CN107955272B - Low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material - Google Patents
Low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material Download PDFInfo
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Abstract
The invention provides a low-blushing, oil-bath-resistant, low-temperature-toughened and glass fiber-reinforced polypropylene material, which is prepared from the following raw materials in parts by weight: 10-50 parts of polypropylene copolymer, 25-40 parts of PPR, 15-20 parts of glass fiber, 5 parts of POE, 5 parts of grafted polypropylene, 0-10 parts of Vistamaxx0, 0.8-1.0 part of synthetic mica powder and 0.8-1.0 part of processing aid. The low-whitening, oil-bath-resistant, low-temperature-toughening and glass fiber-reinforced polypropylene material disclosed by the invention improves the low-temperature toughness of the polypropylene material by utilizing the toughening effect of POE. And the compatibility of the ethylene phase and the propylene phase of the copolymerized polypropylene is improved by adding Vistamax, and the interface strength of the ethylene phase and the propylene phase is improved, so that the stress whitening resistance of the material is improved.
Description
Technical Field
The invention belongs to the field of modified plastics, and particularly relates to a low-whitening, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material.
Background
In recent years, the new energy automobile industry in China develops rapidly, and the core technology of the new energy automobile lies in the power battery technology, and the power battery is required to have longer endurance, can provide higher voltage and has longer service life, so that the requirement on the use strength of a shell material is very high. Compared with other high polymer power battery shell materials, the glass fiber reinforced polypropylene (PP) has obvious cost advantage, good comprehensive performance, good solvent resistance, stable property and extremely high strength which can be compared with engineering plastics, and a plurality of domestic battery manufacturers select the glass fiber reinforced material as the shell of the power battery at present. However, most glass fiber reinforced polypropylene materials have poor low-temperature toughness; some glass fiber reinforced polypropylene materials modified by toughening means have certain low-temperature toughness, but stress whitening is easy to occur under the condition of impact, and the power battery is close to an automobile engine and is easy to be influenced by grease such as engine oil, so that the glass fiber reinforced polypropylene is easy to swell under the action of the engine oil for a long time to influence the service performance, and the service life of the power battery is shortened. At present, no glass fiber reinforced polypropylene material which can simultaneously give consideration to three performances of stress whitening resistance, oil bath resistance and high-low temperature toughness exists in the market. The power battery shell material commonly used in the market has the problems of easy stress whitening, poor low-temperature toughness, poor grease resistance, low material strength and the like.
Chinese patent CN 2010243936 discloses a glass fiber reinforced polypropylene, which has poor low-temperature toughness and is easy to crack under impact at low temperature. Chinese patent CN201110364743 discloses a high-strength high-toughness flame-retardant polypropylene composite material, and the reinforced polypropylene material has limited low-temperature toughening effect and is not resistant to stress whitening. Chinese patent CN201611223575 discloses a high-strength high-toughness continuous glass fiber reinforced polypropylene material, which is a PP/PA alloy, has limited corrosion resistance and is not resistant to grease, and cannot be used as a power battery material close to an engine for long-term work. Chinese patent CN201010526058 discloses a power battery shell flame-retardant material based on a PP material, which has limited grease resistance and poor low-temperature toughness and is easy to whiten under impact.
Disclosure of Invention
In view of the above, the invention aims to provide a low-whitening, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material, and the compatibility of a copolymer polypropylene ethylene phase and a propylene phase is improved by adding high-molecular random copolymer polypropylene, so that the interfacial strength of the ethylene phase and the propylene phase is improved, and the stress whitening resistance of the material is improved.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the low-whitening, oil-bath-resistant, low-temperature-toughened and glass fiber-reinforced polypropylene material is prepared from the following raw materials in parts by weight:
preferably, the material is prepared from the following raw materials in parts by weight:
further, the copolymerized polypropylene is copolymerized polypropylene with high ethylene content; the melt flow rate of the polypropylene copolymer is 3-6g/10min (230 ℃, 2.16 kg); the impact strength of the izod notch of the copolymerized polypropylene is more than 30kJ/m2。
Further, the melting point of the PPR is 155-160 ℃; the melt flow rate of the PPR is 0.5-1.5g/10min (230 ℃, 2.16 kg); the PPR has the Izod notch impact strength of 20-40.
