CN114573979B - Flame-retardant nylon composite material and preparation method and application thereof - Google Patents
Flame-retardant nylon composite material and preparation method and application thereof Download PDFInfo
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- CN114573979B CN114573979B CN202210362754.6A CN202210362754A CN114573979B CN 114573979 B CN114573979 B CN 114573979B CN 202210362754 A CN202210362754 A CN 202210362754A CN 114573979 B CN114573979 B CN 114573979B
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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 89
- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
- 239000004677 Nylon Substances 0.000 title claims abstract description 66
- 229920001778 nylon Polymers 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920006117 poly(hexamethylene terephthalamide)-co- polycaprolactam Polymers 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 31
- 230000009477 glass transition Effects 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 238000000465 moulding Methods 0.000 claims abstract description 14
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 12
- -1 aliphatic lactam Chemical class 0.000 claims description 11
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 239000002667 nucleating agent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012763 reinforcing filler Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 40
- 238000012545 processing Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010998 test method Methods 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 229920003231 aliphatic polyamide Polymers 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006374 copolyamide PA6I/6T Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011990 functional testing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical group 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
-
- 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
Abstract
The invention discloses a flame-retardant nylon composite material, and a preparation method and application thereof, and belongs to the technical field of flame-retardant material processing. The flame-retardant nylon composite material comprises the following components in parts by mass: the flame-retardant nylon composite material provided by the method comprises the following components of 670-95 parts of PA 6T/95 and 5-30 parts of flame retardant, wherein the glass transition temperature of PA6T/6 is 60-120 ℃, the melting point is less than 280 ℃, the PA6T/6 material with specific glass transition temperature and melting point is used as main resin, and the flame retardant is added into the main resin, so that the nylon flame-retardant material with high temperature resistance, high processing fluidity and short molding cycle can be prepared, and the product requirements of the electronic and electric industry are met.
Description
Technical Field
The invention relates to the technical field of flame-retardant material processing, in particular to a flame-retardant nylon composite material, and a preparation method and application thereof.
Background
Polyamide materials are widely used in the electronics and electrical industry due to their excellent mechanical strength and processability, but as the size of the products in the electronics and electrical industry becomes smaller, the flowability of the materials is required to be higher. Secondly, based on the requirement that the production efficiency is higher and higher, the processing period of the required material is shorter and shorter, and new requirements are put forward on the performance requirement of the material. With the current requirements of industries such as mobile phones, new energy sources and the like for quick charging, the requirements on the temperature resistance of materials are higher and higher. At present, the industry generally adopts aliphatic nylon (such as PA66 and PA 6) to add flame retardant to meet the demands, but the glass transition temperature of the aliphatic nylon material is generally lower than 60 ℃, and the strength of the aliphatic nylon material is rapidly reduced in a high-temperature environment, so that the market demands are hardly met. Secondly, semi-aromatic nylons (such as PA9T, PA6T/66 and PA 10T) are also commercially available, but they are poor in processability because they generally have a melting point higher than 300 ℃.
In the comprehensive view, no nylon flame-retardant material with high temperature resistance, high processing fluidity and short molding cycle exists in the market.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a flame-retardant nylon composite material, and a preparation method and application thereof.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a flame-retardant nylon composite material which comprises the following components in parts by mass: 670-95 parts of PA 6T/and 5-30 parts of flame retardant, wherein the glass transition temperature of the PA6T/6 is 60-120 ℃, and the melting point is less than 280 ℃.
The invention also provides a preparation method of the flame-retardant nylon composite material, which comprises the following steps: and (3) mixing the components in proportion, and controlling the extrusion temperature of the double screws to 280-330 ℃ to obtain the flame-retardant nylon composite material.
The invention also provides application of the flame-retardant nylon composite material in preparing electronic and electrical equipment and household appliances.
The invention has the following beneficial effects:
the invention provides a flame-retardant nylon composite material, a preparation method and application thereof, wherein the flame-retardant nylon composite material comprises the following components in parts by mass: 70-95 parts of PA6T/6 and 5-30 parts of flame retardant, wherein the glass transition temperature of PA6T/6 is 60-120 ℃, the melting point is less than 280 ℃, the flame retardant nylon composite material provided by the method adopts PA6T/6 material with specific glass transition temperature and melting point as main resin, and the flame retardant is added into the main resin, so that the nylon flame retardant material with high temperature resistance, high processing fluidity and short molding cycle can be prepared, and the product requirement of the electronic and electric industry is met.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The flame-retardant nylon composite material provided by the embodiment of the invention, and a preparation method and application thereof are specifically described below.
