material.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of a polypropylene composite material, which comprises the following steps:
providing deactivated molecular sieve powder, wherein the chemical composition of the deactivated molecular sieve powder comprises aluminum oxide and silicon oxide;
modifying the inactivated molecular sieve powder by using a coupling agent to obtain a modified molecular sieve;
and mixing the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent, and sequentially carrying out melt blending and injection molding on the obtained mixed material to obtain the polypropylene composite material.
Preferably, the median particle size of the deactivated molecular sieve powder is less than or equal to 2 mu m
Preferably, the method of modification comprises the steps of:
mixing a coupling agent with an ethanol aqueous solution, and performing hydrolysis reaction under an acidic condition to obtain a coupling agent hydrolysate; the coupling agent is a silane coupling agent;
mixing the coupling agent hydrolysate with the inactivated molecular sieve powder for modification reaction;
and sequentially cleaning, drying, grinding and sieving the product of the modification reaction to obtain the modified molecular sieve.
Preferably, the volume ratio of the coupling agent to the ethanol aqueous solution is (1-1.5): 100, respectively; the volume fraction of ethanol in the ethanol aqueous solution is more than or equal to 95 percent; the hydrolysis reaction time is 5-10 min.
Preferably, the ratio of the coupling agent hydrolysate to the inactivated molecular sieve is (1-1.5) m L (15-20) g based on the mass ratio of the volume of the coupling agent to the inactivated molecular sieve.
Preferably, the temperature of the modification reaction is 55-65 ℃ and the time is 10-60 min.
Preferably, the mass ratio of the modified molecular sieve to the polypropylene to the polyolefin elastomer to the dispersant to the nucleating agent is (3-15): (65-77): (20-32): (0.1-0.5): (0.06-0.10).
Preferably, the temperature of the melt blending is 190-195 ℃; the melt blending equipment is a double-screw extruder; the rotating speed of the screw in the melt blending is 20-25 rpm;
preferably, the injection molding equipment is an injection molding machine; the temperature of the injection molding head in the injection molding process is 195 ℃, the temperature of the mold is 30-35 ℃, the injection molding pressure is 0.5-0.8 MPa, the injection molding time is 18-24 s, the pressure maintaining pressure is 0.2-0.3 MPa, and the mold closing time is 24-30 s.
The invention also provides the polypropylene composite material prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a polypropylene composite material, which comprises the following steps: providing deactivated molecular sieve powder, wherein the chemical composition of the deactivated molecular sieve powder comprises aluminum oxide and silicon oxide; modifying the inactivated molecular sieve powder by using a coupling agent to obtain a modified molecular sieve; and mixing the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent, and sequentially carrying out melt blending and injection molding on the obtained mixed material to obtain the polypropylene composite material. In the invention, the deactivated molecular sieve powder has a hierarchical pore structure, contains a large amount of cavities and pore channels inside, has an ultra-large specific surface area, is easy to modify on the surface, and has excellent physical properties, such as high strength, high modulus and small density, and meanwhile, electronegativity generated by a silicon-oxygen and aluminum-oxygen structure contained in the deactivated molecular sieve powder and a large specific surface area generated by a large amount of microporous structures endow the deactivated molecular sieve with excellent ion adsorption capacity and ion exchange capacity; modifying the inactivated molecular sieve powder by using a coupling agent is favorable for improving the compatibility with polypropylene; the polypropylene composite material is light in weight and high in mechanical property by taking polypropylene as a base material, a modified molecular sieve as a reinforcing filler and a polyolefin elastomer as a toughening agent.
The test result of the embodiment shows that the density of the polypropylene composite material prepared by the preparation method is 0.902-0.974 g/cm3The shrinkage rate is 1.01-1.03%, and the density is low; the tensile strength is 32 to 40.8MPa, the bending strength is 45.6 to 49MPa, the bending modulus is 1147 to 1290MPa, and the impact strength is 32 to 40.8KJ/m2And the mechanical property is excellent.
