CN114085520A - Modified high-flame-retardant-temperature nylon 66 and preparation method thereof - Google Patents
Modified high-flame-retardant-temperature nylon 66 and preparation method thereof Download PDFInfo
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- CN114085520A CN114085520A CN202111440734.8A CN202111440734A CN114085520A CN 114085520 A CN114085520 A CN 114085520A CN 202111440734 A CN202111440734 A CN 202111440734A CN 114085520 A CN114085520 A CN 114085520A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to a modified nylon 66 with high flame retardant temperature and a preparation method thereof, wherein the modified nylon 66 with high flame retardant temperature comprises the following components in parts by weight: nylon 66: 79-88, fine melamine cyanurate: 12-20, polyethylene glycol: 0.1-0.3, polytetrafluoroethylene: 0.0 to 0.4. The preparation method adopts a double-screw extruder. Compared with the prior art, the invention effectively improves the dispersibility of the flame retardant in the nylon 66, improves the flame retardant temperature of the nylon 66, and the tensile strength and the impact strength of the modified nylon 66 material are not obviously reduced, even are improved to a certain extent.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to modified high-flame-retardant-temperature nylon 66 and a preparation method thereof.
Background
Nylon is an engineering plastic with the widest application and most varieties, particularly nylon 66 has good mechanical property, heat resistance, wear resistance, chemical solvent resistance and self-lubricating property, and meanwhile, the material has excellent processing property, can be integrally molded into complex structural parts, and is widely applied to the fields of automobiles, electronic and electric appliances, machinery, rail transit, sports equipment and the like. However, unmodified nylon 66 is inferior in flame retardancy in terms of flame retardancy, only reaching V-2 or HB ratings according to UL-94 vertical burning test standards. At present, the main method for realizing the flame retardance of nylon is to use an additive flame retardant auxiliary agent. The flame retardant additives include, for example, halogen flame retardants, nitrogen flame retardants, phosphorus flame retardants, and inorganic compounds, and the difference between different flame retardants is large in the flame retardant mechanism, flame retardant efficiency, and influence on material properties.
Melamine Cyanurate (MCA) is a nitrogen-based halogen-free flame retardant with excellent performance, compared with phosphorus-containing and halogen-containing flame retardants, MCA has the advantages of low toxicity, high temperature resistance, good thermal stability, high flame retardant efficiency, strong applicability, low price and the like, is particularly suitable for flame retardant modification of nylon 66 materials without filling, and can realize the V-0 level of UL-94 combustion test standard.
As disclosed in patent application CN201510674124.2, a halogen-free, low-toxicity, low-smoke, flame-retardant nylon 66 composition is disclosed, wherein said composition is formed from: 90-95 parts by weight of nylon 66; 5-10 parts by weight of melamine cyanurate halogen-free flame retardant; 1-5 parts by weight of melamine orthophosphate halogen-free flame retardant; 0.1 to 0.3 parts by weight of a lubricant; 0.1 to 0.2 parts by weight of distilled water; 0.5-2 parts by weight of an optional auxiliary agent; wherein the nylon 66 composition does not contain any halogen-containing ingredients. The physical properties of the product of the invention reach the same product quality abroad, and the flame retardant property reaches the optimal V0 grade of flame retardant property in the American UL-94 standard. But the highest notch impact strength can only be achieved3.8kj/m is reached2And the mechanical property is poor.
In fact, the conventional MCA flame retardant is rod-shaped or block-shaped particles with irregular particle diameters, the particle diameter is larger and is generally larger than 2 μm, and the flame retardant efficiency is lower. In order to obtain the UL 94V-0 flame retardant property, a larger filling amount is needed, which causes difficulty in extrusion molding processing of the material, and the tensile strength and the impact strength of the prepared modified nylon 66 material are seriously reduced, so that the application range of the material is limited.
Disclosure of Invention
The invention aims to solve the technical problems and provide a modified nylon 66 with high flame retardant temperature and a preparation method thereof, which can improve the flame retardant temperature of the nylon 66 not only by a UL 94V 0 test, but also by a glow wire flammability index test (GWFI 960/2.0) at higher temperature. Meanwhile, the tensile strength and the impact strength of the modified nylon 66 material are not obviously reduced, and even are improved to a certain degree.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide modified nylon 66 with high flame retardant temperature, which comprises the following components in parts by weight: nylon 66: 79-88, fine melamine cyanurate: 12-20, polyethylene glycol: 0.1-0.3, polytetrafluoroethylene: 0.0 to 0.4.
