CN117946478B - Toughened isotactic polypropylene composite material, preparation method thereof and method for improving impact strength of isotactic polypropylene - Google Patents
Toughened isotactic polypropylene composite material, preparation method thereof and method for improving impact strength of isotactic polypropylene Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 105
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 104
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000571 Nylon 11 Polymers 0.000 claims abstract description 80
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 21
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 15
- 239000000806 elastomer Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 33
- 238000000465 moulding Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 10
- OXJCOJXHCPVIPV-UHFFFAOYSA-N 4-n,4-n-dicyclohexylbenzene-1,4-dicarboxamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N(C1CCCCC1)C1CCCCC1 OXJCOJXHCPVIPV-UHFFFAOYSA-N 0.000 claims description 4
- VXROOKJCZCDMMS-UHFFFAOYSA-N dcht Chemical compound CC(=O)OC1C(OC(C)=O)C2(C)CC(C)CCC2C(OC(C)=O)C2CC(=O)C(C)=C1C2(C)C VXROOKJCZCDMMS-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 10
- 239000004677 Nylon Substances 0.000 abstract description 9
- 229920001778 nylon Polymers 0.000 abstract description 9
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- 239000000463 material Substances 0.000 abstract description 4
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- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241000533950 Leucojum Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses a toughened isotactic polypropylene composite material, a preparation method thereof and a method for improving the impact strength of isotactic polypropylene, and belongs to the field of high polymer materials. The toughened isotactic polypropylene composite material comprises isotactic polypropylene, a second monomer and N' N-dicyclohexyl terephthalamide, wherein the second monomer is nylon 11, nylon 1212 or thermoplastic polyurethane elastomer; when the second monomer is nylon 11 or nylon 1212, the raw materials are as follows: 70-97 parts of isotactic polypropylene, 3-30 parts of second monomer and 0.05-1 part of N' -N-dicyclohexyl terephthalamide. According to the invention, DCHT can form different self-assembly morphologies at different temperature concentrations, and the mechanical properties of the isotactic polypropylene blend can be regulated and controlled by changing the processing temperature and the concentration, so that the preparation requirements of isotactic polypropylene with different mechanical property materials are met.
Description
Technical Field
The application relates to a toughened isotactic polypropylene composite material, a preparation method thereof and a method for improving the impact strength of isotactic polypropylene, belonging to the field of high polymer materials.
Background
The isotactic polypropylene has the advantages of excellent comprehensive mechanical property, good electrical insulation, chemical corrosion resistance and the like, and is low in price, and the isotactic polypropylene is widely applied to the fields of daily necessities, household appliances, automobiles and the like. However, the isotactic polypropylene has poor impact resistance and limits the application range, so that the toughening of the isotactic polypropylene is always an important research content at home and abroad.
For example, chinese patent application CN201310193831.0 discloses a process for toughening isotactic polypropylene iPP articles with atactic polypropylene as elastomer, comprising the steps of: melt blending and extruding atactic polypropylene aPP and isotactic polypropylene iPP granules in a double-screw extruder, wherein the content of atactic polypropylene in the blend is lower than 30wt%; the aPP/iPP blend pellets were then processed into articles on a conventional injection molding machine by drying and injection molding.
The Chinese patent application CN201910933449.6 discloses a toughened isotactic polypropylene composite material and a preparation method thereof, and the composite filler prepared by the scheme is prepared by carrying out melt blending modification on the equivalent isotactic polypropylene by titanate whisker with SiO 2 coated on the surface and the multi-wall carbon nano tube composite filler, so that the impact strength of the obtained composite material is greatly improved, and the tensile strength is hardly affected under the condition that the Young modulus of the material is also improved.
Chinese patent application CN201510000542.3 discloses a preparation method of in-situ toughening polypropylene alloy, which grafts high vinyl polybutadiene on a polypropylene molecular chain in situ by a reaction extrusion method so as to improve the interfacial compatibility degree of polypropylene and the high vinyl polybutadiene.
At present, the main mode of blending and toughening isotactic polypropylene is to introduce rubber, elastomer or semi-crystalline polymer, such as ethylene propylene diene monomer, high-density polyethylene and the like, and polypropylene grafted maleic anhydride is often required to be used as a compatibilizer because of poor compatibility.
For this reason, a new method and/or material is urgently needed to solve the above-mentioned problems.
Disclosure of Invention
The application aims to provide a toughened isotactic polypropylene composite material, a preparation method thereof and a method for improving the impact strength of isotactic polypropylene so as to realize the toughening effect of isotactic polypropylene.
