CN111363348A - Halogen-free flame-retardant polyamide compound with biological mildew-resistant function and application thereof - Google Patents
Halogen-free flame-retardant polyamide compound with biological mildew-resistant function and application thereof Download PDFInfo
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- CN111363348A CN111363348A CN202010217389.0A CN202010217389A CN111363348A CN 111363348 A CN111363348 A CN 111363348A CN 202010217389 A CN202010217389 A CN 202010217389A CN 111363348 A CN111363348 A CN 111363348A
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- C—CHEMISTRY; METALLURGY
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention relates to a halogen-free flame-retardant polyamide compound with biological mildew-resistant function and application thereof, comprising polyamide resin, a mildew-resistant agent, a filling agent, an MCA flame retardant and other auxiliary agents; wherein the anti-mildew agent is an organic anti-mildew agent. The organic mildew inhibitor added in the invention has excellent mildew resistance, has no negative influence on the electrical property, mechanical property and the like of the material, ensures that the material does not mildew in the using process, and has good application prospect.
Description
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to a halogen-free flame-retardant polyamide compound with a biological mildew-resistant function and application thereof.
Background
The glass fiber reinforced polyamide has very wide application in the fields of industrial appliances, household appliances and the like. The flame retardant property of most reinforced polyamides cannot meet the requirements of electric products, and the flame retardant property of the material is poorer due to the candle wick effect brought by the introduction of the glass fiber. Therefore, it is necessary to improve flame retardancy before use in electrical equipment (household appliances, molded case circuit breakers, connectors, etc.).
Melamine Cyanurate (MCA) is a very mature halogen-free flame retardant with high nitrogen content and generates NH when decomposed by heat3、H2O、N2、CO2Inert gases can absorb heat and cool, and can dilute the concentration of combustible gases, so that the flame retardant nylon material is widely used for flame retardant modification. Compared with the traditional bromine-antimony flame retardant material and organic phosphorus flame retardant material, MCA flame retardant nylon has higher cost performance, so the MCA flame retardant nylon is widely used in the field of low-voltage electric appliances, especially in the shell material of a Miniature Circuit Breaker (MCB). MCB for part of industrial and rail transit or other electrical equipment are difficult to avoid encountering a damp and hot environment in the use process, and the system is rich in nitrogen-containing organic matters, the surface of a workpiece is easy to generate biological mildew behaviors which are expressed as mildew black spots and the like, the enrichment of microorganisms and metabolites not only influence the appearance of the product, but also are more likely to cause negative influence on the electrical property of the product, so that the product fails, and the influence on certain specific industries such as rail transit is immeasurable. Therefore, the method has very important significance for carrying out anti-mildew modification on the MCA flame-retardant nylon material.
Compared with nylon antibacterial modification, the nylon antibacterial modification method has higher difficulty in mildew resistance modification of nylon and fewer related reports. This is mainly because the general inorganic antibacterial materials have low mildew-resistant efficiency and are difficult to meet the high-demand mildew-resistant demand, on the other hand, although the organic mildew-resistant agents have high mildew-resistant efficiency, the heat resistance is generally poor, the organic mildew-resistant agents are easily decomposed and failed in the high nylon processing process (above 230 ℃), so that the mildew-resistant efficiency is reduced and even the mildew-resistant function is completely lost, and part of the organic mildew-resistant agents are accompanied with strong unfriendly odor, so that the application range of the organic mildew-resistant agents is limited. The patents reported above have some problems, such as patent CN110028728A, which uses low melting point PP and EVA resin as carriers of mildewproof master batch, and uses organic zinc substances as antibacterial and mildewproof auxiliary, but the patents do not distinguish antibacterial and mildewproof concepts. In patent CN 107746597A, sodium diacetate is used as an antimycotic aid, which does not distinguish between antibiosis and antimycotic and compares the effects. In patent CN101402792A, 5 different inorganic substances such as rare earth oxide, high-temperature bamboo charcoal powder, nano oxide and the like are compounded, so that the mildew resistance level 0 can be achieved, and meanwhile, the antibacterial effect is better, but more inorganic substances can reduce the electrical property of the material in an electric product, and the product is invalid.
