CN114395248B - Red phosphorus flame-retardant polyamide composite material and preparation method and application thereof - Google Patents
Red phosphorus flame-retardant polyamide composite material and preparation method and application thereof Download PDFInfo
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- CN114395248B CN114395248B CN202111599785.5A CN202111599785A CN114395248B CN 114395248 B CN114395248 B CN 114395248B CN 202111599785 A CN202111599785 A CN 202111599785A CN 114395248 B CN114395248 B CN 114395248B
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000004952 Polyamide Substances 0.000 title claims abstract description 42
- 229920002647 polyamide Polymers 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title description 6
- 239000003365 glass fiber Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000004760 aramid Substances 0.000 claims abstract description 23
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 23
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 11
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 9
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 239000003094 microcapsule Substances 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 26
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 9
- 238000002347 injection Methods 0.000 abstract description 8
- 239000007924 injection Substances 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 24
- 238000007667 floating Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012747 synergistic agent Substances 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- 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 red phosphorus flame-retardant polyamide composite material, which comprises the following components in parts by weight: 20-70 parts of aliphatic polyamide resin; 5-20 parts of aromatic polyamide resin; 10-50 parts of glass fiber; 8-20 parts of red phosphorus master batch; 1-5 parts of synergist. According to the red phosphorus flame-retardant polyamide composite material, through introducing aromatic polyamide with a special structure and the synergistic effect of the aromatic polyamide, glow wire performance (GWIT can reach 775 ℃) and flame retardant performance (reaching UL 94V-0 flame retardant grade of 0.8 mm) of the material can be remarkably improved, meanwhile, higher mechanical strength and modulus are maintained, and the composite material has good appearance of an injection molded part, can meet the use requirement of the electronic and electric appliance industry on the material under the development trend of high current, thinning, miniaturization and integration, and further widens the application of the red phosphorus flame-retardant polyamide composite material in the electronic and electric appliance field.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a red phosphorus flame-retardant polyamide composite material, and a preparation method and application thereof.
Background
The red phosphorus flame-retardant polyamide has the advantages of excellent flame retardance, mechanical property, low smoke, high cost performance, electric property and the like, and is widely applied to the fields of electronic appliances such as electric switches, connectors, low-voltage circuit breakers and the like. With the continuous iterative updating of technology, the electronic and electric industry shows the development trend of high current, thinning, miniaturization and integration, which requires the red phosphorus flame-retardant polyamide material to have better flame retardant property and glowing filament property.
In the prior art, the flame retardant performance of the material is usually improved by increasing the consumption of the red phosphorus flame retardant or introducing a flame retardant synergist such as zinc borate, magnesium hydroxide or montmorillonite. However, it was found that the above method for improving flame retardant properties does not improve the glow wire properties of the material well.
Chinese patent CN106336658A discloses a red phosphorus flame-retardant PA66/POK alloy, which has higher GWIT, but POK is easy to degrade, has poor heat aging performance and poor processing matching property with PA66, is not suitable for industrial application, and mostly stays in a research stage. Chinese patent CN102702734A compounds PA66, PPE, red phosphorus master batch and glass fiber to prepare the red phosphorus flame retardant nylon with high heat resistance and high glowing filament, but the PPE has poor toughness and poor compatibility with PA66, can seriously reduce the notch impact property of the composite material, and in addition, the poor fluidity of the PPE can influence the injection molding appearance of the material. The U.S. patent 4136154A adopts organic aluminum hypophosphite and red phosphorus master batch to synergistically flame-retardant PA66, and improves the glowing filament temperature of the material, which is a better scheme in the prior industry, but the organic aluminum hypophosphite has larger damage to the mechanical property of the flame-retardant polyamide compound, and the organic aluminum hypophosphite has poorer thermal stability, and has certain degradation in the injection molding process, so that excessive gas is caused, the phenomena of tracking, scorching and trapping gas on the surface of a product are caused, and the appearance of the material is seriously influenced. It can be seen that a certain technical difficulty still exists in how to efficiently improve the glow wire performance of the red phosphorus flame-retardant polyamide at present.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the red phosphorus flame-retardant polyamide composite material which has excellent flame retardant property and glowing filament property and good appearance of injection molded parts.
