CN113278286A - Halogen-free flame-retardant poly (p-phenylene terephthalamide) material, and preparation method and application thereof - Google Patents
Halogen-free flame-retardant poly (p-phenylene terephthalamide) material, and preparation method and application thereof Download PDFInfo
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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
- 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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- 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
Abstract
The invention provides a halogen-free flame-retardant polybutylene terephthalate material, a preparation method and application thereof. The material comprises the following components in percentage by weight: 50 to 70 portions of poly-p-phenylene terephthamide, 10 to 20 portions of polyamide, 10 to 15 portions of halogen-free flame retardant, 30 to 40 portions of glass fiber, 0.2 to 0.5 portion of antioxidant and 0.2 to 0.5 portion of lubricant. According to the halogen-free flame-retardant polybutylene terephthalate material provided by the invention, polyamide is added, so that the viscosity of polybutylene terephthalate is improved, the material flowability is improved, the processing temperature and the processing difficulty are greatly reduced, a novel halogen-free flame-retardant reinforced material is realized by selecting different flame-retardant systems, and the use requirements of more electronic and electrical industry fields (such as automobile connectors) can be met. Meanwhile, the halogen-free flame-retardant polybutylene terephthalate material provided by the invention has the advantages of mature preparation process, low cost, high profit and good economic benefit.
Description
Technical Field
The application relates to a halogen-free flame-retardant polybutylene terephthalate material, in particular to a preparation method of the halogen-free flame-retardant polybutylene terephthalate material and application of the material in an automobile high-temperature wire harness connector, belonging to the field of high polymer materials.
Background
Poly (butylene terephthalamide) (PA4T for short) PA4T is the first high-temperature nylon synthesized in the 21 st century, is derived from Tesmann who holds the only industrial scheme of butanediamine worldwide, and has the advantages of high rigidity, high heat resistance, high strength, high electrical property and the like. Similar to PA6T, the melting point is high (330 ℃), and the high-temperature-resistant resin has excellent space stability, lead-free welding compatibility, high melting point, high hardness and good mechanical strength under high temperature conditions, and has better performance than other high-temperature resins such as polyphthalamide (PPA), Liquid Crystal Polymer (LCP) and the like.
The PA4T material has high temperature resistance level due to high symmetry of molecular structure and high molecular weight, so that the PA4T material has poor fluidity during processing, and is difficult to process. At present, the domestic technology for modifying the poly (butylene terephthalamide) is very few, and basically, a feasible and simple-operation modification technology cannot be found. Special technological parameters are required to be used, the performance of machine equipment is good, and screw combination is reasonable. Therefore, how to provide a halogen-free flame-retardant polybutylene terephthalate composite material with good fluidity, easy processing, lower cost and excellent material performance is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant polybutylene terephthalate material, a preparation method and application thereof, aiming at overcoming the defects in the prior art, improving the flowability of the halogen-free flame-retardant polybutylene terephthalate by adding polyamide (PA66), modifying the polybutylene terephthalate by using the halogen-free flame-retardant modified polybutylene terephthalate, and providing a novel polybutylene terephthalate material with good flowability, high strength, halogen-free flame retardance and good processing formability.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the halogen-free flame-retardant polybutylene terephthalate material comprises the following components in percentage by weight:
wherein the halogen-free flame retardant is at least one selected from melamine (MC-30), diethylhypophosphite (8003), red phosphorus (FR9240) and melamine pyrophosphate (MPP).
Optionally, the upper limit of the amount of the polybutylene terephthalamide (PA4T) is selected from 55 parts, 60 parts, 65 parts and 70 parts; the lower limit of the amount of the polybutylene terephthalamide (PA4T) is selected from 50 parts, 55 parts, 60 parts and 65 parts.
Optionally, the upper limit of the amount of the polyamide (PA66) is selected from 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts; the lower limit of the amount of the polyamide (PA66) is selected from the group consisting of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts and 19 parts.
Optionally, the upper limit of the amount of the halogen-free flame retardant is selected from 11 parts, 12 parts, 13 parts, 14 parts and 15 parts; the lower limit of the amount of the halogen-free flame retardant is selected from 10 parts, 11 parts, 12 parts, 13 parts and 14 parts.
Optionally, the upper limit of the amount of the glass fiber is selected from 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts; the lower limit of the amount of the glass fiber is selected from the group consisting of 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts and 39 parts.
Optionally, the antioxidant is present in an amount of 0.2 parts.
Optionally, the antioxidant is present in an amount of 0.3 parts.
Optionally, the antioxidant is present in an amount of 0.4 parts.
Optionally, the antioxidant is present in an amount of 0.5 parts.
Optionally, the lubricant is present in an amount of 0.2 parts.
Optionally, the lubricant is present in an amount of 0.3 parts.
Optionally, the lubricant is present in an amount of 0.4 parts.
Optionally, the lubricant is present in an amount of 0.5 parts.
Optionally, the antioxidant is prepared by mixing a main antioxidant and a secondary antioxidant according to a weight ratio of 1: 1.
Optionally, the primary antioxidant is selected from hindered phenol type antioxidants.
Optionally, the secondary antioxidant is selected from hindered phenol type antioxidants.
Optionally, the primary antioxidant is selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester.
Optionally, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite.
In a more specific embodiment, the halogen-free flame-retardant polybutylene terephthalate material comprises 50 parts of polybutylene terephthalate, 10 parts of polyamide, 10 parts of flame retardant, 30 parts of glass fiber, 0.3 part of antioxidant 1010, 0.3 part of antioxidant 168, 0.3 part of lubricant and 0.3 part of siloxane.
Optionally, the lubricant comprises an internal lubricant and an external lubricant.
Optionally, the internal lubricant is selected from at least one of a fatty acid amide type lubricant and a hydrocarbon type lubricant.
Optionally, the external lubricant is selected from non-polar lubricants.
Optionally, the fatty acid amide lubricant is selected from at least one of N, N' -bis-ethylene-stearyl fatty acid amide (TAF) and stearic acid amide.
Optionally, the hydrocarbon lubricant is selected from at least one of paraffin wax, polyethylene wax, and polypropylene wax.
Optionally, the non-polar lubricant is selected from silicones.
The preparation method of the halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
(1) and (3) drying treatment: drying polybutylene telephthalamide in a vacuum dehumidifying dryer for 3-5h at the temperature of 110-130 ℃ to prepare dried polybutylene telephthalamide; and drying the polyamide for 3-5h in a universal blast type dryer at the temperature of 90-100 ℃ to obtain the dried polyamide.
(2) Preparation of mixture A: putting the polybutylene telephthalide and polyamide dried in the step (1) into a high-speed mixer, uniformly mixing, adding a lubricant and an antioxidant, and continuously mixing for 2-4min to obtain a mixture A;
(3) preparation of mixture B: drying the flame retardant at 90-100 ℃ for 2-3h, adding the flame retardant into the mixture A, and mixing at high speed for 3-5min to obtain a mixture B;
(4) and (3) granulation treatment: and putting the mixture B and the auxiliary agent into a double-screw extruder, and filling, reinforcing, extruding and granulating the glass fiber through double-stage side feeding to obtain the halogen-free flame-retardant polybutylene telephthalamide material.
Optionally, the temperature of each section of the twin-screw extruder in the step (4) is set as follows:
the temperature of the first zone is 270-290 ℃, the temperature of the second zone is 310-340 ℃, the temperature of the third zone is 310-340 ℃, the temperature of the fourth zone is 310-340 ℃, the temperature of the fifth zone is 290-310 ℃, the temperature of the sixth zone is 250-280 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 240-260 ℃ and the temperature of the machine head is 290-310 ℃.
Optionally, the extrusion time of the twin-screw extruder is 1-2 minutes.
Optionally, the pressure in the twin-screw extruder is 10-15 MPa.
The halogen-free flame-retardant polybutylene telephthalamide material or the prepared halogen-free flame-retardant polybutylene telephthalamide material is applied to a connector.
Optionally, the halogen-free flame-retardant polybutylene telephthalamide material is applied to an automobile high-temperature wiring harness connector.
The invention adopts polybutylene telephthalamide and polyamide, and adds filling reinforcement, flame retardant, antioxidant and lubricant to modify polybutylene telephthalamide and polyamide in molten state.
The material can achieve a good flame retardant effect due to the addition of the flame retardant, the PA4T material can partially replace LCP in the connector industry due to the excellent temperature resistance and comprehensive performance, and the flame retardant effect of VO can be achieved due to the fact that less flame retardant can be added due to the fact that the PA4T has relatively high oxygen index, and the flame retardant is a halogen-free flame retardant: melamine (MC-30), diethyl hypophosphite (8003), red phosphorus (FR9240) and melamine pyrophosphate (MPP) are added in different types, and the optimal flame retardant is selected to achieve the optimal flame retardant effect.
The addition of glass fibers in the present application can greatly improve the overall performance of the material, which is common knowledge.
The antioxidant is added to prevent the added additives caused by decomposition of some additives or thermal oxidative decomposition of raw materials due to higher processing temperature of the material and overhigh machine temperature caused by frictional heat generation of the material in a machine screw in the processing process of the material, so that the modification can be promoted better and the modification processing is easier. The antioxidant adopted by the invention is divided into a main antioxidant and an auxiliary antioxidant according to the weight ratio of 1:1, wherein the main antioxidant is hindered phenol antioxidant tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (code: 1098), and the secondary antioxidant is hindered phenol antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (code: 168).
The lubricant in the application mainly has the function of being added into materials to enable other auxiliary agents and raw materials to be better dispersed, and the lubricant comprises an internal lubricant and an external lubricant or is a composite lubricant formed by the internal lubricant and the external lubricant. Wherein the internal lubricant may be a fatty acid amide type lubricant or a hydrocarbon type lubricant and the external lubricant may be a non-polar lubricant. Fatty acid amide lubricants include N, N' -diethenylstearyl fatty acid amide (TAF), stearic acid amide; hydrocarbon lubricants include paraffin wax, polyethylene wax or polypropylene wax; the non-polar lubricant may be a silicone.
Compared with the prior art, the invention has the advantages that: according to the halogen-free flame-retardant polybutylene terephthalate material provided by the invention, polyamide is added, so that the viscosity of polybutylene terephthalate is improved, the material flowability is improved, the processing temperature and the processing difficulty are greatly reduced, a novel halogen-free flame-retardant reinforced material is realized by selecting different flame-retardant systems, and the use requirements of more electronic and electrical industry fields (such as automobile connectors) can be met. The PA4T reinforced modified material provided by the invention has the advantages of mature preparation process, low cost, high profit and good economic benefit, and the PA4T halogen-free flame retardant material has few modification technologies in China and is immature in technology, is basically monopolized by foreign DSM companies, causes high price in China, cannot be developed in the application field, and lays a solid foundation for industrialization of the material in future.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
Poly (butylene terephthalamide) is a material of high crystallinity, selected from raw materials of the Dusmann (DSM) Netherlands.
The polyamide material is PA66, and in consideration of fluidity, stability and low water absorption, the PA66 EPR27 raw material of Hippocampus Temminck is adopted.
The glass fiber is specially used for high-temperature nylon materials such as PA4T and the like, and the glass fiber type is as follows: short glass fiber 301HP produced by Chongqing composite glass fiber factories.
The technical solution of the present invention is further explained below with reference to several examples.
Example 1
Weighing 50 parts of polybutylene terephthalate (PA4T), 10 parts of polyamide (PA66), 0 part of flame retardant MC-3010 part, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1098 and 168 parts, and 0.3 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material comprises the following steps:
a. weighing raw materials, namely polybutylene terephthalate (110 ℃ for 4 hours) and polyamide (90 ℃ for 4 hours), respectively drying the raw materials, drying the polybutylene terephthalate by adopting a vacuum dehumidification dryer, and drying the polyamide by adopting a general blast dryer;
b. adding fully dried poly (butylene terephthalamide) and polyamide into a high-speed mixer, adding a lubricant and an antioxidant, and carrying out high-speed mixing for about 2 min;
c. putting the flame retardant into a drying oven, drying for 2 hours at 90 ℃, and then adding the flame retardant into the mixed materials for fully mixing for about 3 min;
d. and (3) putting the fully mixed raw materials and the auxiliary agent into a double-screw extruder, and filling, reinforcing, extruding and granulating the glass fibers by double-stage side feeding to obtain the halogen-free flame-retardant polybutylene telephthalamide material.
Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 270 ℃, the temperature of the second zone is 310 ℃, the temperature of the third zone is 310 ℃, the temperature of the fourth zone is 310 ℃, the temperature of the fifth zone is 290 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃ and the temperature of the machine head is 290 ℃. The residence time in the twin-screw extruder was 2 minutes and the pressure was 15 megapascals (MPa).
Example 2
Weighing 60 parts of polybutylene terephthalate (PA4T), 10 parts of polyamide (PA66), 0.3 part of flame retardant FR 924012, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1098 and 168 and 0.3 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material comprises the following steps:
a. weighing raw materials, namely polybutylene terephthalate (120 ℃ for 4 hours) and polyamide (100 ℃ for 4 hours), respectively drying the raw materials, drying the polybutylene terephthalate by adopting a vacuum dehumidification dryer, and drying the polyamide by adopting a general blast dryer;
b. adding fully dried poly (butylene terephthalamide) and polyamide into a high-speed mixer, adding a lubricant and an antioxidant, and carrying out high-speed mixing for about 3 min;
c. putting the flame retardant into a drying oven, drying for 3 hours at 95 ℃, and then adding the flame retardant into the mixed materials for fully mixing for about 4 min;
d. and (3) putting the fully mixed raw materials and the auxiliary agent into a double-screw extruder, and filling, reinforcing, extruding and granulating the glass fibers by double-stage side feeding to obtain the halogen-free flame-retardant polybutylene telephthalamide material.
The temperature of each section of the twin-screw extruder is set as follows:
the temperature of the first zone is 280 ℃, the temperature of the second zone is 320 ℃, the temperature of the third zone is 320 ℃, the temperature of the fourth zone is 310 ℃, the temperature of the fifth zone is 300 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃ and the temperature of the head is 300 ℃. According to the preparation method, the residence time in the double-screw extruder is 2 minutes, and the pressure in the double-screw extruder is 16 MPa.
Example 3
Weighing 60 parts of polybutylene terephthalate (PA4T), 15 parts of polyamide (PA66), 800313 parts of flame retardant, 30 parts of short glass fiber 301HP, 0.3 part of antioxidant 1098 and 168, and 0.3 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material comprises the following steps:
a. weighing raw materials, namely polybutylene terephthalate (at 130 ℃ for 4 hours) and polyamide (at 100 ℃ for 3 hours), respectively drying the raw materials, drying the polybutylene terephthalate by adopting a vacuum dehumidification dryer, and drying the polyamide by adopting a general blast dryer;
b. adding fully dried poly (butylene terephthalamide) and polyamide into a high-speed mixer, adding a lubricant and an antioxidant, and carrying out high-speed mixing for about 3 min;
c. putting the flame retardant into a drying oven, drying for 3 hours at 100 ℃, and then adding the flame retardant into the mixed materials for fully mixing for about 4 min;
d. and (3) putting the fully mixed raw materials and the auxiliary agent into a double-screw extruder, and filling, reinforcing, extruding and granulating the glass fibers by double-stage side feeding to obtain the halogen-free flame-retardant polybutylene telephthalamide material.
The temperature of each section of the double-screw extruder is set as follows:
the temperature of the first zone is 290 ℃, the temperature of the second zone is 320 ℃, the temperature of the third zone is 330 ℃, the temperature of the fourth zone is 330 ℃, the temperature of the fifth zone is 290 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃ and the temperature of the machine head is 300 ℃. According to the preparation method, the residence time in the double-screw extruder is 2 minutes, and the pressure in the double-screw extruder is 15 MPa.
Example 4
Weighing 50 parts of polybutylene terephthalate (PA4T), 10 parts of polyamide (PA66), 800310 parts of flame retardant, 301HP 30 parts of short glass fiber, 0.3 part of antioxidants 1098 and 168, and 0.3 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material comprises the following steps:
a. weighing raw materials, namely polybutylene terephthalate (at 130 ℃ for 3h) and oligoamide (at 100 ℃ for 4h), respectively drying the raw materials, drying the polybutylene terephthalate by using a vacuum dehumidification dryer, and drying the polyamide by using a general blast dryer;
b. adding fully dried poly (butylene terephthalamide) and polyamide into a high-speed mixer, adding a lubricant and an antioxidant, and carrying out high-speed mixing for about 3 min;
c. putting the flame retardant into a drying oven, drying for 3 hours at 90 ℃, and then adding the flame retardant into the mixed materials for fully mixing for about 3 min;
d. and (3) putting the fully mixed raw materials and the auxiliary agent into a double-screw extruder, and filling, reinforcing, extruding and granulating the glass fibers by double-stage side feeding to obtain the halogen-free flame-retardant polybutylene telephthalamide material.
Wherein the temperature of each section of the double-screw extruder is set as follows:
the temperature of the first zone is 300 ℃, the temperature of the second zone is 330 ℃, the temperature of the third zone is 340 ℃, the temperature of the fourth zone is 340 ℃, the temperature of the fifth zone is 300 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃ and the temperature of the machine head is 300 ℃. According to the preparation method, the residence time in the double-screw extruder is 1 minute, and the pressure in the double-screw extruder is 14 MPa.
Example 5
Weighing 50 parts of polybutylene terephthalate (PA4T), 10 parts of polyamide (PA66), 15 parts of flame retardant MPP, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1098 and 168 and 0.3 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material is the same as the example 1.
Example 6
Weighing 60 parts of polybutylene terephthalate (PA4T), 15 parts of polyamide (PA66), 0.3 part of flame retardant MC-3015 parts, 40 parts of short glass fiber 301HP, 0.3 part of antioxidants 1098 and 168 parts of lubricant TAF and 0.3 part of siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material is the same as the example 1.
Example 7
Weighing 60 parts of polybutylene terephthalate (PA4T), 20 parts of polyamide (PA66), 0.3 part of flame retardant FR 924015, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1098 and 168 and 0.3 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material is the same as the example 1.
Example 8
Weighing 60 parts of polybutylene terephthalate (PA4T), 10 parts of oligoamide (PA66), 0 part of flame retardant FR 924010 part, 35 parts of short glass fiber 301HP, 0.2 part of antioxidants 1098 and 168 and 0.4 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material is the same as the example 1.
Example 9
Weighing 50 parts of polybutylene terephthalate (PA4T), 15 parts of polyamide (PA66), 10 parts of flame retardant MPP, 40 parts of short glass fiber 301HP, 0.3 part of antioxidant 1098 and 168, and 0.3 part of lubricant TAF and siloxane according to parts by weight to prepare the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material is the same as the example 1.
Example 10
Weighing 60 parts of polybutylene terephthalate (PA4T), 20 parts of polyamide (PA66), 800315 parts of flame retardant, 40 parts of short glass fiber 301HP, 0.4 part of antioxidant 1098 and 168, and 0.5 part of lubricant TAF and siloxane according to parts by weight, and preparing the halogen-free flame-retardant polybutylene terephthalate material.
The method for preparing the halogen-free flame-retardant poly (butylene terephthalamide) material is the same as the example 1.
Example 11
The composite materials prepared in the above 10 examples were evaluated for properties using the following test methods, procedures, conditions and criteria.
Drying the granulated halogen-free flame-retardant polybutylene telephthalide material particles in a blast oven at 120-140 ℃ for 4-6 hours, and then carrying out injection molding on the dried particles on an 80T injection molding machine to prepare a sample, wherein the mold temperature is kept between 130-150 ℃ in the sample preparation process.
Tensile strength was tested according to ASTM-D638: specimen type is type I, specimen size (mm): 180 (length) × (12.68 ± 0.2) (neck width) × (3.23 ± 0.2) (thickness), and the drawing speed was 5 mm/min.
Flexural strength and flexural modulus were tested according to ASTM-D790: specimen type is specimen size (mm): (128. + -. 2) × (12.8. + -. 0.2) × (3.21. + -. 0.2), and the bending speed was 2 mm/min.
Notched impact strength was tested according to ASTM-D256: sample type is V-notch type, sample size (mm): (63 ± 2) × (12.58 ± 0.2) × (4.21 ± 0.2); the notch type is V-notch type, and the residual thickness of the notch is 2.44 mm.
Heat distortion temperature was tested according to ASTM-D648, with a load of 1.82MPa, a span of 100mm, specimen size (mm): (128. + -. 2) × (13. + -. 0.2) × (6.4. + -. 0.2), the maximum deformation amount was 0.25 mm.
Flame resistance test checked according to the international UL-94 standard, specimen size (mm): 3.2mm sample bar: (128 ± 2) × (12.8 ± 0.2) × (3.21 ± 0.2); 1.6mm specimen: (128. + -. 2) × (12.66. + -. 0.2) × (1.59. + -. 0.2).
The halogen-free flame-retardant polybutylene terephthalate materials prepared in the embodiments 1 to 7 of the application are subjected to performance tests and the results thereof are analyzed. For clear comparison, the following table 1 shows the raw material components of the composite materials of examples 1 to 7.
TABLE 1 example 1-7 halogen-free flame retardant polybutylene terephthalamide material weight parts (unit: parts)
| Composition (in parts) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| PA4T | 50 | 60 | 60 | 50 | 50 | 60 | 60 |
| PA66 | 10 | 10 | 15 | 10 | 10 | 15 | 20 |
| 301HP | 30 | 30 | 30 | 30 | 30 | 40 | 30 |
| Flame retardant | MC-30 | FR9240 | 8003 | 8003 | MPP | MC-30 | FR9240 |
| Content of flame retardant | 10 | 12 | 13 | 10 | 15 | 15 | 15 |
| Antioxidant 1098 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Antioxidant 168 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Internal lubricant | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| External lubricant | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
The performance of the halogen-free flame retardant polybutylene terephthalate materials of examples 1-7 was evaluated by the above-mentioned testing methods and procedures, and the results are shown in table 2 below.
Table 2 examples 1-7 performance test results of halogen-free flame retardant polybutylene terephthalate material
From the results in table 2, it can be seen that: under the condition that other conditions are unchanged or only small fluctuation is changed, after different flame retardants are added, the compatibility effect on the whole composite material system is different in degree and has very large influence. The selection of a proper flame retardant can directly reflect the great improvement of the comprehensive performance, and the dosage of the flame retardant also directly influences the flame retardant grade and the comprehensive performance. In comparison, the high-temperature resistant flame retardant and the glass fiber special for the high-temperature nylon have a crucial influence on the comprehensive performance of the whole formula system. Some flame retardants with a low thermal decomposition temperature, such as MC-25, can cause slight decomposition of the flame retardant due to the relatively high processing temperature, so that overall material performance is reduced. The test proves that the following components have the best effect according to the proportion: according to parts by weight, 50 parts of polybutylene terephthalate (PA4T), 10 parts of polyamide (PA66), 123010 parts of flame retardant OP, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1010 and 168, and 0.3 part of lubricant TAF and siloxane. According to the proportion, firstly, the most suitable domestic glass fiber is selected for reinforcing and modifying, the material is economical and easy to purchase, secondly, the high-temperature-resistant special flame retardant is selected, the proportion of the flame retardant is greatly reduced, the cost problem in the material modification process can be greatly reduced, and the polyamide is selected for mixing with the flame retardant, so that the material flowability is greatly improved, the processing difficulty is reduced, and the beneficial guarantee is provided for subsequent processing. Therefore, the proportion combination is the optimal combination selected, and simultaneously, the main problems to be discussed in the application are reflected, and the superiority and novelty of the patent are reflected.
The halogen-free flame-retardant polybutylene terephthalate material provided by the application can be well fused with a PA4T material due to the characteristics of good fluidity and similar molecular structure by adding the polyamide material, so that the fluidity of PA4T is greatly improved, the processing temperature is greatly reduced, and the processing is simplified. The flame retardant is selected from different types of flame retardants for flame retardant modification treatment, so that the optimal flame retardant is found out, the overall performance of the material is improved, a solid foundation is laid for large-scale mass production of the subsequent material in the field of connectors, a gap is filled in the field in China, and the material has a wider application prospect in China.
The application has the advantages that different flame retardant systems are selected, the comprehensive performance of the whole material system is influenced, the deep research on the modification of the halogen-free flame-retardant PA4T is realized, a solid foundation is laid for the subsequent processing and preparation of the material in the industries such as connectors and automobile high-temperature wire harness connectors, and the like, meanwhile, the preparation process is simple, the cost is low, the prepared halogen-free flame-retardant modified polybutylene telephthalamide with high performance and low cost can also be widely applied to various fields, the prospect is wider, and good economic benefits can be obtained. The method makes fundamental contribution to the modification, research and development and mass production of the material in China in future, so that the material can be accepted by the market more quickly, and the situation that foreign companies monopolize the market is broken.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The halogen-free flame-retardant polybutylene terephthalate material is characterized by comprising the following components in percentage by weight:
wherein the halogen-free flame retardant is at least one selected from melamine, diethyl hypophosphite, red phosphorus and melamine pyrophosphate.
2. The halogen-free flame-retardant polybutylene terephthalate material as claimed in claim 1, wherein the antioxidant is prepared by mixing a main antioxidant and an auxiliary antioxidant in a weight ratio of 1: 1;
preferably, the primary antioxidant is selected from hindered phenol type antioxidants;
preferably, the secondary antioxidant is selected from hindered phenol type antioxidants;
preferably, the primary antioxidant is selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester;
preferably, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite.
3. The halogen-free flame-retardant polybutylene telephthalamide material according to claim 1, wherein the material comprises 50 parts of polybutylene telephthalamide, 10 parts of polyamide, 10 parts of flame retardant, 30 parts of glass fiber, 0.3 part of antioxidant 1010, 0.3 part of antioxidant 168, 0.3 part of lubricant and 0.3 part of siloxane.
4. The halogen-free flame retardant polybutylene terephthalate material as claimed in claim 1, wherein the lubricant comprises an internal lubricant and an external lubricant,
preferably, the internal lubricant is selected from at least one of a fatty acid amide type lubricant and a hydrocarbon type lubricant;
preferably, the external lubricant is selected from non-polar lubricants;
preferably, the fatty acid amide lubricant is selected from at least one of N, N' -diethenylstearyl fatty acid amide and stearic acid amide;
preferably, the hydrocarbon lubricant is selected from at least one of paraffin wax, polyethylene wax and polypropylene wax;
preferably, the non-polar lubricant is selected from silicones.
5. A method for preparing the halogen-free flame-retardant polybutylene terephthalate material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) and (3) drying treatment: drying polybutylene telephthalamide in a vacuum dehumidifying dryer for 3-5h at the temperature of 110-130 ℃ to prepare dried polybutylene telephthalamide; and drying the polyamide for 3-5h in a universal blast type dryer at the temperature of 90-100 ℃ to obtain the dried polyamide.
(2) Preparation of mixture A: putting the polybutylene telephthalide and polyamide dried in the step (1) into a high-speed mixer, uniformly mixing, adding a lubricant and an antioxidant, and continuously mixing for 2-4min to obtain a mixture A;
(3) preparation of mixture B: drying the flame retardant at 90-100 ℃ for 2-3h, adding the flame retardant into the mixture A, and mixing at high speed for 3-5min to obtain a mixture B;
(4) and (3) granulation treatment: and putting the mixture B and the auxiliary agent into a double-screw extruder, and filling, reinforcing, extruding and granulating the glass fiber through double-stage side feeding to obtain the halogen-free flame-retardant polybutylene telephthalamide material.
6. The method for preparing the halogen-free flame-retardant polybutylene terephthalate material as claimed in claim 5, wherein the temperature of each section of the twin-screw extruder in the step (4) is set as follows:
the temperature of the first zone is 270-290 ℃, the temperature of the second zone is 310-340 ℃, the temperature of the third zone is 310-340 ℃, the temperature of the fourth zone is 310-340 ℃, the temperature of the fifth zone is 290-310 ℃, the temperature of the sixth zone is 250-280 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 240-260 ℃ and the temperature of the machine head is 290-310 ℃.
7. The preparation method of the halogen-free flame-retardant polybutylene terephthalate material as claimed in claim 5, wherein the extrusion time of the twin-screw extruder is 1-2 minutes;
preferably, the pressure in the double-screw extruder is 10-15 MPa.
8. The method for preparing the non-halogen flame-retardant polybutylene terephthalate material as claimed in claim 5, wherein the non-halogen flame retardant is at least one selected from melamine, diethylphosphinate, red phosphorus and melamine pyrophosphate;
preferably, the antioxidant is formed by mixing a main antioxidant and a secondary antioxidant according to the weight ratio of 1: 1;
preferably, the primary antioxidant is selected from hindered phenol type antioxidants;
preferably, the secondary antioxidant is selected from hindered phenol type antioxidants;
preferably, the primary antioxidant is selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester;
preferably, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite;
preferably, the lubricant comprises an inner lubricant and an outer lubricant;
preferably, the internal lubricant is selected from at least one of a fatty acid amide type lubricant and a hydrocarbon type lubricant;
preferably, the external lubricant is selected from non-polar lubricants;
preferably, the fatty acid amide lubricant is selected from at least one of N, N' -diethenylstearyl fatty acid amide and stearic acid amide;
preferably, the hydrocarbon lubricant is selected from at least one of paraffin wax, polyethylene wax and polypropylene wax;
preferably, the non-polar lubricant is selected from silicones.
9. Use of the halogen-free flame-retardant polybutylene terephthalate material as defined in any one of claims 1 to 4 or the halogen-free flame-retardant polybutylene terephthalate material as defined in any one of claims 5 to 8 in a connector.
10. Use according to claim 9, wherein the halogen-free flame retardant polybutylene terephthalate material is used in automotive high temperature wiring harness connectors.
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| CN102408707A (en) * | 2011-06-24 | 2012-04-11 | 深圳市科聚新材料有限公司 | Glass fiber strengthened poly-hexamethylene terephthalamide material and preparation method thereof |
| CN103534313A (en) * | 2011-05-13 | 2014-01-22 | 帝斯曼知识产权资产管理有限公司 | Flame retardant semi-aromatic polyamide composition and moulded products made therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103534313A (en) * | 2011-05-13 | 2014-01-22 | 帝斯曼知识产权资产管理有限公司 | Flame retardant semi-aromatic polyamide composition and moulded products made therefrom |
| CN102408707A (en) * | 2011-06-24 | 2012-04-11 | 深圳市科聚新材料有限公司 | Glass fiber strengthened poly-hexamethylene terephthalamide material and preparation method thereof |
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