The technical scheme of the invention is as follows:
The first technical problem to be solved by the invention is to provide a toughened isotactic polypropylene composite material, which comprises isotactic polypropylene, a second monomer and N' N-dicyclohexyl terephthalamide, wherein the second monomer is nylon 11, nylon 1212 or thermoplastic polyurethane elastomer;
when the second monomer is nylon 11 or nylon 1212, the raw materials are as follows:
70 to 97 parts by weight of isotactic polypropylene,
3 To 30 parts by weight of a second monomer,
0.05 To 1 weight part of N' N-dicyclohexyl terephthalamide;
when the second monomer is thermoplastic polyurethane elastomer, the proportion of the raw materials is as follows:
80 parts by weight of isotactic polypropylene,
20 Parts by weight of a second monomer,
0.05 To 1 part by weight of N' -dicyclohexyl terephthalamide.
When the second monomer is nylon 11 or nylon 1212, the raw materials are as follows:
80 parts by weight of isotactic polypropylene,
20 Parts by weight of a second monomer,
0.05 To 1 part by weight of N' -dicyclohexyl terephthalamide.
The composite material has a core-shell structure.
Further, the second technical problem to be solved by the invention is to provide a preparation method of the toughened isotactic polypropylene composite material, which comprises the following steps: uniformly mixing isotactic polypropylene and a second monomer according to a proportion, adding N' N-dicyclohexyl terephthalamide, and carrying out melt blending to obtain a first melt; and then cooling and granulating the obtained first melt, and performing hot press molding to obtain the toughened isotactic polypropylene composite material.
Further, under the conditions of 180-200 ℃ and 6-30min and 30-60rpm of rotating speed, the first melt is obtained by melt blending.
Further, melt blending was performed at 180℃for 10min at a rotation speed of 50 rpm.
Further, the hot press molding temperature is 200-240 ℃.
The third technical problem to be solved by the invention is to provide a method for improving the impact strength of isotactic polypropylene, which comprises the steps of introducing N' N-dicyclohexyl terephthalamide and a second monomer into isotactic polypropylene, wherein the second monomer is selected from nylon 11 or nylon 1212 or thermoplastic polyurethane elastomer;
when the second monomer is nylon 11 or nylon 1212, the raw materials are as follows:
70 to 97 parts by weight of isotactic polypropylene,
3 To 30 parts by weight of a second monomer,
0.05 To 1 weight part of N' N-dicyclohexyl terephthalamide;
when the second monomer is thermoplastic polyurethane elastomer, the proportion of the raw materials is as follows:
80 parts by weight of isotactic polypropylene,
20 Parts by weight of a second monomer,
0.05 To 1 part by weight of N' -dicyclohexyl terephthalamide.
The method comprises the following steps of: uniformly mixing isotactic polypropylene and a second monomer according to a proportion, adding N' N-dicyclohexyl terephthalamide, and carrying out melt blending to obtain a first melt; and then cooling and granulating the obtained first melt, and performing hot press molding to obtain the toughened isotactic polypropylene composite material.
Drawings
FIG. 1 is an electron micrograph of impact fracture of the iPP/20% PA11 blend system of example 1: corresponds to a DCHT content of 0.1% at 240 ℃, a DCHT content of 1.0% at 200 ℃ and a DCHT content of 0.3% at 240 ℃ in order from left to right.
FIG. 2 is an electron micrograph of the iPP/20% PA11 blend system of example 1 at various DCHT concentrations and at various temperatures: the first row corresponds to 0.05% DCHT content at 200 ℃, 0.1% DCHT content at 200 ℃, 0.3% DCHT content at 200 ℃, 0.5% DCHT content at 200 ℃, 1% DCHT content at 200 ℃ in order from left to right, and the second row corresponds to 0.05% DCHT content at 240 ℃, 0.1% DCHT content at 240 ℃, 0.3% DCHT content at 240 ℃, 0.5% DCHT content at 240 ℃ and 1% DCHT content at 240 ℃ in order from left to right.
FIG. 3 is a graph showing the mechanical properties of the iPP/20% PA11 composite material prepared in example 1: the left plot shows the tensile strength of iPP/20% PA11 at various DCHT levels and processing temperatures, and the right plot shows the impact strength of iPP/20% PA11 at various DCHT levels and processing temperatures.
