CN112920598B - Precipitation-free low-water-absorption halogen-free flame-retardant reinforced nylon 66 and preparation method and application thereof - Google Patents
Precipitation-free low-water-absorption halogen-free flame-retardant reinforced nylon 66 and preparation method and application thereof Download PDFInfo
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
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- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The reinforced nylon 66 is free of precipitation, low in water absorption and halogen-free, and the preparation method and the application thereof are disclosed, wherein the reinforced nylon 66 comprises the following components: nylon 66 resin, halogen-free flame retardant, synergist, glass fiber, anti-precipitation agent, nucleating agent, dispersant, lubricant and antioxidant. Adding nylon 66 resin into a main material scale, adding a halogen-free flame retardant, a synergist, a precipitation preventing agent, a nucleating agent, a dispersant, a lubricant and an antioxidant into a mixer, mixing, adding an auxiliary material scale, adding glass fiber into a side feeding metering scale, starting a double-screw extruder, sequentially starting the main material metering extruder and the auxiliary material metering extruder, discharging, starting the side feeding metering extruder, heating, melting, blending and extruding in the double-screw extruder, cooling, and granulating to obtain the flame retardant. The reinforced nylon 66 has the advantages of high strength, high flame retardance, no precipitation, low water absorption, stable size, no toxicity and environmental protection. The method has simple process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to a flame-retardant reinforced nylon 66 and a preparation method and application thereof, in particular to a precipitate-free low-water-absorption halogen-free flame-retardant reinforced nylon 66 and a preparation method and application thereof.
Background
The flame-retardant reinforced PA66 is widely applied to electric, electronic and electrical appliance structural parts due to excellent mechanical properties and heat resistance. In the last century, the manufacturing of the flame-retardant reinforced PPA66 composite material adopts a brominated flame retardant which has the characteristics of good flame-retardant effect, small using amount and small influence on the mechanical property of the composite material, so that the brominated flame retardant is widely applied. Because the brominated flame retardant can generate dioxin in the combustion process and cause serious pollution to the environment, the application of the brominated flame retardant in the flame-retardant reinforced PPA66 composite material is greatly limited by environmental protection regulations in the European Union at the beginning of the century.
Since this century, halogen-free flame retardants were developed in succession in the industry to replace brominated flame retardants: red phosphorus is nontoxic, the addition amount is small, but only black products can be produced; the melamine cyanurate is nontoxic and tasteless, but can only produce pure flame-retardant nylon; the alkylated hypophosphite has good flame retardant effect, can be used for reinforcing flame retardant nylon, has higher decomposition temperature and has wider applicability. Therefore, attempts have been made to use phosphates as flame retardant materials.
CN101503569A discloses a glass fiber reinforced halogen-free flame retardant PA66 and a preparation method thereof, wherein phosphate melamine and melamine phosphate are used as flame retardants to prepare the halogen-free flame retardant reinforced PA66, which can reach UL94V-0 level (3.2 mm); CN 110183849A discloses a novel halogen-free flame-retardant reinforced PA66 composite material and a preparation method thereof, diethyl aluminum hypophosphite and diisobutyl aluminum hypophosphite are adopted as flame retardants, and melamine phosphate, ammonium polyphosphate, dipentaerythritol, pentaerythritol and sorbitol are adopted as synergists to prepare halogen-free flame-retardant reinforced PA66; CN109608878A discloses a moisture-heat aging resistant halogen-free flame-retardant reinforced PA/POK alloy material, which is prepared by compounding diethyl aluminum hypophosphite and polysilane; CN109852050A discloses a glass fiber reinforced low-smoke halogen-free flame-retardant PA66 material and a preparation method thereof, and the low-smoke halogen-free flame-retardant reinforced PA66 is prepared by adopting triazine resin coated ammonium polyphosphate as a flame retardant. However, the inventors have found that these materials generally have a problem of bleeding of the flame retardant, which is a problem generally found in phosphorus-based flame retardants. The electric insulation of the parts is affected by the precipitation of low molecular substances such as flame retardants, or the voltage breakdown resistance of the parts is reduced, so that the safety of the electric appliance parts is adversely affected; meanwhile, the water absorption of the material is high, which affects the dimensional stability of the component and further affects the stability of signal transmission, especially as an electrical equipment connector, the dimensional change of the material can cause poor contact of the conductive element to generate heat or sparks, and in severe cases, the material can cause fire.