Further, the processing aid is at least one of an antioxidant, an anti-sticking agent or a lubricant; the synthetic mica is fluorophlogopite. The fluorophlogopite is monoclinic mica, and has high transparency.
Further, the grafted polypropylene is a grafted oligomer of polypropylene and unsaturated acid or unsaturated anhydride; the grafting rate of the grafted polypropylene is 0.3-1.2%, and the melt index is 50-120g/10min (230 ℃, 2.16 kg); preferably, the grafted polypropylene is one of polypropylene grafted maleic acid, polypropylene grafted itaconic acid or polypropylene grafted acrylic acid.
The preparation method of the low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following steps: uniformly mixing the polypropylene copolymer, the PPR, the POE, the grafted polypropylene, the Vistamaxx, the synthetic mica powder and the processing aid, feeding the mixture from a main feeding port of an extruder, and feeding the glass fiber into a screw cylinder of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low temperature toughening and high strength.
Further, the extruder is a double-screw extruder.
Further, the melting temperature of the melting step is 180-250 ℃.
Further, the processing conditions of the melting step are as follows: the temperature of the first zone is 170-.
The low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material is applied to the fields of energy batteries and automobile industry.
Compared with the prior art, the low-blushing, oil-bath-resistant, low-temperature-toughened and glass fiber-reinforced polypropylene material has the following advantages:
(1) the low-whitening, oil-bath-resistant, low-temperature-toughening and glass fiber-reinforced polypropylene material disclosed by the invention improves the low-temperature toughness of the polypropylene material by utilizing the toughening effect of POE. And the compatibility of the ethylene phase and the propylene phase of the copolymerized polypropylene is improved by adding Vistamax, and the interface strength of the ethylene phase and the propylene phase is improved, so that the stress whitening resistance of the material is improved.
(2) The PPR pipe material added with the low-blushing, oil-bath-resistant, low-temperature-toughened and glass fiber reinforced polypropylene material is not easy to generate silver lines when being impacted by external force, and has good blushing resistant effect. The addition of the PPR pipe material further improves the stress whitening resistance of the material.
(3) The low-whitening, oil-bath-resistant, low-temperature-toughened and glass fiber reinforced polypropylene material disclosed by the invention has the advantages that the rheological property of the material is improved by adding a proper processing aid and screening a proper co-polypropylene material, so that the welding performance of the material is optimized, and the characteristics of easiness in welding, high welding strength and the like are realized.
(4) According to the low-whitening, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material, the transparent synthetic mica powder is added, so that the sheet structure of the synthetic mica powder effectively prevents small-molecule grease from being immersed, and the grease resistance of polypropylene is improved.
(5) The low-whitening, oil-bath-resistant, low-temperature-toughened and glass fiber-reinforced polypropylene material improves the compatibility of glass fibers and polypropylene parts by adding the grafted polypropylene, so that the glass fiber-reinforced polypropylene has higher mechanical strength.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
The low-whitening, oil-bath-resistant, low-temperature-toughened and glass fiber-reinforced polypropylene material is prepared from the following raw materials in parts by weight:
preferably, the material is prepared from the following raw materials in parts by weight:
the copolymerized polypropylene is copolymerized polypropylene with high ethylene content; the melt flow rate of the polypropylene copolymer is 3-6g/10min (230 ℃, 2.16 kg); the impact strength of the izod notch of the copolymerized polypropylene is more than 30kJ/m2. The melting point of the PPR is 155-160 ℃; the melt flow rate of the PPR is 0.5-1.5g/10min (230 ℃, 2.16 kg); the PPR has the Izod notch impact strength of 20-40. The processing aid is at least one of an antioxidant, an anti-sticking agent or a lubricant; the synthetic mica is fluorophlogopite. The fluorophlogopite is monoclinic mica, and has high transparency. The grafted polypropylene is a grafted oligomer of polypropylene and unsaturated acid or unsaturated anhydride; the grafting rate of the grafted polypropylene is 0.3-1.2%, and the melt index is 50-120g/10min (230 ℃, 2.16 kg); preferably, the grafted polypropylene is one of polypropylene grafted maleic acid, polypropylene grafted itaconic acid or polypropylene grafted acrylic acid.
