CN115960417A - Plant fiber reinforced polypropylene material and preparation method and application thereof - Google Patents
Plant fiber reinforced polypropylene material and preparation method and application thereof Download PDFInfo
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- CN115960417A CN115960417A CN202310047616.3A CN202310047616A CN115960417A CN 115960417 A CN115960417 A CN 115960417A CN 202310047616 A CN202310047616 A CN 202310047616A CN 115960417 A CN115960417 A CN 115960417A
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- glycol dimethacrylate
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 170
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 170
- -1 polypropylene Polymers 0.000 title claims abstract description 161
- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002667 nucleating agent Substances 0.000 claims abstract description 40
- 241000196324 Embryophyta Species 0.000 claims description 139
- 239000002202 Polyethylene glycol Substances 0.000 claims description 62
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 62
- 229920001223 polyethylene glycol Polymers 0.000 claims description 62
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- 229920005989 resin Polymers 0.000 claims description 27
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 26
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- 235000013162 Cocos nucifera Nutrition 0.000 claims description 14
- 244000060011 Cocos nucifera Species 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 235000011615 Pinus koraiensis Nutrition 0.000 claims description 6
- 240000007263 Pinus koraiensis Species 0.000 claims description 6
- 241000209140 Triticum Species 0.000 claims description 6
- 235000021307 Triticum Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
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- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005034 decoration Methods 0.000 description 5
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- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- FXDGCBFGSXNGQD-FAESFXMKSA-L disodium;(1s,2s,3r,4r)-bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical compound [Na+].[Na+].C1C[C@H]2[C@@H](C([O-])=O)[C@@H](C(=O)[O-])[C@@H]1C2 FXDGCBFGSXNGQD-FAESFXMKSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a plant fiber reinforced polypropylene material and a preparation method and application thereof, belonging to the technical field of plastic materials. The plant fiber reinforced polypropylene material improves the compatibility of polypropylene and plant fiber by adding the nucleating agent and the specific compatilizer, greatly improves the thermal-oxidative aging resistance, the tensile strength, the impact strength and other mechanical properties, has more excellent comprehensive performance, is suitable for being used as automobile decorative materials, and has simple preparation method and convenient industrial production.
Description
Technical Field
The invention relates to the technical field of plastic materials, in particular to a plant fiber reinforced polypropylene material and a preparation method and application thereof.
Background
Polypropylene (PP) is widely used in the fields of automobiles, home appliances, electric tools, etc. because of its advantages of abundant raw material sources, light specific gravity, low price, etc. Various plastic products derived from polypropylene occupy an important position in daily life of people, but because polypropylene is extracted from petroleum, the use of the plastic products in large quantity inevitably causes a great deal of consumption of petroleum resources; and the plastic products have short service life and are not easy to degrade after being discarded, which can stress and destroy the natural ecological environment, thus promoting the increasing demand of people on biodegradable and non-petroleum-based renewable resources. The natural plant fiber is a renewable resource with the most abundant reserves in the nature, has higher strength due to the existence of a huge hydrogen bond network structure, is a reinforcing filler of a plurality of high polymer materials, and has irreplaceable effect on solving the problems of energy and environmental protection. The plant fiber composite plastic material is durable, has long service life, has the appearance similar to wood, has higher hardness than plastic, does not have the defects of wood products, such as wooden knots, inclined textures, decay and the like, and is more and more favored by designers of automobile decorative materials.
The plant fiber reinforced polypropylene material has the following problems: (1) Because the polypropylene has side methyl, tertiary carbon atoms alternately appear on the molecular chain of the polypropylene, and the tertiary carbon atoms are easily attacked by heat and oxygen to generate oxidation reaction, so that the material has the problems of poor oxidation resistance, easy pulverization, great attenuation of mechanical property and the like; (2) The plant fiber surface contains a large amount of hydroxyl groups and has strong hydrophilicity, but the hydrophobic polypropylene resin lacks groups capable of reacting with the hydroxyl groups, so that the compatibility of the plant fiber and the polypropylene resin is poor, gaps and defects are easily formed at the interface, the tensile strength and the impact resistance of the material are poor, and the defects can further induce a thermal oxidation reaction, accelerate the pulverization of the material and reduce the mechanical property.