FIG. 4 is an electron micrograph of the blend system with different PA11 content at iPP/0.3% DCHT of example 2: the first row corresponds to 3% PA11 content at 200 ℃, 10% PA11 content at 200 ℃, 15% PA11 content at 200 ℃, 20% PA11 content at 200 ℃ and 30% PA11 content at 200 ℃ in order from left to right, and the second row corresponds to 3% PA11 content at 240 ℃, 10% PA11 content at 240 ℃, 15% PA11 content at 240 ℃, 20% PA11 content at 240 ℃ and 30% PA11 content at 240 ℃ in order from left to right.
FIG. 5 is a graph showing the mechanical properties of the blend system of different PA11 content at iPP/0.3% DCHT in example 2: the left plot shows the tensile strength of iPP/0.3% DCHT at different PA11 levels and processing temperatures, and the right plot shows the impact strength of iPP/0.3% DCHT at different PA11 levels and processing temperatures.
FIG. 6 is an electron micrograph of the iPP/20% TPU372X blend system of example 3 at various DCHT concentrations and at various temperatures: the first row corresponds to 0.05% DCHT content at 200 ℃, 0.1% DCHT content at 200 ℃, 0.3% DCHT content at 200 ℃, 0.5% DCHT content at 200 ℃, 1% DCHT content at 200 ℃ in order from left to right, the second row corresponds to 0.05% DCHT content at 220 ℃, 0.1% DCHT content at 220 ℃, 0.3% DCHT content at 220 ℃, 0.5% DCHT content at 220 ℃, 1% DCHT content at 220 ℃, and the third row corresponds to 0.05% DCHT content at 240 ℃, 0.1% DCHT content at 240 ℃, 0.3% DCHT content at 240 ℃, 0.5% DCHT content at 240 ℃, 1% DCHT content at 240 ℃.
FIG. 7 is a graph of the mechanical properties of the iPP/20% TPU372X blend system of example 3: the left plot shows the tensile strength of iPP/20% tpu372x at different DCHT levels and processing temperatures, and the right plot shows the impact strength of iPP/20% tpu372x at different DCHT levels and processing temperatures.
FIG. 8 is a graph of the mechanical properties of the iPP/10% TPU372X/10% TPU1135AU blend system of example 4: the left plot shows the tensile strength of iPP/10% tpu372x/10% tpu1135au at different DCHT levels and processing temperatures, and the right plot shows the impact strength of iPP/10% tpu372x/10% tpu1135au at different DCHT levels and processing temperatures.
The DSC spectra of comparative example 4, comparative example 1, comparative example 2, comparative example 3, example 6, example 5 are given in fig. 9: the first row corresponds to iPP/0.05% DCHT, iPP/3% PA6/0.05% DCHT, iPP/3% PA610/0.05% DCHT, in order from left to right, and the second row corresponds to iPP/3% PA612/0.05% DCHT, iPP/3% PA11/0.05% DCHT, iPP/3% PA1212/0.05% DCHT, in order from left to right.
Fig. 10 shows the polarization microscope images of comparative example 4, comparative example 1, comparative example 2, comparative example 3, example 6, example 5: corresponding to each other from top to bottom iPP/0.05%DCHT、iPP/3%PA6/0.05%DCHT、iPP/3%PA610/0.05%DCHT、iPP/3%PA612/0.05%DCHT、iPP/3%PA11/0.05%DCHT、iPP/3%PA1212/0.05%DCHT.
Fig. 11 shows the rheological profiles of example 6 and comparative example 4.
Detailed Description
Aiming at the problem of toughening equivalent polypropylene, the application provides a toughened equivalent polypropylene composite material and a preparation method thereof. More specifically, the application provides a toughened isotactic polypropylene composite material and a preparation method thereof. In the formula of the application, DCHT is not only a nucleating agent of isotactic polypropylene, but also can induce the isotactic polypropylene to form beta crystals, and simultaneously amide bonds on DCHT can form hydrogen bonds with PA11 (or PA 1212) and TPU, thereby playing a role in compatibilization. Furthermore, in the composite material prepared by the application, PA11 (or PA 1212) or TPU is taken as an inner core, DCHT is adsorbed on the surface of the PA11 (or PA 1212) or TPU, meanwhile, DCHT induces isotactic polypropylene to crystallize, DCHT and partially crystallized isotactic polypropylene form an outer shell, so that the toughened isotactic polypropylene composite material with a core-shell structure is formed. Test results show that the application can improve the toughness of the isotactic polypropylene blend. Furthermore, DCHT can form different self-assembly morphologies under different temperature concentrations, and the mechanical properties of the isotactic polypropylene blend can be regulated and controlled by changing the processing temperature and the concentration, so that the preparation requirements of isotactic polypropylene with different mechanical property materials are met.
