CN114276677B - Flame-retardant nylon composite material and preparation method and application thereof - Google Patents
Flame-retardant nylon composite material and preparation method and application thereof Download PDFInfo
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- CN114276677B CN114276677B CN202111554855.5A CN202111554855A CN114276677B CN 114276677 B CN114276677 B CN 114276677B CN 202111554855 A CN202111554855 A CN 202111554855A CN 114276677 B CN114276677 B CN 114276677B
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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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
- 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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Abstract
The invention relates to a flame-retardant nylon composite material, and a preparation method and application thereof. The flame-retardant nylon composite material provided by the invention takes specific nylon resin as a base material, and simultaneously, a smaller amount of aromatic dicarboxylic acid is added for flame-retardant modification, so that stable flame-retardant V-2 grade can be achieved, and the mechanical property of the flame-retardant nylon composite material is not negatively influenced.
Description
Technical Field
The invention belongs to the field of engineering plastic application, and particularly relates to a flame-retardant nylon composite material and a preparation method and application thereof.
Background
Nylon has the advantages of excellent electrical performance (CTI, electrical breakdown strength), low price and the like, and is widely applied to industries such as electronics, electrics and the like. Melamine cyanurate is a very effective flame retardant for nylon, but because melamine cyanurate interacts with nylon, the processing stability of nylon is affected. Under the condition of heating, the nylon material is easy to change in crystallinity, and the flame-retardant stability of the nylon material is also affected.
The prior patent discloses an MAC flame-retardant nylon 66 composite material, which takes MAC (melamine cyanurate) as a flame retardant, takes a long carbon chain monobasic saturated carboxylic acid compound or a long carbon chain dibasic saturated carboxylic acid compound with specific carbon atoms as a flame retardant stabilizer, and can reach the flame retardant V-0 grade; it also indicates that only V-2 grades can be achieved without the addition of flame retardant stabilizers. However, melamine cyanurate is still used as a flame retardant, and the flame retardant stability is poor. In addition, the addition of the long-carbon-chain mono-saturated carboxylic acid compound or the long-carbon-chain binary saturated carboxylic acid compound with specific carbon atoms can also have negative influence on the mechanical properties of the nylon material.
Therefore, development of a nylon material with better mechanical property, flame retardant property and flame retardant stability has important research significance.
Disclosure of Invention
The invention aims to overcome the defects of poor flame-retardant stability and influenced mechanical properties of a compound flame-retardant stabilizer caused by taking melamine cyanurate as a flame retardant in the nylon material in the prior art. The flame-retardant nylon composite material provided by the invention takes the specific nylon resin as a base material, and simultaneously, a small amount of aromatic dicarboxylic acid is added for flame-retardant modification, so that stable flame-retardant V-2 grade can be achieved, and the mechanical property of the flame-retardant nylon composite material is not negatively influenced.
The invention also aims to provide a preparation method of the flame-retardant nylon composite material.
Another object of the invention is to provide the use of flame retardant nylon composite materials in the preparation of 3D printing consumables.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the flame-retardant nylon composite material comprises the following components in parts by weight:
97-99.95 parts of nylon resin;
0.05-2 parts of aromatic dicarboxylic acid;
the content of the oligomer in the nylon resin is not higher than 1.6%.
The inventors of the present invention studied and found that if only C is added 8～18 Long carbon chain monobasic saturated carboxylic acid compound or C 8～18 The long carbon chain binary saturated carboxylic acid compound is used for nylon materialThe flame retardant grade of the modified flame retardant can reach V-2 grade, but the flame retardant stability is poor, the V-2 grade cannot be maintained after 168H is treated at 70 ℃, and the modified flame retardant has a larger negative effect on mechanical properties.
According to repeated researches, when nylon resin with lower oligomer content is selected as a base material, and aromatic dicarboxylic acid is added to modify the nylon material, the flame retardant V-2 grade can be achieved by only a small amount of addition, and the flame retardant V-2 grade can be still maintained after 168H is treated at 70 ℃, so that the flame retardant has excellent flame retardant stability; in addition, the addition of small amounts of aromatic dicarboxylic acids has little negative effect on the mechanical properties. The reasons for this may be: (1) The nylon resin contains a certain amount of oligomers (the content is generally 0.5-2.5% by mass), the oligomers are excessive, and the nylon resin is easy to generate fuzzing during spinning, so that the mechanical property of the nylon composite material is influenced, and the flame-retardant stability of V-2 is also influenced; (2) The melting point of the aromatic dicarboxylic acid is higher, the aromatic dicarboxylic acid is more stable in the processing temperature range of nylon, the amide bond is difficult to attack, and the adverse effect on the mechanical property is small; meanwhile, during the combustion (600-700 ℃) process, the aromatic dicarboxylic acid is decomposed and attacks an amide bond, and a dripping effect is generated, so that a large amount of heat is taken away, combustion is prevented, and the flame-retardant stability is better.
