CN114395124A - Polyamide composite material and synthetic method thereof - Google Patents
Polyamide composite material and synthetic method thereof Download PDFInfo
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- CN114395124A CN114395124A CN202210147231.XA CN202210147231A CN114395124A CN 114395124 A CN114395124 A CN 114395124A CN 202210147231 A CN202210147231 A CN 202210147231A CN 114395124 A CN114395124 A CN 114395124A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
The invention discloses a polyamide composite material and a synthesis method thereof, wherein the polyamide composite material is synthesized by the following raw materials: hexamethylene diamine, terephthalic acid, caprolactam, a reactive phosphorus flame retardant, coated melamine cyanurate and tetramethyl piperidine amine. The polyamide composite material has excellent mechanical property and flame retardant property, and can be applied to high-temperature resistant flame retardant components of electronics, electrics, automobiles, 5G and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polyamide composite material and a synthetic method thereof.
Background
With the environmental protection concept being further into the mind and the promulgation and implementation of a series of environmental regulations at home and abroad, safe and environment-friendly high-performance materials are receiving increasing attention from people. The notification of the ban on decabromodiphenyl oxide (DBDPO) by RoHS as in 2008 was overruled by the european court; the flame-retardant product identification management method approved by fire department of European ministry of public Security sets higher requirements on flame-retardant modification and harmlessness of high polymer materials in 2007 5-1.5.
Polyamides belong to a class of flammable resins, commonly used PA1010, PA66 and PA6 having oxygen indices of 25.5, 24.3 and 26.4, respectively. Lower values necessitate flame retardant modifications, especially for use in electrical related products. Semi-aromatic polyamides, despite the introduction of aromatic ring structures which are easily carbonizable and have improved flame retardancy, are still not self-extinguishing and require modification.
There are two main ways of flame retarding polyamides: (1) blending and flame-retardant modification. In this process, the flame retardant is homogeneously mixed into the polyamide by mechanical mixing, so that flame retardancy is obtained. The method is relatively simple, is suitable for most polymers, has good effect, and is a main polyamide flame-retardant method. The additive flame retardant mainly comprises decabromodiphenyl ether, aluminum hypophosphite and the like. (2) And (3) in-situ polymerization flame-retardant modification. In the process, a reaction monomer with a flame-retardant effect is grafted on the main chain or the side chain of the polyamide through in-situ polymerization, so that the molecular-level flame-retardant effect is achieved. Its advantages are low toxicity, high stability, basically no volatile matter in product, and less influence to service performance of material.
Currently, some studies on flame retardant polyamide materials are made in the prior art, such as: chinese patent CN 107603214a provides a flame retardant polyamide composition comprising: (A) polyamide, and (B) 5 to 40% of a flame retardant, the percentages being percentages by mass relative to the polyamide; the polyamide has a melting point of over 230 ℃ and a weight-average molecular weight of 25000-40000, and belongs to blending flame-retardant modification; chinese patent CN 102532600A provides a melamine salt flame retardant, a flame-retardant polyamide film added with the flame retardant and a preparation method thereof. The flame retardant is melamine phosphonate containing a tetrahydrofuran ring structure, the viscosity of polyamide is not reduced by adding the melamine salt flame retardant, the obtained film has excellent comprehensive performance and no environmental pollution, the preparation method is simple and is beneficial to industrial production, and the patent belongs to blending flame retardant modification; chinese patent CN 111607221A provides an in-situ coated red phosphorus flame retardant, a flame-retardant polyamide material based on the in-situ coated red phosphorus flame retardant and a preparation method thereof, red phosphorus powder and caprolactam monomers are used as raw materials, the caprolactam monomer is activated, then the caprolactam reacts and polymerizes on the surface of the red phosphorus powder in the presence of a cocatalyst, and the microcapsule coated red phosphorus flame retardant is prepared, and the flame-retardant polyamide material is prepared by extruding 40-68% of polyamide, 6-12% of the in-situ coated red phosphorus flame retardant, 20-50% of glass fiber, 0.2-1.0% of stabilizer and 0.1-0.7% of lubricant by a double-screw extruder according to the weight ratio, wherein the patent belongs to in-situ compatibilization flame-retardant modification by the double-screw extruder; chinese patent CN 105153415A provides a flame-retardant nylon 66 copolymer material and a preparation method thereof, in particular to a phosphorus-containing reactive flame retardant, a block flame-retardant nylon 66 copolymer material is obtained by polymerization reaction and a preparation method thereof. The preparation method is characterized in that a flame retardant is reacted with diamine or dihydric alcohol to obtain a flame retardant prepolymer, and then the flame retardant prepolymer is reacted with a nylon 66 prepolymer to obtain a flame-retardant nylon 66 copolymer material, wherein the patent belongs to in-situ polymerization flame-retardant modification.
