CN115746293B - In-situ polymerization flame-retardant nylon material, and preparation method and application thereof - Google Patents
In-situ polymerization flame-retardant nylon material, and preparation method and application thereof Download PDFInfo
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- CN115746293B CN115746293B CN202211470993.XA CN202211470993A CN115746293B CN 115746293 B CN115746293 B CN 115746293B CN 202211470993 A CN202211470993 A CN 202211470993A CN 115746293 B CN115746293 B CN 115746293B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 142
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000004677 Nylon Substances 0.000 title claims abstract description 54
- 229920001778 nylon Polymers 0.000 title claims abstract description 54
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 17
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- 230000000536 complexating effect Effects 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 38
- 238000002425 crystallisation Methods 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 19
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 235000011037 adipic acid Nutrition 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 6
- 230000000670 limiting effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- -1 iron ions Chemical class 0.000 claims description 2
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- 238000005452 bending Methods 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 7
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- 230000007547 defect Effects 0.000 abstract description 6
- 238000002464 physical blending Methods 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
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- Polyamides (AREA)
Abstract
The invention discloses an in-situ polymerization flame-retardant nylon material, and a preparation method and application thereof. The preparation method comprises the following steps: the nylon monomer is subjected to salt forming reaction, and a flame retardant and complex metal ions are added into the nylon salt solution to obtain a mixed solution, wherein the complex metal ions can perform coordination complexing with the flame retardant; and carrying out a prepolymerization reaction and a polycondensation reaction to obtain the in-situ polymerization flame-retardant nylon material. The preparation method provided by the invention adopts an intrinsic flame retardant mode, the flame retardant performance of the obtained nylon material is excellent, a series of defects of low flame retardant efficiency, difficult dispersion, obvious reduction of the comprehensive performance of the material and the like existing in physical blending are effectively avoided, meanwhile, the thermal stability of the flame retardant in polymerization reaction is improved, and the problem of melt viscosity reduction caused by high-temperature decomposition of the flame retardant can be effectively avoided; the prepared in-situ polymerization flame-retardant nylon material has excellent flame retardant property and processability.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to the technical field of flame-retardant polymer materials, and particularly relates to an in-situ polymerization flame-retardant nylon material, a preparation method and application thereof.
Background
Nylon materials are very widely used, for example: nylon 66 is one of the most widely used types in nylon families, is formed by polycondensation of adipic acid and hexamethylenediamine, has regular molecular chain arrangement and higher crystallinity, can form intramolecular and intermolecular hydrogen bonds, has excellent mechanical properties, processability, corrosion resistance, wear resistance, self-lubricating property, chemical resistance and the like, and is widely applied to the fields of electronic appliances, automobile industry, packaging films, clothing fibers, aerospace and the like.
But nylon 66 Limiting Oxygen Index (LOI) is not more than 24%, the vertical burning test grade is UL 94V-2, and the flame retardant is still a combustible material, and meanwhile, the flame retardant is often accompanied by combustible molten drops in the burning process, so that the flame is easy to rapidly spread. Therefore, flame retardant modification of nylon 66 is important to promote high-quality and multidirectional development of the material, and more than 30% of polyamide materials are required to have flame retardant properties especially in the field of electronics and appliances.
Currently, flame retardants used in nylon 66 mainly include inorganic flame retardants, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, intumescent flame retardants, phosphorus-silicon cage flame retardants, and the like. Wherein, melamine Cyanurate (MCA) is used as a nitrogen flame retardant with high nitrogen content, has low price, high efficiency, low smoke, no color change, environmental friendliness and the like, and is widely used in the field of nylon 66 flame retardance.
The preparation routes of the MCA flame retardant nylon 66 can be divided into two main types of additive flame retardant routes and reactive flame retardant routes according to different preparation routes.