In addition, more amide groups with strong water absorption exist in the PA66 macromolecular chain, the saturated water absorption rate of the amide groups reaches 3.6%, the water absorption of the amide groups changes along with the changes of the environmental humidity and the temperature, for example, when the humidity is high and the temperature is low in spring, the water absorption rate of the amide groups is high, for example, when the humidity is low and the temperature is high in autumn, the water absorption rate of the amide groups is reduced, the change process of the water absorption rate of the PA66 resin is actually the migration process of water molecules in the PA66 resin matrix, when the environmental humidity is reduced and the temperature is increased, water in the resin can migrate from the interior of the material to the surface to be separated from the resin, the size of a product is reduced, and when the environmental humidity is increased, the water molecules permeate into the interior of the product from the surface of the product, and the size of the product is increased. Resulting in variations in component dimensions; meanwhile, migration of water molecules in the PA66 resin promotes migration of low-molecular compounds to a great extent, so that water absorption of the PA66 resin greatly increases migration of low-molecular compounds such as flame retardants.
Therefore, the method solves the technical problems of precipitation and water absorption of the halogen-free flame-retardant reinforced nylon material and is very important for the safety of electric and electronic parts.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the precipitation-free low-water-absorption halogen-free flame-retardant reinforced nylon 66 which has high strength, high flame retardance, stable size, no toxicity and environmental friendliness.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method and application of the precipitation-free, low-water-absorption, halogen-free and flame-retardant reinforced nylon 66, which is simple in process, low in cost and suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: the precipitation-free low-water-absorption halogen-free flame-retardant reinforced nylon 66 comprises the following components: nylon 66 resin, halogen-free flame retardant, synergist, glass fiber, anti-precipitation agent, nucleating agent, dispersant, lubricant and antioxidant.
The inventor researches and discovers that the existing halogen-free flame-retardant reinforced PA66 is mainly precipitated due to three reasons: firstly, due to the precipitation characteristic of the flame retardant, for example, the compatibility between phosphate and PA66 is poor, the flame retardant is unevenly dispersed in the PA66 resin, and precipitation is easily generated when part of the flame retardant is accumulated; secondly, the low molecular auxiliary agent which is easy to separate out such as the used synergist can accelerate the separation out of the flame retardant; thirdly, the water absorption of PA66 also accelerates the precipitation of the flame retardant. Therefore, to solve the problem of precipitation of the halogen-free flame retardant reinforced PA66 material, the design of the material composition is used for the following steps: selecting a halogen-free flame retardant, a synergist and a lubricant which have certain compatibility or larger molecular weight with PA66; a dispersing agent is selected to improve the dispersibility of the flame retardant; a precipitation preventing agent and a nucleating agent are selected to change the aggregation structure of PA66 and form the speed of preventing or slowing the precipitation of low molecules; by reducing the water absorption of PA66; by adding the antioxidant, the decomposition of PA66 in the heating melting process, particularly the low molecular substances generated by hydrolysis, is prevented. The addition of the glass fiber can greatly improve the strength of the flame-retardant reinforced PA66 material, and can reduce the water absorption of the composite material and the precipitation of the flame retardant to a certain extent.
Preferably, the precipitation-free, low-water-absorption, halogen-free, flame-retardant and reinforced nylon 66 comprises the following components in parts by weight: 100 parts of nylon 66 resin, 10-16 parts of halogen-free flame retardant, 4-8 parts of synergist, 30-50 parts of glass fiber, 5-20 parts of anti-precipitation agent, 0.1-0.5 part of nucleating agent, 0.3-1.0 part of dispersant, 0.3-0.6 part of lubricant and 0.4-0.8 part of antioxidant.