Drawings
FIG. 1 is a graph showing the density of the polypropylene composite material obtained in examples 1 to 5 as a function of the content of the deactivated molecular sieve;
FIG. 2 is a graph showing the variation of flexural modulus of the polypropylene composite material obtained in examples 1 to 5 with the content of the deactivated molecular sieve;
FIG. 3 is a graph showing the variation of bending strength of the polypropylene composite material obtained in examples 1 to 5 with the content of the deactivated molecular sieve;
FIG. 4 is a SEM image of a cross section of the polypropylene composite obtained in example 1;
FIG. 5 is a SEM image of a cross section of the polypropylene composite material obtained in example 2;
FIG. 6 is a SEM image of a cross section of the polypropylene composite obtained in example 3;
FIG. 7 is a SEM image of a cross section of the polypropylene composite obtained in example 4;
FIG. 8 is a SEM image of a cross section of the polypropylene composite obtained in example 5;
FIG. 9 is a SEM image of a cross section of a pure polypropylene material obtained in comparative example 1;
FIG. 10 is a POM photograph of the polypropylene composite obtained in example 2;
FIG. 11 is a POM photograph of the polypropylene composite obtained in example 3;
FIG. 12 is a POM photograph of the polypropylene composite obtained in example 5;
FIG. 13 is a POM photograph of a pure polypropylene material obtained in comparative example 1;
FIG. 14 is a DSC plot of the non-isothermal crystallization curves of the polypropylene composites obtained in examples 1-5 and comparative example 1, wherein the left graph is the non-isothermal crystallization curve and the right graph is the non-isothermal melting curve.
Detailed Description
The invention provides a preparation method of a polypropylene composite material, which comprises the following steps:
providing deactivated molecular sieve powder, wherein the chemical composition of the deactivated molecular sieve powder comprises aluminum oxide and silicon oxide;
modifying the inactivated molecular sieve powder by using a coupling agent to obtain a modified molecular sieve;
and mixing the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent, and sequentially carrying out melt blending and injection molding on the obtained mixed material to obtain the polypropylene composite material.
In the present invention, the components are commercially available products well known to those skilled in the art, unless otherwise specified.
The invention provides deactivated molecular sieve powder, and the chemical composition of the deactivated molecular sieve powder comprises aluminum oxide and silicon oxide.
In the present invention, the median particle diameter of the deactivated molecular sieve powder is preferably 2 μm or less. In the invention, the deactivated molecular sieve powder is preferably a deactivated molecular sieve catalyst (MTP-DC) in the industry of preparing propylene (MTP) from methanol. In the embodiment of the invention, the deactivated molecular sieve catalyst is from the institute of coal chemical industry, the national Ningxia coal industry group.
In the invention, the ball milling equipment is preferably a planetary ball mill, particularly a Miqi planetary ball mill, in the embodiment of the invention, the ball milling equipment is a Mitsu Miqi apparatus limited company with the model of MITR-YXQM-4L, in the invention, the diameters of the grinding balls in the ball milling are preferably 5mm, 3mm and 1mm, the mass ratio of the grinding balls with the diameters of 5mm, 3mm and 1mm is preferably (2-3): 3-5): 5-8, more preferably (2-2.5): 3-4: (5-6), most preferably 2: 3: 5, in the invention, the material ball ratio in the ball milling is preferably (1-2): 5-10), more preferably (1-1.5): 5), most preferably 1: 5, in the invention, the speed of the ball milling is preferably 1-1: 5, most preferably 300-300, and the grain size of the ball milling is preferably equal to or less than 380 μ rpm, and the median particle size of the ball milling is preferably equal to or less than 360 μ rpm.
The invention preferably tests the median particle size of the deactivated molecular sieve powder by a laser particle sizer. When the test result does not meet the requirement of the median particle size of the deactivated molecular sieve powder, the ball milling treatment is preferably continued.
After the inactivated molecular sieve powder is obtained, the coupling agent is adopted to modify the inactivated molecular sieve powder to obtain the modified molecular sieve.
In the present invention, the coupling agent is preferably a silane coupling agent, more preferably KH550, KH560, KH570 or KH580, and still more preferably KH 560.