The preparation method of the low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following steps: uniformly mixing the polypropylene copolymer, the PPR, the POE, the grafted polypropylene, the Vistamaxx, the synthetic mica powder and the processing aid, feeding the mixture from a main feeding port of an extruder, and feeding the glass fiber into a screw cylinder of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low temperature toughening and high strength.
The extruder is a double-screw extruder. The melting temperature of the melting step is 180-250 ℃. The processing conditions of the melting step are as follows: the temperature of the first zone is 170-.
Example 1
The low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following components in percentage by weight: the processing aid comprises an antioxidant, a lubricant and an anti-sticking agent, wherein the antioxidant is an antioxidant 1010 and an antioxidant 168, the antioxidant 1010 and the antioxidant 168 are compounded according to the mass ratio of 1:1, the lubricant is a polyethylene wax lubricant, the anti-sticking agent is FX-5920A (tetrafluoroethylene processing aid), and the component ratio is shown in Table 1.
The preparation method of the low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following steps: uniformly mixing the polypropylene copolymer, the PPR, the POE, the grafted polypropylene and the processing aid, then feeding from a main feeding port of an extruder, and feeding the glass fiber into a screw cylinder of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low temperature toughening and high strength.
The processing conditions of the melting step are as follows: the temperature of the first zone is 170-.
Example 2
The low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following components in percentage by weight: the processing aid comprises an antioxidant, a lubricant and an anti-sticking agent, wherein the antioxidant is an antioxidant 1010 and an antioxidant 168, the antioxidant 1010 and the antioxidant 168 are compounded according to the mass ratio of 1:1, the lubricant is a polyethylene wax lubricant, the anti-sticking agent is FX-5920A (tetrafluoroethylene processing aid), and the component ratio is shown in Table 1.
The preparation method of the low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following steps: uniformly mixing the polypropylene copolymer, the PPR, the POE, the grafted polypropylene, the Vistamaxx and the processing aid, feeding from a main feeding port of an extruder, and feeding the glass fiber into a screw cylinder of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low temperature toughening and high strength.
Example 3
The low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following components in percentage by weight: the processing aid comprises an antioxidant, a lubricant and an anti-sticking agent, wherein the antioxidant is an antioxidant 1010 and an antioxidant 168, the antioxidant 1010 and the antioxidant 168 are compounded according to the mass ratio of 1:1, the lubricant is a polyethylene wax lubricant, the anti-sticking agent is FX-5920A (tetrafluoroethylene processing aid), and the component ratio is shown in Table 1.
The preparation method of the low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following steps: uniformly mixing the polypropylene copolymer, the PPR, the POE, the grafted polypropylene, the Vistamaxx, the synthetic mica powder and the processing aid, feeding the mixture from a main feeding port of an extruder, and feeding the glass fiber into a screw cylinder of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low temperature toughening and high strength.
Example 4
The low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following components in percentage by weight: the processing aid comprises an antioxidant, a lubricant and an anti-sticking agent, wherein the antioxidant is an antioxidant 1010 and an antioxidant 168, the antioxidant 1010 and the antioxidant 168 are compounded according to the mass ratio of 1:1, the lubricant is a polyethylene wax lubricant, the anti-sticking agent is FX-5920A (tetrafluoroethylene processing aid), and the component ratio is shown in Table 1.
The preparation method of the low-blushing, oil-bath-resistant, low-temperature toughening and glass fiber reinforced polypropylene material comprises the following steps: uniformly mixing the polypropylene copolymer, the PPR, the POE, the grafted polypropylene, the Vistamaxx, the synthetic mica powder and the processing aid, feeding the mixture from a main feeding port of an extruder, and feeding the glass fiber into a screw cylinder of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low temperature toughening and high strength.
