CN114196199B - Flame-retardant nylon composition and preparation method and application thereof - Google Patents
Flame-retardant nylon composition and preparation method and application thereof Download PDFInfo
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- 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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- 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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- G—PHYSICS
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The invention discloses a flame-retardant nylon composite material, which comprises the following components in parts by weight: 50 parts of aliphatic polyamide resin; 15-30 parts of brominated polystyrene; 15-30 parts of hydrotalcite; 6-15 parts of polytetrafluoroethylene, wherein the content of free bromine is less than or equal to 26ppm based on the total weight of the flame-retardant nylon composite material. According to the invention, brominated polystyrene with low free bromine content is selected to replace other types of brominated flame retardants, and is matched with IPT improver hydrotalcite and polytetrafluoroethylene, so that the flame retardant grade of the composite material is achieved, meanwhile, the arc resistance of the composite material is further improved, the IPT reaches the level of more than or equal to 900V, and the application of the composite material in the fields of photovoltaics, energy storage and the like is further expanded.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant nylon composition, a preparation method and application thereof.
Background
The polyamide resin has excellent comprehensive properties such as mechanical property, barrier property, heat resistance, wear resistance, chemical corrosion resistance and the like, and the composite material is widely applied to the fields of machinery manufacturing industry, household appliances, electric tools, electronic appliances, transportation and the like. In a plurality of application scenes, the requirements on the flame retardant performance of the composite material are higher and higher, and the environment-friendly brominated flame retardant system has the characteristics of no frosting, easy coloring, excellent mechanical property and the like due to high flame retardant efficiency, and is still the product with the largest market specification and the widest application in flame retardant nylon products at present.
However, for products with higher requirements on electrical properties, such as polymers specified in the new energy storage system connector (UL 4128 standard) that are in direct or intimate contact with the charged components (less than 0.8 mm), higher IPT values are required when the creepage distance is less than 16mm when the voltage is greater than 600V.
There is not much report on how to obtain high IPT performance of flame retardant nylon.
Disclosure of Invention
The invention aims to provide a flame-retardant nylon composition which has the advantages of good flame retardant property and good arc resistance. It is a further object of the invention to provide a method of preparation and use.
The invention is realized by the following technical scheme:
the flame-retardant nylon composition comprises the following components in parts by weight:
50 parts of aliphatic polyamide resin;
15-30 parts of brominated polystyrene;
15-30 parts of hydrotalcite;
6-15 parts of IPT improver;
the content of free bromine is less than or equal to 26ppm based on the total weight of the flame-retardant nylon composite material.
Preferably, the composition comprises the following components in parts by weight:
50 parts of aliphatic polyamide resin;
15-30 parts of brominated polystyrene;
18-25 parts of hydrotalcite;
8-12 parts of IPT improver;
the content of free bromine is less than or equal to 20ppm based on the total weight of the flame-retardant nylon composite material.
More preferably, the free bromine content is less than or equal to 11ppm based on the total weight of the flame retardant nylon composition.
The method for testing the content of free bromine in the flame-retardant nylon composition comprises the following steps: a) Crushing the sample in a high-speed crusher, sieving with a 40-mesh screen, accurately weighing 10.00+/-0.05 g of the sieved sample, putting the sample into a 250ml beaker with a rotor, adding 20ml of methanol solution into the beaker, slightly shaking to ensure that the sample is completely soaked in the solution for 10 minutes, and adding 200ml of distilled water; placing the beaker added with the sample into ultrasonic waves, preserving heat and ultrasonic waves for 1 hour at 60 ℃, taking out, cooling to room temperature, and completing sample preparation; b) Potentiometric titration is carried out by adopting a potentiometric titrator, about 0.1g of dextrin is added into a sample, and 2ml of nitric acid (25 ml of analytically pure nitric acid is slowly stirred and added into 25ml of distilled water) with the volume ratio of 50% is added dropwise; when the fluctuation of the instrument potential is less than 0.2mv in 30s, the instrument starts titration, a titration curve is displayed on an operation interface, the instrument buzzes at the titration end point, and the titration end point V is displayed 1 Performing experiments in parallel for three times, and performing blank experiments simultaneously; 3) Bromine ion calculation, W 1 =（V 1 －V 0 ) C. 79.904/1000m, wherein:
W 1 -bromide content in ppm;
V 0 blank consumes the volume, mL, of silver nitrate standard solution;
V 1 first endpoint consumption silver nitrate standardVolume of solution, mL;
c, the mass concentration of the substances of the silver nitrate standard solution is 0.01mol/L;
m-weighing the mass of the sample, g;
79.904-molar mass of bromine, g/mol;
and calculating the average value of data obtained in three experiments to obtain the bromide ion content.