In the present invention, the method of modification preferably comprises the steps of:
mixing a coupling agent with an ethanol aqueous solution, and performing hydrolysis reaction under an acidic condition to obtain a coupling agent hydrolysate;
mixing the coupling agent hydrolysate with the inactivated molecular sieve powder for modification reaction;
and sequentially cleaning, drying, grinding and sieving the product of the modification reaction to obtain the modified molecular sieve.
The coupling agent is mixed with an ethanol aqueous solution, and hydrolysis reaction is carried out under an acidic condition to obtain coupling agent hydrolysate.
In the invention, the volume ratio of the coupling agent to the ethanol aqueous solution is preferably (1-1.5): 100, more preferably (1 to 1.4): 100, respectively; the volume fraction of ethanol in the ethanol aqueous solution is preferably more than or equal to 95 percent. According to the invention, the pH value of the ethanol aqueous solution is preferably adjusted to 4-6, and then the ethanol aqueous solution is mixed with the coupling agent. In the present invention, the pH adjuster for adjusting pH is preferably 4 to 6, more preferably 4.5 to 5.5, and most preferably 5. The mixing method of the present invention is not particularly limited, and a mixing method known to those skilled in the art may be used. In the invention, the temperature of the hydrolysis reaction is preferably room temperature, specifically, 18-25 ℃; the time is preferably 5 to 10min, and more preferably 5 to 8 min. In the present invention, the hydrolysis reaction is preferably carried out under a static condition.
After the coupling agent hydrolysate is obtained, the coupling agent hydrolysate and the inactivated molecular sieve powder are mixed for modification reaction.
In the invention, the ratio of the coupling agent hydrolysate to the inactivated molecular sieve is (1-1.5) m L (15-20) g, and more preferably (1-1.4) m L (15-18) g, in terms of the mass ratio of the volume of the coupling agent to the inactivated molecular sieve.
In the invention, the temperature of the modification reaction is preferably 55-65 ℃, more preferably 57-62 ℃, most preferably 60 ℃, and the time is preferably 10-60 min, more preferably 20-40 min, most preferably 30 min.
After the modification reaction is finished, the product of the modification reaction is sequentially cleaned, dried, ground and sieved to obtain the modified molecular sieve.
In the present invention, the cleaning agent is preferably ethanol. The cleaning method of the present invention is not particularly limited, and a cleaning method known to those skilled in the art may be used. The coupling agent hydrolysate physically adsorbed on the surface of the modified reaction product is removed by ethanol cleaning. In the invention, the drying temperature is preferably 100-130 ℃, and the drying time is preferably 8-10 h. The present invention is not particularly limited to the above-mentioned grinding, and a grinding known to those skilled in the art may be used. In the present invention, the mesh number of the sieving screen is preferably not less than 5000 mesh. The sieving mode is not particularly limited in the invention, and the sieving mode known to the person skilled in the art can be adopted.
Before the cleaning, the invention preferably also comprises the step of preserving the heat of the modified reaction product; the temperature of the heat preservation is preferably 20 ℃, and the time is preferably 30-60 min.
According to the invention, the inactivated molecular sieve is modified, as the coupling agent can be hydrolyzed under an acidic condition to generate silicon hydroxyl and epoxy group, the silicon hydroxyl and hydroxyl on the surface of the inorganic micromolecule MTP-DC are subjected to condensation reaction to form a chemical bond, and the epoxy group can be subjected to epoxy ring opening under the action of heat to perform chemical reaction with a side group of polypropylene (PP), so that the coupling between the MTP-DC and the PP is realized through subsequent two-phase reaction, the compatibility between the MTP-DC and the PP is improved, and the mechanical property of the polypropylene composite material is further improved.
After the modified molecular sieve is obtained, the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent are mixed, and are sequentially subjected to melt blending and injection molding to obtain the polypropylene composite material.
In the present invention, the mass ratio of the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent is preferably (3-15): 65-77): 20-32): 0.1-0.5): 0.06-0.10), more preferably (5-13): 67-75): 21-29): 0.15-0.3): 0.07-0.09, and more preferably (3-15): 65-77): 23: 0.2: 0.08. in the present invention, the polypropylene is preferably isotactic polypropylene, in the present invention, the polypropylene is preferably polypropylene pellets, the present invention has no specific limitation on the particle size of the polypropylene pellets, and polypropylene pellets known to those skilled in the art are used.
