CN112266606A - High-wear-resistance and high-weather-resistance polyamide composition and preparation method and application thereof - Google Patents
High-wear-resistance and high-weather-resistance polyamide composition and preparation method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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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- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The invention discloses a high-wear-resistance and high-weather-resistance polyamide composition, and a preparation method and application thereof. The polyamide composition comprises the following components: polyamide resin, a toughening agent, methyl triallyl isocyanurate, glass fiber and an auxiliary agent. The methyl triallyl isocyanurate is used as an auxiliary crosslinking agent to promote the polyamide material to carry out efficient intermolecular crosslinking under irradiation, and the toughening agent and the glass fiber have synergistic effect, thereby improving the comprehensive performance of the polyamide composition. The polyamide composition has excellent wear resistance and weather resistance, and a polyamide product prepared by irradiation crosslinking treatment is suitable for being used as a wear-resistant part in the automobile industry or rail transit in a severe environment with large temperature difference.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-wear-resistance and high-weather-resistance polyamide composition and a preparation method and application thereof.
Background
The polyamide material is widely applied to industries such as rail transit, electric tools and the like, the performance of the material is continuously improved in each industry along with continuous development and progress of science and technology, particularly for the rail transit industry, along with continuous promotion and deepening of new capital construction, the region involved in rail transit construction is wider, the facing climate conditions are more complex, and therefore the requirement on the comprehensive performance of the material is higher. Particularly in some high-cold or high-altitude areas, such as the tibetan line, the altitude is high, the temperature difference between day and night is large, and higher requirements are provided for the wear resistance and weather resistance of the polyamide material, but the traditional polyamide material cannot meet the related requirements.
The irradiation crosslinking is a technical means for initiating crosslinking reaction between polymer long chains by using various radiations, and the irradiation source can be selected from electron beams, gamma rays, neutron beams, particle beams and the like according to the polymer category and performance requirements. For polyamide materials, due to the strong hydrogen bonding between molecular chains, the cross-linking of polyamide is difficult to initiate by simple irradiation treatment, and therefore, it is necessary to promote the cross-linking reaction of the system by introducing an auxiliary cross-linking agent, so as to obtain the irradiation cross-linked material. Radiation crosslinkers which can be used for polyamides in general are triallyl cyanurate (TAC), triallyl isocyanurate (TAIC).
In the prior art, the radiation cross-linked polyamide is mainly researched by focusing on a polyamide material of a flame retardant system, so that the flame retardant property and the heat distortion temperature of the polyamide material are improved. However, the addition of flame retardant in polyamide composition can cause the mechanical properties and weather resistance of polyamide material to be reduced, and thus the polyamide composition cannot be applied to wear-resistant and weather-resistant polyamide products. The Chinese patent application CN105153690A discloses a chloride salt stress corrosion cracking resistant polyamide composition, which is a non-flame retardant system, and the addition of glass fiber, a cross-linking agent and a radiation stabilizer improves the salt stress corrosion cracking resistance of the polyamide composition by irradiation treatment, so as to realize the cracking protection of polyamide automobile parts when contacting with a chloride salt snow melting agent. However, the abrasion resistance and the weather resistance of the polyamide material are not concerned, especially the abrasion resistance and the weather resistance under the severe environment with large temperature difference.
Therefore, it is required to develop a polyamide composition having high abrasion resistance and high weather resistance.
Disclosure of Invention
The invention provides a high-wear-resistance and high-weather-resistance polyamide composition for overcoming the defects of poor wear resistance and poor weather resistance in the prior art, and the polyamide composition has excellent wear resistance and weather resistance and can be applied to complex and severe working conditions.
Another object of the present invention is to provide a process for producing the above polyamide composition.
Another object of the present invention is to provide the use of the above polyamide composition for the preparation of polyamide articles for the automotive industry or for the rail transit field.
In order to solve the technical problems, the invention adopts the technical scheme that:
the high-wear-resistance and high-weather-resistance polyamide composition comprises the following components in parts by weight:
30-80 parts of polyamide resin,
1-10 parts of a toughening agent,
2-10 parts of methyl triallyl isocyanurate,
10-50 parts of glass fiber,
0-10 parts of an auxiliary agent.