When polyamide is modified by blending and flame retarding, the difference of compatibility exists between the flame retardant and polyamide macromolecules, so that the agglomeration and precipitation of the flame retardant are easily caused, and in the blending process, the defects that the phosphorus-nitrogen flame retardant is not easily uniformly dispersed in base material resin and the addition amount is large exist; the problem can be well solved by screening proper flame retardants and carrying out in-situ polymerization flame-retardant modification.
Disclosure of Invention
Based on the above, one of the objects of the present invention is to provide a polyamide composite material, which can effectively solve the problems that the phosphorus-nitrogen flame retardant is not easily uniformly dispersed in the base resin and the amount of the phosphorus-nitrogen flame retardant is large in the blending process by introducing the flame retardant unit reaction type phosphorus flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid and the nitrogen flame retardant coated melamine cyanurate into the polymerization process of hexamethylenediamine, terephthalic acid and caprolactam monomers. The polyamide composite material can be applied to high-temperature-resistant flame-retardant components such as electronics, electrics, automobiles, 5G and the like.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
the polyamide composite material is prepared from the following raw materials in parts by weight:
the reactive phosphorus flame retardant is 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid;
the coated melamine cyanurate is the melamine cyanurate coated by the silica sol; the silica sol is prepared from the following components in a mass ratio of 1: 5-7: 0.07-0.1 of tetraethyl orthosilicate, deionized water and hydrochloric acid.
In some embodiments, the polyamide composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the polyamide composite material is prepared from the following raw materials in parts by weight:
in some of these embodiments, the method for preparing the encapsulated melamine cyanurate comprises the following steps: dissolving melamine cyanurate in a reaction kettle filled with absolute ethyl alcohol, then adding silica sol which accounts for 7-13 wt% of the mass of the melamine cyanurate, heating the reaction kettle to 85-95 ℃, stirring and reacting for 3-5 hours, and then filtering, drying and crushing to obtain the coated melamine cyanurate.
In some of these embodiments, the silica sol is prepared from a mixture of silica sol and silica sol in a mass ratio of 1: 5.5-6.5: 0.08-0.09 of tetraethyl orthosilicate, deionized water and hydrochloric acid.
In some embodiments, the silica sol is added in an amount of 9-11% by mass of the melamine cyanurate.
In some of these embodiments, the temperature of the reaction kettle is between 89 ℃ and 91 ℃.
In some embodiments, the stirring speed of the stirring reaction is 35r/min to 45r/min, and the stirring reaction time is 3.5 hours to 4.5 hours.