The invention selects nylon resin with lower oligomer content, and simultaneously adds a smaller amount of aromatic dicarboxylic acid to carry out flame-retardant modification, thus not only achieving stable flame-retardant V-2 grade, but also having no negative effect on the mechanical property of the flame-retardant nylon composite material.
Preferably, the weight part of the aromatic dicarboxylic acid in the flame-retardant nylon composite material is 0.1-1 part.
Nylon materials conventional in the art may be used in the present invention.
Preferably, the nylon resin is one or more of PA6, PA66 or PA 66/6.
Preferably, the content of the oligomer in the nylon resin is 1.0-1.6%.
Preferably, the number average molecular weight of the oligomer is not higher than 1000.
Preferably, the aromatic dicarboxylic acid is one or more of naphthalene diacid and phthalic acid.
More preferably, the naphthalene dicarboxylic acid is one or more of 1, 4-naphthalene dicarboxylic acid and 2, 6-naphthalene dicarboxylic acid.
More preferably, the phthalic acid is one or more of terephthalic acid, isophthalic acid or phthalic acid.
More preferably, the aromatic dicarboxylic acid is one or both of naphthalene diacid (1, 4-naphthalene diacid) or terephthalic acid.
Preferably, the flame retardant nylon composite also includes other processing aids.
More preferably, the other processing aid is one or more of an antioxidant, a lubricant, a nucleating agent or an antistatic agent.
Preferably, the antioxidant is one or more of hindered phenol antioxidants, copper salt antioxidants, aromatic amine antioxidants, phosphite antioxidants or thioester antioxidants.
Preferably, the antioxidant is 0.05-1 part by weight.
More preferably, the hindered phenol antioxidant is one or more of N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide (Irganox 1098), tetra [1093,5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (Irganox 1010), triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Iragnox 259), beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (Iragno 1076) or spiro ethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (ADK AO-80).
More preferably, the copper salt antioxidant is cuprous iodide.
More preferably, the aromatic amine antioxidant is one or two of 4, 4' -bis (alpha (-dimethylbenzyl) diphenylamine (Naugard 445)) or a mixture of polyamines (Flexamine Granular).
More preferably, the phosphite antioxidant is one or two of 2, 4-di-tert-butylphenol (Irganox 168) and bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol phosphite (ADK PEP-36).
More preferably, the thiol antioxidant is bis (octadecyl) thiodipropionate (IrganoxPS 802) pentaerythritol tetrakis (3-laurylthiopropionate) (THANOX 412S).
Preferably, the lubricant is one or more of amide type lubricant, ester type lubricant or fatty acid salt type lubricant.
Preferably, the weight portion of the lubricant is 0.2 to 1.5 portions.
More preferably, the amide lubricant is one or both of Ethylene Bis Stearamide (EBS) or ethylene bis (12 hydroxymethyl) stearamide (TAF).
More preferably, the ester lubricant is pentaerythritol tetrastearate (PETS).
More preferably, the fatty acid salt type lubricant is one or more of zinc stearate, calcium stearate or calcium montanate.
Further preferably, the nucleating agent is one or more of amide nucleating agent, silicate nucleating agent or phosphate nucleating agent.
Preferably, the nucleating agent is 0.1-0.5 parts by weight.
Still more preferably, the amide nucleating agent is one or more of polyethylene diamine oxalic acid, polydecamethylene diamine terephthalic acid, polydecamethylene diamine isophthalic acid, polynonamine terephthalic acid or polynonamine isophthalic acid.
Still more preferably, the silicate nucleating agent is one or more of talc, kaolin or hydrotalcite.
Still more preferably, the phosphate nucleating agent is one or more of sodium phenylphosphinate, sodium 2,2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate, or aluminum bis [2,2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate.
Preferably, the antistatic agent is one or more of polyethylene glycols.
Preferably, the antistatic agent is preferably 10 to 30 parts by weight.
Further preferably, the antistatic agent is preferably 15 to 25 parts by weight.
The preparation method of the flame-retardant nylon composite material comprises the following steps: and uniformly mixing the components to obtain a mixture, and then carrying out melt extrusion and granulation on the mixture to obtain the flame-retardant nylon composite material.
Preferably, the preparation method of the flame retardant nylon composite material comprises the following steps: uniformly mixing the components in a high-speed mixer to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, and granulating to obtain the flame-retardant nylon composite material; wherein, the length-diameter ratio of the screw of the double-screw extruder is 40-48:1, the temperature of the screw cylinder is 250-320 ℃, and the rotating speed of the screw is 200-550 rpm.