If the amount of the halogen-free flame retardant is too small, the flame retardant effect is limited, and if the amount of the halogen-free flame retardant is too large, the dispersibility is poor. If the dosage of the synergist is too small, the synergistic effect on the halogen-free flame retardant is limited, and if the dosage of the synergist is too large, the mechanical property of the material is greatly influenced. If the glass fiber consumption is too small, the reinforcement performance of the nylon composite material is poor, the wrapping performance of the nylon composite material on resin is poor, the flame retardant and the auxiliary agent are easy to migrate, and if the glass fiber consumption is too large, the uniform dispersion is not easy to occur, and the toughness of the nylon composite material is also reduced. If the addition amount of the anti-precipitation agent is too small, the anti-precipitation functionalization is not obvious, or a micro-layered structure is difficult to form, and the barrier effect is reduced, if the addition amount of the anti-precipitation agent is too large, low molecular substances are easy to decompose at high temperature due to the fact that the blending extrusion temperature is higher than the melting point of the anti-precipitation agent, the mechanical property of the material and the appearance quality of a processing part are influenced, or the blend forms a two-phase separation structure, and the mechanical property and the flame retardance of the material are reduced. If the amount of the nucleating agent is too small, the structure of the nylon composite material is not compact and regular enough, and the flame retardant and the auxiliary agent are difficult to be separated out in a synergistic manner, and if the amount of the nucleating agent is too large, the preparation cost of the material is increased. Although the use amount of the dispersing agent is increased to facilitate dispersion of the glass fiber and the flame retardant, the flame retardancy of the glass fiber and the flame retardant is affected when the addition amount is too large.
More preferably, the precipitation-free, low-water-absorption, halogen-free, flame-retardant and reinforced nylon 66 comprises the following components in parts by weight: 100 parts of nylon 66 resin, 12-15 parts of halogen-free flame retardant, 4-6 parts of synergist, 30-50 parts of glass fiber, 10-18 parts of anti-precipitation agent, 0.2-0.4 part of nucleating agent, 0.3-0.8 part of dispersant, 0.3-0.6 part of lubricant and 0.4-0.6 part of antioxidant.
Preferably, the nylon 66 resin has a relative intrinsic viscosity of 2.4 to 3.2 (more preferably 2.5 to 2.8). The relative intrinsic viscosity indicates its molecular weight, and if the viscosity is low, the molecular weight is small, and vice versa. If the viscosity of the PA66 is too low, the mechanical property of the prepared flame-retardant reinforced PA66 composite material is low; if the viscosity of PA66 is too high, the melt flowability of the PA66 resin is low, and the dispersibility of the flame retardant is affected.
Preferably, the particle size of the halogen-free flame retardant is 50 to 150nm (more preferably 80 to 120 nm). If the particle size is too large, the addition amount is large, the dispersibility is poor, the flame retardant effect is poor, and if the particle size is too small, agglomeration is likely to occur.
Preferably, the halogen-free flame retardant is an alkyl phosphate.
Preferably, the alkyl phosphate is one or more of diethyl aluminum hypophosphite, diethyl calcium hypophosphite or diethyl sodium hypophosphite. More preferably, the alkyl phosphate is a complex of diethyl aluminum hypophosphite and diethyl sodium hypophosphite, and still more preferably OP1400 manufactured by clariant corporation.
Preferably, the synergist is one or more of macromolecular ammonium polyphosphate, polysiloxane, phenoxycyclotriphosphazene or triphenyl phosphate. The polyphosphoric acid amine and the polysiloxane are high molecular polymers, and have a good synergistic effect on the flame retardant; the phenoxy cyclotriphosphazene has certain compatibility with PA66 and has better synergistic effect with a flame retardant; the triphenyl phosphate has better synergistic effect. The zinc borate as the conventional synergist has a good synergistic effect on flame retardance, but because the zinc borate contains crystal water, the crystal water volatilizes in the melt blending process, so that PA66 can be hydrolyzed to generate low-molecular PA66, and the mechanical property of the composite material is reduced.
More preferably, the synergist is a compound of macromolecular polyphosphoric acid amine and polysiloxane resin in a mass ratio of 1-3.