Therefore, the plant fiber reinforced polypropylene material with excellent thermal-oxidative aging resistance and mechanical property has excellent industrial application prospect.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a plant fiber reinforced polypropylene material, and a preparation method and application thereof.
In order to achieve the above object, in a first aspect, the present invention provides a plant fiber reinforced polypropylene material, which comprises the following components in parts by weight: 76-88 parts of polypropylene resin, 12-24 parts of plant fiber, 2-8 parts of compatilizer, 0.2-0.6 part of nucleating agent and 0.2-0.6 part of first antioxidant, wherein the compatilizer comprises polypropylene grafted polyethylene glycol dimethacrylate. The plant fiber has a special structure, high crystallinity and a compact hydrogen bond network, and strong intramolecular/intermolecular acting force; the polyethylene glycol dimethacrylate grafted with polypropylene has large polyethylene glycol dimethacrylate functional group size and small interaction, and can be used for replacing hydroxyl in plant fibers, so that the hydrogen bond effect among plant fiber components can be weakened, the bonding force among molecules can be reduced, and the crystal structure of the plant fibers can be damaged, thereby improving the movement capability of molecular chains in the plant fibers, greatly improving the compatibility between hydrophilic plant fibers and hydrophobic polypropylene resin in the thermal processing process, enhancing the interface bonding force of the hydrophilic plant fibers and the hydrophobic polypropylene resin, promoting the polypropylene and the plant fibers to form a stable blending structure, and remarkably improving the thermal-oxidative aging resistance, tensile strength, impact strength and other mechanical properties of the plant fiber reinforced polypropylene material.
The nucleating agent can refine polypropylene spherulites and make the crystallization more uniform and regular, thereby reducing gaps and defects of polypropylene and plant fiber interfaces, obstructing the entry of oxygen and improving the thermal-oxidative aging resistance of the material.
Under the combined action of the polypropylene grafted polyethylene glycol dimethacrylate and the nucleating agent, the thermal-oxidative aging resistance (the pulverization time is more than 200h, the testing method is the same as the effect example, the following is the same) and the mechanical properties such as tensile strength, impact strength and the like of the plant fiber reinforced polypropylene material are obviously improved, the comprehensive performance is more excellent, and the plant fiber reinforced polypropylene material is suitable for being used as an automobile exterior material and even an automobile interior material (wherein the pulverization time required by the automobile exterior material is more than 200h, and the pulverization time required by the automobile interior material is more than 400 h).
In the polypropylene grafted polyethylene glycol dimethacrylate, polypropylene is used as a main chain, and polyethylene glycol dimethacrylate is used as a branched chain.
Preferably, the plant fiber reinforced polypropylene material comprises the following components in parts by weight: 79 to 87 portions of polypropylene resin, 18 to 21 portions of plant fiber, 4 to 6 portions of compatilizer, 0.3 to 0.5 portion of nucleating agent and 0.4 to 0.6 portion of first antioxidant. Under the specific formula, the plant fiber reinforced polypropylene material has higher tensile strength and impact strength, longer pulverization time and more excellent comprehensive performance.
Optionally, the grafting ratio of the polypropylene grafted polyethylene glycol dimethacrylate is 0.3% to 1.5%. Preferably, the grafting rate of the polypropylene grafted polyethylene glycol dimethacrylate is 0.5-1.5%. When the grafting rate of the polypropylene grafted polyethylene glycol dimethacrylate is lower than 0.5%, the improvement effect on the compatibility of the plant fiber and the polypropylene is weaker, so that the improvement degree of the thermal oxidation aging resistance, the tensile strength, the impact strength and other mechanical properties of the plant fiber reinforced polypropylene material is lower; the higher the grafting ratio of polypropylene grafted polyethylene glycol dimethacrylate, the more difficult the preparation, especially after the grafting ratio exceeds 1.5%. The degree of difficulty in obtaining the polypropylene grafted polyethylene glycol dimethacrylate and the degree of improvement of the thermal oxidation aging resistance, the tensile strength, the impact strength and other mechanical properties of the plant fiber reinforced polypropylene material are comprehensively considered, and the grafting rate of the polypropylene grafted polyethylene glycol dimethacrylate is preferably 0.5-1.5%.