The aliphatic polyamide is at least one selected from PA6, PA66, PA610, PA1010 and the like; the weight average molecular weight of the aliphatic polyamide is 10000-24000.
The hydrotalcite is prepared mainly by magnesium ions (Mg 2+ ) Aluminum ion (Al) 3+ ) Is a metal cation, hydroxide (OH) - ) With carbonic acid radical (CO) 3 2- ) As the layered double hydroxide of anions, experiments show that the hydrotalcite has good effect of adsorbing ions, wherein the D50 particle size of the hydrotalcite is 0.08-1.0 mu m.
Preferably, the D50 particle size is 0.1 μm to 0.4. Mu.m.
The IPT improver is polytetrafluoroethylene.
The preparation method of the flame-retardant nylon composition comprises the following steps: according to the proportion, the components are uniformly mixed, and then extruded and granulated by a double-screw extruder, wherein the temperature range of the screw is 240-280 ℃, and the rotating speed range is 300-500 rpm, so as to obtain the flame-retardant nylon composition.
The flame-retardant nylon composition is applied to high-voltage connectors of electronic appliances, household appliances and new energy sources, and is particularly suitable for connector parts in the photovoltaic and energy storage fields with higher requirements on IPT.
The invention has the following beneficial effects
In the technical scheme of the invention, the sources of the free bromine are mainly free bromine carried in the brominated polystyrene raw material and the free bromine broken off in the brominated polystyrene chain segment in the high-temperature processing process. According to the invention, the free bromine in the system is adsorbed by using the hydrotalcite (the hydrotalcite has ion exchange property at a certain temperature and can absorb free ions in the composition), so that the content of the free bromine in the brominated polystyrene is further controlled, and the content of the free bromine in the flame-retardant nylon composition can be controlled to be lower than 26ppm. Further, by adding a specific amount of polytetrafluoroethylene as an IPT improver, tetrafluoroethylene gas is decomposed when the temperature exceeds 400 ℃ to play a role in striking arcs, and the method has an obvious effect on improving the IPT. The brominated flame-retardant nylon system is more than or equal to 900V, and the preferable range passes the 1000V IPT test, and can reach the UL 94V-0 flame retardant grade, so that the brominated flame-retardant nylon system can be applied to the field with higher arc resistance performance requirements.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials used in the examples and comparative examples are as follows:
PA66: PA66 EP-158 with a weight average molecular weight of 15450, a Zhejiang Huafeng group;
PA6: PA6 HY-2500A with a weight average molecular weight of 13800, manufactured by Jiangsu sea yang chemical fiber Co., ltd;
PA610: PA 610F 120, weight average molecular weight 21500, new materials, inc. Boundary, shandong.
Flame retardant a: brominated polystyrene, BPS 7010, 75ppm free bromide, available from Shandong Tian-Chemie Co., ltd;
flame retardant B: brominated polystyrene, SR-7010, free bromide 85ppm, shandong Xudi New Material Co., ltd;
flame retardant C: brominated polystyrene, SAYTEX HP-5010PST, free bromide content 158ppm, yabao group.