Disclosure of Invention
The invention aims to solve the technical problem of providing a halogen-free flame-retardant polyamide compound with a biological mildew-resistant function and application thereof, and overcomes the defect that the conventional inorganic mildew-resistant auxiliary has negative influence on the electrical property and the mechanical property of a material.
The invention provides a halogen-free flame-retardant polyamide compound with a biological mildew-resistant function, which comprises the following components in percentage by weight:
the polyamide resins include polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid with an aliphatic or cyclic or cycloaliphatic or arylaliphatic diamine, such as PA66, PA610, PA612, PA1010, PA106, PA1212, PA46, MXD6, PA92, PA 102; or polyamides obtained by polycondensation between at least one aromatic dicarboxylic acid and an aliphatic or aromatic diamine, such as polyterephthalamides of the type PA9T, PA10T, PA11T, PA12T, PA13T or PA6T/MT, PA6T/6I, PA6T/66, PA66/6T, polyisophthalamides of the type PA6I, PA6I/6T, polynaphthalene amides of the type PA10N, PA11N, PA12N, polyaramides, such as aramides, or blends thereof and (co) polyamide resins thereof. The polyamide resin of the invention can also be chosen from polyamide resins obtained by polycondensation of at least one amino acid or lactam with itself, it being possible for this amino acid to be produced by hydrolytic opening of the lactam ring, such as PA6, PA7, PA11, PA12 or PA13, or blends thereof and (co) polyamide resins thereof. Types of copolyamide resins which may be mentioned in particular include polyamide 6/66, polyamide 6/11, polyamide 6/12 and polyamide 11/12.
The organic anti-mildew agent is at least one of phenol alcohol substance Iheir-JS117 containing nitrogen heterocyclic rings and Zinc pyrithione active substance Zinc Omadine Powder.
The filler is at least one of chopped glass fiber, carbon fiber, talcum powder, mica, calcium carbonate, barium sulfate, wollastonite, kaolin, clay and titanium dioxide. The chopped glass fibers preferably have a typical length in the range of 1.5mm to 6.0mm, and the milled glass fibers are preferably 7 to 16 μm, more preferably 8 to 12 μm, directly. Meanwhile, the ground glass fiber strands comprise A-, E-, C-, D-, S-and R-glass fibers, and the cross sections of the fibers have other cross section shapes such as round, oval or square.
The MCA flame retardant is melamine cyanurate, the content of residual melamine in the flame retardant is less than 0.04 wt%, the content of residual cyanuric acid is 0.01-0.3%, and the pH value is 5.0-7.0.
The other auxiliary agents comprise a heat stabilizer and/or a lubricant.
The heat stabilizer is at least one of hindered phenols, amines and phosphate esters; the lubricant is at least one of stearamides, alcohol stearates, stearates and long-chain saturated linear carboxylates.
The invention also provides application of the halogen-free flame-retardant polyamide compound with the biological mildew-resistant function.
Different from the prior patent technology, the mildew resistance and the antibacterial performance are not distinguished, and the invention focuses on the mildew resistance of the material; the organic mildew inhibitor added in the invention has excellent mildew resistance, has no negative influence on the electrical property, mechanical property and the like of the material, ensures that the material does not mildew in the using process, and has good application prospect.
Drawings
FIG. 1 is a photograph of comparative example 1 after being subjected to a 28-day anti-mold test.
FIG. 2 is a photograph of example 3 after a 28-day anti-mold test.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw materials used in the specific examples and comparative examples are as follows:
the organic anti-mildew agent is selected from Iheir-JS117 (available from Ahaole mildew-proof and antibacterial science and technology Limited, Guangzhou) and Zincomadine Powder (available from Longsha, brand: VANQUISH 100); the inorganic antifungal agent is selected from DXN-KD30S (available from Darcy concentrated nanotechnology (Heizhou) Co., Ltd.) and AGZ330 (available from Toyo Synthesis Co., Ltd.); among other auxiliary agents, IRGANOX 1098 (from BASF) was used as the heat stabilizer, TR044W (from Struktol) was used as the lubricant, and MCA flame retardant was obtained from the institute of Fine chemical engineering, Sichuan province.
The present invention will be further described with reference to comparative examples 1 to 11 and examples 1 to 8.
