CN113493607A - Nylon flame-retardant composite material and preparation method thereof - Google Patents
Nylon flame-retardant composite material and preparation method thereof Download PDFInfo
- Publication number
- CN113493607A CN113493607A CN202110843750.5A CN202110843750A CN113493607A CN 113493607 A CN113493607 A CN 113493607A CN 202110843750 A CN202110843750 A CN 202110843750A CN 113493607 A CN113493607 A CN 113493607A
- Authority
- CN
- China
- Prior art keywords
- nylon
- flame
- retardant
- composite material
- polyphosphonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nylon flame-retardant composite material and a preparation method thereof, belonging to the technical field of polymer composite materials. The material is prepared from the following raw materials in percentage by mass: 59-94.5% of nylon 10T resin; 5-40% of a polyphosphonate flame retardant; 0.5-1% of antioxidant; wherein, the polyphosphonate flame retardant has the following structural formula:
and n in the structural formula is a positive integer of 21-50. The high-temperature nylon flame-retardant composite material designed by the invention has high mechanical strength, good dimensional stability and good flame-retardant effect.
Description
Technical Field
The invention relates to a flame-retardant polyester composite material, belongs to the technical field of polymer composite materials, and particularly relates to a nylon flame-retardant composite material and a preparation method thereof.
Background
The semi-aromatic high temperature nylon (PA) has the advantages of high melting point, low water absorption, good dimensional stability and the like, and is widely applied to electronic and electric appliances and related fields. The main varieties of the high-temperature nylon comprise PA4T, PA6T, PA9T, PA10T and the like. When the electronic and electric products work, high temperature and high pressure, short circuit and the like occur, and plastic components are easy to cause fire. Therefore, materials which can be widely applied to electronic and electric appliances need to be subjected to corresponding flame retardant treatment, and the existing flame retardant which can meet the processing temperature of high-temperature nylon has poor dispersibility and seriously influences the mechanical properties of nylon. Therefore, the development of flame retardant products meeting the processing performance and application requirements of high temperature nylon is urgent.
At present, the commercial flame retardant system capable of withstanding the high temperature nylon processing temperature is mainly alkyl phosphinates such as aluminum diethylphosphinate, sodium phosphinate and the like, but aluminum diethylphosphinate causes high processing viscosity and poor dispersibility during high temperature nylon processing, thereby causing deterioration of mechanical properties of products. The phosphorus-containing organic flame retardant or the polymer flame retardant has good compatibility with a polymer matrix and has small influence on the mechanical property of the composite material. However, some small-molecular organic phosphorus flame retardants have a low decomposition temperature, cannot meet the processing requirements of high-temperature nylon, and are volatile.
In summary, there is a need for a flame retardant that can withstand the processing temperature of high-temperature nylon and does not affect the mechanical properties of the composite material after being processed and compounded with the high-temperature nylon, so that the obtained high-temperature nylon flame-retardant composite material can meet the use requirements of the composite material, and the processing technology is more convenient and simpler.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a nylon flame-retardant composite material and a preparation method thereof.
In order to realize the technical purpose, the invention discloses a nylon flame-retardant composite material which is prepared from the following raw material components in percentage by mass:
59-94.5% of nylon 10T resin;
5-40% of a polyphosphonate flame retardant;
0.5-1% of antioxidant;
wherein the polyphosphonate flame retardant has the following structural formula:
and n in the structural formula is a positive integer of 21-50.
Further, the tensile strength of the nylon flame-retardant composite material is 80-88 MPa, and the limiting oxygen index is 25-45%.
Further, the polyphosphonate flame retardant is prepared by catalyzing methyl diphenyl phosphate and phenolphthalein with sodium metaaluminate; the molar ratio of the methyl diphenyl phosphate to the phenolphthalein is (1-1.1): 1.
Further, the antioxidant comprises one or two or more of antioxidant 1010, antioxidant 1076, antioxidant 1098 and antioxidant 168.