Flame retardant D: decabromodiphenylethane, FR-102WE, free bromine content 163ppm, shandong Seawang chemical Co., ltd;
hydrotalcite 1: AC-320, D50 particle size of 0.1 μm, is of the same technology;
hydrotalcite 2: DHT-4A, D50 particle size of 0.4 μm, manufactured by Nippon Kagaku Kogyo Co., ltd;
hydrotalcite 3: FM300 FM803, D50 particle size of 0.8 μm, kang Gaote New Material technologies Co., ltd;
IPT improver: polytetrafluoroethylene, GR-C525, new material inc. Of singe, zhejiang;
preparation method of flame retardant nylon compositions of examples and comparative examples: according to the proportion, the components are uniformly mixed, and then extruded and granulated by a double-screw extruder, wherein the temperature range of the screw is 240-280 ℃, and the rotating speed range is 300-500 rpm, so as to obtain the flame-retardant nylon composition.
The testing method comprises the following steps:
(1) IPT testing was performed with reference to ASTM D2303 standard using a constant voltage method, but instead of taking 250V as a test grade in the standard, 100V is stepped up or down as a grade. In addition, when the IPT test result is lower than 600V, no lower voltage test is performed, indicating that the material is not suitable for the anti-tracking material under the high voltage condition.
(2) Flame retardant rating testing was performed with reference to UL 94-2013 standard, test spline size 125mm 13mm 2.0mm.
(3) a) crushing a sample in a high-speed crusher, sieving the crushed sample by a 40-mesh screen, accurately weighing 10.00+/-0.05 g of the sieved sample, putting the sieved sample into a 250ml beaker with a rotor, adding 20ml of methanol solution into the beaker, slightly shaking the beaker, fully soaking the sample in the solution for 10 minutes, and adding 200ml of distilled water; placing the beaker added with the sample into ultrasonic waves, preserving heat and ultrasonic waves for 1 hour at 60 ℃, taking out, cooling to room temperature, and completing sample preparation; b) Potentiometric titration is carried out by adopting a potentiometric titrator, about 0.1g of dextrin is added into a sample, and 2ml of nitric acid (25 ml of analytically pure nitric acid is slowly stirred and added into 25ml of distilled water) with the volume ratio of 50% is added dropwise; when the fluctuation of the instrument potential is less than 0.2mv in 30s, the instrument starts titration, a titration curve is displayed on an operation interface, the instrument buzzes at the titration end point, and the titration end point V is displayed 1 Three times of experiments are carried out in parallel,simultaneously performing a blank test; 3) Bromine ion calculation, W 1 =（V 1 －V 0 ) C. 79.904/1000m, wherein:
W 1 -bromide content in ppm;
V 0 blank consumes the volume, mL, of silver nitrate standard solution;
V 1 -the first endpoint consumes a volume, mL, of silver nitrate standard solution;
c, the mass concentration of the substances of the silver nitrate standard solution is 0.01mol/L;
m-weighing the mass of the sample, g;
79.904-molar mass of bromine, g/mol;
and calculating the average value of data obtained in three experiments to obtain the bromide ion content.
Table 1: examples 1-7 flame retardant nylon compositions component content (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| PA66 | 50 | 50 | 50 | 50 | 50 | ||
| PA6 | 50 | ||||||
| PA610 | 50 | ||||||
| Flame retardant C | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Hydrotalcite 1 | 20 | 20 | 20 | 15 | 18 | 25 | 30 |
| IPT improver | 10 | 10 | 10 | 6 | 8 | 12 | 15 |
| Free bromine content, ppm | 18 | 18 | 17 | 23 | 19 | 14 | 13 |
| IPT，V | 1000 | 1000 | 1000 | 900 | 1000 | 1000 | 1000 |
| Flame retardancy | V0 | V0 | V0 | V0 | V0 | V0 | V0 |
As is clear from example 1, the theoretical free bromine content was calculated to be 31.6ppm, but the free bromine content could be reduced to 18ppm by absorption of free bromine by hydrotalcite.
