CN111748203A - Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof - Google Patents
Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and a preparation method thereof. The composition is prepared from the following components in parts by mass: 32.4-60.3 parts of high-temperature nylon, 10-50 parts of reinforcing fibers, 12-20 parts of brominated flame retardant, 3-6 parts of boehmite, 1-3 parts of caprolactam, 0.5-1 part of antioxidant and 0.2-0.6 part of lubricant. The prepared caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material has high strength (tensile strength, bending strength, impact strength and dielectric strength) and good flame-retardant effect, and reaches the V-0 level. The heat distortion temperature is higher relative to the tracking index. Meanwhile, the product particles have compact appearance, do not foam and have light yellow or yellow color. Meeting the market demand.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and a preparation method thereof.
Background
The semi-aromatic nylon has the characteristics of high mechanical strength, high temperature resistance, chemical resistance, good thermal stability, excellent electrical performance and the like, and is widely applied to the field of electronics and electricity. Due to the requirements of miniaturization and high performance of electronic, electrical and information related equipment, various electrical elements are smaller and smaller, and more rigorous requirements are provided for the electrical, flame retardant and insulating properties of plastic elements. At present, the most economical and convenient method is to add an additive with a flame-retardant function into a plastic matrix to enable the material to meet the requirement of difficult combustion, and the flame-retardant additive is divided into a halogen-containing halogen flame retardant and a halogen-free flame retardant containing flame-retardant elements such as phosphorus, nitrogen, sulfur, silicon and the like. The halogen flame retardant is commonly used for brominated flame retardants such as brominated polystyrene, brominated triazine and the like, the melting point of the halogen flame retardants is matched with that of a plastic substrate, the halogen flame retardants are co-melted with a plastic melt during processing, the material popularity is good, the mechanical property is not influenced, the main mechanism is gas-phase flame retardance, the bond of C-Br can be decomposed to produce HBr gas to block oxygen and capture free radicals, but the HBr has low density and can not completely block oxygen, and the combustion surface of the plastic substrate can not form a compact blocking layer, so the single use efficiency is low, and the halogen flame retardants need to be matched with metal oxides for use. The industrial use of the material is generally metal oxides such as antimony trioxide and zinc borate, the addition of the antimony trioxide can reduce the electric breakdown strength and the relative tracking index of the material, the material is easy to corrode a mold and is easy to discolor at high temperature, the zinc borate generally contains crystal water, the water loss temperature is about 300 ℃, the water loss temperature is lower than that of the high-temperature nylon processing, the material is easy to foam, and the anhydrous zinc borate is easy to absorb water and is not beneficial to storage; the halogen-free flame retardant has a high melting point which is generally far greater than that of the plastic matrix, exists in the form of solid small particles, and has poor compatibility with the plastic matrix. The flame retardant is required to be added in a large amount to meet the flame retardant requirement, so that the physical properties of the material are deteriorated, the material is easy to separate out, and the material is not resistant to boiling and is not suitable for being applied to plastic shells and transmission parts with mechanical strength requirements and in severe working environments; when boehmite is used as a synergistic flame retardant, the boehmite surface has a large amount of hydroxyl groups, the surface polarity is large, the compatibility with a plastic matrix is poor, and the boehmite powder is easily dispersed unevenly, so that the flame retardant effect and the impact strength of the material are reduced.
Disclosure of Invention
The invention aims to provide a caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material which is good in flame-retardant effect, high in strength and high in relative tracking index. The impact strength of the material added with caprolactam is from 10kj/m2Increased to 12kj/m2The flame retardant grade is improved from the original V-1 to V-0, and the bonding strength of the interface of the two can be improved and the dispersion of boehmite can be promoted by adding caprolactam for compatibilization.
In order to achieve the purpose, the invention provides a caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material which is characterized by being prepared from the following components in parts by mass:
further, the high-temperature nylon is one or more than one of copolymer of poly (hexamethylene terephthalate) and m-hexamethylene diamine, namely PA6T/6I, copolymer of poly (hexamethylene terephthalate) and caprolactam, namely PA6T/6, copolymer of poly (hexamethylene terephthalate) and hexamethylene diamine adipate, namely PA 6T/66; preferably, the high-temperature nylon has a nylon concentration of 0.05g/ml, a m-toluene solvent and an intrinsic viscosity of 0.6-1.0 at 25 ℃.
Further, the reinforcing fiber is at least one of glass fiber, carbon fiber, boron fiber and basalt fiber; preferably, the reinforcing fiber is glass fiber with the chopped length of 3-5mm and the diameter of 7-11 mu M.
Further, the brominated flame retardant is brominated polystyrene, the bromine content of which is 68.5 percent, and the molecular weight of which is 67000-15000.
Further, the boehmite is gamma-AlOOH white powder; preferably, the whiteness is more than 95%, and the particle size D50 is 0.8-8 μm of gamma-AlOOH white powder.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 9228 and antioxidant 168.