Wherein the antioxidant 1010 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester; the antioxidant 1076 is (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid N-octadecyl ester), the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and the antioxidant 168 is tris [2, 4-di-tert-butylphenyl ] phosphite.
Further, the nylon 10T resin is poly (decamethylene terephthalamide).
Specifically, the preparation process of the polyphosphonate flame retardant is as follows:
putting methyl diphenyl phosphate and phenolphthalein into a reaction device according to the molar ratio of 1.05:1, adding a catalyst sodium metaaluminate under the protection of inert gas, slowly heating to 120-150 ℃ for reaction for 1-3 h, continuously heating to 170-190 ℃ for reaction for 2-5 h, then reacting for 3-5 h under a reduced pressure state, cooling to room temperature, and performing purification treatment to obtain the polyphosphonate flame retardant. Wherein the addition amount of the catalyst sodium metaaluminate is 1-5% of the weight of phenolphthalein.
In addition, the invention also discloses a preparation method of the nylon flame-retardant composite material, which comprises the following steps:
1) uniformly mixing nylon 10T resin, a polyphosphonate flame retardant and an antioxidant to obtain a mixed base material;
2) putting the mixed base material obtained in the step 1) into a co-rotating double-screw extruder to be processed to obtain granules;
3) and (3) carrying out molding processing on the granules obtained in the step 2) by using an injection molding machine to obtain the high-temperature nylon flame-retardant composite material.
Further, in the step 2), the processing temperature is 300-350 ℃, and the rotating speed is set to be 160-220 r/min.
Further, in the step 3), the molding temperature of the injection molding machine is 300-350 ℃.
Has the advantages that:
1. the polyphosphonate flame retardant adopted by the design of the invention belongs to an aromatic flame retardant, which not only meets the requirement of high processing temperature of high-temperature nylon, but also has good compatibility with PA10T, and hardly influences the original physical and mechanical properties of the high-temperature nylon.
2. The composite material designed by the invention has high mechanical strength, good flame retardant property and good dimensional stability.
Drawings
FIG. 1 is an infrared spectrum of a polyphosphonate flame retardant prepared according to an embodiment of the present invention;
FIG. 2 is a thermal decomposition spectrum of a polyphosphonate flame retardant prepared according to an example of the present invention;
FIG. 3 is a carbon layer electron micrograph of comparative example 1 and example 2 of the present invention after burning.
Detailed Description
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific examples, but the content of the invention is not limited to the following examples.
Example 1
This example discloses the preparation of a polyphosphonate flame retardant:
26.04g of methyl diphenyl phosphate and 31.8g of phenolphthalein are added into a four-neck flask provided with an electromechanical stirrer and a reduced pressure distillation device, 0.32g of catalyst sodium metaaluminate (the mass of the catalyst is 1 percent of that of the phenolphthalein) is added, nitrogen is introduced under the stirring state, the mixture reacts for 1 hour at 140 ℃, and reacts for 3 hours at 180 ℃, generated micromolecular phenol is separated in the reaction process, and then the reaction is continued for 4 hours under the reduced pressure state.
After the reaction is finished, crushing the solid crude product obtained after the reaction, fully stirring for 3 hours in hot water at 60 ℃, filtering while hot, collecting a filter cake, drying the filter cake in an oven at 50 ℃ for 12 hours in vacuum, and drying to obtain the solid product polyphosphonate.
The specific synthetic route is as follows:
wherein the polyphosphonate has the structural characterization shown in FIG. 1.
Specifically, the infrared analysis spectrogram of the polyphosphonate is shown in figure 1, and can be known by combining figure 1 to be 1257cm-1And 1199cm-1Is a characteristic absorption peak of P ═ O, 918cm-1Is the characteristic absorption peak of P-O-C (C on the benzene ring).
As can be seen from the graph in FIG. 2, the temperature of the polyphosphonate obtained by the design of the invention is as high as 370 ℃ when the thermal weight loss is 5%, and the carbon residue rate can reach 56%. Such a high carbon residue rate can make it have a good flame retardant effect in the presence of a condensed phase in the material.