The present invention preferably comprises drying the modified molecular sieve and the polypropylene prior to mixing the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent. In the invention, the drying treatment of the modified molecular sieve is preferably vacuum drying, the drying temperature is preferably 130 ℃, and the drying time is preferably 8 h. In the invention, the polypropylene is preferably dried in vacuum at 80 ℃ for 8 hours. The present invention prevents decomposition of the processed product and generation of air bubbles in the sample due to the presence of moisture by the drying treatment.
In the present invention, the apparatus for melt blending is preferably a twin-screw extruder, more preferably a conical twin-screw extruder. In an embodiment of the present invention, the twin screw extruder is a miniature conical twin screw extruder, model SJZS-10A, manufactured by Wuhanrui plastics machinery manufacturing company. In the invention, the melt blending temperature is preferably 190-195 ℃, and specifically, according to the direction from the first temperature zone to the fourth temperature zone, the temperatures of the four temperature zones of the double-screw extruder in the melt blending process are preferably 190-195 ℃, 195 ℃ and 195 ℃ in sequence. In the present invention, the rotation speed of the screw in the melt blending is preferably 20 to 25rpm, and more preferably 21 to 24 rpm.
In the present invention, the injection molding apparatus is preferably an injection molding machine. In an embodiment of the invention, the injection molding equipment is a micro injection molding machine manufactured by Wuhanrui plastics machinery manufacturing company, and the model is SZS-15. In the invention, the injection molding process is to perform pressure maintaining after the melt blended product is injected into a mold. In the invention, the temperature of the injection head in the injection molding is preferably 195 ℃, and the temperature of the mold is preferably 30-35 ℃, and more preferably 32-35 ℃. In the invention, the injection pressure in the injection molding is preferably 0.5-0.8 MPa, more preferably 0.6-0.7 MPa, and most preferably 0.6 MPa; the injection time is preferably 18 to 24 seconds, and more preferably 19 to 23 seconds. In the invention, the pressure maintaining pressure in the injection molding is preferably 0.2-0.3 MPa, and more preferably 0.22-0.28 MPa; the mold clamping time is preferably 24 to 30 seconds, and more preferably 25 to 29 seconds.
The invention also provides the polypropylene composite material prepared by the preparation method in the technical scheme. In the present invention, the polypropylene composite includes polypropylene, a polyolefin elastomer, a dispersant and a nucleating agent.
In the invention, the density of the polypropylene composite material is preferably 0.902-0.974 g/cm3The shrinkage rate is preferably 1.01-1.03%; the tensile strength is preferably 32 to 40.8MPa, the bending strength is preferably 45.6 to 49MPa, the bending modulus is preferably 1147 to 1290MPa, and the impact strength is preferably 32 to 40.8KJ/m2。
In order to further illustrate the present invention, the following examples are provided to describe a polypropylene composite material and a method for preparing the same in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
According to the gradation, the ratio of 2: 3: 5, placing grinding balls with the diameters of 5mm, 3mm and 1mm into a ball mill, wherein the material-ball ratio is 1: 5, ball milling the inactivated molecular sieve MTO-DC at the ball milling rotation speed of 360rpm, detecting the particle size of a ball milling product by using a laser particle sizer until the median particle size of the ball milling product is less than or equal to 2 mu m, and obtaining inactivated molecular sieve powder;
adjusting pH to 4 with 100m L volume fraction 95% ethanol, adding 1m L silane coupling agent KH560, standing and hydrolyzing for 5min to obtain coupling agent hydrolysate;
adding 15g of inactivated molecular sieve powder into the obtained coupling agent hydrolysate while stirring at a constant temperature of 60 ℃, reacting for 0.5h, standing for 1h at 20 ℃, repeatedly washing the reacted suspension with ethanol after cooling, drying for 24h at 100 ℃, grinding, and sieving with a 5000-mesh sieve to obtain a modified molecular sieve;
drying the obtained modified molecular sieve for 8 hours in vacuum at the temperature of 130 ℃; carrying out vacuum drying on the polypropylene granules for 8h at the temperature of 80 ℃;
mixing the dried modified molecular sieve, the dried polypropylene, the polyolefin elastomer POE, the dispersing agent TAS-2A and the nucleating agent HPN-68L according to the mass ratio of 3: 77: 23: 0.2: 0.08, carrying out melt blending by adopting a double-screw extruder, wherein the temperatures of four temperature zones of the double-screw extruder from the first temperature zone to the fourth temperature zone are 190 ℃, 195 ℃ and 195 ℃ respectively, the screw rotating speed is 20rpm, and then carrying out injection molding on an injection molding machine, wherein the temperature of an injection molding head is 195 ℃, the mold temperature is 35 ℃, the injection molding pressure is 0.6MPa, the injection molding time is 18s, the holding pressure is 0.25MPa, and the mold closing time is 24s, thus obtaining the polypropylene composite material.