The application of the flame retardant nylon composite material in the preparation of electronic appliances (such as connectors and switch panels) is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the flame-retardant nylon composite material provided by the invention takes the specific nylon resin as a base material, and simultaneously, a small amount of aromatic dicarboxylic acid is added for flame-retardant modification, so that stable flame-retardant V-2 grade can be achieved, and the mechanical property of the flame-retardant nylon composite material is not negatively influenced.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
The reagents selected for the examples and comparative examples of the present invention are described below:
nylon material 1#,50bwfs, pa66, ascend company, the content of oligomers having a number average molecular weight below 1000 was 1%;
nylon material 2#,88x, pa66/6, ascend company, the content of oligomers with number average molecular weight below 1000 was 1.6%;
nylon material 3#, M2400, PA66, new meeting meida chemical industry limited company, the content of oligomer with the number average molecular weight lower than 1000 is 1.3%;
nylon material 4#, EP-158, pa66, peak group limited, oligomer content of number average molecular weight below 1000 of 2.6%;
aromatic dicarboxylic acid 1#:1, 4-naphthalenedicarboxylic acid, chemically pure, aladine;
aromatic dicarboxylic acid # 2: isophthalic acid, chemically pure, aladine;
aromatic dicarboxylic acid 3#: phthalic acid, chemically pure, aletin;
aromatic monocarboxylic acids: benzoic acid, chemically pure, aletin;
long carbon chain dibasic saturated carboxylic acid: sebacic acid, chemically pure, aledine;
melamine cyanurate: melamine cyanurate, commercially available;
other processing aids: antistatic agents, polyethylene glycols, 3600, commercially available.
It should be understood that, unless otherwise specified, some of the components (e.g., aromatic dicarboxylic acids 1 to 3#, melamine cyanurate, antioxidants, lubricants, nucleating agents, antistatic agents) included in the examples or comparative examples are all the same commercially available products.
The preparation method of the nylon composite material of each embodiment and the comparative example comprises the following steps: weighing the raw materials according to the proportion, and premixing in a high-speed mixer to obtain premix; then, the premix is put into a double screw extruder for melt mixing, and extrusion granulation is carried out, so as to obtain a nylon composite material; wherein, the length-diameter ratio of the double-screw extruder is 36:1; the screw barrel temperature one-nine zones were set as: 250-260-270-280-290-290-290-300-320℃; the screw rotating speed is 350 revolutions per minute, and the product is obtained.
The nylon composite of each example and comparative example of the present invention was tested as follows:
(1) Flame retardant performance test: the sample bar was clamped 6mm from the upper end and the length direction was down, the lower end of the sample was kept at a distance of 300.+ -.10 mm from the surface of the layer of pre-fabricated cotton, the thickness of the cotton was not more than 6mm, the dimensions were 50 mm. Times.50 mm, and the weight was about 0.08g. The burner adopts methane flow rate of 105ml/min, is pressed by 0.1kpa, and has flame height of 20+/-1 mm. The flame center is arranged at the middle point of the lower edge of the sample, the distance from the top of the burner to the lower end of the sample is 10+/-1 mm, the distance is maintained for 10+/-0.5 seconds, if the shape and the position of the burner change in the combustion process, the burner needs to be adjusted, if molten materials drop in the test process, the burner can be inclined to 45 degrees, the burner is removed at least 150mm at the speed of 300mm/min after the burner is combusted for 10+/-0.05 seconds, the after-flame time t1 is recorded, the after-flame is immediately combusted for 10+/-0.5 seconds again after the after-flame is stopped, and the after-flame time t2 is recorded after the removal. The following pretreatment was performed before the test: treating 48H at 23 ℃ under 50% RH; testing 5 templates for each group of samples;
(2) Flame retardant stability test: the prepared samples were treated at 70℃for 168H, then at 23℃for 48H at 50% humidity, and then subjected to UL94 flame retardant rating test.
(3) Elongation at break test: tensile testing was performed according to ISO527 standard injection molded bars, at a tensile speed of 50mm/min, and elongation at break was recorded.
Examples 1 to 10
This example provides a series of flame retardant nylon composites with the amounts of the components in the formulation shown in table 1.
Table 1 formulations (parts) of examples 1 to 10
Comparative examples 1 to 7
This comparative example provides a series of nylon composites with the amounts of the components in the formulation shown in table 2.
The nylon composite provided in each example and comparative example was tested as shown in table 3.