In a first aspect, an embodiment of the present invention provides a flame retardant nylon composite material, including the following components in parts by mass: 70-95 parts of PA6T/6 and 5-30 parts of flame retardant, wherein the glass transition temperature of the PA6T/6 is 60-120 ℃, and more preferably the glass transition temperature is 65-110 ℃. The melting point is less than 300 ℃, more preferably less than 280 ℃, preferably more than 200 ℃, more preferably more than 220 ℃, most preferably more than 240 ℃.
The embodiment of the invention provides a flame-retardant nylon composite material, which is prepared by taking a PA6T/6 material with specific glass transition temperature and melting point as main resin and adding a flame retardant into the main resin. Experimental study shows that the melting point is too low, the benzene ring content in the molecular chain is reduced, the dimensional stability of the material is reduced, and the temperature resistance of the material is deteriorated; too high melting point, increased benzene ring content, increased molecular chain rigidity, decreased fluidity, and poor processability; meanwhile, the glass transition temperature is too low, and the mechanical property of the material, especially the strength of the material at high temperature, is fast reduced; the glass transition temperature is too high and the flowability of the material is lowered, so that the processability is poor. Preferably, the melting point and the glass transition temperature of the semiaromatic copolymerized nylon resin satisfy the above-mentioned condition ranges at the same time.
The experimental results show that: the nylon material is PA6T/6, the melting point is 310 ℃, the fluidity of the flame-retardant nylon composite material obtained by the flame-retardant nylon composite material is poor, and the molding period is long; the nylon material is PA6I/6T, the melting point is 270 ℃, the glass transition temperature is 90 ℃, and the obtained flame-retardant nylon composite material has poor fluidity and longer molding period; the nylon material is PA66, the glass transition temperature is 50 ℃, and the strength retention rate of the flame-retardant nylon composite material obtained by the nylon material at high temperature is low; the nylon material is PA6T/6, the glass transition temperature is 50 ℃, and the strength retention rate of the obtained flame-retardant nylon composite material at high temperature is low.
In an alternative embodiment, the composition comprises the following components in parts by mass: 80-90 parts of PA6T/6 and 10-20 parts of flame retardant, wherein the glass transition temperature of the PA6T/6 is 60-120 ℃, and the melting point is less than 280 ℃.
In an alternative embodiment, the PA6T/6 is prepared by the following preparation method: dissolving PA6T salt, aliphatic lactam and an auxiliary agent in water, and heating to perform prepolymerization to obtain a prepolymer; then, carrying out solid phase tackifying on the prepolymer after vacuum drying to obtain PA6T/6;
preferably, the preparation of the prepolymer comprises the following steps: dissolving PA6T salt, aliphatic lactam and an auxiliary agent in water, heating to 200-280 ℃ at a heating rate of less than 20 ℃/min, preserving heat at 220-280 ℃ for 0.1-24 hours, maintaining pressure and exhausting for 0.1-12 hours at 1-5MPa, reducing pressure to normal pressure at a reducing rate of less than 1MPa/min, and reacting for 0.1-12 hours at normal pressure;
preferably, the solid-phase tackifying treatment of the prepolymer comprises the following steps: the prepolymer starts to vacuumize after reacting for 0.1-36 hours under normal pressure, keeps the negative pressure of 2-500Pa, and discharges after reacting for 0.1-36 hours to obtain PA6T/6 resin;
preferably, the aliphatic lactam comprises one or more mixtures of caprolactam or laurolactam, the weight ratio of PA6T salt to aliphatic lactam being 50-80:20-50 parts; the auxiliary agent comprises a catalyst and a blocking agent; the catalyst is one or a mixture of more of phosphoric acid, phosphorous acid, hypophosphorous acid or salts or esters thereof, and the amount of the catalyst is 0.01-1% of the total weight of the PA6T salt and the aliphatic lactam; the end-capping agent is monocarboxylic acid, and the amount of the end-capping agent is 0.1-1% of the total weight of the PA6T salt and the aliphatic lactam.
