CN107501546B - High-viscosity flame-retardant polyamide 6 and preparation method thereof - Google Patents
High-viscosity flame-retardant polyamide 6 and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-viscosity flame-retardant polyamide 6 and a preparation method thereof. The preparation method of the high-viscosity flame-retardant polyamide 6 comprises the following steps: the phosphorus-containing flame retardant, diamine and dihydric alcohol are subjected to prepolymerization reaction and polymerization reaction in water in sequence to obtain a flame retardant prepolymer; adding a flame retardant prepolymer in the polymerization process of polyamide 6 to obtain the flame retardant. In the prior art, due to the addition of the flame retardant, the in-situ polymerization flame-retardant polyamide 6 has the problems of low temperature resistance of the flame retardant, large steric hindrance effect and the like, so that the viscosity of the flame-retardant polyamide 6 is low, the polymerization is difficult, and even the flame-retardant polyamide 6 cannot be cut into particles, so that the flame-retardant polyamide 6 is not suitable for spinning or spinning and has a large amount of floating filaments. According to the invention, the problem of low temperature resistance of the flame retardant is solved by a method of preparing the flame-retardant prepolymer through prepolymerization, the problem of low polymer viscosity caused by adding the flame retardant in the early stage is solved by adding the flame-retardant prepolymer in the middle and later stages of the polymerization process, the viscosity reaches 2.8-3.2 pa.s, and the flame-retardant polyamide 6 with high viscosity is successfully prepared.
Description
Technical Field
The invention relates to high-viscosity flame-retardant polyamide 6 and a preparation method thereof, belonging to the field of preparation of flame retardants.
Background
Polyamide is one of the most important engineering plastics and textile fiber materials, has many excellent properties such as high strength and wear resistance, and is widely applied to the fields of buildings, textiles, military affairs and the like, but the flammability of polyamide influences the wider application of polyamide. Most of the development of flame-retardant polyamide currently stays in the blending granulation of a polyamide matrix and a blended flame retardant and related synergistic flame retardants, and the application range of the blended flame-retardant polyamide is narrowed by factors such as a large amount of added flame retardant, poor dispersibility of the flame retardant in the polyamide matrix, and limited performances of the polyamide.
In recent years, researchers pay attention to copolymerization type flame-retardant polyamide, and the preparation method mainly adopts a reactive flame retardant and a polyamide monomer to carry out in-situ polymerization reaction, and in the preparation process of the polyamide, a flame-retardant unit is introduced into a polyamide macromolecular chain to realize the permanent flame retardance of the polyamide. At present, a great number of patents related to copolymerization flame-retardant polyamide emerge, for example, invention patent 201310017151.3 discloses a preparation method of an inorganic modified melamine cyanurate flame-retardant nylon 6 composite material, wherein molten caprolactam is adopted as a reaction medium, melamine cyanurate is firstly prepared, water, an inorganic modified component (or a precursor for generating the inorganic component) and other auxiliary agents are added in an in-situ polymerization process, and finally the flame-retardant nylon 6 composite material is prepared. The invention patent 201410489935.0 discloses a method for preparing an organic phosphorus copolymerization flame-retardant polyamide material, which comprises the steps of preparing a prepolymer containing a flame retardant in advance, and carrying out copolymerization reaction on a polyamide monomer, a catalyst and the prepolymer to obtain the organic phosphorus copolymerization flame-retardant polyamide material.
The method for preparing the flame-retardant polyamide polymer by copolymerizing the reactive flame retardant or the flame-retardant prepolymer and the polyamide monomer is an effective scheme for improving the flame-retardant performance of the polyamide product, but in the copolymerized flame-retardant polyamide, a large amount of steric effect is formed due to the introduction of the flame retardant, so that the viscosity of the copolymerized flame-retardant polyamide is low, a tackifying process is needed, the problems of yellowing or mismatch of terminal amino groups and the like are easily caused, and troubles are brought to subsequent processing or spinning.
Disclosure of Invention
The invention aims to provide high-viscosity flame-retardant polyamide 6 and a preparation method thereof, so as to solve the problem that the viscosity of the copolymerized flame-retardant polyamide is low.