Example 2
The mass ratio of the dried modified molecular sieve, the dried polypropylene, the polyolefin elastomer POE, the dispersant TAS-2A and the nucleating agent HPN-68L was 5: 75: 23: 0.2: 0.08, and the rest was the same as in example 1, to obtain the polypropylene composite material.
Example 3
The mass ratio of the dried modified molecular sieve, the dried polypropylene, the polyolefin elastomer POE, the dispersant TAS-2A and the nucleating agent HPN-68L was 10: 70: 23: 0.2: 0.08, and the rest was the same as in example 1, to obtain the polypropylene composite material.
Example 4
The mass ratio of the dried modified molecular sieve, the dried polypropylene, the polyolefin elastomer POE, the dispersant TAS-2A and the nucleating agent HPN-68L was 12: 68: 23: 0.2: 0.08, and the rest was the same as in example 1, to obtain the polypropylene composite material.
Example 5
The mass ratio of the dried modified molecular sieve, the dried polypropylene, the polyolefin elastomer POE, the dispersant TAS-2A and the nucleating agent HPN-68L was 15: 65: 23: 0.2: 0.08, and the rest was the same as in example 1, to obtain the polypropylene composite material.
Comparative example 1
Directly performing melt extrusion and injection molding on the polypropylene granules, wherein the melt extrusion parameters are the same as those of the melt blending extrusion parameters in the example 1; the injection molding parameters were the same as in example 1, resulting in a pure polypropylene material.
Comparative example 2
The application of the literature "anlin, zhao haiying, li xue, zhongguang-liang" low density polypropylene materials in automotive interiors studies [ J ] automotive processes and materials, 2018 (06): 8-10 "of a low density polypropylene material.
The polypropylene composite materials obtained in examples 1 to 5 and the materials in comparative examples 1 to 2 were tested as follows:
1. the densities of the polypropylene composite materials obtained in examples 1-5 and the polypropylene composite materials obtained in comparative examples 1-2 were measured according to GB 1033-86 test methods for Plastic Density and relative Density, the test results are shown in Table 1, and FIG. 1 is drawn from Table 1.
TABLE 1 Density measurement results of materials obtained in examples 1 to 5 and comparative examples 1 to 2
| Density/(g/cm)3) | |
| Example 1 | 0.902 |
| Example 2 | 0.925 |
| Example 3 | 0.947 |
| Example 4 | 0.956 |
| Example 5 | 0.974 |
| Comparative example 1 | 0.898 |
| Comparative example 2 | 1.040 |
As can be seen from Table 1 and FIG. 1, the density of the polypropylene composite material provided by the invention is 0.902-0.974 g/cm3And is beneficial to reducing the weight of the polypropylene composite material.
2. The shrinkage of the polypropylene composite materials obtained in examples 1 to 5 and the polypropylene composite materials obtained in comparative examples 1 to 2 were measured according to GB/T17037.4-2003 "measurement of shrinkage in part 4 of injection molded specimens of thermoplastic materials", and the results are shown in Table 2.