In an alternative embodiment, the flame retardant is a flame retardant substance having flame retardant properties;
preferably, the flame retardant is a phosphorus-based or nitrogen-based flame retardant.
In an alternative embodiment, the flame retardant nylon composite further comprises a nucleating agent;
preferably, the nucleating agent comprises at least one of Bruggemann P22, crain CAV102 and Hangzhou N03 HF;
preferably, the nucleating agent is added in an amount of 0.1 to 0.6 parts.
The nucleating agent has the main effects of accelerating the crystallization speed and the crystallization degree of the material, thereby improving the forming speed of the material.
In an alternative embodiment, the flame retardant nylon composite further comprises a flame retardant synergist;
preferably, the flame retardant synergist comprises at least one of anhydrous boric acid and zinc stannate;
preferably, the flame retardant synergist is added in an amount of 0-10%.
In an alternative embodiment, the flame retardant nylon composite further comprises a reinforcing filler;
preferably, the reinforcing filler comprises at least one of glass fiber, basalt fiber, carbon fiber, organic fiber, wollastonite fiber, mica and talc,
preferably, the reinforcing filler is added in an amount of 0 to 50 parts.
In an alternative embodiment, the flame retardant nylon composite has a flame retardant rating of UL 94V-0.
In an alternative embodiment, the flame retardant nylon composite has a thin wall flow length greater than 30cm, a molding cycle less than 10s, and a tensile strength retention of greater than 80% at 100 ℃.
In a second aspect, the invention also provides a preparation method of the flame retardant nylon composite material, which comprises the following steps: and (3) mixing the components in proportion, adding the mixture into a hopper of a double-screw extruder, controlling the temperature of the double-screw extruder to 280-330 ℃, and carrying out melt mixing to form a granular composition, namely the flame-retardant nylon composite material.
In a third aspect, the invention also provides application of the flame-retardant nylon composite material in preparing electronic and electrical equipment and household appliances.
The features and capabilities of the present invention are described in further detail below with reference to examples.
Preparation of PA6T/6 (sample No. Polyamide A)
70KG PA6T salt, 30KG caprolactam, 20KG high-purity water, 0.5KG acetic acid and 0.1KG sodium hypophosphite are added into a 200L autoclave with mechanical stirring and vacuumizing, the temperature is evenly increased to 220 ℃ for 2 hours, the temperature is kept constant for 2 hours at 220 ℃, then the pressure is maintained and exhausted for 3 hours under 2MPa, the pressure is reduced to normal pressure at 1MPa per hour, the vacuumizing is started after the reaction is carried out for half an hour under the normal pressure, the negative pressure is kept to-0.1 MPa for 1 hour, and the PA6T/6 resin is obtained after discharging. Through testing, the melting point of the resin is 275 ℃, and the viscosity is reduced: 1.2dl/g, glass transition temperature: 80 ℃. Sample number is: polyamide a.
Preparation of PA6T/6 (sample No. Polyamide B)
Adding 78KG PA6T salt, 22KG caprolactam, 20KG high-purity water, 0.5KG acetic acid and 0.1KG sodium hypophosphite into a 200L autoclave with mechanical stirring and vacuumizing, uniformly heating to 220 ℃ for 2 hours, keeping the temperature at 220 ℃ for 2 hours, keeping the pressure at 2MPa for 3 hours, exhausting the air for 3 hours, reducing the pressure to normal pressure at 1MPa per hour, reacting for half an hour at normal pressure, starting vacuumizing, keeping the negative pressure for-0.1 MPa for 1 hour, and discharging to obtain PA6T/6 resin. Through testing, the melting point of the resin is 310 ℃, and the reduced viscosity is as follows: 1.1dl/g, glass transition temperature: 90 ℃. Sample number is: polyamide B.