Further, the modified high flame retardant temperature nylon 66 preferably comprises the following components in parts by weight: nylon 66: 80-85, fine melamine cyanurate: 15-18, polyethylene glycol: 0.15-0.25, polytetrafluoroethylene: 0.1 to 0.3.
Furthermore, the fine melamine cyanurate has a submicron size and a sheet structure, the diameter of the fine melamine cyanurate is 0.2-0.6 mu m, the thickness of the fine melamine cyanurate is 10-90 nm, and the specific surface area of the fine melamine cyanurate is 30-220 m2/cm3In the meantime.
Further, the nylon 66 is dried and thermally treated to remove water before use; the technological conditions for drying, heat treatment and water removal are that the drying is carried out by a blast oven at 80-90 ℃ for 14-18 hours or the drying is carried out by a vacuum drum at 140-160 ℃ for 2-3 hours.
Further, the polyethylene glycol is PEG 6000.
Further, the polytetrafluoroethylene is polytetrafluoroethylene micro powder with a basic particle size of 0.15-1.5 mu m.
The invention also provides a preparation method of the modified nylon 66 with high flame retardant temperature, which is characterized by comprising the following steps:
(1) drying and heat-treating nylon 66 to remove water until the water content in the raw material is less than or equal to 1000ppm to form a pretreatment material (A).
(2) And premixing and dispersing the fine melamine cyanurate, polyethylene glycol and polytetrafluoroethylene uniformly to form premix (B).
(3) And (3) putting the pretreatment material (A) obtained in the step (1) and the premix (B) obtained in the step (2) into a double-screw extruder for extrusion and granulation to obtain a product.
Further, the drying heat treatment of the step (1) is carried out in a forced air oven or a vacuum drum for removing water.
Further, the premixing and dispersing of the step (2) are carried out in a three-dimensional motion mixer.
Further, the twin-screw extrusion granulator in the step (3) is a co-rotating twin-screw extruder, and the length-diameter ratio is 36D-44D. In order to enhance the dispersion of the fine melamine cyanurate, the temperature setting of a screw is different from the ordinary low-high-low temperature, the invention adopts the high-low temperature setting, namely the temperature of a feeding, conveying and mixing section is set to be 270-280 ℃, the temperature of a subsequent melting section, a metering section and a die head are set in a stepped cooling way, the temperature of the die head is lower than the temperature of the metering section, and the lowest temperature is not lower than 260 ℃;
the pretreatment material (A) and the premix (B) are mixed according to the design proportion and directly fed into a double-screw extrusion granulator; or respectively metering and distributing the pretreatment material (A) and the premix (B) by adopting a metering scale to enter a double-screw extrusion granulator, adjusting the rotating speed and the feeding speed of the screw, stabilizing the rotating speed of the screw under the working condition of 160-plus-180 rpm, stabilizing the temperature of the extruded melt within the range of 265-plus-275 ℃, and carrying out bracing or water ring granulation to obtain the low-cost modified high-flame-retardant-temperature nylon 66 material.
Compared with the prior art, the invention has the following advantages:
the invention utilizes a specific submicron-sized fine MCA flame retardant with a sheet structure, the diameter of the fine MCA flame retardant is 0.2-0.6 mu m, the thickness of the fine MCA flame retardant is dozens of nanometers, the specific surface area of the fine MCA flame retardant is higher than that of the conventional MCA, the flame retardant efficiency is higher, the price of the fine MCA flame retardant is only slightly higher than that of the conventional MCA, and the fine MCA flame retardant is still greatly lower than that of nylon 66. However, the smaller particle size also causes a problem of difficulty in dispersing the flame retardant, and a problem of uneven dispersion of the flame retardant is likely to occur, resulting in unstable flame retardancy. According to the invention, the fine MCA is compatible with the special functional auxiliary agent, and is matched with a special double-screw primary-stage high-temperature blending extrusion granulation process, the coating treatment of the flame-retardant particles with submicron sizes and the blending modification of the flame retardant and the nylon 66 resin are realized in a double-screw granulator in one step, the dispersibility of the flame retardant in the nylon 66 is effectively improved, the flame-retardant temperature of the nylon 66 is increased, and the tensile strength and the impact strength of the modified nylon 66 material are not obviously reduced, even are improved to a certain extent.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The starting materials employed in the present invention are all commercially available materials, e.g.
Nylon 66 can be nylon 66 conventionally used in the art, and nylon 66 available under the designation EPR27 from Shanghai Shenma plastics technology Limited is preferred for use in the present invention.
The fine melamine cyanurate adopted by the invention can be selected from HT-211 model of Taxing company, and the parameters are that the diameter is 0.2-0.6 mu m, the thickness is 10-90 nm, and the specific surface area is 30-220 m2/cm3In the meantime.
PEG6000 is preferably selected as polyethylene glycol.
Polytetrafluoroethylene, optionally POLIS KP 650.
Examples 1 to 5
According to the weight parts of the examples in the table 1, the nylon 66 granules with high flame retardant temperature are obtained according to the following steps:
(1) the nylon 66 raw material resin is placed in a blast oven or a vacuum rotary drum to be dried and dewatered until the water content in the raw material is less than or equal to 1000ppm to form a pretreatment material (A).
(2) In order to improve the dispersion effect of the MCA flame retardant, the MCA flame retardant and auxiliary agents such as PEG powder, PTFE powder and the like are premixed and dispersed uniformly in a three-dimensional motion mixer according to a set proportion to form a premix (B).
(3) And directly stirring and mixing the premixed flame retardant (A) material and the dried nylon 66(B) material resin according to a designed proportion, and putting the mixture into a feeding bin of an extrusion granulator or respectively putting the mixture into a metering feeding weighing bin for later use.
(4) Starting and preheating a double-screw extrusion granulator, wherein the double-screw extrusion granulator is a co-rotating double-screw extruder, the length-diameter ratio is 36D, the temperature of a feeding, conveying and mixing section is set at 270 ℃, and the temperature of a subsequent melting section, a metering section and a die head are set to be stepped for cooling, namely the temperatures of subsequent 8 sections of barrels are respectively 280 ℃, 275 ℃, 270 ℃ and 265 ℃ of the die head.
(5) Starting the extruder, directly feeding the materials A and B which are mixed according to the designed proportion or respectively metering, distributing and feeding the materials A and B by adopting a metering scale, feeding the materials B into the extruder, adjusting the rotating speed and the feeding speed of the screw rod to ensure that the rotating speed of the screw rod is stabilized at the working condition of 160rpm, the temperature of an extruded melt is stabilized at about 270 ℃, and carrying out brace or water ring granulation to obtain the low-cost modified high-flame-retardant-temperature nylon 66 material.
Comparative example
Conventional MCA modified flame-retardant nylon 66 granules are manufactured by using a conventional extrusion granulation process according to the weight part ratio of each proportion in Table 1.
TABLE 1
Test example
The pellets of the examples and comparative examples shown in Table 1 were injection-molded into standard samples, and the tensile properties of the plastics were determined according to GB/T1040.2-2006, part 2: test conditions for molded and extruded plastics "measurement of tensile Strength, [ GB/T1043.1-2008 determination of impact Properties of Plastic simple beams part 1: non-instrumented impact test for measuring notch impact strength of a simply supported beam, GB/T2408 & 2008. plastic combustion performance measurement horizontal method and vertical method for measuring flame retardant performance of vertical combustion (UL94), and GBT 5169.12-2013 part 12 of electrical and electronic product ignition risk test: glow wire/hot wire basic test methods the Glow Wire Flammability Index (GWFI) of a material was measured. The test results are shown in Table 2.
TABLE 2
As can be seen from Table 2, comparative example 1 used only conventional MCA as a flame retardant, and when the conventional MCA content was 12%, although the tensile strength of the specimen was higher than 60MPa and the impact strength of the simple beam notch was higher than 5KJ/m2The vertical burning flame retardant performance can only reach UL 94V-2, and the glow wire flammability index can not pass the GWFI 960/2.0 test. In comparative examples 2 to 3, the impact strength was less than 5KJ/m although the flame retardancy was improved by increasing the amount of conventional MCA2. Example 1 addition of 12% of fine MCA (based on 100% total of nylon 66 and fine MCA and conventional MCA) resulted in vertical flame performance of UL-94V-0 and a glow wire flammability index of GWFI 960/2.0. Examples 2 and 3 by compounding the fine MCA with the conventional MCA, it can be seen that when the fine MCA is reduced and the tensile strength of the conventional MCA is increased, more flame retardant ingredients can be added, the tensile strength is still higher than 60MPa, and the impact strength of the beam notch is also higher than 5.0KJ/m2Since both conventional MCA and fine MCA are less expensive than nylon 66, both formulations are less costly.
Example 4 is only adding nylon 66 and fine MCA, compared with example 1, no PEG is added, and it can be seen that 12% of fine MCA is added, no auxiliary agent is added, although the flame retardant property can be ensured to meet the requirement, the impact strength can only reach the barely standard;
example 5 in order to add polytetrafluoroethylene to example 1, it can be seen that the fine MCA not only can pass the high flame retardant temperature test at 960 ℃, but also the impact strength is obviously improved after the addition of PEG and polytetrafluoroethylene auxiliaries.
The high flame-retardant temperature characteristic can be embodied by the test of high glow wire temperature (namely GWFI 960/2.0) in the embodiments 1 to 5 under the condition of keeping higher tensile strength and simple beam notch impact strength.
Examples 6 to 10
According to the weight parts of the examples in the table 3, the nylon 66 granules with high flame retardant temperature are obtained according to the following steps:
(1) the nylon 66 raw material resin is placed in a blast oven or a vacuum rotary drum to be dried and dewatered until the water content in the raw material is less than or equal to 1000ppm to form a pretreatment material (A).
(2) In order to improve the dispersion effect of the MCA flame retardant, the MCA flame retardant and auxiliary agents such as PEG powder, PTFE powder and the like are premixed and dispersed uniformly in a three-dimensional motion mixer according to a set proportion to form a premix (B).
(3) And directly stirring and mixing the premixed flame retardant (A) material and the dried nylon 66(B) material resin according to a designed proportion, and putting the mixture into a feeding bin of an extrusion granulator or respectively putting the mixture into a metering feeding weighing bin for later use.
(4) Starting and preheating a double-screw extrusion granulator, wherein the double-screw extrusion granulator is a co-rotating double-screw extruder, the length-diameter ratio is 36D, the temperature of a feeding, conveying and mixing section is set at 270 ℃, and the temperature of a subsequent melting section, a metering section and a die head are set to be stepped cooling, namely the temperatures of subsequent 8 sections of barrels are respectively 280 ℃, 275 ℃, 270 ℃ and 265 ℃ of the die head.
(5) Starting the extruder, directly feeding the materials A and B which are mixed according to the designed proportion or respectively metering, distributing and feeding the materials A and B by adopting a metering scale, feeding the materials B into the extruder, adjusting the rotating speed and the feeding speed of the screw rod to ensure that the rotating speed of the screw rod is stabilized under the working condition of 180rpm, the temperature of an extruded melt is stabilized within the range of 270 ℃, and carrying out bracing or water ring granulation to obtain the low-cost modified high-flame-retardant-temperature nylon 66 material.
TABLE 3
| Serial number | Nylon 66 | Fine MCA | PEG | PTFE |
| Example 6 | 79 | 20 | 0.3 | 0.4 |
| Example 7 | 80 | 20 | 0.1 | 0.3 |
| Example 8 | 85 | 15 | 0.15 | 0.25 |
| Example 9 | 82 | 18 | 0.25 | 0.35 |
| Example 10 | 81 | 19 | 0.2 | 0.2 |
The products obtained in examples 6 to 10 were tested for their properties in the same manner as in examples 1 to 5, and the test results are shown in Table 4.
TABLE 4
From the above table 4, it can be seen that the reasonable matching of the PEG, the polytetrafluoroethylene and the fine MCA can stably obtain the low-cost high flame-retardant temperature nylon 66 fuel-resistant product with high MCA addition amount and meeting the requirements of high flame-retardant temperature and proper impact strength.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes that do not depart from the spirit and principle of the present invention should be regarded as equivalent substitutions and all such changes are included in the scope of the present invention.
The above embodiments are merely illustrative of the technical solutions of the present invention, and not restrictive, and those skilled in the art may make changes, substitutions, modifications, and simplifications in the spirit of the present invention and equivalent changes without departing from the spirit of the present invention, and shall fall within the protection scope of the claims of the present invention.
Claims (10)
1. The modified high flame retardant temperature nylon 66 is characterized by comprising the following components in parts by weight: nylon 66: 79-88, fine melamine cyanurate: 12-20, polyethylene glycol: 0.1-0.3, polytetrafluoroethylene: 0.0 to 0.4.
2. The modified nylon 66 with high flame retardant temperature of claim 1, wherein the modified nylon 66 with high flame retardant temperature comprises the following components in parts by weight: nylon 66: 80-85, fine melamine cyanurate: 15-18, polyethylene glycol: 0.15-0.25, polytetrafluoroethylene: 0.1 to 0.3.
3. The modified nylon 66 with high flame-retardant temperature as claimed in claim 1 or 2, wherein the fine melamine cyanurate has a submicron-sized and lamellar structure with a diameter of 0.2-0.6 μm, a thickness of 10-90 nm and a specific surface area of 30-220 m2/cm3In the meantime.
4. The modified nylon 66 with high flame retardant temperature as claimed in claim 1 or 2, wherein the nylon 66 is dried and heat treated to remove water before use; the technological conditions for drying, heat treatment and water removal are that the drying is carried out by a blast oven at 80-90 ℃ for 14-18 hours or the drying is carried out by a vacuum drum at 140-160 ℃ for 2-3 hours.
5. The modified nylon 66 with high flame retardant temperature as claimed in claim 1 or 2, wherein the polyethylene glycol is PEG 6000.
6. The modified nylon 66 with high flame retardant temperature according to claim 1 or 2, wherein the polytetrafluoroethylene is a polytetrafluoroethylene micropowder with a base particle size of 0.15-1.5 μm.
7. The preparation method of the modified high flame retardant temperature nylon 66 according to claim 1, characterized by comprising the following steps:
(1) drying and heat-treating nylon 66 to remove water until the water content in the raw material is less than or equal to 1000ppm to form a pretreatment material (A).
(2) And premixing and dispersing the fine melamine cyanurate, polyethylene glycol and polytetrafluoroethylene uniformly to form premix (B).
(3) And (3) putting the pretreatment material (A) obtained in the step (1) and the premix (B) obtained in the step (2) into a double-screw extruder for extrusion and granulation to obtain a product.
8. The preparation method of the modified nylon 66 with high flame retardant temperature according to claim 1, wherein the drying heat treatment for removing water in the step (1) is carried out in a forced air oven or a vacuum drum.
9. The method for preparing modified nylon 66 with high flame retardant temperature according to claim 1, wherein the premixing and dispersing in step (2) are carried out in a three-dimensional moving mixer.
10. The method for preparing modified nylon 66 with high flame retardant temperature as claimed in claim 1, wherein the twin-screw extrusion granulator in step (3) is a co-rotating twin-screw extruder, the length-diameter ratio is 36D-44D, the temperature of the feeding, conveying and mixing section is set at 270-280 ℃, the temperature of the subsequent melting section, the metering section and the step cooling of the die head are set, the temperature of the die head is lower than the temperature of the metering section, and the lowest temperature is not lower than 260 ℃;
the pretreatment material (A) and the premix (B) are mixed according to the design proportion and directly fed into a double-screw extrusion granulator; or respectively metering and distributing the pretreatment material (A) and the premix (B) by adopting a metering scale to enter a double-screw extrusion granulator, adjusting the rotating speed and the feeding speed of the screw, stabilizing the rotating speed of the screw under the working condition of 160-plus-180 rpm, stabilizing the temperature of the extruded melt within the range of 265-plus-275 ℃, and carrying out bracing or water ring granulation to obtain the low-cost modified high-flame-retardant-temperature nylon 66 material.
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| CN108424639A (en) * | 2018-03-13 | 2018-08-21 | 苏州银禧科技有限公司 | Dedicated modified nylon 6 material of a kind of automobile halogen-free flameproof thermostabilization bellows and preparation method thereof |
| CN110317181A (en) * | 2019-06-13 | 2019-10-11 | 山东泰星新材料股份有限公司 | A kind of preparation method and applications of melamine cyanurate nanometer sheet microballoon |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408926A (en) * | 2013-06-26 | 2013-11-27 | 安徽科聚新材料有限公司 | Polyamide composite material and preparation method thereof |
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