Preferably, the compatibilizing agent further comprises a coupling agent and a second antioxidant; in the compatilizer, the mass of the coupling agent is 2-6% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, and the mass of the second antioxidant is 0.3-0.6% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate.
Preferably, the preparation method of the compatilizer comprises the following steps: mixing polypropylene, polyethylene glycol dimethacrylate, a coupling agent and a second antioxidant, then melting and dispersing in an extruder, and granulating to obtain the compatilizer. In some embodiments, the melt dispersion temperature is 190 to 210 ℃.
Preferably, the mass of the polyethylene glycol dimethacrylate is 5-30% of the total mass of the polypropylene and the polyethylene glycol dimethacrylate, the mass of the coupling agent is 2-6% of the total mass of the polypropylene and the polyethylene glycol dimethacrylate, and the mass of the second antioxidant is 0.3-0.6% of the total mass of the polypropylene and the polyethylene glycol dimethacrylate.
Preferably, the plant fiber reinforced polypropylene material satisfies at least one of the following conditions:
a. the nucleating agent is at least one of an alpha crystal form nucleating agent and a beta crystal form nucleating agent;
b. the plant fiber is at least one of log fiber, korean pine fiber, wheat straw fiber, coconut fiber and bamboo fiber, and the average fiber length of the plant fiber is 2-5 mm;
c. the polypropylene resin is at least one of homopolymerized polypropylene and copolymerized polypropylene.
The average fiber length of the plant fiber can be selected within the range of 0.5-8 mm. However, when the average fiber length of the plant fiber is too short, the contact interface between the plant fiber and the outside is too much, so that the thermal-oxidative aging resistance of the material is reduced, the interweaving and bridging in resin are not facilitated, the mechanical property is reduced, meanwhile, the texture effect of the plant fiber cannot be observed, and the decoration effect cannot be achieved; when the average fiber length of the plant fibers is too long, the plant fibers are easy to accumulate and aggregate in the processing process, the dispersion effect is poor, the heat-oxygen aging resistance and the mechanical property of the material are not good, and the good ornamental effect cannot be achieved, so that the average fiber length of the plant fibers is preferably within the range of 2-5 mm.
Preferably, the plant fiber reinforced polypropylene material satisfies at least one of the following conditions:
i, the nucleating agent is an alpha crystal form nucleating agent;
II, the alpha crystal form nucleating agent comprises at least one of organic salt compounds, and the beta crystal form nucleating agent comprises at least one of aromatic amide compounds;
III, the plant fiber is a coconut fiber;
IV, the polypropylene resin is copolymerized polypropylene.
Compared with a beta crystal form nucleating agent, the alpha crystal form nucleating agent enables the pulverization time of the plant fiber reinforced polypropylene material to be longer and the mechanical properties such as tensile strength, impact strength and the like to be better.
Compared with plant fibers such as Korean pine fiber, wheat straw fiber, coconut fiber, bamboo fiber and the like, the coconut fiber enables the pulverization time of the plant fiber reinforced polypropylene material to be longer, and the mechanical properties such as tensile strength, impact strength and the like to be better.
Compared with homopolymerized polypropylene, the copolymerized polypropylene can enable the plant fiber reinforced polypropylene material to obtain higher impact strength and impact strength, and longer pulverization time.
Preferably, the plant fiber reinforced polypropylene material comprises the following components in parts by weight: 79 to 87 portions of polypropylene resin, 18 to 21 portions of plant fiber, 4 to 6 portions of compatilizer, 0.3 to 0.5 portion of nucleating agent and 0.4 to 0.6 portion of first antioxidant; the compatilizer comprises polypropylene grafted polyethylene glycol dimethacrylate with the grafting rate of 0.5-1.5%; the nucleating agent is an alpha crystal form nucleating agent; the plant fiber is at least one of log fiber, korean pine fiber, wheat straw fiber and coconut fiber, and the average fiber length of the plant fiber is 2-5 mm; the polypropylene resin is copolymerized polypropylene. Under the specific formula, the pulverization time of the plant fiber reinforced polypropylene material is more than 360h, the tensile strength is more than 24MPa, and the notched izod impact strength is more than 1.5MPa (the tensile strength and the notched izod impact strength are tested by the same method as the effect example).