Table 3 results of performance testing of nylon composites provided in examples and comparative examples
As shown by the test results, the flame retardant nylon composite material provided by each embodiment can reach the flame retardant V-2 grade, and can still keep the flame retardant V-2 grade after being treated for 168H at 70 ℃, and has excellent flame retardant stability; in addition, the mechanical properties are not affected substantially negatively. Comparative example 1 was not flame retardant modified, flame retardant rating was no rating; comparative example 2, in which a small amount of melamine cyanurate was added as a flame retardant, the flame retardance was stepless, and the elongation at break was greatly reduced; in comparative example 3, a relatively large amount of melamine cyanurate was added as a flame retardant, and the flame retardant grade could reach V-0 grade, but the flame retardant stability was poor and the elongation at break was significantly reduced; in comparative example 4, the aromatic monocarboxylic acid is added for modification, and the flame retardant grade can reach V-2, but the flame retardant stability is poor, and the mechanical property is seriously reduced; in comparative example 5, a smaller amount of long carbon chain binary saturated carboxylic acid is added for modification, the flame retardant grade can reach V-2, but the flame retardant stability is poor, the mechanical property is poor, and the elongation at break is obviously reduced; comparative example 6 was modified by adding a larger amount of long carbon chain dicarboxylic saturated carboxylic acid, but the flame retardant stability was also poor, the mechanical properties were poor, and the elongation at break was significant; comparative example 7 uses nylon material with higher oligomer content, and has poor mechanical property, low elongation at break and poor flame-retardant stability.
Those of ordinary skill in the art will recognize that the embodiments herein are intended to assist the reader in understanding the principles of the invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (8)
1. The flame-retardant nylon composite material is characterized by comprising the following components in parts by weight:
97-99.95 parts of nylon resin;
0.05-2 parts of aromatic dicarboxylic acid;
the content of the oligomer in the nylon resin is not higher than 1.6%;
the aromatic dicarboxylic acid is naphthalene dicarboxylic acid;
the number average molecular weight of the oligomer is not higher than 1000.
2. The flame retardant nylon composite of claim 1, wherein the weight fraction of aromatic dicarboxylic acid in the flame retardant nylon composite is 0.1-1.
3. The flame retardant nylon composite of claim 1, wherein the nylon resin is one or more of PA6, PA66, or PA 66/6.
4. The flame retardant nylon composite of claim 1, wherein the nylon resin has an oligomer content of 1.0 to 1.6%.
5. The flame retardant nylon composite of claim 1, wherein the naphthalene dicarboxylic acid is one or both of 1, 4-naphthalene dicarboxylic acid or 2, 6-naphthalene dicarboxylic acid.
6. The flame retardant nylon composite of claim 1, further comprising other processing aids.
7. The method for preparing the flame retardant nylon composite material according to any one of claims 1 to 6, which is characterized by comprising the following steps: and uniformly mixing the components to obtain a mixture, and then carrying out melt extrusion and granulation on the mixture to obtain the flame-retardant nylon composite material.
8. Use of the flame retardant nylon composite of any one of claims 1 to 6 in the manufacture of an electronic appliance.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111554855.5A CN114276677B (en) | 2021-12-17 | 2021-12-17 | Flame-retardant nylon composite material and preparation method and application thereof |
| PCT/CN2022/134674 WO2023109490A1 (en) | 2021-12-17 | 2022-11-28 | Flame-retardant nylon composite material and preparation method therefor and application thereof |
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| CN202111554855.5A CN114276677B (en) | 2021-12-17 | 2021-12-17 | Flame-retardant nylon composite material and preparation method and application thereof |
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| CN114276677A CN114276677A (en) | 2022-04-05 |
| CN114276677B true CN114276677B (en) | 2023-09-26 |
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| CN114276677B (en) * | 2021-12-17 | 2023-09-26 | 金发科技股份有限公司 | Flame-retardant nylon composite material and preparation method and application thereof |
| CN116496619B (en) * | 2023-05-10 | 2024-05-14 | 金发科技股份有限公司 | Red nylon composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54132654A (en) * | 1978-04-06 | 1979-10-15 | Asahi Chem Ind Co Ltd | Flame-retardant polyamide composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5652326A (en) * | 1993-03-03 | 1997-07-29 | Sanyo Chemical Industries, Ltd. | Polyetheresteramide and antistatic resin composition |
| JP2000186205A (en) * | 1998-12-22 | 2000-07-04 | Kuraray Co Ltd | Polyamide resin composition |
| FR2789996B1 (en) * | 1999-02-24 | 2001-04-13 | Rhodia Eng Plastics Srl | FLAME RETARDANT POLYAMIDE COMPOSITION |
| TW521082B (en) * | 2000-09-12 | 2003-02-21 | Kuraray Co | Polyamide resin composition |
| CN103013104B (en) * | 2012-12-26 | 2015-06-24 | 上海金发科技发展有限公司 | Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof |
| CN103254423A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
| CN114276677B (en) * | 2021-12-17 | 2023-09-26 | 金发科技股份有限公司 | Flame-retardant nylon composite material and preparation method and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54132654A (en) * | 1978-04-06 | 1979-10-15 | Asahi Chem Ind Co Ltd | Flame-retardant polyamide composition |
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