CN113372714B - Polyamide composite material with low phosphine gas precipitation and high CTI (comparative tracking index) and preparation method thereof - Google Patents
Polyamide composite material with low phosphine gas precipitation and high CTI (comparative tracking index) and preparation method thereof Download PDFInfo
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- CN113372714B CN113372714B CN202110795304.1A CN202110795304A CN113372714B CN 113372714 B CN113372714 B CN 113372714B CN 202110795304 A CN202110795304 A CN 202110795304A CN 113372714 B CN113372714 B CN 113372714B
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention relates to the technical field of composite materials, in particular to a polyamide composite material with low separation of phosphine gas and high CTI (comparative tracking index) and a preparation method thereof, wherein the raw materials of the polyamide composite material with low separation of phosphine gas and high CTI comprise polyamide, red phosphorus master batches, an antioxidant, a lubricant, an acid scavenger and glass fiber; the polyamide is prepared from petroleum-based polyamide and bio-based polyamide according to the weight ratio of 6-12: 1-6; wherein the petroleum-based polyamide is one or two of PA66 and PA6, and the bio-based polyamide is PA56. According to the polyamide composite material with low phosphine gas precipitation and high CTI, after petroleum-based polyamide and bio-based polyamide are mixed according to a specific ratio, the release amount of the phosphine of the red phosphorus master batch added in the components can be reduced on the premise of ensuring high flame retardance of the polyamide composite material, and the polyamide composite material also has high CTI (electromarking index), is low in cost and has high commercial value.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a polyamide composite material with low precipitation of phosphine gas and high CTI (comparative tracking index) and a preparation method thereof.
Background
Polyamide, as an engineering plastic, has high mechanical strength, electrical insulation, wear resistance, oil resistance, weak acid resistance and general organic solvent resistance. In recent years, semi-crystalline polyamides have been widely used in the fields of electronics, electrical, communications, etc., but these fields have high requirements for flame retardant ability of materials.
The polyamide reinforced by the glass fiber is easier to burn due to the candlewick effect of the glass fiber, is very easy to cause fire in the using process, and in order to be applied to the fields of electronic appliances and the like, a flame retardant is required to be added to improve the flame retardance of the material.
With the improvement of the environmental protection requirement, the traditional brominated flame retardant can not meet the requirements of European Union ROHS and WEEE instructions, and the environmental protection brominated flame retardant has the problems of large smoke amount, generation of corrosive gas and the like during combustion. The red phosphorus flame retardant is widely applied to glass fiber reinforced flame retardant nylon due to low cost and high flame retardant efficiency, but the flame retardant polyamide material using red phosphorus releases a small amount of phosphine, particularly in the processing process, firstly the phosphine is toxic, and secondly the phosphine causes the formation of contact precipitates on a metal conductor.
To reduce the generation of phosphine, the current main solution is to add an acid scavenger to the polyamide composite material to prevent the acid-catalyzed disproportionation of phosphine-generating phosphorus, but cannot achieve the effect of continuously preventing the release/formation of a complex of phosphine. Alternatively, the light-colored flame-retardant polyamide disclosed in patent document No. CN104640915A can reduce the generation of phosphine, but the cost is too high due to the Cu (I) compound or Ag (I) compound used, and the application is limited compared with the Comparative Tracking Index (CTI). Ltoreq.400V.
Disclosure of Invention
In order to solve the problems that the release of phosphine cannot be continuously prevented by adopting an acid scavenger and the cost is overhigh by adopting light-color flame-retardant polyamide, the invention provides a polyamide composite material with low precipitation of phosphine gas and high CTI (comparative tracking index), wherein the raw materials comprise polyamide, red phosphorus master batch, an antioxidant, a lubricant, an acid scavenger and glass fiber;
the polyamide is prepared from petroleum-based polyamide and bio-based polyamide according to the weight ratio of 6-12: 1-6;
wherein, the petroleum-based polyamide is one or two of PA66 and PA6, and the bio-based polyamide is PA56.
In one embodiment, the weight portions of petroleum-based polyamide 30-60, bio-based polyamide 5-30 and red phosphorus master batch 8-15; 0.2-0.5 part of antioxidant, 0.2-0.5 part of lubricant, 0.2-0.7 part of acid scavenger and 20-35 parts of glass fiber.
In one embodiment, the PA56 is prepared from bio-based pentanediamine and petroleum-based adipic acid by polymerization.
In one embodiment, the petroleum-based polyamide has a relative viscosity of 2.6 to 2.7.