The invention also aims to provide a preparation method of the red phosphorus flame-retardant polyamide composite material.
It is a further object of the present invention to provide the use of the red phosphorus flame retardant polyamide composite material
The invention is realized by the following technical scheme:
the red phosphorus flame-retardant polyamide composite material comprises the following components in parts by weight:
20-70 parts of aliphatic polyamide resin;
5-20 parts of aromatic polyamide resin;
10-50 parts of glass fiber;
8-20 parts of red phosphorus flame retardant;
1-5 parts of synergist.
Preferably, the red phosphorus flame-retardant polyamide composite material comprises the following components in parts by weight:
30-60 parts of aliphatic polyamide resin;
5-15 parts of aromatic polyamide resin;
20-40 parts of glass fiber;
8-15 parts of red phosphorus flame retardant;
1-2 parts of synergist.
Preferably, the aliphatic polyamide resin is selected from any one or more of PA6, PA56 or PA 66.
The aromatic polyamide resin is selected from any one or more of polyamides formed by polycondensation of monomers with a structure shown in a formula (I);
formula (I);
wherein n is a positive integer of 4-10.
Preferably, the aromatic polyamide resin is selected from any one or more of PA MXD6, PA MXD8, PA MXD10 or PA MXD 12; more preferably, the aromatic polyamide resin is selected from any one or more of PA MXD6 and PA MXD 10.
According to the invention, through the research, the aromatic polyamide formed by condensing the m-xylylenediamine is introduced, has better compatibility with the aliphatic polyamide, can effectively improve the strength and modulus of the material, and the amine group of the m-xylylenediamine reacts with red phosphorus, so that the carbon forming speed and carbon forming quality of the material are improved under the combined action of a synergist, and the glowing filament performance and flame retardant performance of the material are obviously improved; on the other hand, the aromatic polyamide can reduce the crystallization speed of the red phosphorus flame retardant polyamide compound, so that the melt has enough time to cover the glass fiber and the replication mold, thereby effectively improving the appearance of the injection molded part.
The glass fiber is any one or more of E glass fiber, H glass fiber, R, S glass fiber, D glass fiber or C glass fiber; preferably, the glass fibers are selected from E glass fibers.
The red phosphorus flame retardant is selected from any one or more of red phosphorus or red phosphorus master batches; preferably, the red phosphorus flame retardant is selected from microcapsule coated red phosphorus master batches.
The synergist is selected from any one or more of zinc borate, magnesium hydroxide, aluminum hydroxide or montmorillonite; preferably, the synergist is selected from zinc borate.
According to the material performance requirement, the red phosphorus flame-retardant polyamide composite material also comprises 0.1-0.5 part of antioxidant according to parts by weight.
The antioxidant is selected from one or more of hindered phenol antioxidant, hindered amine antioxidant or copper salt. Copper salt is a common name for copper salt antioxidants in the technical field, mainly comes from basf, and inorganic copper salt and organic copper salt are widely applied to the market at present and are mainly used for improving CTI performance.
The invention has no special requirements on the type and source of the antioxidant, and a technician can select the type of the antioxidant to add according to the actual situation requirement.
The invention also provides a preparation method of the red phosphorus flame-retardant polyamide composite material, which comprises the following steps:
uniformly mixing all components except glass fibers according to a proportion to obtain a mixture; and feeding the mixture from a main feeding port, feeding and feeding the glass fiber side, carrying out melt blending extrusion, cooling and granulating to obtain the red phosphorus flame-retardant polyamide composite material.
Further preferably, the melt blending extrusion is performed by a twin screw extruder.
Preferably, the temperature of the twin screw extruder is 80-280 ℃.
Preferably, the twin screw extruder has a screw aspect ratio of (40-48): 1.
preferably, the twin-screw extruder has a screw speed of 250-350rpm.
The invention also provides application of the red phosphorus flame-retardant polyamide composite material in the field of electronic and electric appliances. In particular, it can be used for preparing electric switches, connectors or low-voltage circuit breakers.