TABLE 2 measurement results of shrinkage of materials obtained in examples 1 to 5 and comparative examples 1 to 2
| Shrinkage rate/％ | |
| Example 1 | 1.03 |
| Example 2 | 1.02 |
| Example 3 | 1.03 |
| Example 4 | 1.01 |
| Example 5 | 1.03 |
| Comparative example 1 | 1.42 |
| Comparative example 2 | 1.00 |
As can be seen from Table 2, the shrinkage of the polypropylene composite material provided by the invention is 1.01-1.03%, which is low and indicates that the nucleating agent in the polypropylene composite material provided by the invention is properly selected.
3. The tensile properties of the polypropylene composite materials obtained in examples 1-5 and the materials obtained in comparative examples 1-2 were measured according to GB/T1040-.
TABLE 3 tensile Strength test results of the materials obtained in examples 1 to 5 and comparative examples 1 to 2
| Tensile strength/MPa | |
| Example 1 | 40.8 |
| Example 2 | 38.8 |
| Example 3 | 36.4 |
| Example 4 | 33.05 |
| Example 5 | 32 |
| Comparative example 1 | 38.4 |
| Comparative example 2 | 20 |
As can be seen from table 3, the tensile strength of the polypropylene tends to decrease with increasing MTP-DC content, and when the molecular sieve content is 15%, the tensile strength of the polypropylene composite material is 28.9MPa, which is still 44.5% higher than that of the known polypropylene material with 20 wt.% talc added.
4. The bending properties of the polypropylene composite materials obtained in examples 1-5 and the materials obtained in comparative examples 1-2 are measured according to GB/T9341-2008 'determination of Plastic bending Properties', the results of the flexural modulus are shown in Table 4, and a graph 2 is drawn from Table 4; the results of the flexural strength measurements are shown in Table 5, and FIG. 3 is plotted in Table 5.
TABLE 4 flexural modulus test results for the materials obtained in examples 1-5 and comparative examples 1-2
| Flexural modulus/MPa | |
| Example 1 | 1147 |
| Example 2 | 1238 |
| Example 3 | 1237 |
| Example 4 | 1275 |
| Example 5 | 1290 |
| Comparative example 1 | 1244.6 |
| Comparative example 2 | 1500 |
As can be seen from table 4 and fig. 2, the flexural modulus of the polypropylene composite gradually increased with increasing content of the modified MTP-DC. The modulus of the modified MTP-DC molecular sieve is far higher than that of PP resin, and the molecular sieve is uniformly distributed in PP, so that heterogeneous nucleation of PP is facilitated, the number of spherulites is increased, and the volume of the spherulites is reduced, so that the flexural modulus of the composite material is increased along with the increase of the MTP-DC content, but the acceleration is slow after the MTP-DC content reaches 10%, and the tendency of the increase of the flexural modulus is slowed down due to the agglomeration phenomenon along with the increase of the MTP-DC content in combination with SEM morphology analysis. When the MTP-DC content is more than 5 percent, the flexural modulus is more than 1200 MPa.
TABLE 5 flexural Strength test results of the materials obtained in examples 1 to 5 and comparative examples 1 to 2
| Flexural Strength/MPa | |
| Example 1 | 46.7 |
| Example 2 | 49 |
| Example 3 | 46.5 |
| Example 4 | 46.1 |
| Example 5 | 45.6 |
| Comparative example 1 | 60.1 |
| Comparative example 2 | 30 |
As can be seen from table 5 and fig. 3, as the content of the modified MTP-DC increases, the flexural strength of the polypropylene composite material increases first and then decreases, and when the content of the molecular sieve is 5%, the flexural strength reaches a maximum of 49MPa, which is 39% higher than that of the polypropylene composite material added with 20 wt.% of talc powder. When the MTP-DC content is 15%, the bending strength is 45.6MPa, which is still 34% higher than that of the polypropylene composite material added with 20 wt% of talcum powder.
5. The notched impact strength of the polypropylene composite materials obtained in examples 1-5 and the notched impact strength of the polypropylene composite materials obtained in comparative examples 1-2 were measured according to GB/T1843-2008 "determination of impact strength of Plastic cantilever beam", and the results are shown in Table 6.