All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
Any feature disclosed in this specification may be replaced by alternative features serving the same or equivalent purpose, unless expressly stated otherwise. That is, each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise.
Example 1
TABLE 1 mass ratio of the components in example 1
| Sequence number | Isotactic polypropylene (iPP, brand T30S)/kg | Nylon 11 (PA 11, trade name BESN P/kg) | N' N-dicyclohexyl terephthalamide (DCHT)/kg | DCHT content (%) |
| 01 | 80 | 20 | 0.05 | 0.05 |
| 02 | 80 | 20 | 0.1 | 0.1 |
| 03 | 80 | 20 | 0.3 | 0.3 |
| 04 | 80 | 20 | 0.5 | 0.5 |
| 05 | 80 | 20 | 1.0 | 1.0 |
In table 1, the calculation formula of DCHT content (%) is as follows:
DCHT mass/(iPP mass+nylon 11 mass) = DCHT content (%).
The preparation method of the toughened isotactic polypropylene composite material comprises the following steps:
(1) Weighing the components according to the weight ratio of the table 1 for standby;
(2) Uniformly mixing the weighed isotactic polypropylene with nylon 11, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed to obtain a melt, and cooling and granulating the obtained melt;
(3) And (3) performing hot press molding on the obtained granules at the temperature of 200 ℃ and 240 ℃ by using a flat vulcanizing machine.
FIG. 1 shows an electron micrograph of impact fracture of the iPP/20% PA11 blend system of this example. In FIG. 1, the content of DCHT at 240℃is 0.1%, the content of DCHT at 200℃is 1.0% and the content of DCHT at 240℃is 0.3% in this order from left to right; wherein DCHT content corresponds to DCHT content in table 1, 200 ℃ and 240 ℃ corresponds to hot press molding temperature.
From the left side of fig. 1, the first and second diagrams can see the obvious core-shell structure, the white part of the broken sphere is the inner core PA11, and the gray part of the surface is the outer shell DCHT and isotactic polypropylene crystal. From the left side of fig. 1, the third graph shows that white snowflake polypropylene remains in the hemispherical pits on the impact section, which illustrates that the sphere of the core-shell structure is tightly combined with the polypropylene matrix.
FIG. 2 shows an electron micrograph of the blend system with different PA11 content at iPP/0.3% DCHT in this example. In fig. 2, the first column corresponds to 0.05% dhct content at 200 ℃, 0.1% dhct content at 200 ℃, 0.3% dhct content at 200 ℃, 0.5% dhct content at 200 ℃, 1% dhct content at 200 ℃ in order from left to right, and the second column corresponds to 0.05% dhct content at 240 ℃, 0.1% dhct content at 240 ℃, 0.3% dhct content at 240 ℃, 0.5% dhct content at 240 ℃, 1% dhct content at 240 ℃.
As can be seen from fig. 2, at higher DCHT content (0.5%, 1%) the DCHT on the surface of the sphere is mainly rod-like crystals, and at lower DCHT content (0.05%, 0.1%) the DCHT on the surface of the sphere is textured crystals. DCHT of 0.3% is more special, rod-shaped crystals and patterned crystals coexist at 200 ℃, and DCHT crystals are melted and assembled into a pattern when the temperature is increased by 240 ℃. Fig. 2 conclusion: the crystal morphology of DCHT can be changed at different hot-pressing temperatures, and the patterned crystals are finer and more densely covered on the surface of the PA11, so that the compatibilization effect is better.
The mechanical property results of the toughened isotactic polypropylene composite material prepared in the embodiment are shown in figure 3. As can be seen from FIG. 3, the tensile strength decreases with the increase of DCHT, the notched Izod impact strength increases with the increase of DCHT, and then decreases, preferably 10.1kJ/m 2 at 240% DCHT level of 0.5%, while the tensile strength is maintained at 25.9MPa. It can be found that at higher DCHT concentrations (0.3, 0.5, 1), the notched Izod impact strength of the 240 ℃ sample is greater than 200 ℃, because at higher temperatures, the DCHT crystals are finer after fusion and recombination (as shown in the electron microscope of fig. 2), and the compatibilization effect on PA11 and iPP is better.