Comparative example 1
The polypropylene material comprises: the processing aid comprises an antioxidant and a lubricant, wherein the antioxidant is an antioxidant 1010 and an antioxidant 168, the antioxidant 1010 and the antioxidant 168 are compounded according to the mass ratio of 1:1, the lubricant is a polyethylene wax lubricant, and the component ratio of the components is shown in Table 1.
The preparation method of the polypropylene material comprises the following steps: uniformly mixing the raw materials except the synthetic mica powder, feeding the raw materials from a main feeding port of an extruder, and feeding the synthetic mica into a barrel of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low-temperature toughening and high strength. The pellets were injection molded into corresponding test specimens for testing, the test results are shown in Table 2.
TABLE 1 raw material formulation (in parts by weight) of modified polypropylene materials of examples 1 to 4 and comparative example 1
| Name of raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Polypropylene copolymer | 48.6％ | 41.1％ | 29％ | 14％ | 79.4％ |
| PPR pipe material | 25 | 30％ | 30％ | 40％ | / |
| POE | 5％ | 5％ | 5％ | 5％ | / |
| Vistamaxx | / | 3％ | 5％ | 5％ | / |
| Synthetic mica | / | / | 5％ | 10％ | 5％ |
| Glass fiber | 15％ | 15％ | 20％ | 20％ | 15％ |
| Grafted polypropylene | 5％ | 5％ | 5％ | 5％ | / |
| Antioxidant agent | 0.4％ | 0.4％ | 0.4％ | 0.4％ | 0.4％ |
| Lubricant agent | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ |
| Anti-sticking agent | 0.2％ | 0.3％ | 0.4％ | 0.4％ | / |
TABLE 2 test data for modified Polypropylene materials of examples 1-4 and comparative example 1
Compared with the comparative example 1, the POE is added into the example 1, so that the low-temperature toughness of the example 1 is obviously improved.
Compared with the example 1, the example 2 is added with VISTA AX and PPR pipe materials, and the stress whitening resistance of the example 2 is obviously improved.
Compared with the embodiment 2, the embodiment 3 is added with the synthetic mica powder, and the grease resistance of the embodiment 3 is obviously improved.
In example 4, the content of the PPR tube material was increased as compared with example 3, and the blush resistance of example 4 was further improved.
Compared with the mechanical property, low-temperature toughness, stress whitening resistance, weldability, pressure resistance and oil resistance of the embodiment, the comparative material is a universal power battery shell material in the current market, and the mechanical property, the low-temperature ball drop impact test, the gouging test, the welding test, the pressure resistance test, the engine oil soaking test and the calcium-based grease soaking test of the material are compared in parallel by adopting a common formula and a common processing technology.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material is characterized in that: the material is prepared from the following raw materials in parts by weight:
10-50 parts of co-polypropylene,
25-40 parts of PPR (pentatricopeptide repeats),
15-20 parts of glass fiber,
5 parts of POE (polyolefin elastomer),
5 parts of grafted polypropylene, namely 5 parts of grafted polypropylene,
0-5 parts of Vistamaxx,
0-10 parts of synthetic mica powder,
0.8-1.0 part of processing aid;
the weight parts of the Vistamaxx and the synthetic mica powder are more than 0;
the copolymerized polypropylene is copolymerized polypropylene with high ethylene content; the melt flow rate of the copolymerized polypropylene is 3-6g/10 min; the impact strength of the izod notch of the copolymerized polypropylene is more than 30kJ/m2。
2. The low whitening, oil bath resistant, low temperature toughened, glass fiber reinforced polypropylene material of claim 1, wherein: the melting point of the PPR is 155-160 ℃; the melt flow rate of the PPR is 0.5-1.5g/10 min; the PPR has the Izod notch impact strength of 20-40.
3. The low whitening, oil bath resistant, low temperature toughened, glass fiber reinforced polypropylene material of claim 1, wherein: the processing aid is at least one of an antioxidant, an anti-sticking agent or a lubricant; the synthetic mica is fluorophlogopite.