Example 2
The embodiment discloses a preparation method of a high-temperature nylon flame-retardant composite material, which comprises the following steps:
(1) 10g of the polyphosphonate flame retardant prepared in the embodiment 1, 0.5g of the antioxidant and 89.5g of the nylon 10T resin are fully mixed to obtain a mixed base material, and then the mixed base material is placed in a co-rotating double-screw extruder to be processed and granulated to obtain granules, wherein the temperature range of the double-screw extruder is 300-350 ℃, and the rotating speed of the double-screw extruder is 160-220 r/min.
(2) And (2) taking the granules obtained in the step (1) to perform molding processing in an injection molding machine to obtain the composite material, wherein the temperature of the injection molding machine is 300-350 ℃.
Example 3
This example is different from example 2 in that the amount of the polyphosphonate flame retardant was 15g and the amount of the nylon 10T resin was 84.5g, and the other contents were the same.
Example 4
This example differs from example 2 above in that the amount of polyphosphonate flame retardant added was 20g and the amount of nylon 10T resin was 79.5g, all other things remaining the same.
Example 5
This example differs from example 2 above in that the amount of polyphosphonate flame retardant added was 25g and the amount of nylon 10T resin was 74.5g, all other things remaining the same.
Example 6
This example differs from example 2 above in that the amount of polyphosphonate flame retardant added was 30g and the nylon 10T resin 69.5g, all other things remaining the same.
Example 7
This example differs from example 2 above in that 35g of polyphosphonate flame retardant was added and 64.5g of nylon 10T resin was added, all the other things remaining the same.
Example 8
This example differs from example 2 above in that the amount of polyphosphonate flame retardant added was 40g and the amount of nylon 10T resin was 59.5g, all other things remaining the same.
Comparative example 1
This example differs from example 2 above in that no polyphosphonate flame retardant was added, all else remaining the same.
Comparative example 2
This example differs from example 2 above in that the same proportion of a built-up alkylated hypophosphite system, such as diethyl aluminum hypophosphite, is added.
Comparative example 3
This example differs from example 2 above in that the same proportion of melamine polyphosphate system, such as melamine polyphosphate (MPP), is added.
Comparative example 4
This comparative example differs from example 2 above in that the polyphosphonate flame retardant employed has the following structural formula:
wherein n in the structural formula is a positive integer of 21-50.
Application and testing of the materials: the tensile properties of the products obtained in the above examples and comparative examples were measured by using a universal tester (the tensile rate was 5mm/min, according to GB/T2568-1995), and LOI values thereof were measured by using a JF-3 type oxygen index meter manufactured by Nanjing Jiangning Analyzer factory (the test standard was the national standard GB/T2406 of China) to obtain Table 1.
TABLE 1 product Property List
From the table 1, it can be seen that the flame retardant effect of the high-temperature nylon is obviously improved by adding the polyphosphonate flame retardant, and after the polyphosphonate flame retardant is added, the mechanical properties of the high-temperature nylon composite material are not changed greatly, even are slightly enhanced, which shows that the polyphosphonate flame retardant has good compatibility with the high-temperature nylon and has good stability.
When the carbon layers after the splines of comparative example 1 and example 2 were subjected to SEM spectrum test analysis and compared, as shown in fig. 3, it was found that the nylon 10T exhibited a sparse state on the surface of the carbon layer after combustion and the nylon 10T composite material with the flame retardant added was dense on the surface of the carbon layer after combustion, when the flame retardant was not added.
Therefore, the polyphosphonate flame retardant disclosed by the invention is good in flame retardant effect, strong in synthesis property and strong in practicability.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (6)
1. The flame-retardant nylon composite material is characterized by comprising the following raw material components in percentage by mass:
59-94.5% of nylon 10T resin;
5-40% of a polyphosphonate flame retardant;
0.5-1% of antioxidant;
wherein the polyphosphonate flame retardant has the following structural formula:
and n in the structural formula is a positive integer of 21-50.