Another object of the present invention is to provide a method for synthesizing the above polyamide composite material.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
a synthetic method of a polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated melamine cyanurate, tetramethylpiperidine amine and a proper amount of water; then vacuumizing for 3-7 min, introducing nitrogen for 3-7 min, circulating for 4-8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1-0.4 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to be 30 r/min-50 r/min, heating the stirring type polymerization reactor to 270-280 ℃ in a sealed and uniform manner within 2-4 hours, deflating to 2.3MPa when the temperature of the stirring type polymerization reactor reaches 225 ℃, maintaining the pressure at 2.3MPa, deflating to normal pressure after reacting for 1-2 hours (pre-polymerization reaction), simultaneously raising the temperature to 290-310 ℃, continuing to react for 0.5-1.5 hours at 290-310 ℃ (post-polymerization reaction), continuously vacuumizing for 0.1-1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
In some of these embodiments, the method for synthesizing the polyamide composite material comprises the steps of:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated melamine cyanurate, tetramethylpiperidine amine and a proper amount of water; then vacuumizing for 4-6 min, introducing nitrogen for 4-6 min, circulating for 5-7 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.2-0.3 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 35 r/min-45 r/min, heating the stirring type polymerization reactor to 273-277 ℃ in a sealed and uniform manner within 2.5-3.5 hours, deflating to 2.3MPa when the temperature of the stirring type polymerization reactor reaches 225 ℃, maintaining the pressure at 2.3MPa, deflating to normal pressure after reacting for 1.2-1.8 hours (pre-polymerization reaction), simultaneously raising the temperature to 295-305 ℃, continuing to react for 0.8-1.2 hours at 295-305 ℃ (post-polymerization reaction), continuously vacuumizing for 0.3-0.7 hours at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
The polyamide composite material of the invention has the following functions of the raw materials:
the polyamide has a polar oxygen index of 24.3-26.4% generally, a flame retardant grade of UL-94V-2, and a serious dripping phenomenon in a combustion process, flame retardant polyamide is obtained by adding a flame retardant into polyamide and blending and modifying the flame retardant polyamide, the process is mature, the operation is simple and convenient, but most of flame retardants are small molecules, the flame retardant polyamide has compatibility difference with polyamide polymers, the agglomeration and precipitation of the flame retardant are easily caused, the flame retardant is distributed unevenly in a resin matrix, particularly in miniature precise components in the electronic and electrical industry, the performance reduction caused by the precipitation of the flame retardant is remarkable, and the in-situ polymerization flame retardant high-temperature resistant polyamide can well avoid the problems. According to the invention, a flame-retardant unit reaction type phosphorus flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid and a nitrogen flame retardant coated melamine cyanurate are introduced in the polymerization process of monomers of hexamethylenediamine, terephthalic acid and caprolactam, and the reaction mechanism is that a flame-retardant monomer with a reaction functional group is copolymerized into the main chain of high-temperature resistant polyamide in an in-situ polymerization manner to realize molecular-level flame-retardant modification, so that the high-temperature resistant polyamide has intrinsic flame-retardant performance, and the problems that the phosphorus-nitrogen flame retardant is not easy to uniformly disperse in base material resin and the addition amount is large in the blending process can be effectively solved.
In the invention, the phosphorus-nitrogen flame retardant mainly performs flame retardance by the joint action of a condensed phase and a gas phase. The reactive phosphorus flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid is a novel phosphate flame retardant monomer which has high reactivity of carboxyl groups on two sides and can be copolymerized to a polyamide main chain, is flame-retardant mainly through a condensed phase, is thermally decomposed to generate PO & free radicals in the process of flame-retardant polyamide, and the PO & free radicals are further reacted to generate phosphoric acid, pyrophosphoric acid and the like to promote dehydration, carbonization or crosslinking of polyamide resin and inhibit exchange of heat and oxygen, and the PO & free radicals can capture radicals such as HO & the like which participate in free radical chain locking reaction in the combustion process to stop the combustion reaction; the coated melamine cyanurate is mainly flame-retardant through a gas phase, is decomposed into melamine and cyanuric acid through sublimation heat absorption in the process of flame-retardant polyamide, reduces the surface temperature of a polymer, is decomposed into incombustible gases such as water and ammonia gas, dilutes the oxygen concentration, inhibits combustion, and catalyzes polyamide resin to degrade into oligomers and take away heat in a molten drop form.
In order to solve the defects, tetraethyl orthosilicate is hydrolyzed to form a Si-O-Si network structure to coat the surface of melamine cyanurate, the interfacial compatibility of the melamine cyanurate and polyamide is improved, so that the coated melamine cyanurate is uniformly dispersed in the polyamide resin, and the charring property of the Si-O-Si network structure in the resin combustion process is utilized to improve the charcoal layer quality and improve the condensed phase flame retardant effect of the melamine cyanurate.
In the preparation of high temperature resistant polyamide copolymers, high temperature and high pressure environments are generally required. Under the environment, the high polymer is easily oxidized with oxygen in the air to destroy the molecular chain structure, the product has yellow color, performance is reduced and the like, the use of the product is seriously influenced, and the excessive addition of the inorganic antioxidant can cause the problems of antioxidant precipitation, electric breakdown and the like. Therefore, the invention adopts the end-capping agent tetramethylpiperidylamine with the anti-oxidation function, the main chain of the high-temperature resistant polyamide copolymer can be degraded and broken by thermal oxidation under the high-temperature state, and the main chain capped by the tetramethylpiperidylamine has the capabilities of capturing free radicals and decomposing hydroperoxide as hindered piperidyl can be wound on a high molecular chain, and has the regeneration function, so that the thermal-oxygen stability of the high-temperature resistant polyamide copolymer is improved, and the chain segment is not easy to degrade and break.