The method comprises the steps of firstly, carrying out prepolymerization reaction on reactants such as carboxyphosphonic acid (phosphorus-containing flame retardant), diamine and dihydric alcohol to form a low-molecular-weight flame-retardant prepolymer, wherein the carboxyphosphonic acid is used as a source of flame-retardant element phosphorus. And then, adding the flame-retardant prepolymer in the middle and later stages of the polyamide 6 polymerization process, vacuumizing and the like at the same time, and finally obtaining the high-viscosity flame-retardant polyamide 6 slice.
The preparation method of the high-viscosity flame-retardant polyamide 6 provided by the invention comprises the following steps:
(1) the phosphorus-containing flame retardant, diamine and dihydric alcohol are subjected to prepolymerization reaction and polymerization reaction in water in sequence to obtain a flame retardant prepolymer;
(2) and adding the flame retardant prepolymer in the polymerization process of polyamide 6 to obtain the high-viscosity flame-retardant polyamide 6.
In the preparation method, in the step (1), the weight average molecular weight of the flame retardant prepolymer can be 2000-4000.
In the preparation method, before the prepolymerization reaction in the step (1), the method further comprises the step of mixing the phosphorus-containing flame retardant, the diamine, the diol and the water for 0.5-1 h;
both the prepolymerization and the polymerization are carried out in an inert atmosphere, such as in a nitrogen atmosphere.
In the preparation method, in the step (1), the temperature of the prepolymerization reaction can be 50-90 ℃, and the time can be 0.5-1.5 h;
the temperature of the polymerization reaction can be 180-190 ℃, and the time can be 1-2 h;
the polymerization reaction can be carried out under the pressure of 0.15-0.3 MPa, and specifically can be 0.2 MPa.
In the above preparation method, in the step (1), the molar ratio of the phosphorus-containing flame retardant, the diamine, the diol and the water may be 1: 1.1-1.2: 1: 50 to 100.
In the above preparation method, in step (1), the phosphorus-containing flame retardant may be CEPPA, DDP or their derivatives;
the CEPPA has a structural formula shown in formula I:
the derivative of CEPPA is sodium salt or potassium salt of the CEPPA;
the structural formula of the DDP is shown as a formula II:
the derivative of the DDP is a sodium salt or a potassium salt of the DDP.
In the above preparation method, in the step (1), the diamine may be one or two of ethylenediamine, propylenediamine, butylenediamine and pentylenediamine;
the dihydric alcohol is dihydric alcohol with 2-10 carbon atoms.
In the above preparation method, in the step (2), the polymerization process of the polyamide 6 is as follows:
1) carrying out melt polymerization on caprolactam and water at the temperature of 200-230 ℃ and the pressure of 0.5-0.6 Mpa;
2) continuously carrying out the melt polymerization at the temperature of 240-250 ℃ and the pressure of 0.7-0.8 Mpa;
3) and after the pressure is relieved to normal pressure, adding the flame retardant prepolymer, and continuing to perform the melt polymerization.
In the preparation method, in the step 1), the time for melt polymerization is 4-5 h;
the weight of the water is 4-5% of the total weight of the caprolactam and the water;
in the step 2), the time of melt polymerization is 4-5 h;
in the step 3), the temperature of the melt polymerization is 260-270 ℃, the pressure is 0.3-0.5 MPa, and the time is 2-4 h;
the addition amount of the flame retardant prepolymer is 4-15% of the total weight of the caprolactam, the water and the flame retardant prepolymer, and specifically can be 4%, 6%, 8%, 10% or 15%.
In the preparation method, after the melt polymerization is finished, the method further comprises the step of vacuumizing after the pressure is relieved to normal pressure;
the extraction time is 30-50 min, and the vacuum degree after extraction is 0.01-50 Kpa;
and after vacuumizing, sequentially carrying out grain cutting, extraction and drying to obtain the flame-retardant polyamide 6 slice.
The polyamide 6 chips prepared by the method have the viscosity of 2.8-3.2 pa · s, high viscosity, limit oxygen value of 28-32 and flame retardance.