From examples 1/4 to 9, it is understood that the free bromine content of the brominated polystyrene itself and the addition amount of hydrotalcite significantly affect the free bromine content in the composition, and that the free bromine content is 20ppm or less and the ipt value is higher in the preferable content range; when the free bromine content is 11ppm or less, the IPT value can reach 1100V.
Table 2: examples 8-11 flame retardant nylon compositions component content (parts by weight) and test results
| Example 8 | Example 9 | Example 10 | Example 11 | |
| PA66 | 50 | 50 | 50 | 50 |
| Flame retardant C | 20 | 20 | ||
| Flame retardant A | 20 | |||
| Flame retardant B | 20 | |||
| Hydrotalcite 1 | 20 | 20 | ||
| Hydrotalcite 2 | 20 | |||
| Hydrotalcite 3 | 20 | |||
| IPT improver | 10 | 10 | 10 | 10 |
| Free bromine content, ppm | 9 | 11 | 16 | 21 |
| IPT，V | 1100 | 1100 | 1000 | 900 |
| Flame retardancy | V0 | V0 | V0 | V0 |
As is clear from examples 1/10/11, hydrotalcite having a preferable particle size has the best effect of adsorbing free bromine.
Table 3: comparative flame retardant nylon composition component content (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| PA66 | 50 | 50 | 50 | 50 |
| Flame retardant C | 35 | 20 | 20 | |
| Flame retardant D | 20 | |||
| Hydrotalcite 1 | 20 | 20 | 10 | 20 |
| IPT improver | 10 | 10 | 10 | 1 |
| Free bromine content, ppm | 23 | 32 | 27 | 16 |
| IPT，V | 700 | 700 | 800 | 800 |
| Flame retardancy | V0 | V0 | V0 | V0 |
As is clear from comparative example 1, decabromodiphenylethane was able to control the free bromine content to be less than 26ppm, but it was able to accelerate the generation of free bromine under high voltage conditions, and lower the IPT value.
As is evident from comparative example 2, too high a free bromine content results in a very low IPT.
As is clear from comparative example 3, when the addition amount of hydrotalcite is too low, the adsorption effect on free bromine is insufficient, resulting in a decrease in IPT.
As is evident from comparative example 4, when the IPT improver content is too low, even if the free bromine content is less than 11ppm, sufficient release of tetrafluoroethylene gas cannot be achieved at high voltage, and the IPT value is less than 900V.
Claims (8)
1. The flame-retardant nylon composition is characterized by comprising the following components in parts by weight:
50 parts of aliphatic polyamide resin;
15-30 parts of brominated polystyrene;
15-30 parts of hydrotalcite;
6-15 parts of IPT improver;
the content of free bromine is less than or equal to 26ppm based on the total weight of the flame-retardant nylon composite material;
the IPT improver is polytetrafluoroethylene;
the method for testing the content of free bromine in the flame-retardant nylon composition comprises the following steps: a) Crushing the sample in a high-speed crusher, sieving with a 40-mesh screen, accurately weighing 10.00+/-0.05 g of the sieved sample, putting the sample into a 250ml beaker with a rotor, adding 20ml of methanol solution into the beaker, slightly shaking to ensure that the sample is completely soaked in the solution for 10 minutes, and adding 200ml of distilled water; placing the beaker added with the sample into ultrasonic waves, preserving heat and ultrasonic waves for 1 hour at 60 ℃, taking out, cooling to room temperature, and completing sample preparation; b) By usingPotentiometric titration is carried out by a potentiometric titrator, about 0.1g of dextrin is added into a sample, and 2ml of nitric acid with the volume ratio of 50% is dripped into the sample; when the fluctuation of the instrument potential is less than 0.2mv in 30s, the instrument starts titration, a titration curve is displayed on an operation interface, the instrument buzzes at the titration end point, and the titration end point V is displayed 1 Performing experiments in parallel for three times, and performing blank experiments simultaneously; 3) Bromine ion calculation, W 1 =（V 1 －V 0 ) C. 79.904/1000m, wherein:
W 1 -bromide content in ppm;
V 0 blank consumes the volume, mL, of silver nitrate standard solution;
V 1 -the first endpoint consumes a volume, mL, of silver nitrate standard solution;
c, the mass concentration of the substances of the silver nitrate standard solution is 0.01mol/L;
m-weighing the mass of the sample, g;
79.904-molar mass of bromine, g/mol;
and calculating the average value of data obtained in three experiments to obtain the bromide ion content.