In a second aspect, the invention provides a preparation method of the plant fiber reinforced polypropylene material, which comprises the following steps: and (3) uniformly mixing all the raw materials except the plant fiber or the plant fiber master batch under the protection of inert atmosphere, then putting the mixture into a double-screw extruder for melting and dispersing, adding the plant fiber or the plant fiber master batch, mixing, plasticizing and granulating to obtain the plant fiber reinforced polypropylene material. The preparation method of the plant fiber reinforced polypropylene material has simple operation steps and can realize industrial large-scale production.
Preferably, the length-diameter ratio of the double-screw extruder is (30-50): 1.
preferably, the temperature of the double-screw extruder is set to be 100-200 ℃, the screw rotating speed is 350-500 rpm, and the vacuum degree is-0.04-0.08 MPa.
In a third aspect, the invention provides an application of the plant fiber reinforced polypropylene material in preparing an automobile decoration material. The plant fiber reinforced polypropylene material can be used for preparing automobile interiors such as door panels and stand columns, and automobile exteriors such as guard plates and side skirts.
The plant fiber reinforced polypropylene material has the beneficial effects that the compatibility of plant fiber and polypropylene resin is improved by adding polypropylene grafted polyethylene glycol dimethacrylate; the nucleating agent is added to refine and more uniformly regularize the polypropylene spherulites and crystals, so that gaps and defects of interfaces of the polypropylene and the plant fibers are reduced, the compatibility of the polypropylene and the plant fibers is obviously improved under the combined action of the polypropylene grafted polyethylene glycol dimethacrylate and the nucleating agent, the thermal oxidation aging resistance, the tensile strength, the impact strength and other mechanical properties of the material are greatly improved, the comprehensive performance is more excellent, the material is suitable for being used as an automobile exterior trim material and even an automobile interior trim material, the preparation method of the material is simple, and the industrial production is facilitated.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. Unless otherwise specified, the experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments.
The following raw materials used in the respective examples and comparative examples were as follows:
polypropylene resin 1: copolymerized PP, EP548R, manufactured by Zhonghai Shell;
polypropylene resin 2: homopolymerized PP, Z30S, bassel from the manufacturer;
plant fiber master batch 1: coconut fiber master batch, the average fiber length of which is 3mm, PP XDGYS, and the manufacturer is Xinde height of Yuyao;
2, plant fiber master batch: the log fiber master batch, the average length of the fiber is 3mm, PP XDGMXW, the manufacturer is the height of the Xinde Yuyao;
3, plant fiber master batch: korean pine fiber master batch, with the average fiber length of 3mm, PP XDGHS, and the manufacturer is Yuyao Xinde height;
plant fiber master batch 4: the wheat straw fiber master batch, the average length of the fiber is 3mm, PP XDGMF, the manufacturer is the height of Xinde Yuyao;
5, plant fiber master batch: the bamboo fiber master batch, the average length of the fiber is 3mm, PP XDGZXW, the manufacturer is Xinde height of Yuyao;
6, plant fiber master batch: the coconut fiber master batch is customized, the average fiber length is 0.5mm, and the manufacturer is the Xinde height of the Yuyao;
plant fiber master batch 7: the coconut fiber master batch is customized, the average length of the fiber is 2mm, and the manufacturer is the height of the Yuyao Xinde;
plant fiber master batch 8: the coconut fiber master batch is customized, the average length of the fiber is 5mm, and the manufacturer is the height of the Yuyao Xinde;
plant fiber master batch 9: the cocoanut fiber master batch, the average length of the fiber is 8mm, is customized, and the manufacturer is the height of Xinde Yuyao;
1 part of compatilizer: the graft ratio of the maleic anhydride graft copolymerization polypropylene is 1.0 percent, and the BONDYRAM 1001CN manufacturer is Pulanlang;
a compatilizer 2: maleic anhydride grafted ethylene-octene copolymer, grafting ratio 1%, N493, from DuPont;
a compatibilizer 3: the polypropylene grafted polyethylene glycol dimethacrylate, the silane coupling agent and the second antioxidant are contained, wherein the grafting ratio of the polypropylene grafted polyethylene glycol dimethacrylate is 1.5%, the mass of the silane coupling agent is 3% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, the mass of the second antioxidant is 0.4% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, and the self-made preparation method comprises the following steps:
polypropylene (copolymerized PP, EP548R, manufacturer Zhonghai Shell), polyethylene glycol dimethacrylate, a silane coupling agent and a second antioxidant (a mixture of a commercially available hindered phenol antioxidant and a commercially available phosphite antioxidant in a mass ratio of 1) are mixed according to the mass ratio of polypropylene: polyethylene glycol dimethacrylate: silane coupling agent: the processing aid = 70;
a compatilizer 4: the polypropylene grafted polyethylene glycol dimethacrylate, the silane coupling agent and the second antioxidant are contained, wherein the grafting ratio of the polypropylene grafted polyethylene glycol dimethacrylate is 1.0%, the mass of the silane coupling agent is 3% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, the mass of the second antioxidant is 0.4% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, and the preparation method is self-made except that the mass ratio of the raw materials is polypropylene: polyethylene glycol dimethacrylate: silane coupling agent: the processing aid = 80;
5, a compatilizer: the polypropylene grafted polyethylene glycol dimethacrylate/silane coupling agent/antioxidant composite material comprises polypropylene grafted polyethylene glycol dimethacrylate, a silane coupling agent and a second antioxidant, wherein the grafting ratio of the polypropylene grafted polyethylene glycol dimethacrylate is 0.5%, the mass of the silane coupling agent is 3% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, the mass of the second antioxidant is 0.4% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, and the polypropylene grafted polyethylene glycol dimethacrylate/silane coupling agent composite material is prepared by a self-control method, wherein the preparation method comprises the following steps: polyethylene glycol dimethacrylate: silane coupling agent: the processing aid = 90;
a compatibilizer 6: the polypropylene grafted polyethylene glycol dimethacrylate, the silane coupling agent and the second antioxidant are contained, wherein the grafting ratio of the polypropylene grafted polyethylene glycol dimethacrylate is 0.3%, the mass of the silane coupling agent is 3% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, the mass of the second antioxidant is 0.4% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, the self-control is realized, and the preparation method is characterized in that the polypropylene grafted polyethylene glycol dimethacrylate, the silane coupling agent and the second antioxidant are prepared by the following steps: polyethylene glycol dimethacrylate: silane coupling agent: the processing aid = 95;
nucleating agent 1: the alpha crystal form nucleating agent, the organic salt compound and the HPN-68L are produced by Milliken;
nucleating agent 2: a beta crystal form nucleating agent, an aromatic amide compound, and a model TMB-5, wherein the manufacturer is Shanghai Zhengfeng chemical auxiliary agent Co., ltd;
first antioxidant: the mass ratio of the commercial hindered phenol antioxidant to the commercial phosphite antioxidant is 1.
The plant fiber master batches 1-9 are all composed of plant fibers and PP (copolymerized PP, EP548R, zhonghai shell brand), wherein the mass ratio of the plant fibers to the PP is 6. The plant fiber master batch 6 to 9 are the same as the plant fiber master batch 1 except that the average fiber length of the plant fiber is different from that of the plant fiber master batch 1. The plant fiber master batches 1-9 are finally embodied in the product in two forms of plant fiber and PP.
The component materials used in the examples of the present invention and the comparative examples and the raw materials of the self-made components were all commercially available materials unless otherwise specified, and the component materials used in the respective parallel experiments were all the same.
The preparation methods of the plant fiber reinforced polypropylene materials are the same except for different formulas, and the specific preparation method is as follows: uniformly mixing the polypropylene resin 1 or 2, the compatilizer, the nucleating agent and the first antioxidant in a high-speed mixer under the protection of nitrogen atmosphere, then adding the mixture into a feeding port of a double-screw extruder (the length-diameter ratio L: D =40: 1) for melting and dispersing, and adding the plant fiber master batch in a heating section 4 at the temperature of 200 ℃, mixing, plasticizing and granulating to obtain the corresponding plant fiber reinforced polypropylene material;
the processing temperatures (from feed port to die) were: 100 deg.C, 180 deg.C, 200 deg.C, a main machine rotation speed of 500rpm, and a vacuum degree of-0.04 MPa.