In one embodiment, the glass fibers are alkali-free glass fibers.
In one embodiment, the lubricant is one or more of a stearate, an ethylene acrylic acid copolymer, or an amide-based lubricant.
In one embodiment, the antioxidant is one or more of hindered phenol primary antioxidant and phosphite secondary antioxidant.
In one embodiment, the acid scavenger is ZnO, mg (OH) 2 ,CaCO 3 One or more of (a).
The invention also provides a preparation method of the polyamide composite material with low phosphine gas precipitation and high CTI, wherein all the raw materials are stirred and mixed at a high speed according to the formula proportion, and then are fed into a double-screw extruder for melt extrusion, and the finished product of granules is prepared after bracing and cooling.
In one embodiment, the temperature of each zone of the twin screw extruder is set at 240 ℃ to 280 ℃.
Based on the scheme, compared with the prior art, the polyamide composite material with low phosphine gas precipitation and high CTI provided by the invention at least has the following technical principles and effects:
petroleum-based polyamide and bio-based polyamide are mixed according to a specific proportion, and because odd carbon chains in the bio-based polyamide and the petroleum-based polyamide are combined and inserted according to a certain proportion, the polyamide material is endowed with overall excellent performances such as good self-extinguishing property, fluidity, high toughness and the like; meanwhile, after the petroleum-based polyamide and the bio-based polyamide are mixed according to a specific proportion, the release amount of the phosphine of the red phosphorus master batch added in the components can be reduced on the premise of ensuring the high flame resistance of the polyamide composite material, and the polyamide composite material also has high CTI (tracking index), low cost and high commercial value.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the formulations of the examples shown in Table 1 (unit: parts by weight):
TABLE 1
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Petroleum-based polyamide | 52.8 | 54.8 | 50.8 | 46.8 | 42.8 | 37.8 |
| Bio-based polyamide PA56 | 5 | 5 | 10 | 15 | 20 | 25 |
| 9950A red phosphorus master batch | 11 | 9 | 8 | 7 | 6 | 6 |
| Antioxidant 1098 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Acid scavenger ZN0 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Lubricant calcium stearate | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Alkali-free glass fiber GF560A | 30 | 30 | 30 | 30 | 30 | 30 |
Wherein the petroleum-based polyamide of examples 1-4 is PA66, and the petroleum-based polyamide of examples 5 and 6 is PA6;
PA66 is selected from a commercially available flat-topped mountain Amur EPR27 with a relative viscosity of 2.6-2.7; PA6 is Jiangsu Haiyang HY2800A; PA56 is selected from Shanghai Kaiser E-2260; the red phosphorus master batch is selected from 9950A sold in China with the trade mark Tung Cheng dynasty; the antioxidant is selected from Tianjin Lianlong 1098; the lubricant is calcium stearate produced in the Shangxi province; the acid scavenger is selected from ZnO of Dalian Goldstone with a commercial grade; the glass fiber is made of glass fiber 560A with the trade mark of boulder.
The present invention also provides comparative examples shown below
Comparative example 1
PA56 in example 1 was removed, and PA66 parts was changed to 57.8 parts, which was otherwise identical to example 1.
Comparative example 2
The PA56 in example 2 was removed and the PA66 parts were changed to 59.8 parts, which was otherwise identical to example 2.
Comparative example 3
The PA56 in example 3 was replaced with PA10T, and the rest was identical to example 3.
Comparative example 4
The embodiment 4 is the same as the embodiment 4 except that the PA56 in the embodiment 4 is replaced by the PA 1010.
Comparative example 5
The embodiment 5 was followed except that PA6 in the embodiment 5 was replaced with PA 6T/66.
Comparative example 6
The embodiment 6 is the same as the embodiment 6 except that the PA6 in the embodiment 6 is replaced with the PA 610.
The invention also provides a preparation method of the embodiment, which comprises the following specific operations:
according to the formula proportion, all the raw materials are added into a high-speed stirrer to be fully and uniformly mixed, and the materials are conveyed into a double-screw extruder through a metering feeding device after being fully mixed, wherein the temperature of each area is 240 DEG C
The raw materials are fully fused under the conditions of shearing, mixing and conveying of a screw at the temperature of minus 280 ℃, and finally, the raw materials are extruded, pulled into strips and cooled to prepare a finished product of granules.