TABLE 6 notched impact Strength test results for the materials obtained in examples 1-5 and comparative examples 1-2
| Notched impact strength/(KJ/m) | |
| Example 1 | 40.8 |
| Example 2 | 38.8 |
| Example 3 | 36.4 |
| Example 4 | 33.05 |
| Example 5 | 32 |
| Comparative example 1 | 4.1 |
| Comparative example 2 | 25 |
As can be seen from table 6, when the POE content is 23 wt.%, the notched impact strength of the polypropylene composite tends to decrease as the MTP-DC content increases. The MTP-DC is inorganic rigid particles, and the agglomeration of the MTP-DC in the polymer is intensified along with the increase of the content of the MTP-DC, so that more stress defect points appear, and the impact strength is reduced; when the content of MTP-DC was increased to 15 wt.%, the notched impact strength was 32KJ/m2The toughness of the polypropylene composite material provided by the invention is higher than that of a PP material added with 20 wt.% of talcum powder by 28%.
6. After drying the cross section of the material after impact, spraying gold, observing the cross section morphology by using a scanning electron microscope (ZEISS EV018), wherein the obtained observation picture is shown in figures 4-9, wherein figure 4 is a cross section SEM picture of the polypropylene composite material obtained in example 1, figure 5 is a cross section SEM picture of the polypropylene composite material obtained in example 2, figure 6 is a cross section SEM picture of the polypropylene composite material obtained in example 3, figure 7 is a cross section SEM picture of the polypropylene composite material obtained in example 4, figure 8 is a cross section SEM picture of the polypropylene composite material obtained in example 5, and figure 9 is a cross section SEM picture of a pure polypropylene material obtained in comparative example 1.
As can be seen from the graphs of 4-9, the cracks on the section of the pure polypropylene material are flat and irregular, and are classic brittle fractures, the cracks have small resistance in the extending process, are easy to extend, and have small absorbed impact energy and poor impact toughness; the phenomena of wire drawing and silver streak appear on the impact section of the polypropylene composite material, which are caused by the addition of the POE elastomer, the elastomer shows obvious plastic deformation in the material impact-breaking process, and the number of particles on the section is gradually increased along with the increase of the content of the MTP-DC, and the particles are increased, which are caused by the agglomeration of the MTP-DC due to the increase of the content.
7. The morphology of spherulites of the polypropylene composites obtained in examples 2,3 and 5 and the pure polypropylene obtained in comparative example 1 were analyzed, and the obtained POM photos are shown in FIGS. 10-13, wherein FIG. 10 is the POM photo of the polypropylene composite obtained in example 2, FIG. 11 is the POM photo of the polypropylene composite obtained in example 3, FIG. 12 is the POM photo of the polypropylene composite obtained in example 5, and FIG. 13 is the POM photo of the pure polypropylene obtained in comparative example 1.
As can be seen from FIGS. 10-13, the pure polypropylene material has complete and large spherulites, and the addition of 0.08 wt.% of HPN-68L results in smaller and incomplete spherulites, which indicates that HPN-68L is an effective nucleating agent for PP, and moreover, with the addition of equal amount of HPN-68L, the size of PP spherulites is further reduced, the amount of PP spherulites is increased, the internal defects of the spherulites are increased, and the spherulite morphology becomes fuzzy, which indicates that the addition of a large amount of MTP-DC can destroy the regularity of the spherulite arrangement.
8. Non-isothermal crystallization and melting tests were performed on the polypropylene composite materials obtained in examples 1 to 5 and the pure polypropylene material obtained in comparative example 1, and the non-isothermal crystallization parameters are shown in table 7; the resulting DSC non-isothermal crystallization curve is shown in FIG. 14, wherein the left panel is the non-isothermal crystallization curve and the right panel is the non-isothermal melting curve.