The additive type flame-retardant way, such as China patent No. CN108165002A, discloses an MCA flame-retardant nylon 66 composite material and a preparation method thereof, and the composite material is prepared by carrying out melt extrusion and granulation on a PA66 resin material, an MCA flame retardant, an antioxidant, a lubricant and a flame-retardant stabilizer according to a proportion. The additive flame-retardant way, namely that the flame retardant and the base resin material form the flame-retardant composite material only through physical blending effect, has a series of problems of poor system dispersibility, low flame-retardant efficiency, obvious mechanical property influence, poor compatibility, easy precipitation, difficult realization of long-lasting flame retardance and the like.
The reactive flame-retardant approach is that the flame retardant is associated with the reactive monomer through chemical bonding, so that stable flame-retardant structural units are introduced into the polymer chain segments, and the intrinsic flame-retardant effect is realized. Wherein, for example, chinese patent No. 103408750A discloses a preparation method of melamine cyanurate flame-retardant polyamide material, which takes MCA, nano silicon dioxide and metal oxide as synergistic flame retardant and prepares flame-retardant polyamide by in-situ polymerization. However, the inventor finds in practice that the prior art does not consider the influence of the addition of filler on the mechanical property and the processing property of the system, and the problems of low flame retardant property and poor mechanical property caused by the fact that the actual condition of MCA partial decomposition is easily caused due to continuous reaction of a system with higher melting point such as nylon 66 and the like at a higher temperature.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an in-situ polymerization flame-retardant nylon material, and a preparation method and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the invention provides a method for preparing an in-situ polymerized flame retardant nylon material, comprising the following steps:
Carrying out salt forming reaction on nylon monomers to obtain nylon salt solution, and adding a flame retardant and complexing metal ions into the nylon salt solution to obtain a mixed solution, wherein the flame retardant comprises melamine cyanurate, and the complexing metal ions can carry out coordination complexing with the flame retardant;
Carrying out a prepolymerization reaction on the mixed solution to obtain a prepolymer;
And (3) carrying out polycondensation reaction on the prepolymer to obtain the in-situ polymerized flame-retardant nylon material.
In a second aspect, the invention also provides an in-situ polymerization flame-retardant nylon material prepared by the preparation method.
In a third aspect, the invention also provides application of the in-situ polymerized flame retardant nylon material in manufacturing flame retardant structural members.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the preparation method provided by the invention adopts an intrinsic flame-retardant mode, the flame retardant is associated with the reaction monomer through chemical bonding, a stable flame-retardant structural unit is introduced into the polymer chain segment, the flame-retardant performance of the obtained nylon material is excellent, and a series of defects of low flame-retardant efficiency, difficult dispersion, obvious reduction of the comprehensive performance of the material and the like in physical blending are effectively avoided.
The preparation method provided by the invention improves the thermal stability of the flame retardant in the polymerization reaction, and effectively avoids the problem of melt viscosity reduction caused by catalyzing the degradation reaction of polyamide due to the high-temperature decomposition of the flame retardant into cyanuric acid.
The in-situ polymerized flame-retardant nylon material prepared by the invention not only has excellent flame retardant property, but also can realize rapid crystallization at high temperature, is easy to demould, and has excellent processability.
The above description is only an overview of the technical solutions of the present application, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present application may be implemented according to the content of the specification, and the following description is given of the preferred embodiments of the present application with reference to the detailed drawings.
Drawings
FIG. 1 is a non-isothermal crystallization DSC graph (80 ℃/min cooling rate) of an in situ polymerized flame retardant nylon material according to an exemplary embodiment of the present invention;
FIG. 2 is a non-isothermal crystallization DSC graph (80 ℃/min cooling rate) of an in situ polymerized flame retardant nylon material provided by an exemplary comparative example of the present invention;
FIG. 3 is a DSC graph of isothermal crystallization of an in situ polymerized flame retardant nylon material according to an exemplary embodiment of the present invention;
FIG. 4 is an isothermal crystallization DSC graph of an in situ polymerized flame retardant nylon material provided by an exemplary comparative case of the present invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
The preparation method of the in-situ polymerization flame-retardant nylon material provided by one aspect of the embodiment of the invention comprises the following steps:
And (3) carrying out salt forming reaction on the nylon monomer to obtain a nylon salt solution, and adding a flame retardant and complexing metal ions into the nylon salt solution to obtain a mixed solution, wherein the flame retardant comprises melamine cyanurate, and the complexing metal ions can carry out coordination complexing with the flame retardant.