The invention has the following beneficial effects:
according to the red phosphorus flame-retardant polyamide composite material, through introducing aromatic polyamide with a special structure and the synergistic effect of the aromatic polyamide, glow wire performance (GWIT can reach 775 ℃) and flame retardant performance (reaching UL 94V-0 flame retardant grade of 0.8 mm) of the material can be remarkably improved, meanwhile, higher mechanical strength and modulus are maintained, and the composite material has good appearance of an injection molded part, can meet the use requirement of the electronic and electric appliance industry on the material under the development trend of high current, thinning, miniaturization and integration, and further widens the application of the red phosphorus flame-retardant polyamide composite material in the electronic and electric appliance field.
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 raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
aliphatic polyamide resin 1: PA66, brand PA66 EP-158, huafeng group;
aliphatic polyamide resin 2: PA6, brand PA6 HY-2800, sea-sun chemical fiber company;
aliphatic polyamide resin 3: PA56, trade name 1270W, kesai limited;
aromatic polyamide resin 1: PA MXD6, brand AP-250, gain, inc;
aromatic polyamide resin 2: PA MXD10, inc;
polyamide resin PA66/6T: brand C1504T, shandong guang boundary new materials limited;
polyamide resin PA6T/6I: brand TI1207, shandong Guangdong boundary New Material Co., ltd;
glass fiber 1: e glass fiber, trade name ECS10-3.0-568H, china boulder Co., ltd;
glass fiber 2: s glass fiber, brand S-1 HM435TM, taishan glass fiber Co., ltd;
red phosphorus master batch: the microcapsule coats red phosphorus master batch with the brand FR9950T, and Tungcheng Xin obtained limited company;
synergists: zinc borate, commercially available;
an antioxidant: hindered phenol antioxidant 1098, commercially available.
The preparation method of the red phosphorus flame-retardant polyamide composite material comprises the following steps:
uniformly mixing all components except glass fibers according to a proportion to obtain a mixture; feeding the mixture from a main feeding port, feeding the mixture from the side of glass fiber, carrying out melt blending extrusion by a double-screw extruder, and cooling and granulating to prepare the red phosphorus flame-retardant polyamide composite material; wherein, the length-diameter ratio of the screw is 40:1, the rotation speed of the screw is 300rpm, the segmentation temperature is 80-270-250-240-210-230-250 ℃.
The related performance testing method comprises the following steps:
(1) Flame retardant properties: performing flame retardant performance test on the sample bar according to the related standard of UL 94-2013, wherein the thickness of the sample bar is 0.8mm; the flame retardant property has great significance on electrical safety, and the UL94 flame retardant grade needs to reach V-0 to meet the application requirements.
(2) Glow wire performance: the glow wire ignition temperature of the samples was tested according to IEC 60695-2-11-2014, with sample sizes of 100 x 2mm.
(3) Tensile properties: the stretching speed is 10mm/min according to ISO 527-2-2012 standard test;
(4) Bending properties: the bending speed is 2mm/min according to ISO 178-2010 standard;
(5) Notched Izod impact Strength: the notch type is A type according to ISO 178-2010 standard test;
(6) Crystallization properties: according to ISO 11357-2018 standard test, the temperature rising and reducing rate is 10K/min, the nitrogen atmosphere, the crystallization rate is expressed by the half-width of the crystallization peak; the larger the peak width at half maximum, the slower the crystallization rate.
(7) Appearance: injection-molded color plates (84 x 54 x 2.0 mm), the floating fibers on the surfaces of the color plates were observed, and the evaluation was carried out according to the floating fiber conditions on the surfaces of the color plates, and the color plates were classified into 4 grades, namely, no floating fibers were obvious (fibrous protrusions were less than 5 places and the protrusions were shallower, the appearance of the surfaces of the color plates were not affected), obvious floating fibers (fibrous protrusions were about 5-10 places and the protrusions were higher, only good appearance could be maintained), and more floating fibers (the number of protrusions on the surfaces of the color plates was greater than 10 places, and the appearance of the surfaces of the color plates had been significantly affected).