Preferably, the molecular weight of the high molecular poly phosphoric acid amine is more than or equal to 18000. The synergist can effectively improve the flame retardant effect of the flame retardant, but has a great influence on the precipitation of the flame retardant, the high molecular weight poly (ammonium polyphosphate) has good compatibility with PA66 and a good synergistic effect, the poly (ammonium polyphosphate) is easy to precipitate when the molecular weight of the poly (ammonium polyphosphate) is less than 10000, and the precipitation is very little when the molecular weight of the poly (ammonium polyphosphate) is more than 18000.
Preferably, the glass fiber is alkali-free chopped fiber. More preferably glass fiber 301HP available in Chongqing International.
Preferably, the fibers have a length of 3.5 to 4.5mm and a monofilament diameter of 7 to 13 μm (more preferably 7 to 10 μm). The glass fiber length and the monofilament diameter influence the mechanical property of the composite material and the surface smoothness of the composite material, and the longer the glass fiber dispersed in the PA66 resin, the smaller the monofilament diameter, the higher the strength of the material; and vice versa. If the length of the glass fiber is too long or the diameter of the monofilament is too large, the surface of the material is rougher; if the monofilament diameter or the fiber length of the fiber is smaller, the bonding property, the compactness and the surface finish of the material are higher, the combination between the glass fiber and the PA66 resin is tighter, the PA66 resin is better coated, and the flame retardant and the auxiliary agent are less prone to migration or precipitation.
Preferably, the anti-precipitation agent is PA6T/6I and/or low density polyethylene. The PA6T/6I is a random copolymerization transparent semi-aromatic nylon which is formed by condensation copolymerization of terephthalate/hexamethylene diamine and isophthalic acid/hexamethylene diamine salt/adipic acid/hexamethylene diamine salt, and because the amide groups in molecular chains are less, the water absorption of PA66 can be greatly reduced by blending with PA66, and the PA66 has good compatibility with PA66 and can improve the bending strength of PA66 to a certain extent; similarly, because the low-density polyethylene is a non-polar polymer, it has hydrophobic property and melting point much lower than that of PA66, at the processing temperature of PA66, the low-density polyethylene can easily form a film on the surface of the workpiece, which reduces its water absorption and can improve the impact resistance of PA66 to some extent. More preferably, the PA6T/6I is available from Qingdao Santoward chemical industries, inc. The addition of the two anti-precipitation agent polymers can change the aggregate structure of PA66 to a certain extent; the PA6T/6I is added, the regularity of PA66 molecular chain arrangement is not changed to a certain extent, the amide groups of the blend are reduced, and the PA6T/6I macromolecular chains contain a large number of benzene ring structures, so that the molecular chain movement of the blend is hindered, the migration of low-molecular substances is hindered to a great extent, and the precipitation of low-molecular substances such as flame retardants and the like can be effectively reduced; in the process of melt blending and extruding low-density polyethylene (LDPE) and PA66, the melt flowability of the LDPE is higher than that of the PA66 under the shearing action of a double screw, a film-shaped micro-lamellar structure can be formed in PA66 resin, namely a lamellar structure blend is formed, and the lamellar structure blocks a migration path of a low-molecular substance, namely the migration of the low-molecular substance is blocked, so that the migration speed of the low-molecular substance is reduced, and the precipitation of the low-molecular substance can be well reduced.
Preferably, the PA6T/6I has a relative intrinsic viscosity of 0.8 to 1.2. More preferably, the melting point of PA6T/6I is 315 ℃.
Preferably, the melt index of the low density polyethylene is 0.5 to 2.0. More preferably, the low density polyethylene has a melting point of 190 ℃.
Preferably, the nucleating agent is an organic nano-montmorillonite and/or an ionic polymer/metal oxide mixture. More preferably, the ionomer/metal oxide mixture is P22 of roman hass. The organic nano montmorillonite and ionic polymer/metal oxide mixture has a good nucleating effect on nylon resin, can effectively improve the crystallization speed of PA66, improve the regularity of macromolecular chain aggregates of the resin and increase the compactness of the material, thereby reducing the precipitation of a flame retardant and an auxiliary agent to a certain extent.