Further, the lubricant is one or two of modified high molecular weight silicone lubricant E525 and ethylene acrylic acid copolymer AC 540A.
Further, the preparation method comprises the following steps of,
preparing a premix: weighing high-temperature nylon, a brominated flame retardant, boehmite, an antioxidant and a lubricant according to a proportioning table, and uniformly mixing in a low-speed mixer to obtain a premix;
extruding: adding the premix into a double-screw extruder, adding the reinforcing fiber from a side feed according to the mass ratio, wherein the extrusion temperature is 280-320 ℃, and the rotating speed is 350-500 r/min; preferably, the twin-screw extruder has a major axis of 36 to 44 and a medium-strength screw is used.
The reinforcing fiber is added from the side feed, so that the glass fiber is prevented from being too short, and the flame retardant property is prevented from being influenced. Because the single glass fiber is very fragile, strong shearing force can be formed between the screw rods and the cylinder of the plastic particles which are not melted, the glass fiber is broken, and the length of the fiber needs to be larger than the critical length required by the material to have the reinforcing effect.
The proportion of caprolactam used as a compatilizer is increased along with the increase of the boehmite content, the content of the flame retardant and the content of the reinforcing fiber are matched with each other, so that the material can reach UL-94V-0 grade, and the content of the glass fiber is changed along with the difference of end application of the material.
According to the invention, caprolactam in-situ modified boehmite is used, and caprolactam is utilized to open rings at high temperature to react with hydroxyl on the surface of boehmite and amino and carboxyl at the end of high-temperature nylon, so that the reaction compatibilization effect is achieved. The boehmite prepared by the hydrothermal method is in a fiber shape or a strip shape, has a certain reinforcing effect, has the Mohs hardness of 3.5 which is far lower than the hardness of the glass fiber, is not easy to break the glass fiber in the processing process, and can improve or maintain the mechanical property of the material; the aspect of synergistic flame retardance: compared with zinc borate (dehydration at 300 ℃), boehmite has the decomposition temperature of more than 400 ℃, has the characteristic of difficult dehydration at the processing temperature of high-temperature nylon of about 300 ℃, can improve the condition that zinc borate is added when high electrical performance is required, and anhydrous zinc borate has high cost and is difficult to store; the hydrous zinc borate is easy to lose water at the processing temperature, so that the material is foamed and the processing is poor. On the other hand, compared with antimony trioxide, boehmite has the advantages that the electrical performance of the material is not easily reduced, and the defect that the antimony trioxide is easily reduced into an antimony simple substance at high temperature to blacken the material can be avoided.
The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material prepared in the embodiment has high strength (tensile strength, bending strength, impact strength and dielectric strength) and good flame-retardant effect, and all the flame-retardant effects reach V-0 level. The heat distortion temperature is higher relative to the tracking index. Meanwhile, the product particles have compact appearance, do not foam and have light yellow or yellow color. The requirements of electronic and electric products, such as automobile electronics, personal consumer terminals and the like in the field sensitive to the weight of the product are met.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material is characterized by being prepared from the following components in parts by mass:
further, the high-temperature nylon is one or more than one of copolymer of poly (hexamethylene terephthalate) and m-hexamethylene diamine, namely PA6T/6I, copolymer of poly (hexamethylene terephthalate) and caprolactam, namely PA6T/6, copolymer of poly (hexamethylene terephthalate) and hexamethylene diamine adipate, namely PA 6T/66; preferably, the high-temperature nylon has a nylon concentration of 0.05g/ml, a m-toluene solvent and an intrinsic viscosity of 0.6-1.0 at 25 ℃.
Further, the reinforcing fiber is at least one of glass fiber, carbon fiber, boron fiber and basalt fiber; preferably, the reinforcing fiber is glass fiber with the chopped length of 3-5mm and the diameter of 7-11 mu M.
Further, the brominated flame retardant is brominated polystyrene, the bromine content of which is 68.5 percent, and the molecular weight of which is 67000-15000.
Further, the boehmite is gamma-AlOOH white powder; preferably, the whiteness is more than 95%, and the particle size D50 is 0.8-8 μm of gamma-AlOOH white powder.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 9228 and antioxidant 168.
Further, the lubricant is one or two of modified high molecular weight silicone lubricant E525 and ethylene acrylic acid copolymer AC 540A.
Further, the preparation method comprises the following steps of,
preparing a premix: weighing high-temperature nylon, a brominated flame retardant, boehmite, an antioxidant and a lubricant according to a proportioning table, and uniformly mixing in a low-speed mixer to obtain a premix;
extruding: adding the premix into a double-screw extruder, adding the reinforcing fiber from a side feed according to the mass ratio, wherein the extrusion temperature is 280-320 ℃, and the rotating speed is 350-500 r/min; preferably, the twin-screw extruder has a major axis of 36 to 44 and a medium-strength screw is used.