4. The low whitening, oil bath resistant, low temperature toughened, glass fiber reinforced polypropylene material of claim 1, wherein: the grafted polypropylene is a grafted oligomer of polypropylene and unsaturated acid or unsaturated anhydride; the grafting rate of the grafted polypropylene is 0.3-1.2%, and the melt index is 50-120g/10 min.
5. The low blush, oil bath resistant, low temperature toughened, glass fiber reinforced polypropylene material of claim 4, wherein: the grafted polypropylene is one of polypropylene grafted maleic acid, polypropylene grafted itaconic acid or polypropylene grafted acrylic acid.
6. The process for preparing a low-blushing, oil-bath resistant, low-temperature toughened, glass fiber reinforced polypropylene material according to any one of claims 1 to 5, wherein: the method comprises the following steps: uniformly mixing the polypropylene copolymer, the PPR, the POE, the grafted polypropylene, the Vistamaxx, the synthetic mica powder and the processing aid, feeding the mixture from a main feeding port of an extruder, and feeding the glass fiber into a screw cylinder of the extruder through a side feeding scale; the raw materials are melted, extruded and granulated in an extruder to obtain the glass fiber reinforced polypropylene material with low blushing, oil bath resistance, low temperature toughening and high strength.
7. The method for preparing the low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material according to claim 6, wherein the method comprises the following steps: the extruder is a double-screw extruder.
8. The method for preparing the low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material according to claim 6, wherein the method comprises the following steps: the melting temperature of the melting step is 180-250 ℃.
9. The method for preparing the low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material according to claim 8, wherein the method comprises the following steps: the processing conditions of the melting step are as follows: the temperature of the first zone is 170-.
10. Use of the low blush, oil bath resistant, low temperature toughened, glass fibre reinforced polypropylene material of any one of claims 1 to 5 wherein: the low-blushing, oil-bath-resistant, low-temperature-toughened and glass fiber-reinforced polypropylene material is applied to the fields of energy batteries and automobile industry.
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| CN201711187050.5A CN107955272B (en) | 2017-11-21 | 2017-11-21 | Low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material |
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| CN201711187050.5A CN107955272B (en) | 2017-11-21 | 2017-11-21 | Low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material |
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| CN107955272A CN107955272A (en) | 2018-04-24 |
| CN107955272B true CN107955272B (en) | 2021-02-26 |
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| CN201711187050.5A Active CN107955272B (en) | 2017-11-21 | 2017-11-21 | Low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material |
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Citations (4)
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| US20020055574A1 (en) * | 2000-05-24 | 2002-05-09 | Theodor Uhlenbroich | Use of a modified polypropylene compound for the production of attachments in the automobile industry |
| CN102276924A (en) * | 2011-06-27 | 2011-12-14 | 成都市新津事丰医疗器械有限公司 | High transparency and high toughness material for coat of disposable syringe |
| CN102924805A (en) * | 2012-08-23 | 2013-02-13 | 上海金发科技发展有限公司 | Stress-whitening-resisting glass fiber reinforced polypropylene composite and preparation method thereof |
| CN106832599A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of resistance to stress is turned white low-temperature impact-resistant polypropylene material and preparation method thereof |
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| US20020055574A1 (en) * | 2000-05-24 | 2002-05-09 | Theodor Uhlenbroich | Use of a modified polypropylene compound for the production of attachments in the automobile industry |
| CN102276924A (en) * | 2011-06-27 | 2011-12-14 | 成都市新津事丰医疗器械有限公司 | High transparency and high toughness material for coat of disposable syringe |
| CN102924805A (en) * | 2012-08-23 | 2013-02-13 | 上海金发科技发展有限公司 | Stress-whitening-resisting glass fiber reinforced polypropylene composite and preparation method thereof |
| CN106832599A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of resistance to stress is turned white low-temperature impact-resistant polypropylene material and preparation method thereof |
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| 云母的加工与应用;余力等;《矿冶》;20111231;第20卷(第04期);73-76,81 * |
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