Compared with the prior art, the polyamide composite material and the synthesis method thereof provided by the invention have the following beneficial effects:
1. aiming at the problems that the fire retardant is easy to agglomerate and separate out due to the difference of compatibility between the fire retardant and polyamide macromolecules in the blending flame-retardant modification and the fire retardant is uneven in distribution in a resin matrix, the invention effectively solves the problems that the phosphorus-nitrogen fire retardant is difficult to uniformly disperse in the base material resin and the addition amount is large in the blending process by introducing the flame-retardant unit reaction type phosphorus fire retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid and the nitrogen fire retardant coated melamine cyanurate in the polymerization process of hexamethylenediamine, terephthalic acid and caprolactam monomers; the high-temperature resistant polyamide composite material with excellent mechanical property and flame retardant property is prepared by in-situ polymerization by adjusting the proportion of the raw materials of hexamethylene diamine, terephthalic acid, caprolactam, a reactive phosphorus flame retardant, coated melamine cyanurate and tetramethylpiperidylamine, and can be applied to high-temperature resistant flame retardant parts of electronics, electrics, automobiles, 5G and the like.
2. According to the synthetic method of the polyamide composite material, nitrogen is introduced before reaction, so that the probability of side reaction is reduced; adding a proper amount of water before reaction, thereby increasing the pressure in the kettle and the mass and heat transfer in the heating process; the reaction process is vacuumized, the low-molecular extractables generated in the polymerization reaction process are removed, the forward progress of the polymerization reaction is facilitated, and the performance of the polyamide composite material is not affected by the residual low-molecular extractables, so that the low-molecular extractables are separated without adopting additional extraction equipment, the time can be saved, and the energy can be saved; the synthesis method is simple, all reactions do not need to be carried out in a solvent, and the complex process of removing the solvent subsequently is omitted.
Drawings
FIG. 1 is a flow chart of the synthesis process of the polyamide composite material of the present invention.
FIG. 2 is a thermogravimetric plot of example 7 of the present invention and comparative example 2.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The reaction mechanism of the polyamide composite material of the present invention is as follows (see fig. 1 for a flow chart of the preparation process):
wherein a is 2-5, b is 50-150, c is 30-70, and R is 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid.
Mechanism of reaction
As can be seen from the reaction formula, (1)4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, hexamethylenediamine, terephthalic acid and caprolactam are polymerized in situ to obtain the intrinsic flame-retardant polyamide composite material; (2) the carboxyl end group of the polyamide composite material reacts with the amino end group of the end-capping reagent tetramethyl piperidine amine to ensure that the hindered piperidyl is polymerized on the main chain of the polyamide, and the hindered amine functional group has the capabilities of capturing free radicals and decomposing hydroperoxide and has a regeneration function, so that the thermal oxygen stability of the polyamide composite material is improved, and the chain segment is not easy to degrade and break.
The raw materials used in the examples and comparative examples of the present invention were as follows:
hexamethylenediamine, available from Shenma Nylon chemical, Inc.
Terephthalic acid, available from petrochemical Yangzi oil chemical Co., Ltd, China.
Caprolactam available from Zhongpetrochemical Balng petrochemical company.
4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, available from Doutox chemical industries, Inc.
Melamine cyanurate, available from Jinan Thaxane Fine chemical Co.
Tetraethyl orthosilicate, purchased from chemical agents, Inc., of the national pharmaceutical group.
Deionized water, self-made.
Hydrochloric acid, available from national pharmaceutical group chemical reagents, ltd.
Anhydrous ethanol, purchased from chemical reagents ltd, national pharmaceutical group.
Tetramethylpiperidinamine, available from Guangzhou chemical industries.