Examples 1 to 18 and comparative examples 1 to 6
The compositions of the plant fiber-reinforced polypropylene materials of examples 1 to 18 and comparative examples 1 to 6 are shown in tables 1, 2 and 3, respectively.
TABLE 1
TABLE 2
TABLE 3
| Component/part by weight | Practice ofExample 15 | Example 16 | Example 17 | Example 18 |
| Polypropylene resin 1 | 79 | 79 | 79 | 79 |
| Plant fiber 1 | ||||
| Plant fiber 6 | 21 | |||
| Plant fiber 7 | 21 | |||
| Plant fiber 8 | 21 | |||
| Plant fiber 9 | 21 | |||
| Compatibilizer 3 | 6 | 6 | 6 | 6 |
| Nucleating agent 1 | 0.5 | 0.5 | 0.5 | 0.5 |
| A first antioxidant | 0.4 | 0.4 | 0.4 | 0.4 |
The performance test is carried out on the plant fiber reinforced polypropylene materials of each example and each comparative example, and the test results are shown in the table 4, wherein the relevant test reference standards or methods are as follows:
tensile strength properties: the flexural modulus of the material is tested according to ISO 527-2-2012, with a tensile rate of 10mm/min;
notched izod impact strength: the impact strength of a cantilever notch of the material is tested by adopting ISO180-2000, wherein the impact strength of the cantilever notch is A type notch at 4mm and 23 ℃, and the pendulum impact capacity is 5.5J;
thermal oxidation aging test: the test was carried out according to ISO188-2011, the samples were injection moulded into 50 x 70 x 2mm plaques, placed in an ageing oven at 150 ℃ with 10 ventilations per hour and the time required for the appearance of the chalking was observed and recorded.
TABLE 4
| Sample (I) | Tensile strength/MPa | Notched izod impact strength/(KJ/m) 2 ) | Powdering time/h |
| Example 1 | 26.5 | 1.8 | 284 |
| Example 2 | 27.8 | 3.4 | 411 |
| Example 3 | 30.5 | 3.8 | 521 |
| Example 4 | 28.5 | 3.2 | 374 |
| Example 5 | 27.8 | 2.1 | 320 |
| Example 6 | 29.4 | 3.2 | 467 |
| Example 7 | 29.6 | 3.3 | 486 |
| Example 8 | 29 | 2.9 | 493 |
| Example 9 | 28.9 | 2.6 | 480 |
| Example 10 | 26.2 | 2.0 | 356 |
| Example 11 | 26.4 | 2.1 | 379 |
| Example 12 | 26.3 | 2.0 | 398 |
| Example 13 | 24.6 | 1.8 | 367 |
| Example 14 | 24.3 | 1.7 | 289 |
| Example 15 | 25.6 | 2.2 | 314 |
| Example 16 | 27.2 | 2.2 | 376 |
| Example 17 | 27.8 | 2.8 | 394 |
| Example 18 | 26.3 | 2.6 | 368 |
| Comparative example 1 | 23.8 | 1.0 | 48 |
| Comparative example 2 | 24.2 | 1.5 | 98 |
| Comparative example 3 | 25.6 | 1.9 | 126 |
| Comparative example 4 | 25.8 | 1.7 | 198 |
| Comparative example 5 | 25.4 | 1.8 | 174 |
| Comparative example 6 | 18.5 | 1.6 | 94 |
As can be seen from Table 4, compared with the plant fiber reinforced polypropylene material of comparative example 1 without the addition of the compatilizer and the nucleating agent, the pulverization time of the plant fiber reinforced polypropylene material prepared by the embodiments of the invention is remarkably prolonged (above 200 h), that is, the thermo-oxidative aging resistance is remarkably improved, meanwhile, the mechanical properties such as tensile strength, impact strength and the like are remarkably improved, the comprehensive performance is more excellent, and the requirements of automobile exterior decorations on the material performance can be met. And when the plant fiber reinforced polypropylene material comprises the following components in parts by weight: 79 to 87 parts of polypropylene resin, 18 to 21 parts of plant fiber, 4 to 6 parts of compatilizer, 0.3 to 0.5 part of nucleating agent and 0.4 to 0.6 part of first antioxidant, the plant fiber reinforced polypropylene material has higher tensile strength and impact strength, longer pulverization time and more excellent comprehensive performance.