And (3) carrying out a prepolymerization reaction on the mixed solution to obtain a prepolymer.
And (3) carrying out polycondensation reaction on the prepolymer to obtain the in-situ polymerized flame-retardant nylon material.
As some typical specific application cases of the above exemplary technical solutions, a preparation process of an in-situ polymerized flame retardant nylon material, specifically an in-situ polymerized flame retardant nylon 66 material, may be as follows:
step (1): adipic acid and hexamethylenediamine are subjected to salt forming reaction in deionized water solution according to a certain proportion, and the pH value of a reaction end point system is controlled within the range of 7.5-7.9. And adding a proper amount of MCA flame retardant and water-soluble Fe 3+ salt into the solution, and fully stirring and dissolving to form a mixed solution.
Step (2): and (3) putting the mixed solution into a polymerization high-pressure reaction kettle, closing the reaction kettle, and replacing air in the kettle for at least three times by nitrogen. Heating and boosting under the protection of the nitrogen in a closed environment, and carrying out pre-polycondensation reaction for a certain time under the protection of the nitrogen to obtain the prepolymer after the reaction is finished.
Step (3): and slowly heating the prepolymer in the kettle, continuously exhausting and reducing the pressure to reduce the pressure in the kettle to normal pressure, then vacuumizing, and completing the polycondensation reaction of the prepolymer under the negative pressure condition to obtain the flame-retardant nylon 66 resin material.
In some embodiments, the nylon monomers include diacid monomers and diamine monomers.
In some embodiments, the diacid monomer may be selected from adipic acid.
In some embodiments, the diamine monomer may be selected from hexamethylenediamine.
In some embodiments, the complex metal ion may be selected from iron ions.
In some embodiments, the mass of flame retardant in the salt-forming reaction system may be 1.5 to 3% of the total mass of the nylon monomer.
In some embodiments, the complex metal ion may be provided by a corresponding water-soluble salt, which may be 10-30% of the mass of the flame retardant.
In some embodiments, the water soluble salt may include any one or a combination of two or more of chloride, sulfate, nitrate of the complex metal ion.
In some embodiments, the molar ratio of diacid monomer to diamine monomer in the salt-forming reaction system may be from 1:0.95 to 1.05.
In some embodiments, the salt-forming reaction system may further include water added in an amount of 90% -180% of the total mass of the nylon monomer.
In some embodiments, the reaction endpoint pH of the salt-forming reaction may be 7.5 to 7.9.
In some embodiments, the prepolymerization reaction may be carried out in a protective atmosphere.
In some embodiments, the temperature of the prepolymerization reaction may be 200-220 ℃, the pressure may be 1.5-2.0MPa, and the time may be 1-1.5h.
In some embodiments, the polycondensation reaction may be conducted under negative pressure.
In some embodiments, the polycondensation reaction may be at a temperature of 270 to 280 ℃, a pressure of-0.05 to-0.1 MPa, and a time of 0.5 to 1h.
In some embodiments, the polycondensation reaction may specifically include:
gradually heating the prepolymer to 270-280 ℃ in 2-3h, and simultaneously gradually reducing the pressure of the atmosphere surrounding the prepolymer to normal pressure.
Vacuumizing to-0.05 to-0.1 MPa, and performing the polycondensation reaction.
As some typical application examples of the above exemplary technical solutions, in the preparation process of the in-situ polymerization flame retardant nylon 66 material, in the preparation method step (1), the molar ratio of adipic acid to hexamethylenediamine may be 1:0.95-1.05, and the deionized water may be added in an amount of 90% -180% of the total mass of adipic acid and hexamethylenediamine monomers.
More specifically, the addition amount of the MCA flame retardant is 1.5% -3% of the total mass of adipic acid and hexamethylenediamine monomers.
Further, the water-soluble Fe 3+ salt is one or more selected from ferric chloride, ferric sulfate and ferric nitrate, and the addition amount of the water-soluble Fe 3+ salt is 10-30% of the mass of the MCA flame retardant.
Further, in the step (2), the temperature and the pressure rise specifically mean that the temperature in the kettle reaches 200-220 ℃, the pressure in the kettle is kept at 1.5-2.0MPa, and the reaction time is controlled at 1-1.5 hours.
Further, in the step (3), the temperature is slowly increased, specifically to 270-280 ℃ within 2-3 hours; the continuous exhausting and depressurization specifically means that the pressure in the kettle is reduced to normal pressure within 1-1.5 hours; the negative pressure is particularly preferably-0.05 to-0.1 MPa, and the reaction time is 0.5 to 1 hour.
Compared with the prior art, the MCA in-situ polymerization flame-retardant nylon 66 provided by the specific application example adopts an intrinsic flame-retardant mode, the flame retardant MCA is related to a reaction monomer through chemical bonding, a stable flame-retardant structural unit is introduced into a polymer chain segment, the flame retardant performance is excellent, and a series of defects of low flame retardant efficiency, difficult dispersion, obviously reduced material comprehensive performance and the like in physical blending are effectively avoided; meanwhile, the thermal stability of MCA in the polymerization reaction is improved, and the problem of melt viscosity reduction caused by the catalysis of the degradation reaction of polyamide due to the high-temperature decomposition of MCA into cyanuric acid is effectively avoided. In addition, the flame-retardant nylon 66 resin material has excellent processability, can realize rapid crystallization at high temperature, is easy to demould, and is particularly suitable for the field of electronic connector devices.
Another aspect of the present examples also provides an in situ polymerized flame retardant nylon material made by the method of any of the embodiments described above.
In some embodiments, the crystallization temperature of the in situ polymerized flame retardant nylon material is above 194 ℃ and the isothermal crystallization time is below 1.2 min.
In some embodiments, the in situ polymerized flame retardant nylon material has a tensile strength of 83.8MPa or more, a flexural strength of 124.6MPa or more, a flexural modulus of 2980MPa or more, and a notched impact of 7.2kJ/m 2 or more.
In some embodiments, the in situ polymerized flame retardant nylon material has a vertical burning rating of V-0 and a limiting oxygen index of 37.8% or greater.
Another aspect of the embodiment of the present invention further provides an application of the in-situ polymerized flame retardant nylon material provided in any of the foregoing embodiments in manufacturing flame retardant structural members.
In some embodiments, the application includes application in the manufacture of structural members for electronic appliances, and in some embodiments, further preferred is application in the manufacture of electronic connectors.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
The embodiment illustrates a preparation process of MCA in-situ polymerization flame retardant nylon 66, and the specific synthetic route is as follows:
(1) Salt forming reaction. The total mass part of the monomer adipic acid and hexamethylenediamine is 100 parts. 55 parts of adipic acid are dissolved in 120 parts of deionized water. Under the continuous stirring action, 45 parts of hexamethylenediamine is slowly dripped into the mixed system solution, and the pH value of the system reaction end point is strictly controlled within the range of 7.5-7.9 in the process. 2 parts of MCA flame retardant and 0.5 part of ferric chloride are added into the solution, and the mixed solution is formed after the solution is fully stirred and dissolved.
(2) And (3) pre-polymerization reaction. The mixed solution is put into a 10L high-pressure polymerization reaction kettle, high-purity nitrogen is introduced and vacuumized, and the process is repeated for more than three times to fully replace the air in the kettle. Stirring is started, the temperature in the kettle is increased to 210-220 ℃, and the pressure is maintained (the air pressure in the kettle is kept at 1.5-2.0 MPa) for 1.5 hours to carry out pre-polycondensation reaction.
(3) Post-polymerization. Raising the temperature in the kettle to 270-280 ℃ within 2-3 hours, slowly opening a pressure relief valve in the heating process, and gradually releasing steam in the kettle within 1.5 hours to reduce the pressure in the kettle to normal pressure. Vacuumizing to-0.06 to-0.08 MPa, and reacting for 1 hour to finish the polycondensation reaction. And finally, filling high-purity nitrogen until the pressure in the kettle is positive, standing for a period of time, opening a discharge valve at the bottom of the reaction kettle, allowing the material to pass through a cooling water tank, and performing wiredrawing, granulating and vacuum drying to obtain the MCA in-situ polymerization flame-retardant nylon 66 resin material.
The raw material composition of this example is shown in Table 1. The MCA in-situ polymerization flame-retardant nylon 66 resin material is tested for melting point, viscosity, mechanical property, heat resistance and other properties, and the test results of the properties are shown in Table 2.
Example 2
The preparation process of the MCA in-situ polymerization flame-retardant nylon 66 is exemplified in the embodiment, and is specifically as follows:
The component proportion and the preparation method of the MCA in-situ polymerization flame-retardant nylon 66 resin material of the embodiment are basically the same as those of the embodiment 1, and the difference is that the MCA flame retardant in the embodiment is 1.5 parts, the water-soluble Fe 3+ salt is ferric sulfate, and the amount is 0.45 part. The raw material composition of this example is shown in Table 1, and the results of the performance test are shown in Table 2.
Example 3
The preparation process of the MCA in-situ polymerization flame-retardant nylon 66 is exemplified in the embodiment, and is specifically as follows:
The component proportion and the preparation method of the MCA in-situ polymerization flame-retardant nylon 66 resin material of the embodiment are basically the same as those of the embodiment 1, and the difference is that the MCA flame retardant in the embodiment is 3 parts, the water-soluble Fe 3+ salt is ferric nitrate, and the dosage is 0.3 part. The raw material composition of this example is shown in Table 1, and the results of the performance test are shown in Table 2.
Comparative example 1
The composition ratio and the preparation method of the MCA flame retardant nylon 66 resin material prepared in this comparative example are basically the same as those of example 1, except that the water-soluble Fe 3+ salt is not added in this comparative example. The composition of the raw materials of this comparative example is shown in Table 1, and the results of the performance tests are shown in Table 2.
Comparative example 2
The MCA flame-retardant nylon 66 resin material of the comparative example is prepared by adopting a blending modification process method, wherein the pure nylon 66 base resin material is prepared by polymerizing the scheme of the embodiment 1, and the specific blending modification scheme is as follows: the 100 parts of pure nylon 66 base resin material, 1.5 parts of MCA flame retardant and 0.45 part of ferric sulfate are stirred uniformly under a high-speed stirrer, and are put into a hopper of a double-screw extruder, and the temperature range of the double-screw extruder is controlled to be 260-280 ℃. The specific process parameters are as follows: the temperature of the feeding section is 270 ℃, the temperature of the melting plasticizing section is 280 ℃, the temperature of the mixing homogenizing section is 270 ℃, the temperature of the melt conveying section is 260 ℃, the temperature of the machine head is 275 ℃, and the rotating speed of the host machine is 260rpm. And obtaining the MCA flame-retardant nylon 66 composite material through melt mixing, extrusion and granulation. The composition of the raw materials of this comparative example is shown in Table 1, and the results of the performance tests are shown in Table 2.
Comparative example 3
The preparation method of the MCA flame retardant nylon 66 resin material of this comparative example is basically the same as that of comparative example 2, except that the amount of the MCA flame retardant used in this comparative example is 3 parts and no water-soluble Fe 3+ salt is added. The composition of the raw materials of this comparative example is shown in Table 1, and the results of the performance tests are shown in Table 2.
TABLE 1 raw material composition of examples and comparative examples
Table 2 results of various performance tests of the nylon 66 resin materials of the examples and comparative examples
From the test results in Table 2, it is understood that the overall properties of the examples are superior to those of the comparative examples, in particular, the crystallization temperature and isothermal crystallization time (processability), mechanical properties and flame retarding effects. Because the melting point of nylon 66 is about 260 ℃, the system needs to maintain high temperature for a long time in the polymerization reaction process, part of MCA is easy to generate pyrolysis reaction, cyanuric acid is generated to catalyze the degradation of polyamide into oligomer or end-capped polyamide molecules, and the molecular weight of nylon 66 is reduced. The addition of the water-soluble Fe 3+ salt can play a role in coordination complexing on MCA, so that the structure of the MCA is more stable, and decomposition reaction is not easy to occur, thereby effectively avoiding the failure of the flame retardant MCA in the polymerization reaction process, greatly improving the dispersibility of the flame retardant system in the polyamide structure arrangement, and effectively improving the molecular weight and the intrinsic flame retardant performance of the system. As can be seen from Table 2, the flame retardant properties (vertical burning grade, glowing filament test, limiting oxygen index) of the examples are all better than those of the comparative examples. Compared with comparative examples 2-3, the in-situ polymerization method has better effect than the blending modification method, and is mainly attributed to the fact that the in-situ polymerization method directly introduces stable flame-retardant structural units into polymer chain segments by reacting flame-retardant auxiliary structural units with reactive monomers through chemical bonding in the polymerization stage, so that a series of defects of low flame-retardant efficiency, difficult dispersion, obvious reduction of the comprehensive performance of materials and the like in physical blending are avoided.
In addition, the Fe 3+ is used as micro-nano particles to help promote heterogeneous nucleation of the system, and can greatly improve crystallization performance. As can be seen from fig. 1 and 2, the example 1 has a higher crystallization temperature than the comparative example 1 under the condition of rapid cooling, which indicates that the high temperature crystallization capability of the example 1 is stronger under the actual processing conditions; as can be seen from fig. 3 and 4, the crystallization time of example 1 is much shorter than that of comparative example 1 under the isothermal crystallization condition of 235 ℃, i.e. example 1 can realize rapid crystallization at high temperature, which is beneficial to shortening the processing time and realizing one-die-out, thereby improving the actual processing efficiency.
In the above examples and comparative examples, the test methods and standards of the respective performance parameters were as follows:
(1) Relative viscosity: the relative viscosity of the product at a concentration of 0.5g/dL was measured in a 98% concentrated sulfuric acid solution at (25.+ -. 0.01) ℃ using a Ubbelohde viscometer.
(2) Melting point: DSC test instrument, nitrogen atmosphere, temperature rising rate of 10deg.C/min.
(3) Mechanical properties: tensile strength was tested with reference to standard ISO 527-1/-2, flexural strength and flexural modulus with reference to standard ISO 178, and notched impact strength of the simply supported beams with reference to standard ISO 179/1 eA.
(4) Crystallization temperature: DSC test instrument, nitrogen atmosphere, heating rate of 20 ℃/min, cooling rate of 80 ℃/min.
(5) Isothermal crystallization time: DSC test instrument, nitrogen atmosphere, heating rate of 20 ℃/min, cooling rate of 80 ℃/min, and staying at 235 ℃ for 10min.
(6) Flame retardant properties: with reference to the standard UL94, the vertical burn is 1.6mm thick, and the sample sizes are 125mm by 13mm by 5mm; glowing filament reference standard GB-T5169.10-2017; limiting oxygen index LOI is referred to standard ISO 4589-2.
Based on the above examples and comparative examples, it is clear that the preparation method provided by the embodiment of the invention adopts an intrinsic flame retardant mode, the flame retardant is related to the reaction monomer through chemical bonding, a stable flame retardant structural unit is introduced into the polymer chain segment, the flame retardant performance is excellent, and a series of defects of low flame retardant efficiency, difficult dispersion, obviously reduced material comprehensive performance and the like existing in physical blending are effectively avoided.
The preparation method provided by the embodiment of the invention improves the thermal stability of the flame retardant in the polymerization reaction, and effectively avoids the problem of melt viscosity reduction caused by catalyzing the degradation reaction of polyamide due to the high-temperature decomposition of the flame retardant into cyanuric acid.
The in-situ polymerization flame-retardant nylon material prepared by the embodiment of the invention not only has excellent flame retardant property, but also can realize rapid crystallization at high temperature, is easy to demould, and has excellent processability.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (14)
1. The preparation method of the in-situ polymerization flame-retardant nylon material is characterized by comprising the following steps:
The preparation method comprises the steps of (1) carrying out salt forming reaction on nylon monomers to obtain nylon salt solution, adding a flame retardant and complexing metal ions into the nylon salt solution to obtain mixed solution, wherein the flame retardant comprises melamine cyanurate, and the complexing metal ions can carry out coordination complexing with the flame retardant;
Carrying out a prepolymerization reaction on the mixed solution to obtain a prepolymer;
Carrying out polycondensation reaction on the prepolymer to obtain an in-situ polymerization flame-retardant nylon material;
Wherein the nylon monomer comprises a dibasic acid monomer and a diamine monomer; the complex metal ions are selected from iron ions, provided by the corresponding water-soluble salt, the mass of which is 10-30% of the mass of the flame retardant.
2. The method of claim 1, wherein the diacid monomer is selected from adipic acid and the diamine monomer is selected from hexamethylenediamine.
3. The preparation method according to claim 1 or 2, wherein the mass of the flame retardant in the salifying reaction system is 1.5-3% of the total mass of the nylon monomer.
4.A method of preparing according to claim 3, wherein the water-soluble salt comprises any one or a combination of two or more of chloride, sulfate, nitrate of the complex metal ion.
5. The preparation method according to claim 2, wherein the molar ratio of the diacid monomer to the diamine monomer in the salifying reaction system is 1:0.95-1.05.
6. The preparation method according to claim 5, wherein the salifying reaction system further comprises water, and the addition amount of the water is 90% -180% of the total mass of the nylon monomers.
7. The method according to claim 1, wherein the salt-forming reaction has a reaction end point pH of 7.5 to 7.9.
8. The method of claim 1, wherein the prepolymerization is carried out in a protective atmosphere;
The temperature of the prepolymerization reaction is 200-220 ℃, the pressure is 1.5-2.0 MPa, and the time is 1-1.5h.
9. The method according to claim 1, wherein the polycondensation reaction is carried out under negative pressure;
The temperature of the polycondensation reaction is 270-280 ℃, the pressure is minus 0.05-minus 0.1MPa, and the time is 0.5-1h.
10. The preparation method according to claim 9, wherein the polycondensation reaction specifically comprises:
gradually heating the prepolymer to 270-280 ℃ in 2-3h, and gradually reducing the pressure of the atmosphere surrounding the prepolymer to normal pressure;
Vacuumizing to-0.05 to-0.1 MPa, and performing the polycondensation reaction.
11. An in situ polymerized flame retardant nylon material made by the method of any of claims 1-10.
12. The in-situ polymerized flame retardant nylon material of claim 11, wherein the crystallization temperature of the in-situ polymerized flame retardant nylon material is above 194 ℃ and the isothermal crystallization time is below 1.2 min;
the tensile strength of the in-situ polymerization flame-retardant nylon material is above 83.8MPa, the bending strength is above 124.6MPa, the bending modulus is above 2980MPa, and the notched impact of a simply supported beam is above 7.2kJ/m 2;
the vertical burning grade of the in-situ polymerized flame-retardant nylon material is V-0 grade, and the limiting oxygen index is more than 37.8%.
13. Use of an in situ polymerized flame retardant nylon material according to any of claims 11-12 for the manufacture of flame retardant structural members.
14. The use according to claim 13, characterized in that the use comprises an application in the manufacture of an electrical and electronic structural part.
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| DE102017214048A1 (en) * | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flame retardant polyamide compositions with high filament ignition temperature and their use |
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