The inventors have found through extensive studies that it is difficult to achieve a satisfactory effect of promoting crosslinking in polyamide compositions using, in addition to methyl triallyl isocyanurate (TMAIC), commercially available co-crosslinking agents such as triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC). In comparison, TMAIC has good thermal stability, and in a proper amount of addition, the polyamide material can maintain stable structure through high-temperature melt extrusion and injection molding in a polyamide system, so that the polyamide material obtains a good cross-linked structure after irradiation treatment. TAC and TAIC are easy to decompose at high temperature, TAC or TAIC is used as an auxiliary crosslinking agent under the condition of the same addition amount and the same irradiation, the crosslinking amount of the polyamide composition is small through irradiation treatment, and finally obtained polyamide products are poor in wear resistance and weather resistance and cannot meet actual requirements.
Preferably, the methyl triallyl isocyanurate accounts for 4-8 parts.
When the addition amount of TMAIC is too low, the formation of a cross-linking structure of the polyamide composition is less, the cross-linking degree is not enough, and the satisfactory wear-resistant and weather-resistant performance is difficult to achieve; when TMAIC is too high, the polyamide composition has too many crosslinking structures after irradiation, which results in too strong material rigidity, poor toughness, reduced processing stability and poor comprehensive performance.
Preferably, the toughening agent is one or more of maleic anhydride grafted polyolefin, ethylene propylene terpolymer and ethylene methyl acrylate.
The toughening agent and the auxiliary crosslinking agent can effectively improve the wear resistance and weather resistance of the polyamide composition through synergistic effect. Meanwhile, the toughening agent can effectively improve the compatibility and the dispersibility of each component in a polyamide system, enhance the interface action between polyamide and glass fiber, and obtain the polyamide composition with lower abrasion loss and better aging resistance.
More preferably, the toughening agent is more preferably a maleic anhydride grafted polyolefin. Alternatively, the maleic anhydride grafted polyolefin is DuPont N493D, Dowang N406, Cypress PC-28, and the like.
Most preferably, the weight part of the maleic anhydride grafted polyolefin is most preferably 2-5 parts.
The appropriate amount of the toughening agent can improve the wear resistance of the material and promote the crosslinking of a polyamide system; when the content of the toughening agent is less, the crosslinking promotion effect on a polyamide system is difficult to embody, and the wear resistance of the polyamide composition is deteriorated; when the toughening agent is too much, the weather resistance of the polyamide material can be greatly influenced.
Preferably, the polyamide resin is preferably one of PA6, PA 46, PA66, PA 56.
Preferably, the glass fiber is one or more of E glass fiber, H glass fiber, R, S glass fiber, D glass fiber, C glass fiber and quartz glass fiber.
Most preferably, the glass fibers are most preferably E glass fibers.
Preferably, the diameter of the glass fiber is preferably 7-13 μm.
The auxiliary agent comprises an antioxidant, a lubricant and the like.
The antioxidant may be an antioxidant commonly used in polyamides. Preferably, the antioxidant is preferably a hindered phenolic antioxidant.
The lubricant may be a lubricant commonly used in polyamides. Preferably, the lubricant is preferably a Mondan-type lubricant.
The invention also provides a preparation method of the polyamide composition, which comprises the following steps:
mixing polyamide resin, a toughening agent, methyl triallyl isocyanurate, glass fiber and an auxiliary agent, adding the mixture into an extruder, and performing melt granulation to obtain the high-wear-resistance and high-weather-resistance polyamide composition.
Preferably, the extruder is a double-screw extruder, the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 240-300 ℃, and the rotating speed of the screw is 200-550 rpm.
The invention also relates to the use of the polyamide composition described above for producing polyamide articles for the automotive industry or for the rail transit field.
The invention also provides a polyamide product which is prepared from the polyamide composition by adopting radiation crosslinking processing.
Preferably, the irradiation crosslinking adopts electron beams as a radiation source, and the irradiation dose is 15-25 Mrad.
After the polyamide composition is subjected to irradiation treatment, alpha-carbon beside amino in a polyamide chain segment can be broken, and a new chemical bond is formed with other molecular chains, so that a cross-linked network structure is formed.