Example 2
TABLE 2 mass ratios of the components in example 2
| Sequence number | Isotactic polypropylene (iPP, brand T30S)/kg | Nylon 11 (PA 11, trade name BESN P/kg) | N' N-dicyclohexyl terephthalamide (DCHT)/kg | PA11 content (%) |
| 06 | 97 | 3 | 0.3 | 3 |
| 07 | 90 | 10 | 0.3 | 10 |
| 08 | 85 | 15 | 0.3 | 15 |
| 09 | 80 | 20 | 0.3 | 20 |
| 10 | 70 | 30 | 0.3 | 30 |
In Table 2, the mass sum of isotactic polypropylene and PA11 is 100kg, and the calculation formula of the PA11 content (%) in this example is as follows:
mass of PA 11/100 kg=pa 11 content (%).
The preparation method of the toughened isotactic polypropylene composite material comprises the following steps:
(1) Weighing the components according to the weight ratio of the table 2 for standby;
(2) Uniformly mixing the weighed isotactic polypropylene with nylon 11, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed to obtain a melt, and cooling and granulating the obtained melt;
(3) And (3) performing hot press molding on the obtained granules at the temperature of 200 ℃ and 240 ℃ by using a flat vulcanizing machine.
FIG. 4 shows an electron micrograph of the blend system with different PA11 content at iPP/0.3% DCHT in this example. In fig. 4, the first column corresponds to 3% pa11 content at 200 ℃, 10% pa11 content at 200 ℃, 15% pa11 content at 200 ℃, 20% pa11 content at 200 ℃, 30% pa11 content at 200 ℃ in order from left to right, and the second column corresponds to 3% pa11 content at 240 ℃, 10% pa11 content at 240 ℃, 15% pa11 content at 240 ℃, 20% pa11 content at 240 ℃, 30% pa11 content at 240 ℃ in order from left to right; wherein the PA11 content corresponds to the PA11 content in Table 1, and the temperature of 200 ℃ and 240 ℃ corresponds to the hot press molding temperature.
As can be seen from fig. 4, as the PA11 content increases, the size of the PA11 spheres increases and is more heterogeneous, as is evident on larger spheres, DCHT crystals wrapping around the entire PA11 sphere. Meanwhile, DCHT crystals coexist with rod-shaped and patterned crystals at 200 ℃, and are melted and assembled into a pattern when the temperature is increased by 240 ℃.
The mechanical property results of the toughened isotactic polypropylene composite material prepared in the embodiment are shown in fig. 5. As can be seen from FIG. 5, the tensile strength of the system decreases with increasing PA11 content, and the notched Izod impact strength of the sample decreases first and then, wherein the notched Izod impact strength of the sample at 240 ℃ at 10% PA11 is preferably 10.3kJ/m 2, and the tensile strength can be kept at 28.5MPa. Meanwhile, the notched Izod impact strength of the sample at 240 ℃ is higher than 200 ℃, which is consistent with the reason of figure 3, and is the result of finer DCHT crystals at higher temperature so that the compatibility is better.
Example 3
TABLE 3 mass ratios of the components in example 3
| Sequence number | Isotactic polypropylene (iPP, brand T30S)/kg | Thermoplastic polyurethane elastomer (TPU, brand 372X)/kg | N' N-dicyclohexyl terephthalamide (DCHT)/kg | DCHT content (%) |
| 11 | 80 | 20 | 0.05 | 0.05 |
| 12 | 80 | 20 | 0.1 | 0.1 |
| 13 | 80 | 20 | 0.3 | 0.3 |
| 14 | 80 | 20 | 0.5 | 0.5 |
| 15 | 80 | 20 | 1.0 | 1.0 |
In table 3, the calculation formula of DCHT content (%) is as follows:
DCHT mass/(iPP mass+tpu mass) = DCHT content (%).
The preparation method of the toughened isotactic polypropylene composite material comprises the following steps:
(1) Weighing the components according to the weight ratio of the table 3 for standby;
(2) Uniformly mixing the weighed isotactic polypropylene with TPU, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 190 ℃ for 10min and 50rpm of rotating speed to obtain a melt, and cooling and granulating the obtained melt;
(3) And (3) performing hot press molding on the obtained granules at the temperature of 200 ℃, 220 ℃ and 240 ℃ by using a flat vulcanizing machine.