Table 1: examples 1-8 component ratios (in parts by weight) and related performance test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| PA66 | 30 | 60 | 50 | 50 | 50 | 50 | ||
| PA6 | 50 | |||||||
| PA56 | 50 | |||||||
| PA MXD6 | 5 | 15 | 10 | 10 | 10 | 10 | ||
| PA MXD10 | 10 | 10 | ||||||
| Red phosphorus master batch | 8 | 15 | 12 | 12 | 12 | 12 | 12 | 12 |
| Glass fiber 1 | 40 | 20 | 25 | 25 | 25 | 25 | 25 | |
| Glass fiber 2 | 25 | |||||||
| Synergistic agent | 1 | 4 | 2 | 2 | 2 | 2 | 2 | 2 |
| Antioxidant | 0.1 | 0.5 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | / |
| Tensile Strength/MPa | 189 | 139 | 145 | 138 | 141 | 137 | 148 | 142 |
| Flexural modulus/MPa | 11700 | 7902 | 8100 | 7600 | 7830 | 7730 | 8530 | 8040 |
| Notched impact strength/kJ/m 2 | 10.8 | 6.4 | 6.8 | 7.0 | 7.2 | 6.9 | 7.8 | 6.6 |
| GWIT/℃ | 800 | 775 | 775 | 775 | 775 | 775 | 775 | 775 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Appearance of | Floating fiber is not obvious | No floating fiber | No floating fiber | No floating fiber | No floating fiber | No floating fiber | No floating fiber | No floating fiber |
Table 2: comparative examples 1 to 9 the proportions of the respective components (in parts by weight) and the results of the related performance tests
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | |
| PA66 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | ||
| PA6 | 50 | ||||||||
| PA56 | 50 | ||||||||
| PA MXD6 | 2 | 10 | 35 | 10 | 10 | ||||
| PA MXD10 | 10 | ||||||||
| PA66/6T | 10 | ||||||||
| PA6T/6I | 10 | ||||||||
| Red phosphorus master batch | 12 | 12 | 12 | 12 | 12 | 6 | 22 | 12 | 12 |
| Glass fiber | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
| Synergistic agent | 2 | 2 | 6 | 2 | 2 | 2 | 2 | 2 | |
| Antioxidant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Stretchingstrength/MPa | 133 | 137 | 128 | 140 | 130 | 145 | 127 | 130 | 129 |
| Flexural modulus/MPa | 7210 | 7530 | 7810 | 7900 | 8700 | 7820 | 8100 | 7200 | 7100 |
| Notched impact strength/kJ/m 2 | 6.7 | 6.7 | 4.3 | 7.2 | 4.1 | 6.9 | 6.1 | 6.8 | 6.6 |
| GWIT/℃ | 725 | 725 | 775 | 700 | 775 | 675 | 775 | 725 | 725 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-1 | V-0 | V-2 | V-0 | V-0 | V-0 |
| Appearance of | More floating fibers | Floating fiber is obvious | More floating fibers | No floating fiber | No floating fiber | No floating fiber | More floating fibers | More floating fibers | More floating fibers |
As can be seen from the above examples and comparative examples, the red phosphorus flame retardant polyamide compound prepared by introducing aromatic polyamide with a special structure and synergistically acting with the red phosphorus flame retardant and the synergist has excellent mechanical property, flame retardant property and glowing filament property, and injection molded parts thereof have good appearance.
As can be seen from comparison of comparative example 1/2 with example 3, the aromatic polyamide resin can significantly improve the mechanical properties, glow wire properties and appearance of the material; the material has lower tensile strength, flexural modulus and notch impact strength without adding aromatic polyamide resin or with too little addition, and has no obvious improvement on glowing filament performance of the material, and the GWIT only reaches 725 ℃, so that the surface of an injection molding part has serious fiber floating and bad appearance.
Comparative example 5 compared with example 3, the addition of the aromatic polyamide resin was excessive, but the tensile strength and notched impact strength of the material were significantly lowered.
Compared with the embodiment 5, the comparative example 3 has the advantages that the zinc borate content is too high, so that the mechanical property of the material can be reduced, and the appearance of an injection molded part is also affected to a certain extent; the analysis is due to poor material flowability and thermal stability caused by excessive zinc borate, which results in poor appearance of the injection molded article.
Comparative example 4 compared to example 6, without the addition of zinc borate, the material reached only a flame retardant rating of 0.8mmV-1 and GWIT was only 700 ℃.