The polyamide composite materials obtained in the above examples and comparative examples were subjected to tests of relevant indexes,
wherein the tensile strength is GB/T1040.2-2006; the bending strength is referred to GB/T9341-2008; the reference of the notch impact strength is GB/T1043.1-2008; flame retardancy of 1.6mm according to IEC60695-11-10; CTI/V is referred to IEC60112; the melt volume flow rate is referred to GB/T3682-2000.
The phosphorus release of the plastic parts was tested as follows:
a plastic sample (125x12.5x1.6mm) was aliquoted in two halves, each half being placed in a10 ml glass beaker. Silver contact material (10x50x0.125mm) was placed in a short test tube. The three samples were then placed in 100ml screw-cap bottles, 5ml water was added and the closed system was placed in a drying oven at 70 ℃. After 28 days, the test tube was removed and filled to the top with water and the entire contents placed in a glass beaker. 5ml of concentrated sulphuric acid are added and the mixture is evaporated to substantial dryness. The metal sample was then removed and washed with water; 1ml of sulfuric acid was mixed with the residue and the mixture was evaporated again to substantial dryness. This was followed by dilution with 20ml of water, addition of 4ml of 5% strength potassium persulfate solution and heating of the mixture for 30 minutes. The phosphorus was then determined photometrically using molybdenum blue, based on ug phosphorus/plastic samples.
The test results are shown in tables 2 and 3:
TABLE 2
TABLE 3
As can be seen from the test results of tables 2 and 3, the performance test of the example is overall superior to that of the comparative example; wherein:
besides the phosphorus release index, the performance indexes of the embodiment 1 and the comparative example 1 are basically similar, and the phosphorus release index in the embodiment 1 is lower than that in the comparative example 1, which shows that under the condition of the same addition amount of the red phosphorus master batch, the PA56 is adopted to replace part of the PA66, so that the release amount of the hydrogen phosphide in the polyamide composite material can be continuously and effectively reduced.
The phosphorus release index of example 2 is lower than that of example 1, and the other indexes are both relatively close to each other, which shows that under the condition of the same flame retardant property, the PA66 of the PA56 replacing part can also reduce the addition amount of the red phosphorus master batch, so that the release amount of phosphine is further reduced; the test results of comparative example 2 show that when only PA66 was added, the amount of the red phosphorus masterbatch was reduced, and the amount of phosphine released was reduced, but the basic flame retardant requirement could not be achieved.
From examples 2 to 6, it can be seen that the proportion of the red phosphorus masterbatch decreases with the increase in the proportion of PA56 in the raw material, and the amount of phosphine released further decreases, without affecting the flame retardant characteristics and other basic properties of the polyamide composite material.
From comparison of the test results of comparative example 3 and example 3, it can be seen that the semi-aromatic bio-based polyamide is used instead of the aliphatic bio-based polyamide, and the polyamide composite material prepared by using the semi-aromatic bio-based polyamide has the same flame retardant effect, but the release amount of phosphine is obviously increased, the melt volume flow rate is low, and the processability is poor.
Combining the test results of comparative example 4 and example 4, it can be seen that by using aliphatic bio-based polyamide other than PA56 instead of PA56, although the amount of released phosphine can be kept low, the flame retardant performance is significantly reduced, and the basic flame retardant requirements of electronic appliances cannot be met.
Comparing the test results of example 5 and comparative example 5, it can be seen that the use of semi-aromatic petroleum-based polyamide instead of aliphatic petroleum-based polyamide with the same ratio of PA56 results in lower melt volume flow rate, unfavorable processing, and a significant reduction in CTI index.
From comparison of the test results of comparative example 6 and example 6, it can be seen that, in the case of using the same proportion of PA56, by using an aliphatic bio-based polyamide other than PA6 in place of PA6, although the flame retardancy and CTI index are not greatly different, the amount of phosphine released is high.
From the test results of the above examples and comparative examples, it can be seen that the polyamide composite material provided by the present invention has the best effect, that is, only the polyamide composite material prepared by using the bio-based polyamide PA56 in combination with the petroleum-based polyamide PA66 and/or PA6 can effectively reduce the release amount of phosphine in the red phosphorus flame retardant system while having good mechanical properties and flame retardancy, and maintain a high CTI, while the polyamide composite material prepared by using other polyamide combinations in the comparative examples cannot achieve such excellent effect.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The polyamide composite material with low hydrogen phosphide gas evolution and high CTI is characterized in that the raw materials comprise, by weight, 62.8 parts of polyamide, 6 parts of red phosphorus master batch, 0.2 part of antioxidant, 0.5 part of lubricant, 0.5 part of acid scavenger and 30 parts of glass fiber;
the polyamide consists of 42.8 parts of petroleum-based polyamide and 20 parts of PA 56;
wherein the petroleum-based polyamide is PA6;
the acid scavenger is ZnO.