Weighing the raw materials according to the proportion in the following table 1 and table 2, mixing in a high-speed mixer, and then passing through a double screwThe extruder carries out extrusion granulation (the screw diameter is 65mm, the extrusion temperature is 200-. The composites prepared in the examples and comparative examples described above were injection molded into plaques having a diameter of 50mm and a thickness of 4mm and then tested according to ASTM G21. For better detection of the mildew resistance of the material, the spore suspension prepared in the test process has the concentration of 107one/mL, 10 times that of ASTM G21 standard. The mildew condition of the surface of the sample is regularly observed, and the mildew resistance grades of the material are judged to be 0 grade, 1 grade, 2 grade, 3 grade and 4 grade according to ASTMG21, wherein the 0 grade is optimal, and the 4 grade is worst.
TABLE 1 results of proportioning and performance test of comparative example 1 and examples 1-8
TABLE 2 comparative examples 2-11 ratios and performance test results
As can be seen from the results in tables 1 and 2, the mildew resistance level 0 can be realized by using the organic mildew inhibitor material with the proportion of less than 1%, and the electrical property (CTI) can be kept above 600V, which is important for the electric-related products. The inorganic mildew inhibitor is added in a higher proportion to achieve the same mildew-resistant effect, meanwhile, the inorganic mildew inhibitor has a large negative effect on the electrical property of the material, and when the mildew-resistant level 0 or 1 is achieved, the CTI is reduced to 200V, so that the material cannot be applied to most of electric-related products.
As can be seen from the comparison between fig. 1 and fig. 2, in comparative example 1 in which no antifungal agent was added, severe mildew occurred on and around the surface of the sample after the 28-day experiment, and the grade of antifungal activity reached only 4. In example 3 with 0.5% of Iheir-JS117 added, after 28 days of test, no mildew spots are formed on the surface of the sample, meanwhile, a ring-shaped mildew-free area is formed around the sample, and the mildew resistance grade can reach 0.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (9)
1. A halogen-free flame-retardant polyamide compound with biological mildew-resistant function is characterized in that: comprises the following components in percentage by weight:
2. polyamide compound according to claim 1, characterized in that: the polyamide resin comprises polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid with an aliphatic or cyclic or cycloaliphatic or arylaliphatic diamine; or polyamides obtained by polycondensation of at least one aromatic dicarboxylic acid with an aliphatic or aromatic diamine; or a polyamide resin obtained by polycondensation of at least one amino acid or lactam with itself.
3. Polyamide compound according to claim 1, characterized in that: the organic anti-mildew agent is at least one of phenol alcohol substance Iheir-JS117 containing nitrogen heterocyclic rings and Zinc pyrithione active substance Zinc Omadine Powder.
4. Polyamide compound according to claim 1, characterized in that: the filler is at least one of chopped glass fiber, carbon fiber, talcum powder, mica, calcium carbonate, barium sulfate, wollastonite, kaolin, clay and titanium dioxide.
5. Polyamide compound according to claim 4, characterized in that: the length of the chopped glass fiber is within the range of 1.5mm to 6.0mm, the ground glass fiber is 7-16 mu m, and the ground glass fiber precursor comprises precursor A-, E-, C-, D-, S-or R-glass fiber; the fiber cross-section has a circular, oval or square shape.
6. Polyamide compound according to claim 1, characterized in that: the MCA flame retardant is melamine cyanurate, the content of residual melamine in the flame retardant is less than 0.04 wt%, the content of residual cyanuric acid is 0.01-0.3%, and the pH value is 5.0-7.0.
7. Polyamide compound according to claim 1, characterized in that: the other auxiliary agents comprise a heat stabilizer and/or a lubricant.
8. Polyamide compound according to claim 7, characterized in that: the heat stabilizer is at least one of hindered phenols, amines and phosphate esters; the lubricant is at least one of stearamides, alcohol stearates, stearates and long-chain saturated linear carboxylates.
9. Use of the halogen-free flame retardant polyamide compound with biological mildew resistance as defined in claim 1.
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| CN202010217389.0A CN111363348A (en) | 2020-03-25 | 2020-03-25 | Halogen-free flame-retardant polyamide compound with biological mildew-resistant function and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656780A (en) * | 2022-03-10 | 2022-06-24 | 桂林理工大学 | Halogen-free flame-retardant mildew-proof nylon material and preparation method and application thereof |
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