The coated melamine cyanurate used in the following examples and comparative examples was prepared by a process comprising the steps of: firstly, tetraethyl orthosilicate is added: deionized water: the mass ratio of the hydrochloric acid is 1: 6: 0.085 formulated as a silica sol. Dissolving 100g of melamine cyanurate in a reaction kettle filled with 800mL of absolute ethyl alcohol, then adding 10g of silica sol (10 wt% of the mass of the melamine cyanurate), raising the temperature of the reaction kettle to 90 ℃, stirring at 40r/min for reaction for 4 hours, and filtering, drying and crushing to obtain the coated melamine cyanurate.
The present invention will be described in detail with reference to specific examples.
Example 1 Polyamide composite Material and method for synthesizing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, tetramethylpiperidine amine and 200mL of water; then vacuumizing for 3min, introducing nitrogen for 3min, circulating for 8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to be 30r/min, sealing the stirring type polymerization reactor within 2 hours, heating to 270 ℃ at a constant speed, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after 2 hours of reaction (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 290 ℃, continuing to react for 1.5 hours at 290 ℃ (post-polymerization reaction), continuously vacuumizing for 0.1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Example 2 Polyamide composite Material and method for synthesizing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, tetramethylpiperidine amine and 200mL of water; then vacuumizing for 7min, introducing nitrogen for 7min, circulating for 4 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.4 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 50r/min, sealing the stirring type polymerization reactor within 4 hours, heating at a constant speed to 280 ℃, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1 hour (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 310 ℃, continuing to react for 0.5 hour (post-polymerization reaction) at 310 ℃, continuously vacuumizing for 1 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Example 3 Polyamide composite Material and method for synthesizing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, tetramethylpiperidine amine and 200mL of water; then vacuumizing for 4min, introducing nitrogen for 4min, circulating for 7 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.2 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 35r/min, heating the stirring type polymerization reactor to 273 ℃ within 2.5 hours in a sealed and uniform manner, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1.8 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 295 ℃, continuing to react for 1.2 hours (post-polymerization reaction) at 295 ℃, continuously vacuumizing for 0.3 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Example 4 Polyamide composite Material and method for synthesizing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, tetramethylpiperidine amine and 200mL of water; then vacuumizing for 6min, introducing nitrogen for 6min, circulating for 5 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.3 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 45r/min, heating the stirring type polymerization reactor to 277 ℃ within 3.5 hours in a sealed and uniform manner, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1.2 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 305 ℃, continuing to react for 0.8 hour (post-polymerization reaction) at 305 ℃, continuously vacuumizing for 0.7 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Example 5 Polyamide composite Material and method of Synthesis thereof
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, tetramethylpiperidine amine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, sealing the stirring type polymerization reactor within 3 hours, heating to 275 ℃ at a constant speed, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1.5 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 300 ℃, continuing to react for 1 hour at 300 ℃ (post-polymerization reaction), continuously vacuumizing for 0.5 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
EXAMPLE 6 Polyamide composite Material and method for synthesizing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, tetramethylpiperidine amine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, sealing the stirring type polymerization reactor within 3 hours, heating to 275 ℃ at a constant speed, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1.5 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 300 ℃, continuing to react for 1 hour at 300 ℃ (post-polymerization reaction), continuously vacuumizing for 0.5 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Example 7 Polyamide composite Material and method of Synthesis thereof
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, tetramethylpiperidine amine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, sealing the stirring type polymerization reactor within 3 hours, heating to 275 ℃ at a constant speed, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1.5 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 300 ℃, continuing to react for 1 hour at 300 ℃ (post-polymerization reaction), continuously vacuumizing for 0.5 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Comparative example 1
The polyamide composite material of the comparative example is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding ammonium polyphosphate, melamine cyanurate, tetramethyl piperidine amine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, sealing the stirring type polymerization reactor within 3 hours, heating to 275 ℃ at a constant speed, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1.5 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 300 ℃, continuing to react for 1 hour at 300 ℃ (post-polymerization reaction), continuously vacuumizing for 0.5 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
Comparative example 2
The polyamide composite material of the comparative example is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide composite material comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, sealing the stirring type polymerization reactor within 3 hours, heating to 275 ℃ at a constant speed, when the temperature of the stirring type polymerization reactor reaches 225 ℃, discharging gas to 2.3MPa, maintaining the pressure at 2.3MPa, after reacting for 1.5 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 300 ℃, continuing to react for 1 hour at 300 ℃ (post-polymerization reaction), continuously vacuumizing for 0.5 hour at constant temperature (tackifying reaction), finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
The following is a summary of the raw material compositions of examples 1-7 and comparative examples 1-2.