Compared with the example 2, the polypropylene resin has poor compatibility with the plant fiber, weak intermolecular bonding force, shorter pulverization time, poorer mechanical properties such as tensile strength, impact strength and the like without adding a compatilizer.
Compared with the example 2, the nucleating agent is added in too much amount and dispersed unevenly, so that the nucleating agent is easy to agglomerate, the effects of refining polypropylene grains and increasing the compatibility with plant fibers cannot be achieved, the pulverization time is obviously shortened, the requirements of automobile exterior and interior decorations cannot be met, and the mechanical properties such as impact strength and the like are obviously poor.
Compared with example 2, the addition amount of the compatilizer is too much, which is contrary to the action of a bridge, the excessive compatilizer is stacked, the most effective combination of the PP resin and the surface of the plant fiber is prevented, the branched chains of the polyethylene glycol dimethacrylate functional groups are tangled, the flexibility of the polypropylene resin is reduced, and the impact strength is greatly reduced; and the aging level is obviously reduced.
Example 12 compares with comparative examples 3-4 and shows that, compared with conventional compatibilizers 1 and 2, the compatibilizer 4 has a better effect of improving the thermo-oxidative aging resistance and mechanical properties of the material, because the polyethylene glycol dimethacrylate functional group of the compatibilizer 4 has a large size and a small interaction, and replaces hydroxyl in the plant fiber with the polyethylene glycol dimethacrylate functional group, so that the hydrogen bonding effect between the components of each plant fiber can be weakened, the bonding force between molecules can be reduced, and the crystalline structure of the plant fiber can be destroyed, thereby improving the mobility of molecular chains in the plant fiber, greatly improving the compatibility between the hydrophilic plant fiber and the hydrophobic polypropylene resin in the thermal processing process, enhancing the interfacial bonding force between the hydrophilic plant fiber and the hydrophobic polypropylene resin, promoting the polypropylene and the plant fiber to form a stable blending structure, effectively blocking oxygen from entering the air, and remarkably improving the thermo-oxidative aging resistance and the comprehensive mechanical properties (such as tensile strength and impact resistance) of the plant fiber reinforced polypropylene material.
Comparing examples 2 and 12-14, it can be seen that, with the increase of the grafting rate of polypropylene grafted polyethylene glycol dimethacrylate, the powdering time of the plant fiber reinforced polypropylene material is longer, and the mechanical properties such as tensile strength, impact strength and the like are better. The polypropylene grafted polyethylene glycol dimethacrylate is difficult to prepare after the grafting rate of the polypropylene grafted polyethylene glycol dimethacrylate exceeds 1.5 percent, so the grafting rate of the polypropylene grafted polyethylene glycol dimethacrylate is preferably within the range of 0.5 to 1.5 percent to obtain better heat-resistant oxygen aging resistance and mechanical property.
Comparing example 3 with examples 6 to 9, it can be seen that the coconut fiber can prolong the powdering time of the plant fiber reinforced polypropylene material and improve the mechanical properties such as tensile strength and impact strength, compared with the plant fibers such as Korean pine fiber, wheat straw fiber, coconut fiber and bamboo fiber.
The comparison of examples 2 and 15-18 shows that the average fiber length of the plant fibers can affect the thermal-oxidative-aging-resistant performance and the mechanical property of the plant fiber reinforced polypropylene material, the average fiber length of the plant fibers is too short, so that the contact interface between the plant fibers and the outside is too many, the thermal-oxidative-aging-resistant performance is reduced, the interweaving and bridging in resin are not facilitated, the mechanical property is reduced, meanwhile, the texture effect of the plant fibers cannot be observed, and the decoration effect cannot be achieved; the average fiber length of the plant fibers is too long, the plant fibers are easy to accumulate and aggregate in the processing process, the dispersion effect is not good, the heat-resistant oxygen aging resistance and the mechanical property of the material are not good, and meanwhile, the good ornamental effect cannot be achieved; in addition, the excess length is crushed by the twin-screw extruder during the processing, and the partial actual remaining length is reduced to a normal level, so that the average fiber length of the vegetable fiber is preferably in the range of 2 to 5 mm.