Compared with the prior art, the invention has the beneficial effects that:
the polyamide composition with high wear resistance and high weather resistance is prepared by mutually matching the polyamide resin, the toughening agent, the glass fiber, the methyl triallyl isocyanurate and other components. The methyl triallyl isocyanurate is used as an auxiliary crosslinking agent to promote the polyamide material to carry out efficient intermolecular crosslinking under irradiation, and the toughening agent and the glass fiber have synergistic effect, thereby improving the comprehensive performance of the polyamide composition. The polyamide composition has excellent wear resistance and weather resistance, and a polyamide product prepared by irradiation crosslinking treatment is suitable for being used as a wear-resistant part in the automobile industry or rail transit in a severe environment with large temperature difference.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The starting materials in the examples and comparative examples are commercially available as follows:
polyamide resin a: type 6 polyamide, and Kadsura chemical fiber HY-2800A;
polyamide resin B: type 66 polyamide, Huafeng group PA66 EP-158;
a toughening agent A: maleic anhydride grafted ethylene-octene copolymer, Nicotiana tabacum N406;
a toughening agent B: ethylene-methyl acrylate (MAA) was used,
AC1125；
a toughening agent C: ethylene propylene terpolymer, designation 3072 EPM;
auxiliary crosslinking agent A: TMAIC, FaridA H-2, Farida Chemicals, Inc.;
and (3) auxiliary crosslinking agent B: TAC, winning degussa investments limited;
and (3) auxiliary crosslinking agent C: TAIC, winning degussa investments ltd;
glass fiber: e glass fiber, China boulder ECS11-4.5-560A, diameter 11 μm;
antioxidant: hindered phenolic antioxidants, IRGANOX 1098, BASF;
lubricant: long chain fatty acid esters, LOXIOL G32, Emery.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Examples 1 to 14
The contents of the respective components in the highly abrasion-resistant and highly weather-resistant polyamide compositions of examples 1 to 14 are shown in Table 1.
The preparation method comprises the following steps: the components are uniformly mixed according to the table 1, and then the mixture is added into a double-screw extruder for melt blending and extrusion granulation to obtain the polyamide composition with high wear resistance and high weather resistance.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 40:1, the temperature of a screw cylinder is 240-300 ℃, and the rotating speed of the screw is 200-550 rpm.
TABLE 1 component contents (parts by weight) of the polyamide compositions of examples 1 to 14
Comparative examples 1 to 6
The contents of the respective components in the polyamide compositions of comparative examples 1 to 6 are shown in Table 2.
The preparation method comprises the following steps: the components are uniformly mixed according to the table 2, and then the mixture is added into a double-screw extruder for melt blending and extrusion granulation to obtain the high-wear-resistance and high-weather-resistance polyamide composition.
Wherein the length-diameter ratio of a screw of the double-screw extruder is 40:1, the temperature of a screw cylinder is 240-300 ℃, and the rotating speed of the screw is 200-550 rpm.
TABLE 1 component contents (parts by weight) of the polyamide compositions of comparative examples 1 to 6
Comparative example 1 differs from example 1 in that toughening agent a is 0.5 parts;
comparative example 2 differs from example 1 in that toughener a is 12 parts;
the comparative example 3 is different from the example 1 in that the auxiliary crosslinking agent is TAC;
comparative example 4 differs from example 1 in that the co-crosslinking agent is TAIC;
comparative example 5 is different from example 1 in that the auxiliary crosslinking agent A is 1 part;
comparative example 6 is different from example 1 in that the auxiliary crosslinking agent A is 12 parts.
Performance testing
The polyamide compositions prepared in the above examples and comparative examples were injection molded and subjected to irradiation crosslinking treatment to prepare polyamide articles.
Wherein the injection temperature of the injection molding is 270-300 ℃, and the injection pressure is 55-100 MPa; the irradiation crosslinking treatment adopts electron beams as a radiation source, and the irradiation dose is 20 Mrad.
The above polyamide articles were subjected to a performance test.