FIG. 6 shows electron microscopy images at different DCHT concentrations and at different temperatures in the iPP/20% TPU372X blend system in this example. In fig. 6, the first column corresponds to 0.05% dcht content at 200 ℃, 0.1% dcht content at 200 ℃, 0.3% dcht content at 200 ℃, 0.5% dcht content at 200 ℃, 1.0% dcht content at 200 ℃, in order from left to right, the second column corresponds to 0.05% dcht content at 220 ℃, 0.1% dcht content at 220 ℃, 0.3% dcht content at 220 ℃, 0.5% dcht content at 220 ℃, 1.0% dcht content at 220 ℃, and the third column corresponds to 0.05% dcht content at 240 ℃, 0.1% dcht content at 240 ℃, 0.3% dcht content at 240 ℃, 0.5% dcht content at 240 ℃, and 1.0% dcht content at 240 ℃. In FIG. 6, the same 8 μm scale is used.
As can be seen from FIG. 6, DCHT is mainly rod-like crystals at a temperature of 200℃and 220℃in hot press molding; at the temperature of 240 ℃,0.05%, 0.1% and 0.3% of DCHT are fine patterned crystals; when the temperature of hot press molding is 240 ℃,0.5 percent of DCHT and 1 percent of DCHT are rod-shaped crystals; this is because the complete melting temperature of the nucleating agent DCHT increases with the content, and the incompletely melted DCHT forms rod-like crystals.
The mechanical property results of the toughened isotactic polypropylene composite material prepared in the embodiment are shown in fig. 7. As can be seen from FIG. 7, similar to the iPP/PA11 system, the tensile strength decreases with increasing DCHT concentration, and the notched Izod impact strength increases and decreases with increasing DCHT concentration. However, after TPU is added, the mechanical properties are improved more obviously, and the tensile strength can be kept at 26.6MPa at 240 ℃ with 0.5% DCHT content of 12.5kJ/m 2.
Example 4
TABLE 4 mass ratios of the components in example 4
| Sequence number | Isotactic polypropylene (iPP, brand T30S)/kg | Thermoplastic polyurethane elastomer (TPU, brand 372X)/kg | Thermoplastic polyurethane elastomer (TPU, trade name 1135 AU)/kg | N' N-dicyclohexyl terephthalamide (DCHT)/kg | DCHT content (%) |
| 16 | 80 | 10 | 10 | 0.05 | 0.05 |
| 17 | 80 | 10 | 10 | 0.1 | 0.1 |
| 18 | 80 | 10 | 10 | 0.3 | 0.3 |
| 19 | 80 | 10 | 10 | 0.5 | 0.5 |
| 20 | 80 | 10 | 10 | 1.0 | 1.0 |
In table 4, the calculation formula of DCHT content (%) is as follows:
DCHT mass/(iPP mass+tpu mass) = DCHT content (%).
The preparation method of the toughened isotactic polypropylene composite material comprises the following steps:
(1) Weighing the components according to the weight ratio of the table 3 for standby;
(2) Uniformly mixing the weighed isotactic polypropylene with TPU, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 190 ℃ for 10min and 50rpm of rotating speed to obtain a melt, and cooling and granulating the obtained melt;
(3) And (3) performing hot press molding on the obtained granules at the temperature of 200 ℃ and 240 ℃ by using a flat vulcanizing machine.
The mechanical property results of the toughened isotactic polypropylene composite material prepared in the embodiment are shown in fig. 8. As can be seen from FIG. 8, the introduction of softer TPU1135AU to form a core-shell structure of soft core-shell can greatly improve the toughness of the iPP system, wherein the 0.1% DCHT240 ℃ performance is best, the notched Izod impact strength can reach 18.5kJ/m 2, and the tensile strength is 24.9MPa.
Comparative example 1
In this example, the composite material was prepared as follows.
(1) Weighing the following components in parts by mass: 97kg of isotactic polypropylene (iPP, brand T30S), 3kg of nylon 6 (PA 6, brand 73G30L NC010), 0.05kg of N' N-dicyclohexyl terephthalamide (DCHT) for later use.
(2) Uniformly mixing the weighed isotactic polypropylene with nylon 6, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed, obtaining a melt, and cooling and granulating the obtained melt.
(3) And (3) respectively carrying out hot press molding on the obtained granules at 200 ℃ by using a flat vulcanizing machine.
Comparative example 2
In this example, the composite material was prepared as follows.
(1) Weighing the following components in parts by mass: 97kg of isotactic polypropylene (iPP, brand T30S), 3kg of nylon 610 (PA 610, brand RS32617L NC 010), 0.05kg of N' N-dicyclohexyl terephthalamide (DCHT) for later use.