TABLE 1 summary of the raw material compositions of examples 1-7 and comparative examples 1-2
Remarking: a, replacing a reactive phosphorus flame retardant with ammonium polyphosphate; and b, replacing the coated melamine cyanurate with melamine cyanurate.
Examples 1 to 7 were conducted to prepare polyamide composite materials by adjusting the amounts of caprolactam, reactive phosphorus flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, coated melamine cyanurate, and tetramethylpiperidylamine, comparative examples 1 to 2 were polyamide composite materials prepared by replacing the type of flame retardant and not adding tetramethylpiperidylamine on the basis of the raw materials of example 7, in comparative example 1, the reactive phosphorus flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid was replaced with ammonium polyphosphate, the coated melamine cyanurate was replaced with melamine cyanurate, and in comparative example 2, tetramethylpiperidylamine was not added. The polyamide composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile strength: the tensile rate was 50mm/min according to the test of GB/T1040-2006 standard.
Limiting oxygen index: the test specimens were 80mm by 10mm by 4mm in size, tested according to GB/T2406.2-2009.
Vertical burning test: the test specimens were 125mm by 13mm by 0.8mm in size, tested according to the UL94 standard.
Intrinsic viscosity: tested according to GB/T1632-2008 standard, the solvent is concentrated sulfuric acid, and the testing temperature is 25 ℃.
Melting temperature: testing according to GB/T19466.3-2004 standard.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the polyamide composite materials of examples 1-7 and comparative examples 1-2
As can be seen from table 2:
the tensile strength, the intrinsic viscosity and the melting temperature of the polyamide composite material show a decreasing trend with increasing addition amounts of caprolactam and tetramethylpiperidylamine. The reason is that on one hand, the more the addition amount of caprolactam is, the less the proportion of benzene ring structures in rigid terephthalic acid is, the smaller the steric hindrance of polymer molecular chains is, and in the process of stretching the polyamide composite material by external force, the relative slippage among the polymer molecular chains is easy to occur, so that the tensile strength is reduced, on the other hand, the addition amount of the polymerization inhibitor tetramethylpiperidine amine is increased, and the terminal amino groups of the tetramethylpiperidine amine can react with the terminal carboxyl groups of polyamide, so that the effect of terminating the polymer molecular chain is achieved, so that the intrinsic viscosity of the polymer is reduced, and the van der waals force of the polymer is also reduced, so that in the process of stretching the polyamide composite material by external force, the relative slippage among the polymer molecular chains is easy to occur, so that the tensile strength is reduced. The more the addition amount of caprolactam is, the less the proportion of benzene ring structures in rigid terephthalic acid is, the smaller the steric hindrance of polymer molecular chains is, and the relative displacement of the polymer molecular chains can occur at a lower temperature, so that the melting temperature of the polymer is reduced.
With the decrease of the addition amount of the reactive phosphorus flame retardant 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid and the coated melamine cyanurate, the limiting oxygen index of the polyamide composite material shows a gradually decreasing change trend, and the vertical burning test (UL940.8mm) shows V0 grade. This is because the phosphorus-nitrogen-based flame-retardant polyamide is mainly flame-retardant by the interaction of the condensed phase and the gas phase. The reactive phosphorus flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid is a novel phosphate flame retardant monomer which has high reactivity of carboxyl groups on two sides and can be copolymerized to a polyamide main chain, is flame-retardant mainly through a condensed phase, is thermally decomposed to generate PO & free radicals in the process of flame-retardant polyamide, and the PO & free radicals are further reacted to generate phosphoric acid, pyrophosphoric acid and the like to promote dehydration, carbonization or crosslinking of polyamide resin and inhibit exchange of heat and oxygen, and the PO & free radicals can capture radicals such as HO & the like which participate in free radical chain locking reaction in the combustion process to stop the combustion reaction; the melamine cyanurate is mainly used for inflaming retarding through gas phase, melamine and cyanuric acid are decomposed through sublimation heat absorption in the process of inflaming retarding polyamide, the surface temperature of a polymer is reduced, non-combustible gases such as water, ammonia gas and the like are generated through decomposition, the oxygen concentration is diluted, combustion is inhibited, and polyamide resin is catalyzed to be degraded into oligomer and take away heat in a molten drop mode.