2. The flame-retardant nylon composite material of claim 1, wherein the flame-retardant nylon composite material has a tensile strength of 80-88 MPa and a limiting oxygen index of 25-45%.
3. The nylon flame-retardant composite material as claimed in claim 1 or 2, wherein the polyphosphonate flame retardant is methyl diphenyl phosphate and phenolphthalein which are obtained under the catalysis of sodium metaaluminate; the molar ratio of the methyl diphenyl phosphate to the phenolphthalein is (1-1.1): 1.
4. The preparation method of the nylon flame-retardant composite material is characterized by comprising the following steps:
1) uniformly mixing nylon 10T resin, a polyphosphonate flame retardant and an antioxidant to obtain a mixed base material;
2) putting the mixed base material obtained in the step 1) into a co-rotating double-screw extruder to be processed to obtain granules;
3) and (3) carrying out molding processing on the granules obtained in the step 2) by using an injection molding machine to obtain the high-temperature nylon flame-retardant composite material.
5. The preparation method of the nylon flame-retardant composite material according to claim 4, wherein in the step 2), the processing temperature is 300-350 ℃, and the rotating speed is set to be 160-220 r/min.
6. The preparation method of the nylon flame-retardant composite material according to claim 4, wherein in the step 3), the molding temperature of an injection molding machine is 300-350 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110843750.5A CN113493607B (en) | 2021-07-26 | 2021-07-26 | Nylon flame-retardant composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110843750.5A CN113493607B (en) | 2021-07-26 | 2021-07-26 | Nylon flame-retardant composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113493607A true CN113493607A (en) | 2021-10-12 |
| CN113493607B CN113493607B (en) | 2022-04-08 |
Family
ID=77996451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110843750.5A Active CN113493607B (en) | 2021-07-26 | 2021-07-26 | Nylon flame-retardant composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113493607B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3613491A1 (en) * | 1986-04-22 | 1987-10-29 | Bayer Ag | Mixtures of polyamides and polyphosphonates |
| JPS62252454A (en) * | 1986-04-22 | 1987-11-04 | バイエル・アクチエンゲゼルシヤフト | Fire retardant polyamide material |
| US4788259A (en) * | 1986-04-22 | 1988-11-29 | Bayer Aktiengesellschaft | Flame-proof polyamides |
| CN102786694A (en) * | 2012-09-07 | 2012-11-21 | 贵州师范大学 | Biphenol polyphosphate fire retardant and preparation method and application thereof |
| CN102796253A (en) * | 2012-09-07 | 2012-11-28 | 贵州师范大学 | ODOPB (10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)-base polyphosphate flame retardant, and preparation method and application thereof |
| US20140329942A1 (en) * | 2011-10-21 | 2014-11-06 | Toyobo Co., Ltd. | Flame-retardant resin composition and melt-molded body |
| US20160185961A1 (en) * | 2013-08-08 | 2016-06-30 | Polyone Corporation | Flame retardant poly(hexano-6-lactam) |
| WO2020184113A1 (en) * | 2019-03-12 | 2020-09-17 | 帝人株式会社 | Organic-inorganic composite material |
-
2021
- 2021-07-26 CN CN202110843750.5A patent/CN113493607B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3613491A1 (en) * | 1986-04-22 | 1987-10-29 | Bayer Ag | Mixtures of polyamides and polyphosphonates |
| JPS62252454A (en) * | 1986-04-22 | 1987-11-04 | バイエル・アクチエンゲゼルシヤフト | Fire retardant polyamide material |
| US4788259A (en) * | 1986-04-22 | 1988-11-29 | Bayer Aktiengesellschaft | Flame-proof polyamides |
| US20140329942A1 (en) * | 2011-10-21 | 2014-11-06 | Toyobo Co., Ltd. | Flame-retardant resin composition and melt-molded body |
| CN102786694A (en) * | 2012-09-07 | 2012-11-21 | 贵州师范大学 | Biphenol polyphosphate fire retardant and preparation method and application thereof |