The test method specifically comprises the following steps:
abrasion loss: GB/T5478-;
powdering time: ISO 4892-2-1994cycle 1, wherein a test sample is a flat plate part, and the time for starting powdering on the surface of the sample is recorded, and the unit of the powdering time is h;
tensile strength decay time: UL 746B-2011 UL Standard for evaluation of Long-term Performance of Standard Polymer materials, wherein the aging temperature is 170 ℃, an ISO 527-2-19931 BA sample is used as a test sample, the thickness is 0.8mm, the time required for the tensile strength to decay to 50% of the initial performance is recorded, and the unit of the decay time of the tensile strength is h;
the abrasion loss of the polyamide product is adopted to reflect the abrasion resistance of the polyamide composition, and the pulverization time and the tensile strength decay time of the polyamide product reflect the weather resistance of the polyamide composition.
The test results of examples 1 to 14 are shown in Table 3.
Table 3 results of performance test of examples 1 to 14
As can be seen from Table 3, the polyamide compositions prepared in examples 1 to 14 all have high crosslinking degree and excellent wear resistance and weather resistance, wherein the abrasion loss of the polyamide product is less than or equal to 65mg, the pulverization time is more than or equal to 1770h, and the pull-up strength decay time is more than or equal to 5440 h.
According to the test results of the examples 1 to 4, when the addition amount of the maleic anhydride grafted ethylene-octene copolymer is 2 to 5, the abrasion loss of the polyamide product is less than or equal to 36mg, the powdering time is greater than or equal to 2000h, the tensile strength decay time is greater than or equal to 6600h, and the wear resistance and the weather resistance of the polyamide composition are relatively better. Comparing the embodiment 1 with the embodiment 5-6, the polyamide composition prepared by using the ethylene methyl acrylate or the ethylene terpolymer as the toughening agent has slightly poor wear resistance and weather resistance, so the toughening agent is preferably maleic anhydride grafted ethylene-octene copolymer. According to the test results of the embodiment 1 and the embodiments 7 to 9, when the amount of TMAIC added is 4 to 8 parts, the polyamide composition has proper crosslinking degree and excellent wear resistance and weather resistance.
The test results of comparative examples 1 to 6 are shown in Table 4.
TABLE 4 comparative examples 1-6 Performance test results
As can be seen from Table 4, when the amount of the toughening agent is too much or too little, the abrasion loss of the polyamide product is not less than 80mg, the wear resistance of the polyamide composition is poor, and the powdering time and the pull-up strength decay time cannot meet the requirements. When the assistant crosslinking agent is TAC or TAIC, the abrasion loss is 72mg and 70mg respectively, the powdering time is about 1000h, and the tensile strength decay time is short, which indicates that the prepared polyamide composition has poor wear resistance and weather resistance. When the addition amount of the auxiliary crosslinking agent A (TAMIC) is too small, a sufficient crosslinking structure is difficult to form through irradiation treatment, and the wear resistance and weather resistance of the polyamide composition are poor. When the addition amount of the auxiliary crosslinking agent A is too much, the material system still has structural defects caused by insufficient thermal stability after shearing, and the overall performance of the material is reduced.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The high-wear-resistance and high-weather-resistance polyamide composition is characterized by comprising the following components in parts by weight: 30-80 parts of polyamide resin, 1-10 parts of a toughening agent, 2-10 parts of methyl triallyl isocyanurate, 10-50 parts of glass fiber and 0-10 parts of an auxiliary agent.
2. The polyamide composition of claim 1, wherein the methyl triallyl isocyanurate is 4 to 8 parts.
3. The polyamide composition of claim 1, wherein the toughening agent is one or more of maleic anhydride grafted polyolefin, ethylene terpolymer, or ethylene methyl acrylate.
4. Polyamide composition according to claim 1 or 3, characterized in that the toughening agent is a maleic anhydride grafted polyolefin.
5. The polyamide composition according to claim 4, wherein the maleic anhydride-grafted polyolefin is present in an amount of 2 to 5 parts by weight.
6. Polyamide composition according to claim 1, characterized in that the polyamide resin is one of PA6, PA 46, PA66 or PA 56.
7. The polyamide composition according to claim 1, wherein the glass fiber is one or more of E glass fiber, H glass fiber, R, S glass fiber, D glass fiber, C glass fiber, or quartz glass fiber.