Example 1: preparation of caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Example 2: preparation of caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Example 3: preparation of caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 1: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 2: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 3: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 4: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 5: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
TABLE 1 tables for the amounts of the examples and comparative examples in the data sheet (parts by weight)
Note: PA6T/66 terephthalic acid: adipic acid: the molar ratio of the hexamethylene diamine is 1:1: 2.
TABLE 2 table of functional test results of examples and comparative examples
When the boehmite loses water at 400 ℃, a large amount of heat can be absorbed, the sheet structure of the boehmite forms a labyrinth effect, combustible substances can be prevented from migrating to the combustion surface, a fuel channel is cut off, and therefore a compact alumina layer is formed through dehydration at high temperature. Reduce smoke while isolating oxygen, and part of aluminum can react with HBr to produce AlBr3The boehmite prepared by the hydrothermal method is in a fiber shape or a strip shape and has a certain reinforcing effect, the Mohs hardness is 3.5 and is far lower than the hardness of the glass fiber, the glass fiber is not easy to break in the processing process, and the mechanical property of the material can be improved or maintained. Compared with the comparative example 1, the flame retardant property of the material is improved from V-2 to V-0 by adding the boehmite in the example 2, which shows that the boehmite has a synergistic flame retardant effect and a certain strength enhancing effect. The decomposition temperature of boehmite is more than 400 ℃, the boehmite has the characteristic of being difficult to dehydrate at the processing temperature of about 300 ℃ of high-temperature nylon, and compared with the comparative example 2, the appearance of the particles added with boehmite is dense, and the foaming phenomenon cannot occur; oxidation of oxygenThe metal oxides such as antimony can be promoted to carbon in a catalytic mode, so that the dielectric strength of the material is reduced, and compared with the comparative example 3, by adding antimony trioxide in the embodiment 2, boehmite can maintain the dielectric strength and the relative tracking index of the material, and the material cannot be blackened due to discoloration; the melting point of the halogen-free flame retardant is far higher than the processing temperature of the material, the halogen-free flame retardant is distributed in a plastic matrix in the form of filler in the processing process, and the addition is large, so that the physical properties of the material are easily deteriorated, and the embodiment 2 and the comparative example 4 show that compared with the halogen-free flame retardant material, the material compounded by adding the brominated flame retardant and the boehmite has more mechanical strength and can be used for a shell and a mechanical transmission part with mechanical strength requirements; the compatibility of boehmite and matrix resin is low in interfacial bonding strength when not compatibilized by caprolactam, and the boehmite and the matrix resin are easily debonded under the action of external force to form pores, so that stress concentration is caused, and the mechanical strength and the impact strength of the material are poor, which can be obtained by comparing example 2 with comparative example 5, and comparing comparative example 5, the impact strength of the material added with caprolactam is from 10kj/m2Increased to 12kj/m2The flame retardant grade is improved from the original V-1 to V-0, and the bonding strength of the interface of the two can be improved and the dispersion of boehmite can be promoted by adding caprolactam for compatibilization.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (8)
1. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material is characterized by being prepared from the following components in parts by mass:
2. the caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the high temperature nylon is one or more of poly (hexamethylene terephthalate) and m-hexamethylene terephthalate copolymer (PA 6T/6I), poly (hexamethylene terephthalate) and caprolactam copolymer (PA 6T/6), poly (hexamethylene terephthalate) and adipic acid hexamethylene diamine copolymer (PA 6T/66); preferably, the high-temperature nylon has a nylon concentration of 0.05g/ml, a m-toluene solvent and an intrinsic viscosity of 0.6-1.0 at 25 ℃.
3. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the reinforcing fiber is at least one of glass fiber, carbon fiber, boron fiber and basalt fiber; preferably, the reinforcing fiber is glass fiber with the chopped length of 3-5mm and the diameter of 7-11 mu M.
4. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material as set forth in claim 1, wherein the brominated flame retardant is brominated polystyrene, the bromine content of which is 68.5%, and the molecular weight of which is 67000-15000.
5. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the boehmite is gamma-AlOOH white powder; preferably, the whiteness is more than 95%, and the particle size D50 is 0.8-8 μm of gamma-AlOOH white powder.
6. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material as claimed in claim 1, wherein the antioxidant is one or a mixture of more than one of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 9228 and antioxidant 168.
7. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the lubricant is one or two of modified high molecular weight silicone lubricant E525, ethylene acrylic acid copolymer AC 540A.
8. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, which is prepared by the steps of,
preparing a premix: weighing high-temperature nylon, a brominated flame retardant, boehmite, an antioxidant and a lubricant according to a proportioning table, and uniformly mixing in a low-speed mixer to obtain a premix;
extruding: adding the premix into a double-screw extruder, adding the reinforcing fiber from a side feed according to the mass ratio, wherein the extrusion temperature is 280-320 ℃, and the rotating speed is 350-500 r/min; preferably, the twin-screw extruder has a major axis of 36 to 44 and a medium-strength screw is used.
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