(2) The weighed isotactic polypropylene and nylon 610 are uniformly mixed, added into an internal mixer, and simultaneously added with N' N-dicyclohexyl terephthalamide, and subjected to melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed to obtain a melt, and the obtained melt is cooled and pelletized.
(3) And (3) respectively carrying out hot press molding on the obtained granules at 200 ℃ by using a flat vulcanizing machine.
Comparative example 3
In this example, the composite material was prepared as follows.
(1) Weighing the following components in parts by mass: 97kg of isotactic polypropylene (iPP, brand T30S), 3kg of nylon 612 (PA 612, brand 151L NC010), 0.05kg of N' N-dicyclohexyl terephthalamide (DCHT) for later use.
(2) And uniformly mixing the weighed isotactic polypropylene with nylon 612, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed to obtain a melt, and cooling and granulating the obtained melt.
(3) And (3) respectively carrying out hot press molding on the obtained granules at 200 ℃ by using a flat vulcanizing machine.
Example 5
In this example, the composite material was prepared as follows.
(1) Weighing the following components in parts by mass: 97kg of isotactic polypropylene (iPP, brand T30S), 3kg of nylon 1212 (PA 1212, brand 3300) and 0.05kg of N' N-Dicyclohexylterephthalamide (DCHT) are prepared for use.
(2) Uniformly mixing the weighed isotactic polypropylene with nylon 1212, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed, obtaining a melt, and cooling and granulating the obtained melt.
(3) And (3) respectively carrying out hot press molding on the obtained granules at 200 ℃ by using a flat vulcanizing machine.
Comparative example 4
In this example, the composite material was prepared as follows.
(1) Weighing the following components in parts by mass: 100kg of isotactic polypropylene (iPP, brand T30S) and 0.05kg of N' N-dicyclohexyl terephthalamide (DCHT) were used.
(2) Adding the weighed isotactic polypropylene into an internal mixer, adding N' N-dicyclohexyl terephthalamide at the same time, carrying out melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed to obtain a melt, and cooling and granulating the obtained melt.
(3) And (3) respectively carrying out hot press molding on the obtained granules at 200 ℃ by using a flat vulcanizing machine.
Example 6
In this example, the composite material was prepared as follows.
(1) Weighing the following components in parts by mass: 97kg of isotactic polypropylene (iPP, brand T30S), 3kg of nylon 11 (PA 11, brand BESN P) and 0.05kg of N' N-dicyclohexyl terephthalamide (DCHT) are ready for use.
(2) Uniformly mixing the weighed isotactic polypropylene with nylon 11, adding into an internal mixer, simultaneously adding N' N-dicyclohexyl terephthalamide, carrying out melt blending under the conditions of 180 ℃ for 10min and 50rpm of rotating speed, obtaining a melt, and cooling and granulating the obtained melt.
(3) And (3) respectively carrying out hot press molding on the obtained granules at 200 ℃ by using a flat vulcanizing machine.
In fig. 9, six pictures correspond to the DSC profile of comparative example 4, the DSC profile of comparative example 1, the DSC profile of comparative example 2, the DSC profile of comparative example 3, the DSC profile of example 6, and the DSC profile of example 5, respectively, in the order from left to right and from top to bottom.
As can be seen from the DSC chart of FIG. 9, only the system incorporating PA11 and PA1212 has a significantly reduced crystallization temperature at high temperatures, indicating that DCHT is not nucleated at this time. This is because DCHT has strong hydrogen bond interactions with PA11 (or PA 1212), while the DCHT content is low, allowing complete dissociation at high temperatures; when the free DCHT molecules are cooled, the free DCHT molecules are attracted by PA11, the self-assembly process is delayed, the self-assembly is not completed when the iPP is crystallized, and the nucleation effect is not achieved. PA1212 has an attractive effect on DCHT similar to PA11, and DCHT may also have a compatibilizing effect on PA1212 and iPP, and may form a core-shell structure. The other three PAs are similar to pure iPP added with DCHT at high temperature, the crystallization temperature is not changed greatly, which indicates that the adsorption effect on DCHT is not good, the subsequent compatibilization in the system is not good, and the core-shell structure is possibly not formed.
In fig. 10, the polarization microscope images of comparative example 4, comparative example 1, comparative example 2, comparative example 3, example 6, and example 5 are shown in order from top to bottom, and the polarization microscope images of different times are shown in order from left to right. In fig. 10, the observation times are 0s, 60s, 300s, 600s in order from left to right.
The test conditions of fig. 10 are as follows: the temperature of the polarized light microscope is increased to 280 ℃, the temperature is reduced to 130 ℃ at the speed of 10 ℃/min, and the isothermal crystallization is carried out for 10min. As can be seen from fig. 10, the crystallization rates of the PA11 and PA1212 systems are significantly lower and the final crystal size formed is smaller, which is the same as DCS results, indicating that DCHT does not act as nucleation.
As can be seen from fig. 11, the complex viscosity of the normal self-assembled DCHT iPP/0.05DCHT system (i.e., the composite material prepared in comparative example 4) in iPP had a rising step around 150 ℃, indicating that DCHT self-assembly was completed at this time, and DCHT crystals raised the complex viscosity of the melt at this temperature; whereas iPP/3PA11/0.05DCHT (i.e., the composite prepared in example 6) did not have this step, indicating that self-assembly was retarded. The warpage of the curve at the low temperature end region is due to the crystallization of iPP, and the warpage temperature of the iPP/3PA11/0.05DCHT system is lower, and the crystallization temperature is lower, which is consistent with DSC and POM (namely the result of a polarized light microscope test).
The invention is not limited to the specific embodiments described above. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, as well as to any novel one, or any novel combination, of the steps of the method or process disclosed.
Claims (8)
1. The toughened isotactic polypropylene composite material is characterized by comprising isotactic polypropylene, a second monomer and N' N-dicyclohexyl terephthalamide, wherein the second monomer is nylon 11 or thermoplastic polyurethane elastomer;
when the second monomer is nylon 11, the proportion of the raw materials is as follows:
70 to 90 parts by weight of isotactic polypropylene,
10 To 30 parts by weight of a second monomer,
0.05 To 1 weight part of N' N-dicyclohexyl terephthalamide;
when the second monomer is thermoplastic polyurethane elastomer, the proportion of the raw materials is as follows:
80 parts by weight of isotactic polypropylene,
20 Parts by weight of a second monomer,
0.05 To 1 weight part of N' N-dicyclohexyl terephthalamide;
and, the composite material has a core-shell structure.
2. The toughened isotactic polypropylene composite of claim 1, wherein when the second monomer is nylon 11, the ratio of the raw materials is:
80 parts by weight of isotactic polypropylene,
20 Parts by weight of a second monomer,
0.05 To 1 part by weight of N' -dicyclohexyl terephthalamide.
3. The method for preparing the toughened isotactic polypropylene composite material of claim 1 or 2, wherein the preparation method is as follows: uniformly mixing isotactic polypropylene and a second monomer according to a proportion, adding N' N-dicyclohexyl terephthalamide, and carrying out melt blending to obtain a first melt; and then cooling and granulating the obtained first melt, and performing hot press molding to obtain the toughened isotactic polypropylene composite material.
4. The method according to claim 3, wherein the first melt is obtained by melt blending at 180℃to 200℃for 6 to 30 minutes at a rotational speed of 30 to 60 rpm.
5. The process according to claim 4, wherein the melt blending is carried out at 180℃for 10min at a rotation speed of 50 rpm.
6. The method according to claim 3, wherein the hot press molding temperature is 200℃to 240 ℃.
7. A method for improving the impact strength of isotactic polypropylene, which is characterized in that N' N-dicyclohexyl terephthalamide and a second monomer are introduced into isotactic polypropylene, wherein the second monomer is selected from nylon 11 or thermoplastic polyurethane elastomer;
when the second monomer is nylon 11, the proportion of the raw materials is as follows:
70 to 90 parts by weight of isotactic polypropylene,
10 To 30 parts by weight of a second monomer,
0.05 To 1 weight part of N' N-dicyclohexyl terephthalamide;
when the second monomer is thermoplastic polyurethane elastomer, the proportion of the raw materials is as follows:
80 parts by weight of isotactic polypropylene,
20 Parts by weight of a second monomer,
0.05 To 1 weight part of N' N-dicyclohexyl terephthalamide;
And the obtained composite material has a core-shell structure.
8. The method of claim 7, wherein the isotactic polypropylene impact strength is improved by a method comprising the steps of: uniformly mixing isotactic polypropylene and a second monomer according to a proportion, adding N' N-dicyclohexyl terephthalamide, and carrying out melt blending to obtain a first melt; and then cooling and granulating the obtained first melt, and performing hot press molding to obtain the toughened isotactic polypropylene composite material.
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