8. A process for producing a polyamide composition as claimed in any one of claims 1 to 7, characterized by comprising the steps of:
mixing polyamide resin, a toughening agent, methyl triallyl isocyanurate, glass fiber and an auxiliary agent, adding the mixture into an extruder, and performing melt granulation to obtain the high-wear-resistance and high-weather-resistance polyamide composition.
9. Use of a polyamide composition according to any one of claims 1 to 7 for the preparation of polyamide articles for the automotive industry or for the rail transit field.
10. A polyamide product, characterized in that the polyamide composition is prepared by irradiation crosslinking processing according to any one of claims 1 to 7.
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| CN202011048419.6A CN112266606A (en) | 2020-09-29 | 2020-09-29 | High-wear-resistance and high-weather-resistance polyamide composition and preparation method and application thereof |
| PCT/CN2021/077797 WO2022068143A1 (en) | 2020-09-29 | 2021-02-25 | Polyamide composition having high wear resistance and weathering resistance, preparation method therefor and use thereof. |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113017195A (en) * | 2021-04-13 | 2021-06-25 | 温州市三盟鞋业有限公司 | Tear-resistant heel nail and preparation process thereof |
| WO2022068143A1 (en) * | 2020-09-29 | 2022-04-07 | 金发科技股份有限公司 | Polyamide composition having high wear resistance and weathering resistance, preparation method therefor and use thereof. |
| WO2023279984A1 (en) * | 2021-07-09 | 2023-01-12 | 金发科技股份有限公司 | Pbt/pc alloy with stable mechanical properties, and preparation method therefor and article thereof |
| CN115746547A (en) * | 2022-11-18 | 2023-03-07 | 中广核高新核材科技（苏州）有限公司 | Irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403922B (en) * | 2022-08-11 | 2023-10-31 | 天津金发新材料有限公司 | Polyamide composite material and preparation method and application thereof |
| CN115584125A (en) * | 2022-09-19 | 2023-01-10 | 金发科技股份有限公司 | Lubricating ester-resistant PA composition and preparation method and application thereof |
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| JP2005350536A (en) * | 2004-06-09 | 2005-12-22 | Toyobo Co Ltd | Heat-resistant polyamide-based film, electronic element and mold-releasing film for copper-clad laminate |
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| JP2014234503A (en) * | 2013-06-05 | 2014-12-15 | 日立化成株式会社 | Thermoplastic resin composition and method of producing the same |
| CN105153690B (en) * | 2015-07-24 | 2018-01-02 | 中广核俊尔新材料有限公司 | A kind of daiamid composition for the stress corrosion cracking of resistance to chlorate and its preparation method and application |
| CN112266606A (en) * | 2020-09-29 | 2021-01-26 | 金发科技股份有限公司 | High-wear-resistance and high-weather-resistance polyamide composition and preparation method and application thereof |
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- 2020-09-29 CN CN202011048419.6A patent/CN112266606A/en active Pending
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- 2021-02-25 WO PCT/CN2021/077797 patent/WO2022068143A1/en active Application Filing
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| JP2005350536A (en) * | 2004-06-09 | 2005-12-22 | Toyobo Co Ltd | Heat-resistant polyamide-based film, electronic element and mold-releasing film for copper-clad laminate |
| CN111138850A (en) * | 2019-12-12 | 2020-05-12 | 金发科技股份有限公司 | Polyamide composite material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022068143A1 (en) * | 2020-09-29 | 2022-04-07 | 金发科技股份有限公司 | Polyamide composition having high wear resistance and weathering resistance, preparation method therefor and use thereof. |
| CN113017195A (en) * | 2021-04-13 | 2021-06-25 | 温州市三盟鞋业有限公司 | Tear-resistant heel nail and preparation process thereof |
| WO2023279984A1 (en) * | 2021-07-09 | 2023-01-12 | 金发科技股份有限公司 | Pbt/pc alloy with stable mechanical properties, and preparation method therefor and article thereof |
| CN115746547A (en) * | 2022-11-18 | 2023-03-07 | 中广核高新核材科技（苏州）有限公司 | Irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon composite material and preparation method thereof |
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| WO2022068143A1 (en) | 2022-04-07 |
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Application publication date: 20210126 |