CN110564060A - Reinforced and toughened polypropylene composite material and preparation method thereof - Google Patents
Reinforced and toughened polypropylene composite material and preparation method thereof Download PDFInfo
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- CN110564060A CN110564060A CN201910777421.8A CN201910777421A CN110564060A CN 110564060 A CN110564060 A CN 110564060A CN 201910777421 A CN201910777421 A CN 201910777421A CN 110564060 A CN110564060 A CN 110564060A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- 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
- C08L23/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
the invention relates to a reinforced and toughened polypropylene composite material and a preparation method thereof, wherein nano calcium carbonate master batches, carbon nano tube/graphene master batches and PA6 resin are used as reinforced and toughened fillers, maleic anhydride grafted polyolefin copolymer is used as a compatilizer, and the strength and toughness of the PP composite material are remarkably improved through the synergistic reinforcement and toughening effect among the nano calcium carbonate, the carbon nano tube/graphene and the PA6 resin, so that the problem that the polypropylene composite material filled with a single inorganic filler is insufficient in strength and toughness is solved, and the application range of the polypropylene composite material is widened.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a reinforced and toughened polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP) is one of 5 general plastics in the world, has the advantages of low price, low density, simple production process, easy processing and the like, has good comprehensive performance, and is widely applied to the fields of food packaging, automobile parts and the like. However, due to some special requirements in the fields of chemical engineering, building materials, household appliances, automobiles and the like, the general PP can not well meet the requirements of engineering application, so that the modification of PP, especially the engineering of general PP, has become a key point and a hot spot of the current domestic and foreign research.
PP has large spherulite, and crystal boundary defects and cracks are easy to appear on a spherulite interface to cause brittle fracture; PP has the disadvantages of low modulus, low impact strength, and poor performance, which limits its applications. Therefore, the invention aims to strengthen and modify PP while toughening, and the development of the high-performance reinforced and toughened polypropylene composite material has very important significance.
Disclosure of Invention
in order to solve the technical problems of poor toughness and strength of a PP material and poor compatibility with an inorganic filler, a reinforced and toughened polypropylene composite material and a preparation method thereof are provided.
The invention is realized by the following technical scheme:
the reinforced and toughened polypropylene composite material comprises the following components in parts by weight:
60-80 parts of polypropylene resin,
8-20 parts of polyamide 6 resin,
30-50 parts of carbon nano tube/graphene master batch and nano calcium carbonate master batch composite filler,
10-20 parts of maleic anhydride grafted ethylene-octene copolymer.
Preferably, the reinforced and toughened polypropylene composite material comprises the following components in parts by weight:
70-75 parts of polypropylene resin,
10-12 parts of polyamide 6 resin,
40-50 parts of carbon nano tube/graphene master batch and nano calcium carbonate master batch composite filler,
12 parts of maleic anhydride grafted ethylene-octene copolymer.
Further, the polypropylene resin is a copolymerized PP resin.
Further, the polyamide 6 resin is a PA6 resin with the relative viscosity of 2.45-2.75.
Further, the carbon nanotube/graphene master batch comprises the following components in parts by weight: 40-60 parts of nano calcium carbonate, 100 parts of polypropylene, 2-4 parts of coupling agent, 0.06-0.15 part of composite antioxidant and 5 parts of lubricant;
the nano calcium carbonate master batch comprises the following components in parts by weight: 5-7 parts of carbon nano tube/graphene, 100 parts of polypropylene, 1-3 parts of coupling agent and 0.06-0.15 part of composite antioxidant.
Preferably, the carbon nanotube/graphene master batch comprises the following components in parts by weight: 50 parts of nano calcium carbonate, 100 parts of polypropylene, 3 parts of coupling agent, 0.08 part of composite antioxidant and 5 parts of lubricant;
the nano calcium carbonate master batch comprises the following components in parts by weight: 6 parts of carbon nano tube/graphene, 100 parts of polypropylene, 2 parts of coupling agent and 0.08 part of composite antioxidant.
Further, the coupling agent is a mixture of any two of KH550, KH560 and KH570, and the mass ratio of any two coupling agents is 1: 1.
Further, the composite antioxidant is 1010 and 168, and the mass ratio of 1010 to 168 is 1: 2.
the invention also aims to provide a preparation method of the reinforced and toughened polypropylene composite material, which comprises the following steps:
(1) Drying polyamide 6 resin at 90 deg.C for 10 hr;
(2) Adding the polypropylene resin, the dried polyamide 6 resin, the dried nano calcium carbonate master batch, the carbon nano tube/graphene master batch and the compatilizer into a mixer, and mixing at 1000rpm for 5-6 min to obtain a premix;
(3) Carrying out double-screw extrusion granulation on the premix to obtain a polypropylene composite material; the temperature of the twin-screw extrusion granulation is as follows: t is1＝160～170℃，T2＝170～180℃，T3＝180～190℃，T4＝190～200℃，T5＝200～210℃，T6＝210～220℃，T7＝220～225℃，T8＝225～230℃，TDie＝220～225℃。
The beneficial technical effects are as follows: the invention provides a reinforced and toughened polypropylene composite material and a preparation method thereof, wherein nano calcium carbonate master batches, carbon nano tube/graphene master batches and PA6 resin are used as reinforced and toughened fillers, maleic anhydride grafted polyolefin copolymer is used as a compatilizer, and the strength and toughness of the PP composite material are remarkably improved through the synergistic reinforcement and toughening effect among the nano calcium carbonate, the carbon nano tube/graphene and the PA6 resin, so that the problem that the polypropylene composite material filled with a single inorganic filler is insufficient in strength and toughness is solved, and the application range of the polypropylene composite material is widened.