TABLE 7 non-isothermal crystallization parameters of the polypropylene composites obtained in examples 1-5 and the pure polypropylene material in comparative example 1
| Tc/℃ | Tonset/℃ | Tonset-Tc/℃ | ΔW/℃ | Tm/℃ | |
| Example 1 | 127.5 | 130.7 | 3.2 | 4.3 | 159.2 |
| Example 2 | 127.5 | 130.9 | 3.4 | 4.4 | 159.2 |
| Example 3 | 125.6 | 129.3 | 3.7 | 4.5 | 159.8 |
| Example 4 | 125.6 | 129.3 | 3.7 | 4.5 | 159.6 |
| Example 5 | 124.4 | 128.3 | 3.9 | 4.7 | 159.3 |
| Comparative example 1 | 115.5 | 120.0 | 4.5 | 5.5 | 157.1 |
As can be seen from Table 7 and FIG. 14, as the content of MTP-DC molecular sieve increases, the position of the crystallization peak of the polypropylene composite material shifts to a high temperature direction as a whole and the half width of the crystallization peak becomes smaller, which shows that the PP crystallizes at a higher temperature with the addition of HPN-68L and the crystallization rate is faster than that of pure PP, the difference between the crystallization initiation temperature (Tonset) and the crystallization temperature (Tc) of the crystallization peak is measured as the crystallization rate of the PP, the smaller the value of the crystallization rate is, the faster the crystallization rate is, and as the content of MTP-DC increases, the Tonset-Tc value of the MTP-DC/PP composite material increases and is smaller than that of pure PP, the crystallization and melting half width (Δ W) is significantly smaller than that of pure PP, and again, the addition of HPN-68L has a nucleating effect on the crystallization of PP, but the nucleating effect is relatively weakened as the content of MTP-DC molecular sieve increases.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the polypropylene composite material is characterized by comprising the following steps:
providing deactivated molecular sieve powder, wherein the chemical composition of the deactivated molecular sieve powder comprises aluminum oxide and silicon oxide;
modifying the inactivated molecular sieve powder by using a coupling agent to obtain a modified molecular sieve;
and mixing the modified molecular sieve, the polypropylene, the polyolefin elastomer, the dispersant and the nucleating agent, and sequentially carrying out melt blending and injection molding on the obtained mixed material to obtain the polypropylene composite material.
2. The method of claim 1, wherein the deactivated molecular sieve powder has a median particle size of 2 μm or less.
3. The method of claim 1, wherein the modifying comprises the steps of:
mixing a coupling agent with an ethanol aqueous solution, and performing hydrolysis reaction under an acidic condition to obtain a coupling agent hydrolysate; the coupling agent is a silane coupling agent;
mixing the coupling agent hydrolysate with the inactivated molecular sieve powder for modification reaction;
and sequentially cleaning, drying, grinding and sieving the product of the modification reaction to obtain the modified molecular sieve.
4. The preparation method according to claim 3, wherein the volume ratio of the coupling agent to the ethanol aqueous solution is (1-1.5): 100, respectively; the volume fraction of ethanol in the ethanol aqueous solution is more than or equal to 95 percent; the hydrolysis reaction time is 5-10 min.
5. The preparation method of claim 3, wherein the ratio of the coupling agent hydrolysate to the deactivated molecular sieve is (1-1.5) m L (15-20) g based on the mass ratio of the volume of the coupling agent to the deactivated molecular sieve.
6. The preparation method according to claim 3, wherein the temperature of the modification reaction is 55-65 ℃ and the time is 10-60 min.
7. The preparation method of claim 1, wherein the mass ratio of the modified molecular sieve to the polypropylene to the polyolefin elastomer to the dispersant to the nucleating agent is (3-15): (65-77): (20-32): (0.1-0.5): (0.06-0.10).
8. The preparation method according to claim 1, wherein the temperature of the melt blending is 190-195 ℃; the melt blending equipment is a double-screw extruder; the rotating speed of the screw in the melt blending is 20-25 rpm.
9. The method of manufacturing according to claim 1, wherein the injection molding apparatus is an injection molding machine; the temperature of the injection molding head in the injection molding process is 195 ℃, the temperature of the mold is 30-35 ℃, the injection molding pressure is 0.5-0.8 MPa, the injection molding time is 18-24 s, the pressure maintaining pressure is 0.2-0.3 MPa, and the mold closing time is 24-30 s.
10. The polypropylene composite material prepared by the preparation method of any one of claims 1 to 9.
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