| CN102796253A (en) * | 2012-09-07 | 2012-11-28 | 贵州师范大学 | ODOPB (10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)-base polyphosphate flame retardant, and preparation method and application thereof |
| US20160185961A1 (en) * | 2013-08-08 | 2016-06-30 | Polyone Corporation | Flame retardant poly(hexano-6-lactam) |
| WO2020184113A1 (en) * | 2019-03-12 | 2020-09-17 | 帝人株式会社 | Organic-inorganic composite material |
Non-Patent Citations (1)
| Title |
|---|
| S.R.RAFIKOV ET AL.: "PHOTOCHEMICAL DEGRADATION OF POLYARYLATES CONTAINING PHOSPHORUS", 《VYSOKOMOL. SOYED》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113493607B (en) | 2022-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103709717B (en) | Ethylene benzyl is etherified DOPO compound resins composition and preparation and application | |
| Fang et al. | An effective flame retardant for poly (ethylene terephthalate) synthesized by phosphaphenanthrene and cyclotriphosphazene | |
| CN109971166B (en) | Polyhydroxy-substituted aromatic Schiff base synergistic halogen-free flame-retardant nylon 6 composition and preparation method thereof | |
| CN105745278B (en) | Fire retardant resin composition and solar electrical energy generation module connection structural bodies | |
| Peng et al. | A bio-based phosphaphenanthrene-containing derivative modified epoxy thermosets with good flame retardancy, high mechanical properties and transparency | |
| CN114426701B (en) | Preparation of P-N compound synergistic graphene oxide flame retardant and application of P-N compound synergistic graphene oxide flame retardant in epoxy resin | |
| CN104119673A (en) | Halogen-free flame-retardant high-temperature nylon | |
| Xu et al. | Effects of different metal ions in phosphonitrile-modified organometallic complexes on flame retardancy of epoxy resin | |
| CN115304913B (en) | Reinforced flame-retardant hypophosphite/nylon composite material with high glow wire ignition temperature and preparation method thereof | |
| Luo et al. | Synergistic flame-retardant behavior and mechanism of tris (3-nitrophenyl) phosphine and DOPO in epoxy resins | |
| CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
| CN113861241A (en) | Bridged DOPO phosphorus-nitrogen flame retardant and preparation method and application thereof | |
| CN116478357A (en) | DOPO-based reactive flame retardant containing terminal isocyanate groups, and preparation method and application thereof | |
| CN112679545A (en) | Melamine-based nitrogen-phosphorus-containing compound, preparation method and application thereof, and flame-retardant epoxy resin composition thereof | |
| CN113493607B (en) | Nylon flame-retardant composite material and preparation method thereof | |
| CN108129825B (en) | high-CTI high-heat-resistance halogen-free flame-retardant PC/ABS composition and preparation method thereof | |
| CN113372695A (en) | Environment-friendly flame-retardant polyester composite material and preparation method thereof | |
| JP5754663B2 (en) | Cyclic phosphazene compound having oligolactic acid segment and method for producing the same | |
| CN113372717A (en) | High-temperature nylon flame-retardant material and preparation method thereof | |
| CN114213761B (en) | High-gloss low-precipitation flame-retardant polypropylene composition and preparation method and application thereof | |
| CN113416413B (en) | Glass fiber reinforced nylon 10T flame-retardant composite material and preparation method and application thereof | |
| CN114479385A (en) | Conductive flame-retardant biodegradable PBAT composite material and preparation method and application thereof | |
| CN108623985B (en) | Rare earth synergistic flame-retardant ABS material | |
| CN103660306A (en) | Method for molding halogen-free flame-retardant thermoplastic polyester composition | |
| CN113502035A (en) | Halogen-free flame-retardant polyester composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |