CN113372717A - High-temperature nylon flame-retardant material and preparation method thereof - Google Patents
High-temperature nylon flame-retardant material and preparation method thereof Download PDFInfo
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- CN113372717A CN113372717A CN202110843733.1A CN202110843733A CN113372717A CN 113372717 A CN113372717 A CN 113372717A CN 202110843733 A CN202110843733 A CN 202110843733A CN 113372717 A CN113372717 A CN 113372717A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a high-temperature nylon flame-retardant material and a preparation method thereof, belonging to the technical field of polymer composite materials. The material comprises 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:
wherein n in the structural formula is a positive integer of 21-50. The composite material prepared by the invention has good flame retardant effect, good mechanical property and strong practicability.
Description
Technical Field
The invention relates to a flame-retardant material, belongs to the technical field of polymer composite materials, and particularly relates to a high-temperature nylon flame-retardant 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 provides a high-temperature nylon flame-retardant material and a preparation method thereof. The high-temperature-resistant polyphosphonate flame retardant is adopted, the molecular structure of the polyphosphonate flame retardant is similar to that of high-temperature nylon, the compatibility of the polyphosphonate flame retardant and the high-temperature nylon is good, and the prepared flame-retardant material has a good flame-retardant effect and good physical and mechanical properties.
In order to achieve the aim, the invention discloses a high-temperature nylon flame-retardant material which comprises 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:
wherein n in the structural formula is a positive integer of 21-50. (ii) a
Further, the polyphosphonate flame retardant is prepared by carrying out one-step melt polycondensation reaction on methyl diphenyl phosphate and bisphenol A.
Further, the nylon 10T resin is poly (decamethylene terephthalamide). It is produced by Jinfa technology, and the product brand is Vicnyl.
Further, the limited oxygen index of the flame-retardant material is 25-45%, and the tensile strength is 79-100 MPa.
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.
The invention also aims to provide a preparation method of the high-temperature nylon flame-retardant material, which comprises the following steps:
1) uniformly mixing nylon 10T resin, polyphosphonate flame retardant and antioxidant according to a formula 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 flame-retardant material.
Further, in the step 2), the processing temperature is 300-350 ℃, and the rotating speed is 160-220 r/min.
Further, in the step 3), the molding processing temperature is 300-350 ℃.
The flame-retardant material prepared by the method can be a particulate matter, and can also be made into sheets or plates and the like by other forming modes.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the prepared flame-retardant material adopts the polyphosphonate flame retardant with good compatibility with high-temperature nylon, so that the composite flame-retardant material has high stability and good flame retardance on the premise of having better mechanical properties, and meets the development requirements of the current society on the flame retardant.
2. The preparation method is relatively simple and has strong practical applicability.
Drawings
FIG. 1 is an infrared spectrum of a polyphosphonate flame retardant used in an example of the present invention.
FIG. 2 is a GPC chart of a polyphosphonate flame retardant used in an example of the present invention.
FIG. 3 is a thermally exploded view of a polyphosphonate flame retardant used in an embodiment of the present invention.
Fig. 4 is a carbon layer electron micrograph of comparative example 1 and example 2 after combustion.
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 22.8g of bisphenol A are added into a four-neck flask provided with an electromechanical stirrer and a reduced pressure distillation device, 0.23g of catalyst sodium metaaluminate (the mass of the catalyst is 1 percent of that of the bisphenol A) is added, nitrogen is introduced under the stirring state, the mixture reacts for 1 hour at 140 ℃, reacts for 3 hours at 180 ℃, generated small molecular phenol is separated during the reaction, 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, fig. 2 and fig. 3.
Specifically, the infrared analysis spectrum of the polyphosphonate is shown in FIG. 1, and 1222cm is obtained by combining FIG. 1-1And 1195cm-1Is CH3-C-CH3Peak of vibration absorption of skeleton, 1259cm-1And 1197cm-1Is a characteristic absorption peak of P ═ O, 918cm-1Is the characteristic absorption peak of P-O-C (C on the benzene ring).
The GPC chart of this polyphosphonate is shown in FIG. 2, and it can be seen from FIG. 2 that the peak average molecular weight is 11494 and the weight average molecular weight is 12737.
The thermal decomposition diagram of the polyphosphonate is shown in fig. 3, and the temperature of the product polyphosphonate flame retardant at 5% weight loss is up to 447 ℃ as can be seen by combining fig. 3.
Example 2
The embodiment discloses a preparation method of a high-temperature nylon 10T flame-retardant composite material, which comprises the following steps:
(1) 10g of the polyphosphonate flame retardant prepared in the example 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 differs from example 2 above in that the amount of polyphosphonate flame retardant added was 15g and the amount of nylon 10T resin was 84.5g, all other things remaining 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.
Application and testing of the materials: the tensile properties of the products prepared 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 known that the flame retardant effect of the high-temperature nylon material can be improved by adding the polyphosphonate flame retardant, and the mechanical properties of the high-temperature nylon material are not greatly affected by the addition of the polyphosphonate flame retardant, which indicates that the polyphosphonate flame retardant has good compatibility with the high-temperature nylon and good stability.
According to the invention, after the test of burning of the sample strips prepared in the comparative example 1 and the example 2, the carbon layer is analyzed by SEM spectrogram, as shown in FIG. 4, it can be found that when no flame retardant is added, the surface of the carbon layer of the nylon 10T after burning is in a sparse state, and the surface of the carbon layer of the nylon 10T composite material added with the flame retardant after burning is dense, which indicates that the flame retardant is well compounded inside and outside the nylon 10T structure.
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 (9)
1. The high-temperature nylon flame-retardant 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:
wherein n in the structural formula is a positive integer of 21-50.
2. A high temperature nylon flame retardant material as in claim 1, wherein the polyphosphonate flame retardant is prepared by one-step melt polycondensation of methyl diphenyl phosphate and bisphenol a.
3. A high temperature nylon flame retardant material as recited in claim 1, wherein said nylon 10T resin is poly-paraphenylene terephthalamide.
4. A high-temperature nylon flame-retardant material as in claim 1, 2 or 3, wherein the limit oxygen index of the flame-retardant composite material is 25-45%, and the tensile strength is 79-100 MPa.
5. The high-temperature nylon flame retardant material as claimed in claim 1, 2 or 3, wherein the antioxidant comprises one or two or more of antioxidant 1010, antioxidant 1076, antioxidant 1098 and antioxidant 168.
6. A high temperature nylon flame retardant material as in claim 1 or 2 or 3, wherein the flame retardant material further comprises a lubricant, and the lubricant is pentaerythritol stearyl fatty acid ester.
7. A method for preparing the high-temperature nylon flame-retardant material as claimed in claim 1, which is characterized by comprising the following steps:
1) uniformly mixing nylon 10T resin, polyphosphonate flame retardant and antioxidant according to a formula 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 flame-retardant material.
8. A high-temperature nylon flame retardant material as claimed in claim 7, wherein in the step 2), the processing temperature is 300-350 ℃ and the rotation speed is 160-220 r/min.
9. A high-temperature nylon flame retardant material as claimed in claim 7, wherein in the step 3), the forming temperature is 300-350 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788259A (en) * | 1986-04-22 | 1988-11-29 | Bayer Aktiengesellschaft | Flame-proof polyamides |
| CN104210113A (en) * | 2014-07-09 | 2014-12-17 | 贵州凯科特材料有限公司 | High-performance long glass fiber reinforced nylon 10T composite material and preparation method thereof |
| CN110982063A (en) * | 2019-12-05 | 2020-04-10 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
-
2021
- 2021-07-26 CN CN202110843733.1A patent/CN113372717A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788259A (en) * | 1986-04-22 | 1988-11-29 | Bayer Aktiengesellschaft | Flame-proof polyamides |
| CN104210113A (en) * | 2014-07-09 | 2014-12-17 | 贵州凯科特材料有限公司 | High-performance long glass fiber reinforced nylon 10T composite material and preparation method thereof |
| CN110982063A (en) * | 2019-12-05 | 2020-04-10 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 曲振等: "耐高温尼龙PA10T的合成与表征", 《化工新型材料》 * |
| 王小萌等: "聚甲基膦酸酯的合成及应用研究进展", 《绝缘材料》 * |
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