The high-viscosity flame-retardant polyamide 6 chip can be used for preparing flame-retardant polyamide fibers.
The invention has the following beneficial effects:
in the prior art, due to the addition of the flame retardant, the in-situ polymerization flame-retardant polyamide 6 has the problems of low temperature resistance of the flame retardant, large steric hindrance effect and the like, so that the viscosity of the flame-retardant polyamide 6 is low, the polymerization is difficult, and even the flame-retardant polyamide 6 cannot be cut into particles, so that the flame-retardant polyamide 6 is not suitable for spinning or spinning and has a large amount of floating filaments. According to the invention, the problem of low temperature resistance of the flame retardant is solved by a method of preparing the flame-retardant prepolymer through prepolymerization, the problem of low polymer viscosity caused by adding the flame retardant in the early stage is solved by adding the flame-retardant prepolymer in the middle and later stages of the polymerization process, the viscosity reaches 2.8-3.2 pa.s, and thus the flame-retardant polyamide 6 with high viscosity is successfully prepared.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 high viscosity flame retardant Polyamide 6
1. Preparing a flame retardant prepolymer:
1.1) flame retardant CEPPA, ethylenediamine, ethylene glycol and water 1: 1.1: 1: 100 (mol) for 0.5 h;
1.2) mixing evenly, stirring and reacting for 1h under the protection of nitrogen and at the temperature of 50 ℃;
1.3) stirring for reaction, pressurizing to 0.2MPa, further heating to 180 ℃ under the protection of nitrogen for polymerization reaction, and reacting for 1h to obtain a flame retardant prepolymer;
1.4) the weight average molecular weight of the prepared flame retardant prepolymer is 2000.
2. Preparation of highly viscous flame-retardant Polyamide 6
2.1) melting and mixing caprolactam and deionized water, wherein the amount of water accounts for 4 percent of the total weight;
2.2) heating the molten reactant to 200 ℃ for reaction, wherein the polymerization pressure is 0.5MPa, and the reaction lasts for 4 hours; then, the temperature is increased to 240 ℃, the pressure is increased to 0.7MPa, the reaction is carried out for 4 hours, and the pressure is released to normal pressure;
2.3) starting a stirrer, stirring at a high speed, adding 4% of flame retardant prepolymer, continuously heating to 260 ℃, boosting the pressure to 0.3MPa, reacting for 2 hours, and releasing the pressure to normal pressure;
2.4) finally vacuumizing, wherein the reaction vacuum degree is 0.01KPa, and the pumping time is 30 min;
2.5) granulating, extracting and drying to obtain the high-viscosity flame-retardant polyamide 6 slice.
The chip obtained in this example had a viscosity of 3.2pa · s and a limiting oxygen number of 28.
Example 2 high viscosity flame retardant Polyamide 6
1. Preparing a flame retardant prepolymer:
1.1) flame retardant DDP, ethylenediamine, ethylene glycol and water in a ratio of 1: 1.2: 1: mixing at a ratio of 50 (mol) for 1 h;
1.2) mixing evenly, stirring and reacting for 1h at 90 ℃ under the protection of nitrogen;
1.3) stirring for reaction, pressurizing to 0.2MPa, further heating to 190 ℃ under the protection of nitrogen for polymerization reaction, and reacting for 2 hours to obtain a flame retardant prepolymer;
1.4) the weight average molecular weight of the prepared flame retardant prepolymer is 3000.
2. Preparation of highly viscous flame-retardant Polyamide 6
2.1) melting and mixing caprolactam and deionized water, wherein the amount of water accounts for 5 percent of the total weight;
2.2) heating the molten reactant to 230 ℃ for reaction, wherein the polymerization pressure is 0.6MPa, and the reaction lasts for 5 hours; then, the temperature is increased to 250 ℃, the pressure is increased to 0.8MPa, the reaction is carried out for 5 hours, and the pressure is released to normal pressure;
2.3) starting a stirrer, stirring at a high speed, adding 15 wt% of flame retardant prepolymer, continuously heating to 270 ℃, boosting the pressure to 0.5MPa, reacting for 4h, and releasing the pressure to normal pressure;
2.4) finally vacuumizing, wherein the reaction vacuum degree is 50KPa, and the pumping time is 50 min;
2.5) granulating, extracting and drying to obtain the high-viscosity flame-retardant polyamide 6 slice.