2. The polyamide composite material with low phosphine gas evolution and high CTI as claimed in claim 1, wherein: the petroleum-based polyamide has a relative viscosity of 2.6 to 2.7.
3. The polyamide composite material with low phosphine gas evolution and high CTI as claimed in claim 1, wherein: the PA56 is prepared by polymerizing bio-based pentanediamine and petroleum-based adipic acid.
4. The polyamide composite material with low phosphine gas evolution and high CTI as claimed in claim 1, wherein: the glass fiber is alkali-free glass fiber.
5. The polyamide composite material with low phosphine gas evolution and high CTI as claimed in claim 1, wherein: the lubricant is one or more of stearate, ethylene acrylic acid copolymer or amide lubricant.
6. The polyamide composite material with low phosphine gas evolution and high CTI as claimed in claim 1, wherein: the antioxidant is one or more of hindered phenol main antioxidant and phosphite ester auxiliary antioxidant.
7. A process for the preparation of a polyamide composite material with low phosphine gas evolution and high CTI according to any of claims 1 to 6, characterized in that: according to the formula proportion, all the raw materials are stirred and mixed at a high speed, then are fed into a double-screw extruder for melt extrusion, and are subjected to bracing and cooling to obtain a finished product of granules.
8. The method for preparing the polyamide composite material with low phosphine gas evolution and high CTI according to claim 7, is characterized in that: the temperature of each zone of the double-screw extruder is set to be 240-280 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990548A (en) * | 2005-12-28 | 2007-07-04 | 上海日之升新技术发展有限公司 | Flame-proof polyamide composition with improved electricity insulating property |
| CN102382465A (en) * | 2011-09-30 | 2012-03-21 | 深圳市科聚新材料有限公司 | Halogen-free flame retarding strengthened PA66 material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010113736A1 (en) * | 2009-03-30 | 2010-10-07 | 東レ株式会社 | Polyamide resin, polyamide resin composition, and molded article comprising same |
| CN102382460A (en) * | 2011-10-24 | 2012-03-21 | 浙江俊尔新材料有限公司 | Low-acid-separation red phosphorus inflaming retarding reinforced polyamide material as well as preparation method and application thereof |
| KR20140136921A (en) * | 2012-02-23 | 2014-12-01 | 도레이 카부시키가이샤 | Thermoplastic resin composition and molded article |
| JP5935956B1 (en) * | 2015-02-27 | 2016-06-15 | 東レ株式会社 | Polyamide resin composition for molded articles that come into contact with high-pressure hydrogen and molded articles using the same |
| CN106893315A (en) * | 2017-04-01 | 2017-06-27 | 中蓝晨光化工研究设计院有限公司 | A kind of high performance-price ratio red phosphorus flame-retardant master batch and preparation method thereof |
| CN107793749B (en) * | 2017-09-30 | 2020-02-28 | 中广核俊尔新材料有限公司 | Low-odor red phosphorus flame-retardant reinforced polyamide material |
| CN107629450A (en) * | 2017-10-16 | 2018-01-26 | 中山康诺德新材料有限公司 | A kind of environment friendly non-halogen type fiber glass reinforced polyamide fire retardant |
| CN109181295A (en) * | 2018-08-09 | 2019-01-11 | 浙江大学 | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic and alkyl phosphite |
| CN108997612A (en) * | 2018-08-09 | 2018-12-14 | 江苏利思德新材料有限公司 | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic phosphorous acid metal salt |
| CN110467813A (en) * | 2019-08-16 | 2019-11-19 | 东莞市众一新材料科技有限公司 | A kind of silicon systems halogen-free flameproof biology base nylon and preparation method thereof |
| CN110591350B (en) * | 2019-09-03 | 2022-02-18 | 会通新材料(上海)有限公司 | Smoke-inhibiting polyamide composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1990548A (en) * | 2005-12-28 | 2007-07-04 | 上海日之升新技术发展有限公司 | Flame-proof polyamide composition with improved electricity insulating property |
| CN102382465A (en) * | 2011-09-30 | 2012-03-21 | 深圳市科聚新材料有限公司 | Halogen-free flame retarding strengthened PA66 material and preparation method thereof |
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