Detailed Description
The invention is further described below with reference to specific examples, but without limiting the scope of the invention.
Example 1
The reinforced and toughened polypropylene composite material comprises the following components in parts by weight:
80 parts of polypropylene resin, namely 80 parts of polypropylene resin,
8 parts of polyamide 6 resin, namely 8 parts of polyamide resin,
7 parts of carbon nano tube/graphene master batch,
30 parts of nano calcium carbonate master batch,
10 parts of maleic anhydride grafted ethylene-octene copolymer.
Wherein the polypropylene resin is copolymerized PP resin, and the trade mark K8003.
Wherein the polyamide 6 resin is M2500I with the relative viscosity of 2.5.
The carbon nano tube/graphene master batch comprises the following components in parts by weight: 50 parts of nano calcium carbonate, 100 parts of polypropylene, 3 parts of coupling agent, 0.08 part of composite antioxidant and 5 parts of stearic acid lubricant;
The nano calcium carbonate master batch comprises the following components in parts by weight: 6 parts of carbon nano tube/graphene, 100 parts of polypropylene, 2 parts of coupling agent and 0.08 part of composite antioxidant. Wherein the coupling agent is a mixture of any two of KH550, KH560 and KH570, and the mass ratio of any two coupling agents is 1: 1; the composite antioxidant is 1010 and 168, and the mass ratio of 1010 to 168 is 1: 2.
the preparation method of the reinforced and toughened polypropylene composite material comprises the following steps:
(1) Drying polyamide 6 resin at 90 deg.C for 10 hr;
(2) weighing the polypropylene resin, the dried polyamide 6 resin, the dried nano calcium carbonate master batch, the carbon nano tube/graphene master batch and the compatilizer according to the weight parts, adding the mixture into a mixer, and mixing at 1000rpm for 5-6 min to obtain a premix;
(3) Carrying out double-screw extrusion granulation on the premix to obtain a polypropylene composite material; the temperature of the twin-screw extrusion granulation is as follows: t is1＝165℃，T2＝175℃，T3＝190℃，T4＝200℃，T5＝210℃，T6＝220℃，T7＝225℃，T8＝230℃，Tdie＝220℃。
examples 2 to 5
The preparation methods of the embodiments 2 to 5 are the same as the embodiment 1, except for the weight portion ratio of the components, which is shown in the table 1.
Comparative example 1
The comparative example is the same as the preparation method of example 1, except that the nano calcium carbonate master batch is not added, and the weight part ratio of each component is shown in table 1.
comparative example 2
the comparative example is the same as the preparation method of example 1, except that the carbon nanotube/graphene master batch is not added, and the weight part ratio of each component is shown in table 1.
TABLE 1 weight parts ratios of the components of examples 1-5 and comparative examples 1-2
The reinforced and toughened polypropylene composite particles prepared in the examples 1-5 and the comparative examples 1-2 are dried and then added into an injection molding machine for injection molding to obtain a standard sample, and the standard sample is subjected to performance test, wherein the test results are shown in Table 2.
TABLE 2 mechanical properties of the materials prepared in examples 1-5 and comparative examples 1-2
| Tensile strength/MPa | flexural Strength/MPa | Impact Strength/kJ.m-2 | |
| Pure PP | 31.68 | 35.66 | 7.37 |
| example 1 | 39.59 | 46.27 | 11.35 |
| example 2 | 39.56 | 47.28 | 11.58 |
| example 3 | 41.75 | 48.35 | 13.27 |
| Example 4 | 40.59 | 48.29 | 12.78 |
| example 5 | 41.65 | 47.35 | 12.85 |
| Comparative example 1 | 34.26 | 33.36 | 7.56 |
| comparative example 2 | 33.25 | 37.28 | 8.23 |
| test standard | GB/T1040-2006 | GB/T9341-2000 | GB/T1843-2008 |
As can be seen from table 2, comparing the data of pure PP and example 1 with those of comparative example 1 and comparative example 2, the reinforcing and toughening effects of the PP and PA composite system are not obvious when only the nano calcium carbonate master batch or the carbon nanotube/graphene master batch is added to the PP and PA composite system, but the tensile strength is increased by about 24.9% compared with that of pure PP, the bending strength is increased by about 29.7% compared with that of pure PP, and the impact strength is increased by about 54% compared with that of pure PP by adding two master batches simultaneously in example 1, so that it can be seen that the nano calcium carbonate master batch, the carbon nanotube/graphene master batch, and the PA6 resin are used as reinforcing and toughening fillers, the maleic anhydride grafted polyolefin copolymer is used as a compatibilizer, and the strength and toughness of the PP composite material are both significantly improved by the synergistic effect among the nano calcium carbonate, the carbon nanotube/graphene, and the PA6 resin.
Claims (9)
1. the reinforced and toughened polypropylene composite material is characterized by comprising the following components in parts by weight:
60-80 parts of polypropylene resin,
8-20 parts of polyamide 6 resin,
30-50 parts of carbon nano tube/graphene master batch and nano calcium carbonate master batch composite filler,
10-20 parts of maleic anhydride grafted ethylene-octene copolymer.
2. The reinforced and toughened polypropylene composite material as claimed in claim 1, which comprises the following components in parts by weight:
70-75 parts of polypropylene resin,
10-12 parts of polyamide 6 resin,
40-50 parts of carbon nano tube/graphene master batch and nano calcium carbonate master batch composite filler,
12 parts of maleic anhydride grafted ethylene-octene copolymer.
3. the reinforced and toughened polypropylene composite material as claimed in claim 1 or 2, wherein said polypropylene resin is a co-polypropylene (PP) resin.
4. The reinforced and toughened polypropylene composite material as claimed in claim 1 or 2, wherein the polyamide 6 resin is a PA6 resin having a relative viscosity of 2.45-2.75.
5. the reinforced and toughened polypropylene composite material as claimed in claim 1 or 2, wherein the carbon nanotube/graphene masterbatch comprises the following components in parts by weight: 40-60 parts of nano calcium carbonate, 100 parts of polypropylene, 2-4 parts of coupling agent, 0.06-0.15 part of composite antioxidant and 5 parts of lubricant;
the nano calcium carbonate master batch comprises the following components in parts by weight: 5-7 parts of carbon nano tube/graphene, 100 parts of polypropylene, 1-3 parts of coupling agent and 0.06-0.15 part of composite antioxidant.
6. the reinforced and toughened polypropylene composite material as claimed in claim 5, wherein the carbon nanotube/graphene masterbatch comprises the following components in parts by weight: 50 parts of nano calcium carbonate, 100 parts of polypropylene, 3 parts of coupling agent, 0.08 part of composite antioxidant and 5 parts of lubricant;
the nano calcium carbonate master batch comprises the following components in parts by weight: 6 parts of carbon nano tube/graphene, 100 parts of polypropylene, 2 parts of coupling agent and 0.08 part of composite antioxidant.
7. The reinforced and toughened polypropylene composite material as claimed in claim 6, wherein the coupling agent is a mixture of any two of KH550, KH560 and KH570, and the mass ratio of any two coupling agents is 1: 1.
8. The reinforced and toughened polypropylene composite material as claimed in claim 6, wherein the composite antioxidant is 1010 and 168, and the mass ratio of 1010 to 168 is 1: 2.
9. a method for preparing the reinforced and toughened polypropylene composite material according to claim 1 or 2, comprising the steps of:
(1) drying polyamide 6 resin at 90 deg.C for 10 hr;
(2) adding the polypropylene resin, the dried polyamide 6 resin, the dried nano calcium carbonate master batch, the carbon nano tube/graphene master batch and the compatilizer into a mixer, and mixing at 1000rpm for 5-6 min to obtain a premix;
(3) Carrying out double-screw extrusion granulation on the premix to obtain a polypropylene composite material; the temperature of the twin-screw extrusion granulation is as follows: t is1＝160～170℃，T2＝170～180℃，T3＝180～190℃，T4＝190～200℃，T5＝200～210℃，T6＝210～220℃，T7＝220～225℃，T8＝225～230℃，TDie＝220～225℃。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910777421.8A CN110564060A (en) | 2019-08-22 | 2019-08-22 | Reinforced and toughened polypropylene composite material and preparation method thereof |
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| CN201910777421.8A CN110564060A (en) | 2019-08-22 | 2019-08-22 | Reinforced and toughened polypropylene composite material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483680A (en) * | 2012-06-12 | 2014-01-01 | 中国科学院化学研究所 | Polypropylene long-carbon-chain nylon blend and preparation method thereof |
| CN108373559A (en) * | 2018-02-02 | 2018-08-07 | 桂林理工大学 | A kind of graphene/carbon nano-tube collaboration enhancing polyethylene pipe and preparation method thereof |
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- 2019-08-22 CN CN201910777421.8A patent/CN110564060A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483680A (en) * | 2012-06-12 | 2014-01-01 | 中国科学院化学研究所 | Polypropylene long-carbon-chain nylon blend and preparation method thereof |
| CN108373559A (en) * | 2018-02-02 | 2018-08-07 | 桂林理工大学 | A kind of graphene/carbon nano-tube collaboration enhancing polyethylene pipe and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HA-DA BAO: "Effect of electrically inert particulate filler on electrical resistivity of polymer/multi-walled carbon nanotube composites", 《POLYMER》 * |
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