In conclusion, the polyamide composite material with excellent mechanical property and flame retardant property can be obtained by adjusting the addition amounts of caprolactam, the reactive phosphorus flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid, the coated melamine cyanurate and the tetramethylpiperidine amine under the synergistic cooperation of all the additives. Of these, the polyamide composite material of example 7 has the best overall properties.
Comparative example 1 in comparison to example 7, comparative example 1 replaced the reactive phosphorus based flame retardant 4- (2- (((2-carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid with ammonium polyphosphate and the coated melamine cyanurate with melamine cyanurate. Because the ammonium group particles of the ammonium polyphosphate have poor reactivity with the terminal carboxyl groups of the polyamide and the melamine cyanurate has poor dispersibility in the polyamide resin and is easy to agglomerate, the tensile strength and the limiting oxygen index of the polyamide composite material synthesized in comparative example 1 are lower than those of example 7.
Comparative example 2 in comparison to example 7, no tetramethylpiperidinamine was added to comparative example 2. The intrinsic viscosity of comparative example 2 is much higher than that of example 7, and thus, the processability of comparative example 2 is poor. In addition, when the high-temperature resistant polyamide copolymer is prepared, a high-temperature and high-pressure environment is usually required, and in the environment, the high polymer is easily oxidized by oxygen in the air, the molecular chain structure is damaged, the conditions of yellowing of the product, performance reduction and the like occur, and the use of the product is seriously influenced. Example 7 by using the blocking agent tetramethylpiperidylamine with antioxidant function, thermal oxidation can degrade and break the main chain of the high temperature resistant polyamide copolymer at high temperature, while the blocked main chain with tetramethylpiperidylamine can wind around the high molecular chain, and the blocked amine functional group has the ability of capturing free radicals and decomposing hydroperoxide and has regeneration function, so that the thermal oxygen stability of the high temperature resistant polyamide copolymer is improved and segment degradation and breaking are not easy to occur.
FIG. 2 is a thermogravimetric plot of example 7 and comparative example 2 of the present invention, and it can be seen from FIG. 2 that the initial thermal degradation temperature of example 7 is 441.7 deg.C, the maximum thermal weight loss rate temperature is 470.9 deg.C, and the terminal thermal degradation temperature is 490.3 deg.C, and the initial thermal degradation temperature of comparative example 2 is 436.1 deg.C, the maximum thermal weight loss rate temperature is 460.7 deg.C, and the terminal thermal degradation temperature is 476.2 deg.C, so that the thermal stability of the polyamide composite material of example 7 is better than that of comparative example 2.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The polyamide composite material is characterized by being prepared from the following raw materials in parts by weight:
the reactive phosphorus flame retardant is 4- (2- (((2-carboxyl ethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid;
the coated melamine cyanurate is the melamine cyanurate coated by the silica sol; the silica sol is prepared from the following components in a mass ratio of 1: 5-7: 0.07-0.1 of tetraethyl orthosilicate, deionized water and hydrochloric acid.
2. The polyamide composite material as claimed in claim 1, which is prepared from the following raw materials in parts by weight:
3. the polyamide composite material as claimed in claim 2, which is prepared from the following raw materials in parts by weight:
4. the polyamide composite material as claimed in any one of claims 1 to 3, wherein the preparation method of the coated melamine cyanurate comprises the following steps: dissolving melamine cyanurate in a reaction kettle filled with absolute ethyl alcohol, adding silica sol accounting for 7-13% of the mass of the melamine cyanurate, heating the temperature of the reaction kettle to 85-95 ℃, stirring for reaction for 3-5 hours, and filtering, drying and crushing to obtain the coated melamine cyanurate.
5. Polyamide composite material according to claim 4, characterized in that the silica sol consists of, in mass ratio, 1: 5.5-6.5: 0.08-0.09 of tetraethyl orthosilicate, deionized water and hydrochloric acid.
6. Polyamide composite material according to claim 4 or 5, characterized in that the silica sol is added in an amount of 9 to 11% by mass of melamine cyanurate.