The chip obtained in this example had a viscosity of 2.8pa · s and a limiting oxygen number of 32.
Example 3 high viscosity flame retardant Polyamide 6
1. Preparing a flame retardant prepolymer:
1.1) mixing flame retardant DDP sodium salt, propylene diamine, propylene glycol and water in a ratio of 1: 1.15: 1: mixing at a ratio of 70 (mol) for 0.5 h;
1.2) mixing evenly, stirring and reacting for 1h at 55 ℃ under the protection of nitrogen;
1.3) stirring for reaction, pressurizing to 0.2MPa, further heating to 182 ℃ under the protection of nitrogen for polymerization reaction, and reacting for 1.5h to obtain a flame retardant prepolymer;
1.4) the weight average molecular weight of the prepared flame retardant prepolymer is 2500.
2. Preparation of highly viscous flame-retardant Polyamide 6
2.1) melting and mixing caprolactam and deionized water, wherein the amount of water accounts for 4 percent of the total weight;
2.2) heating the molten reactant to 210 ℃ for reaction, wherein the polymerization pressure is 0.5MPa, and the reaction lasts for 4.5 h; then, the temperature is increased to 246 ℃, the pressure is increased to 0.75MPa, the reaction is carried out for 4 hours, and the pressure is released to normal pressure;
2.3) starting a stirrer, stirring at a high speed, adding 6 wt% of the flame retardant prepolymer, continuously heating to 265 ℃, boosting the pressure to 0.5MPa, reacting for 3.5h, and releasing the pressure to normal pressure;
2.4) finally vacuumizing, wherein the reaction vacuum degree is 0.01KPa, and the pumping time is 45 min;
2.5) granulating, extracting and drying to obtain the high-viscosity flame-retardant polyamide 6 slice.
The chip obtained in this example had a viscosity of 3.1pa · s and a limiting oxygen number of 30.
Example 4 high viscosity flame retardant Polyamide 6
1. Preparing a flame retardant prepolymer:
1.1) mixing the flame retardant CEPPA potassium salt, butanediamine, pentanediamine, butanediol and water in a ratio of 1: 0.6: 0.5: 1: mixing at a ratio of 70 (mol) for 50 min;
1.2) mixing evenly, stirring and reacting for 1.5h at 60 ℃ under the protection of nitrogen;
1.3) stirring for reaction, pressurizing to 0.2MPa, further heating to 185 ℃ under the protection of nitrogen for polymerization reaction, and reacting for 1.5h to obtain a flame retardant prepolymer;
1.4) the weight average molecular weight of the prepared flame retardant prepolymer is 4000.
2. Preparation of highly viscous flame-retardant Polyamide 6
2.1) melting and mixing caprolactam and deionized water, wherein the amount of water accounts for 4.5 percent of the total weight;
2.2) heating the molten reactant to 225 ℃ for reaction, wherein the polymerization pressure is 0.6MPa, and the reaction lasts for 4.5 h; then the temperature is increased to 248 ℃, the pressure is increased to 0.75MPa, the reaction is carried out for 4.5h, and the pressure is released to the normal pressure;
2.3) starting a stirrer, stirring at a high speed, adding 8 wt% of flame retardant prepolymer, continuously heating to 267 ℃, boosting the pressure to 0.4MPa, reacting for 3h, and releasing the pressure to normal pressure;
2.4) finally vacuumizing, wherein the reaction vacuum degree is 0.1KPa, and the pumping time is 45 min;
2.5) granulating, extracting and drying to obtain the high-viscosity flame-retardant polyamide 6 slice.
The chip obtained in this example had a viscosity of 3.1pa · s and a limiting oxygen number of 29.