2. The flame retardant nylon composition of claim 1, comprising the following components in parts by weight:
50 parts of aliphatic polyamide resin;
15-30 parts of brominated polystyrene;
18-25 parts of hydrotalcite;
8-12 parts of IPT improver;
the content of free bromine is less than or equal to 20ppm based on the total weight of the flame-retardant nylon composite material.
3. The flame retardant nylon composition of claim 1, wherein the free bromine is present in an amount of 11ppm or less based on the total weight of the flame retardant nylon composition.
4. The flame retardant nylon composition of claim 1, wherein the aliphatic polyamide is selected from at least one of PA6, PA66, PA610, PA 1010; the weight average molecular weight of the aliphatic polyamide is 10000-24000.
5. The flame retardant nylon composition of claim 1, wherein the hydrotalcite has a D50 particle size of 0.08 μm to 1.0 μm.
6. The flame retardant nylon composition of claim 5, wherein the hydrotalcite has a D50 particle size of 0.1 μm to 0.4 μm.
7. A method of preparing a flame retardant nylon composition according to any one of claims 1-5, comprising the steps of: according to the proportion, the components are uniformly mixed, and then extruded and granulated by a double-screw extruder, wherein the temperature range of the screw is 240-280 ℃, and the rotating speed range is 300-500 rpm, so as to obtain the flame-retardant nylon composition.
8. Use of the flame retardant nylon composition of any of claims 1-5 in electrical appliances, household appliances, new energy high voltage connectors.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0333457A2 (en) * | 1988-03-15 | 1989-09-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Flame-resistant polyamide resin compositions |
| US5543452A (en) * | 1988-03-15 | 1996-08-06 | Asahi Kasei Kogyo Kabushiki Kaisha | Flame-resistant polyamide resin compositions and flame retardants therefor |
| WO2021212819A1 (en) * | 2020-04-24 | 2021-10-28 | 金发科技股份有限公司 | Polyamide composite material and preparation method therefor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100901043B1 (en) * | 2005-05-16 | 2009-06-04 | 미쓰이 가가쿠 가부시키가이샤 | Flame retardant polyamide composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0333457A2 (en) * | 1988-03-15 | 1989-09-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Flame-resistant polyamide resin compositions |
| US5543452A (en) * | 1988-03-15 | 1996-08-06 | Asahi Kasei Kogyo Kabushiki Kaisha | Flame-resistant polyamide resin compositions and flame retardants therefor |
| WO2021212819A1 (en) * | 2020-04-24 | 2021-10-28 | 金发科技股份有限公司 | Polyamide composite material and preparation method therefor |
Non-Patent Citations (4)
| Title |
|---|
| PA66/PTFE复合材料的摩擦磨损性能;刘天涛;金志明;薛平;潘龙;赵峰;;塑料(第05期);全文 * |
| 抗滴落阻燃PET合金材料的研究;张梁;宋治乾;李秋影;郭卫红;吴驰飞;;塑料工业(第02期);全文 * |
| 聚四氟乙烯微粉与硅酮粉在尼龙66中的耐磨效果比较;李会;吴国忠;杨俊杰;黄承辉;;有机氟工业(第01期);全文 * |
| 超临界CO_2发泡阻燃聚苯乙烯研究;王亚桥;王文博;余科松;陈鹏;周洪福;王向东;;中国塑料(第12期);全文 * |
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