7. The polyamide composite material as claimed in claim 4, wherein the temperature of the reaction vessel is 89 ℃ to 91 ℃.
8. The polyamide composite material according to claim 4, wherein the stirring speed of the stirring reaction is 35 to 45r/min, and the stirring reaction time is 3.5 to 4.5 hours.
9. A method for synthesizing a polyamide composite material as claimed in any one of claims 1 to 8, characterized by comprising the steps of:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated melamine cyanurate, tetramethylpiperidine amine and a proper amount of water; then vacuumizing for 3-7 min, introducing nitrogen for 3-7 min, circulating for 4-8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1-0.4 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to be 30 r/min-50 r/min, heating the stirring type polymerization reactor to 270-280 ℃ in a sealed and uniform manner within 2-4 hours, discharging gas to 2.3MPa when the temperature of the stirring type polymerization reactor reaches 225 ℃, maintaining the pressure at 2.3MPa, discharging gas to normal pressure after reacting for 1-2 hours, simultaneously heating to 290-310 ℃, continuing to react for 0.5-1.5 hours at 290-310 ℃, continuously vacuumizing for 0.1-1 hour at constant temperature, finishing the reaction, and supplementing nitrogen gas during discharging to obtain the product.
10. Method for the synthesis of a polyamide composite material according to claim 9, characterized in that it comprises the following steps:
(1) adding the hexamethylene diamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated melamine cyanurate, tetramethylpiperidine amine and a proper amount of water; then vacuumizing for 4-6 min, introducing nitrogen for 4-6 min, circulating for 5-7 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.2-0.3 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to 35 r/min-45 r/min, heating the stirring type polymerization reactor to 273-277 ℃ in a sealed and uniform manner within 2.5-3.5 hours, deflating to 2.3MPa when the temperature of the stirring type polymerization reactor reaches 225 ℃, maintaining the pressure at 2.3MPa, reacting for 1.2-1.8 hours, deflating to normal pressure, simultaneously heating to 295-305 ℃, continuing to react for 0.8-1.2 hours at 295-305 ℃, continuously vacuumizing for 0.3-0.7 hour at constant temperature, finishing the reaction, and supplementing nitrogen during discharging to obtain the catalyst.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473152A (en) * | 2000-11-03 | 2004-02-04 | Cytec | Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same |
| CN106675007A (en) * | 2017-01-06 | 2017-05-17 | 东华大学 | Flame-retarded polyamide 6 and preparation method thereof |
| EP3328916A1 (en) * | 2015-07-31 | 2018-06-06 | Ditf Deutsche Institute Für Textil- Und Faserforschung Stuttgart | Flame-resistant polyamide as reaction product of a lactam, and method for the production and use thereof |
| CN109735103A (en) * | 2019-01-14 | 2019-05-10 | 浙江新力新材料股份有限公司 | It soaks resistance to precipitation flame retardant polyamide composite material and preparation method thereof |
| CN110643036A (en) * | 2019-08-23 | 2020-01-03 | 惠生(中国)投资有限公司 | Copolymerization high-temperature-resistant nylon and preparation method and application thereof |
-
2022
- 2022-02-17 CN CN202210147231.XA patent/CN114395124A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473152A (en) * | 2000-11-03 | 2004-02-04 | Cytec | Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same |
| EP3328916A1 (en) * | 2015-07-31 | 2018-06-06 | Ditf Deutsche Institute Für Textil- Und Faserforschung Stuttgart | Flame-resistant polyamide as reaction product of a lactam, and method for the production and use thereof |
| CN106675007A (en) * | 2017-01-06 | 2017-05-17 | 东华大学 | Flame-retarded polyamide 6 and preparation method thereof |
| CN109735103A (en) * | 2019-01-14 | 2019-05-10 | 浙江新力新材料股份有限公司 | It soaks resistance to precipitation flame retardant polyamide composite material and preparation method thereof |
| CN110643036A (en) * | 2019-08-23 | 2020-01-03 | 惠生(中国)投资有限公司 | Copolymerization high-temperature-resistant nylon and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吕文涛 等: "原位聚合法制备N-P 复配型阻燃PA66 树脂及性能", 《塑料》, vol. 46, no. 4, pages 247 - 248 * |
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