Example 5 high viscosity flame retardant Polyamide 6
1. Preparing a flame retardant prepolymer:
1.1) mixing the flame retardant DDP, ethylenediamine, propylenediamine, decanediol and water in a ratio of 1: 0.5: 0.62: 1: 70 (mol) for 1 h;
1.2) mixing evenly, stirring and reacting for 1.2h at 70 ℃ under the protection of nitrogen;
1.3) stirring for reaction, pressurizing to 0.2MPa, further heating to 188 ℃ under the protection of nitrogen for polymerization reaction, and reacting for 1.5h to obtain a flame retardant prepolymer;
1.4) the weight average molecular weight of the prepared flame retardant prepolymer is 3600.
2. Preparation of highly viscous flame-retardant Polyamide 6
2.1) melting and mixing caprolactam and deionized water, wherein the amount of water accounts for 4.2 percent of the total weight;
2.2) heating the molten reactant to 220 ℃ for reaction, wherein the polymerization pressure is 0.55MPa, and the reaction lasts for 4 hours; then, the temperature is increased to 245 ℃, the pressure is increased to 0.7MPa, the reaction is carried out for 4.5h, and the pressure is released to normal pressure;
2.3) starting a stirrer, stirring at a high speed, adding 10 wt% of flame retardant prepolymer, continuously heating to 270 ℃, boosting the pressure to 0.4MPa, reacting for 3.5h, and releasing the pressure to normal pressure;
2.4) finally vacuumizing, wherein the reaction vacuum degree is 10KPa, and the pumping time is 50 min;
2.5) granulating, extracting and drying to obtain the high-viscosity flame-retardant polyamide 6 slice.
The chips obtained in this example had a viscosity of 2.8pa · s and a limiting oxygen number of 31.
Comparative examples 1,
1. Preparing a flame retardant prepolymer:
1.1) mixing the flame retardant DDP, ethylenediamine, propylenediamine, decanediol and water in a ratio of 1: 0.5: 0.62: 1: 70 (mol) for 1 h;
1.2) mixing evenly, stirring and reacting for 1.2h at 70 ℃ under the protection of nitrogen;
1.3) stirring for reaction, pressurizing to 0.2MPa, further heating to 188 ℃ under the protection of nitrogen for polymerization reaction, and reacting for 1.5h to obtain a flame retardant prepolymer;
1.4) the weight average molecular weight of the prepared flame retardant prepolymer is 3600.
2. Preparation of flame-retardant Polyamide 6
2.1) melting and mixing caprolactam, a flame retardant prepolymer and deionized water, wherein the amount of water accounts for 4.2 percent of the total weight, and the adding amount of the flame retardant prepolymer accounts for 10 percent of the weight;
2.2) heating the molten reactant to 220 ℃ for reaction, wherein the polymerization pressure is 0.55MPa, and the reaction lasts for 4 hours; then, the temperature is increased to 245 ℃, the pressure is increased to 0.7MPa, the reaction is carried out for 4.5h, and the pressure is released to normal pressure;
2.3) starting a stirrer, stirring at a high speed, continuously heating to 270 ℃, boosting the pressure to 0.4MPa, reacting for 3.5h, and releasing the pressure to normal pressure;
2.4) finally vacuumizing, wherein the reaction vacuum degree is 10KPa, and the pumping time is 50 min;
2.5) granulating, extracting and drying to obtain the flame-retardant polyamide 6 slice.
The chips obtained in this comparative example had a viscosity of 2.0pa · s and a limiting oxygen number of 31.
It can be seen that the flame retardant prepolymer is added at the early stage of in-situ polymerization of the flame retardant polyamide 6, and the viscosity of the obtained flame retardant polyamide 6 is significantly lower than that (2.8-3.2) of the flame retardant polyamide 6 obtained by adding the flame retardant prepolymer at the middle and later stages of the polymerization process.
The above embodiments are merely preferred examples to illustrate the present invention, and it should be apparent to those skilled in the art that any obvious variations and modifications can be made without departing from the spirit of the present invention.