Comparison between example 3 and example 10 shows that the polypropylene copolymer can obtain better mechanical properties and longer pulverization time of the plant fiber reinforced polypropylene material than the polypropylene homopolymer.
Comparing example 3 with example 11, it can be known that compared with the beta crystal form nucleating agent, the alpha crystal form nucleating agent enables the pulverization time of the plant fiber reinforced polypropylene material to be longer, and the mechanical properties such as tensile strength, impact strength and the like to be better.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The plant fiber reinforced polypropylene material is characterized by comprising the following components in parts by weight: 76-88 parts of polypropylene resin, 12-24 parts of plant fiber, 2-8 parts of compatilizer, 0.2-0.6 part of nucleating agent and 0.2-0.6 part of first antioxidant, wherein the compatilizer comprises polypropylene grafted polyethylene glycol dimethacrylate.
2. The plant fiber reinforced polypropylene material of claim 1, comprising the following components in parts by weight: 79 to 87 portions of polypropylene resin, 18 to 21 portions of plant fiber, 4 to 6 portions of compatilizer, 0.3 to 0.5 portion of nucleating agent and 0.4 to 0.6 portion of first antioxidant.
3. The plant fiber reinforced polypropylene material according to claim 1 or 2, wherein the grafting ratio of the polypropylene grafted polyethylene glycol dimethacrylate is 0.5-1.5%.
4. The plant fiber reinforced polypropylene material of claim 1 or 2, wherein the compatibilizing agent further comprises a coupling agent and a second antioxidant; in the compatilizer, the mass of the coupling agent is 2-6% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate, and the mass of the second antioxidant is 0.3-0.6% of the weight of the polypropylene grafted polyethylene glycol dimethacrylate.
5. The plant fiber reinforced polypropylene material according to claim 4, wherein the compatibilizer is prepared by the following method: mixing polypropylene, polyethylene glycol dimethacrylate, a coupling agent and a second antioxidant, melting and dispersing in an extruder, and granulating to obtain the compatilizer.
6. The plant fiber reinforced polypropylene material according to claim 5, wherein the mass of the polyethylene glycol dimethacrylate is 5 to 30% of the total mass of the polypropylene and the polyethylene glycol dimethacrylate, the mass of the coupling agent is 2 to 6% of the total mass of the polypropylene and the polyethylene glycol dimethacrylate, and the mass of the second antioxidant is 0.3 to 0.6% of the total mass of the polypropylene and the polyethylene glycol dimethacrylate.
7. The plant fiber reinforced polypropylene material according to claim 1 or 2, wherein at least one of the following conditions is satisfied:
a. the nucleating agent is at least one of an alpha crystal form nucleating agent and a beta crystal form nucleating agent;
b. the plant fiber is at least one of log fiber, korean pine fiber, wheat straw fiber, coconut fiber and bamboo fiber, and the average fiber length of the plant fiber is 2-5 mm;
c. the polypropylene resin is at least one of homo-polypropylene and co-polypropylene.
8. The plant fiber reinforced polypropylene material according to claim 7, wherein at least one of the following conditions is satisfied:
i, the nucleating agent is an alpha crystal form nucleating agent;
II, the alpha crystal form nucleating agent comprises an organic salt compound, and the beta crystal form nucleating agent comprises an aromatic amide compound;
III, the plant fiber is coconut fiber;
IV, the polypropylene resin is copolymerized polypropylene.
9. The method for preparing a plant fiber reinforced polypropylene material according to any one of claims 1 to 8, comprising the steps of: mixing the raw materials except the plant fiber or the plant fiber master batch under the protection of inert atmosphere, then putting the mixture into a double-screw extruder for melting and dispersing, adding the plant fiber or the plant fiber master batch, mixing, plasticizing and granulating to obtain the plant fiber reinforced polypropylene material.
10. Use of the plant fiber reinforced polypropylene material according to any one of claims 1 to 8 in the preparation of automotive trim materials.
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