Compared with the comparative example 6/7 and the example 3, the addition amount of the red phosphorus master batch is too small, the flame retardant property and glowing filament property of the material are poor, the flame retardant grade of 0.8mmV-2 is only achieved, and the GWIT is only 675 ℃; too much red phosphorus master batch is added, which leads to obvious decrease of mechanical properties of materials and poor appearance of injection molded parts.
Compared with the embodiment 3, the comparative example 8/9 has no good improvement effect on the mechanical property, glow wire property and appearance of the material by selecting PA66/6T or PA 6T/6I.
Claims (14)
1. The red phosphorus flame-retardant polyamide composite material is characterized by comprising the following components in parts by weight:
20-70 parts of aliphatic polyamide resin;
5-20 parts of aromatic polyamide resin;
10-50 parts of glass fiber;
8-20 parts of red phosphorus flame retardant;
1-5 parts of synergist;
the aromatic polyamide resin is selected from any one or more of polyamides formed by polycondensation of monomers with a structure shown in a formula (I);
formula (I);
wherein n is a positive integer of 4-10.
2. The red phosphorus flame-retardant polyamide composite material according to claim 1, which is characterized by comprising the following components in parts by weight:
30-60 parts of aliphatic polyamide resin;
5-15 parts of aromatic polyamide resin;
20-40 parts of glass fiber;
8-15 parts of red phosphorus flame retardant;
1-2 parts of synergist.
3. The red phosphorus flame retardant polyamide composite material according to claim 1, wherein said aliphatic polyamide resin is selected from any one or more of PA6, PA56 or PA 66.
4. The red phosphorus flame retardant polyamide composite material according to claim 1, wherein said aromatic polyamide resin is selected from any one or more of PA MXD6, PA MXD8, PA MXD10 and PA MXD 12.
5. The red phosphorus flame retardant polyamide composite material according to claim 4, wherein said aromatic polyamide resin is selected from any one or more of PA MXD6 and PA MXD 10.
6. The red phosphorus flame-retardant polyamide composite material according to claim 1, wherein the glass fiber is any one or more selected from the group consisting of E glass fiber, H glass fiber, R, S glass fiber, D glass fiber and C glass fiber.
7. The red phosphorus flame retardant polyamide composite material according to claim 6, wherein said glass fibers are selected from the group consisting of E glass fibers.
8. The red phosphorus flame-retardant polyamide composite material according to claim 1, wherein the synergist is selected from any one or more of zinc borate, magnesium hydroxide, aluminum hydroxide and montmorillonite.
9. The red phosphorus flame retardant polyamide composite material according to claim 8, wherein said synergist is selected from zinc borate.
10. The red phosphorus flame-retardant polyamide composite material according to claim 1, wherein the red phosphorus flame retardant is selected from any one or more of red phosphorus or red phosphorus master batches.
11. The red phosphorus flame retardant polyamide composite material according to claim 10, wherein the red phosphorus flame retardant is selected from microcapsule coated red phosphorus master batches.
12. The red phosphorus flame-retardant polyamide composite material according to claim 1, which is characterized by further comprising 0.1-0.5 part of antioxidant in parts by weight; the antioxidant is selected from one or more of hindered phenol antioxidant, hindered amine antioxidant or copper salt.
13. The method for preparing the red phosphorus flame retardant polyamide composite material according to any one of claims 1 to 12, comprising the following steps:
uniformly mixing all components except glass fibers according to a proportion to obtain a mixture; and feeding the mixture from a main feeding port, feeding and feeding the glass fiber side, carrying out melt blending extrusion, cooling and granulating to obtain the red phosphorus flame-retardant polyamide composite material.
14. Use of the red phosphorus flame retardant polyamide composite material according to any one of claims 1-12 in the field of electronics.
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| CN103044905A (en) * | 2012-12-28 | 2013-04-17 | 大河宝利材料科技(苏州)有限公司 | Polyamide composition and preparation method thereof |
| CN112194894A (en) * | 2020-09-29 | 2021-01-08 | 金发科技股份有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method thereof |
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| CN103044905A (en) * | 2012-12-28 | 2013-04-17 | 大河宝利材料科技(苏州)有限公司 | Polyamide composition and preparation method thereof |
| CN112194894A (en) * | 2020-09-29 | 2021-01-08 | 金发科技股份有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method thereof |
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