Claims (3)
1. A preparation method of high-viscosity flame-retardant polyamide 6 comprises the following steps:
(1) the phosphorus-containing flame retardant, diamine and dihydric alcohol are subjected to prepolymerization reaction and polymerization reaction in water in sequence to obtain a flame retardant prepolymer;
the molar ratio of the phosphorus-containing flame retardant, the diamine, the glycol and the water is 1: 1.1-1.2: 1: 50-100 parts;
the diamine is one or two of ethylenediamine, propylenediamine, butylenediamine and pentylenediamine;
the dihydric alcohol is dihydric alcohol with 2-10 carbon atoms;
the phosphorus-containing flame retardant is CEPPA, DDP or derivatives thereof;
the CEPPA has a structural formula shown in formula I:
the derivative of CEPPA is sodium salt or potassium salt of the CEPPA;
the structural formula of the DDP is shown as a formula II:
the derivative of the DDP is a sodium salt or a potassium salt of the DDP;
the temperature of the prepolymerization reaction is 50-90 ℃, and the time is 0.5-1.5 h;
the temperature of the polymerization reaction is 180-190 ℃, and the time is 1-2 h;
the polymerization reaction is carried out under the pressure of 0.15-0.3 MPa;
(2) adding the flame retardant prepolymer in the polymerization process of polyamide 6 to obtain the high-viscosity flame-retardant polyamide 6, wherein the viscosity of the high-viscosity flame-retardant polyamide 6 is 2.8-3.2 pa-s;
the polymerization process of the polyamide 6 is as follows:
1) carrying out melt polymerization on caprolactam and water at the temperature of 200-230 ℃ and the pressure of 0.5-0.6 Mpa;
the time for the melt polymerization is 4-5 h;
the weight of the water is 4-5% of the total weight of the caprolactam and the water;
2) continuously carrying out the melt polymerization at the temperature of 240-250 ℃ and the pressure of 0.7-0.8 Mpa; the time for the melt polymerization is 4-5 h;
3) after the pressure is relieved to normal pressure, adding the flame retardant prepolymer, and continuing to perform the melt polymerization;
the temperature of the melt polymerization is 260-270 ℃, the pressure is 0.3-0.5 MPa, and the time is 2-4 h;
the addition amount of the flame retardant prepolymer is 4-15% of the total weight of the caprolactam, the water and the flame retardant prepolymer;
after the melt polymerization is finished, the method also comprises the step of vacuumizing after the pressure is relieved to normal pressure;
the extraction time is 30-50 min, and the vacuum degree after extraction is 0.01-50 KPa.
2. The method of claim 1, wherein: in the step (1), before the prepolymerization reaction, the method further comprises the step of mixing the phosphorus-containing flame retardant, the diamine, the dihydric alcohol and the water for 0.5-1 h;
the prepolymerization reaction and the polymerization reaction are carried out in an inert atmosphere.
3. A high viscosity flame retardant polyamide 6 prepared by the process of claim 1 or 2.
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| CN114591623B (en) * | 2022-04-26 | 2023-08-11 | 华润化学材料科技股份有限公司 | Flame-retardant nylon elastomer material with high impact toughness and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104499076A (en) * | 2014-12-12 | 2015-04-08 | 广东新会美达锦纶股份有限公司 | Preparation method of flame-retarded polyamide 6 fiber |
| CN105155019A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Flame-retardant polyamide 6 fiber and preparation method thereof |
| CN105155033A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Flame-retardant polyamide 6 composite fiber and preparation method thereof |
| CN106675007A (en) * | 2017-01-06 | 2017-05-17 | 东华大学 | Flame-retarded polyamide 6 and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104499076A (en) * | 2014-12-12 | 2015-04-08 | 广东新会美达锦纶股份有限公司 | Preparation method of flame-retarded polyamide 6 fiber |
| CN105155019A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Flame-retardant polyamide 6 fiber and preparation method thereof |
| CN105155033A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Flame-retardant polyamide 6 composite fiber and preparation method thereof |
| CN106675007A (en) * | 2017-01-06 | 2017-05-17 | 东华大学 | Flame-retarded polyamide 6 and preparation method thereof |
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