Preparation of PA6T/6 (sample No. Polyamide C)
22KG PA6T salt, 78KG caprolactam, 20KG high-purity water, 0.5KG acetic acid and 0.1KG sodium hypophosphite are added into a 200L autoclave with mechanical stirring and vacuumizing, the temperature is evenly increased to 220 ℃ for 2 hours, the temperature is kept constant for 2 hours at 220 ℃, then the pressure is maintained and exhausted for 3 hours under 2MPa, the pressure is reduced to normal pressure at 1MPa per hour, the vacuumizing is started after the reaction is carried out for half an hour under the normal pressure, and the PA6T/6 resin is obtained after the material is discharged after the negative pressure is kept for-0.1 MPa for 1 hour. Through testing, the melting point of the resin is 225 ℃, and the reduced viscosity is as follows: 1.2dl/g, glass transition temperature: 55 ℃. Sample number is: polyamide C.
Examples 1 to 5
The ingredients were mixed in the amount ratio shown in Table 1, and the resultant mixture was fed into a twin-screw extruder (CTE-50 machine, keplon mechanical Co., ltd.) with vent holes, the temperature of which was set at 320℃and melt-kneaded to form a granular composition. The evaluation results of the properties of the flame retardant polyamide composition are shown in Table 1.
Test method
1. The melting point and glass transition temperature test methods are referred to test standards ISO 11357-3-2018 and ISO 11357-2-2020.
2. The flame retardant rating test method is referred to UL 94V-0.
3. Thin-wall flow length testing method
The material is injection molded at +20deg.C above its melting point, and the molding die is a spiral die with thickness of 0.5mm and width of 10 mm. The flowability of the material is judged by reading the spiral length, and the better the flowability is, the longer the flow length is.
4. Retention of tensile Strength
Injector using in-table refining mechanismMold clamping force: 80 tons, screw diameter:) Using the polyamide composition obtained in the examples, a multi-functional test piece type A1 (dumbbell-shaped test piece described in JIS K7139) was produced by molding the polyamide composition using a T-type casting die at a die temperature of 80 ℃ with a barrel temperature of 20 to 30 ℃ higher than the melting point of the polyamide; 4mm thick, 170mm full length, 80mm parallel length, 10mm parallel width). The initial tensile strength (F0) of the material was tested with reference to test Standard ISO 527 after a constant time of 24 hours at 25℃and 50% RH humidity, and then with reference to test Standard ISO 527 after a constant time of 48 hours at 100℃F 1. Tensile strength retention = F1/F0 x 100%.
5. Reduced viscosity test method, refer to GB T12006.1-2009
6. Cycle of forming
The material was injection molded at +20deg.C above its melting point, with a molding die being a UL spline die 125mm long, 13mm wide and 0.8mm thick, which continuously and automatically produced 100 dies with a minimum time interval per die as the molding cycle.
Test results
The respective properties of the examples and comparative examples of the present invention were tested, and the results are shown in table 1 below.
Table 1 test results
Wherein PANT I1000 is high-performance nylon produced by Dezhongtai engineering plastics technology Co., ltd, and has a melting point of 270 ℃, a glass transition temperature of 125 ℃ and a reduced viscosity of 1dl/g.
PA66 EPR27 is PA66 resin produced by Shenma group, and has a melting point of 260 ℃, a glass transition temperature of 65 ℃ and a reduced viscosity of 1.53dl/g.
The fluidity of the flame-retardant nylon composite material prepared by the embodiment of the invention is mainly reflected by thin wall flow length, and longer the fluidity is proved to be better; the faster the molding cycle, the shorter the molding cycle; the high-temperature performance of the material is mainly reflected by the retention rate of the tensile strength under the high-temperature condition, and the higher the retention rate is, the better the temperature resistance of the material is. As can be seen from table 1 above: the use of PA6T/6 materials with melting points greater than 280 ℃ or glass transition temperatures below 60 ℃ in comparative example 1 or comparative example 4 does not meet the performance requirements; in comparative example 2, the melting point and glass transition temperature were not satisfactory nor were the expected performance requirements satisfied; in comparative example 3, although the melting point and glass transition temperature of the nylon material reach the standards, the nylon material is not PA6T/6 material, but also fails to meet the expected performance requirements, and in comparative example 5 (extrusion temperature is 350 ℃) the flame-retardant nylon composite material prepared by the preparation method of the embodiment of the invention also fails to meet the expected performance requirements.
In summary, the embodiment of the invention provides a flame-retardant nylon composite material, and a preparation method and application thereof. The flame-retardant nylon composite material comprises the following components in percentage by mass: 70-95 parts of PA6T/6 and 5-30 parts of flame retardant, wherein the glass transition temperature of PA6T/6 is 60-120 ℃, the melting point is less than 280 ℃, the flame retardant nylon composite material provided by the method adopts PA6T/6 material with specific glass transition temperature and melting point as main resin, and the flame retardant is added into the main resin, so that the nylon flame retardant material with high temperature resistance, high processing fluidity and short molding cycle can be prepared, and the product requirement of the electronic and electric industry is met.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The flame-retardant nylon composite material is characterized by comprising the following components in parts by mass: 70-95 parts of PA6T/6 and 5-30 parts of flame retardant, wherein the glass transition temperature of the PA6T/6 is 80 ℃, the melting point is 275 ℃, and the melting point and the glass transition temperature of the PA6T/6 are obtained by testing according to test standards ISO 11357-3-2018 and ISO 11357-2-2020; wherein:
the PA6T/6 is prepared by the following preparation method: dissolving PA6T salt, aliphatic lactam and an auxiliary agent in water, heating to 200-280 ℃ at a heating rate of less than 20 ℃/min, preserving heat at 220-280 ℃ for 0.1-24 and h, maintaining the pressure and exhausting for 0.1-12 hours at 1-5MPa, reducing the pressure to normal pressure at a reducing rate of less than 1MPa/min, and reacting for 0.1-12 hours at normal pressure to obtain a prepolymer, wherein: the aliphatic lactam is caprolactam, and the weight ratio of the PA6T salt to the aliphatic lactam is 70:30;
the prepolymer is vacuumized after being reacted for 0.1 to 36 hours under normal pressure, the negative pressure is kept at 2 to 500Pa, and the PA6T/6 resin is obtained after the reaction for 0.1 to 36 hours;
the preparation method of the flame-retardant nylon composite material comprises the following steps: and (3) mixing the components in proportion, and controlling the extrusion temperature of the double screws to 280-330 ℃ to obtain the flame-retardant nylon composite material.
2. The flame retardant nylon composite of claim 1, wherein the PA6T/6 has a glass transition temperature of 80 ℃ and a melting point of 275 ℃ in 80-90 parts and 10-20 parts of flame retardant.
3. The flame retardant nylon composite of claim 1, wherein the auxiliary comprises a catalyst and a capping agent; the catalyst is one or a mixture of more of phosphoric acid, phosphorous acid, hypophosphorous acid or salts or esters thereof, and the amount of the catalyst is 0.01-1% of the total weight of the PA6T salt and the aliphatic lactam; the end-capping agent is monocarboxylic acid, and the amount of the end-capping agent is 0.1-1% of the total weight of the PA6T salt and the aliphatic lactam.
4. The flame retardant nylon composite of claim 1, wherein the flame retardant is a phosphorus-based or nitrogen-based flame retardant.
5. The flame retardant nylon composite of claim 1, further comprising a nucleating agent.
6. The flame retardant nylon composite of claim 5, wherein the nucleating agent comprises at least one of bragg mann P22 and claway CAV 102.
7. The flame retardant nylon composite of claim 5, wherein the nucleating agent is added in an amount of 0.1 to 0.6 parts.
8. The flame retardant nylon composite of claim 1, further comprising a flame retardant synergist.
9. The flame retardant nylon composite of claim 8, wherein the flame retardant synergist comprises at least one of anhydrous boric acid, zinc stannate.
10. The flame retardant nylon composite of claim 8, wherein the flame retardant synergist is added in an amount of 0-10 parts.
11. The flame retardant nylon composite of claim 1, further comprising a reinforcing filler.
12. The flame retardant nylon composite of claim 11, wherein the reinforcing filler comprises at least one of glass fibers, basalt fibers, carbon fibers, organic fibers, wollastonite fibers, mica, and talc.
13. The flame retardant nylon composite of claim 11, wherein the reinforcing filler is added in an amount of 0 to 50 parts.
14. The flame retardant nylon composite of any one of claims 1-13, wherein the flame retardant nylon composite has a flame retardant rating of UL 94V-0, a thin wall flow length of greater than 30cm, a molding cycle of less than 10s, and a tensile strength retention of greater than 80% at 100 ℃.
15. Use of the flame retardant nylon composite according to any one of claims 1-14 in the preparation of electronic and electrical devices, household appliances.
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