Preferably, the dispersant is grafted ethylene bis-stearamide. More preferably, the grafted ethylene bis-stearamide is grafted EBS (TAF-Sub>A) available from suzhou national photo-chemical. The dispersing agent has better lubricating and dispersing functions, the compatibility of EBS and PA66 is good, polar groups such as carboxyl, hydroxyl and the like are introduced through grafting, the polar groups have better cohesiveness with the surface of glass fiber, and can be chemically combined with amino of PA66 to play a coupling role; meanwhile, the flame retardant has better cohesiveness with the flame retardant and the synergist thereof, and promotes the dispersibility of the flame retardant in PA66 resin; and the decomposition temperature is 320 ℃, so that the flame retardant reinforced PA66 composite material can completely adapt to the processing temperature of a flame retardant reinforced PA66 system.
Preferably, the lubricant is a silicone resin and/or a pentaerythritol ester. The lubricant has the function of improving the fluidity and the demoulding property of the composite material, the silicone resin has good lubricating effect, and the silicone is a high molecular polymer, is not easy to separate out and decompose, and is the best lubricant of nylon; the pentaerythritol ester has good compatibility and lubricity with nylon resin.
Preferably, the antioxidant is a hindered phenolic compound and/or a high molecular weight phosphate ester. More preferably, the hindered phenolic compound is a main antioxidant, the high molecular weight phosphate is an auxiliary antioxidant, and the mass ratio of the hindered phenolic compound to the high molecular weight phosphate is 1-3. Still more preferably, the hindered phenol compound is antioxidant 1098, and the high molecular weight phosphate is antioxidant S9228. The high molecular weight phosphate has the important functions of resisting thermal oxidation, effectively controlling the thermal degradation of the PA66 resin in the heating and melting process, reducing the generation of low molecular weight substances, being beneficial to improving the flame resistance of materials, having excellent hydrolysis resistance and being beneficial to improving the precipitation resistance of flame retardants.
The technical scheme adopted for further solving the technical problems is as follows: a preparation method of non-precipitation and low-water-absorption halogen-free flame-retardant reinforced nylon 66 comprises the steps of adding nylon 66 resin into a main material scale, adding a halogen-free flame retardant, a synergist, a precipitation-preventing agent, a nucleating agent, a dispersing agent, a lubricant and an antioxidant into a mixer, mixing, adding an auxiliary material scale, adding glass fibers into a side feeding metering scale, starting a double-screw extruder, starting the main material and auxiliary material metering extruder in sequence, starting the side feeding metering extruder after discharging, heating, melting, blending and extruding in the double-screw extruder, cooling strips by water, and granulating in a granulator to obtain the non-precipitation and low-water-absorption halogen-free flame-retardant reinforced nylon 66.
Preferably, the temperature of the heating, melting, blending and extruding is 250-270 ℃, the vacuum degree is-0.06-0.09 MPa (more preferably-0.08-0.09 MPa), and the rotating speed of the extrusion is 400-600 rpm (more preferably 500-550 rpm). The extrusion rotating speed is related to the yield, the yield is high when the rotating speed is high, the shearing force of the screw is large, and the dispersibility of the glass fiber and the flame retardant is good when the shearing force of the screw is large. The method adopts a high-shear high-vacuum process, and can improve the dispersibility of the glass fiber and the flame retardant in the PA66 resin; the volatile low molecular weight substance in the blending material is extracted in high vacuum, so that the precipitation of the flame retardant can be controlled in the manufacturing process.
Preferably, the rotating speed of the cut pellets is 800-1000 rpm. The grain cutting speed is irrelevant to the double-screw extrusion speed and is relevant to the thickness of a strip, when the grain cutting speed is high, the strip is stretched to be thinner, the particle size of the manufactured flame-retardant reinforced PA66 composite material is small, the particles of the composite material are small, the processing temperature can be properly reduced during the forming processing, and the thermal degradation of the PA66 resin is favorably reduced.
The technical scheme adopted by the invention for further solving the technical problems is as follows: the application of the precipitation-free and low-water-absorption halogen-free flame-retardant reinforced nylon 66 is to apply the precipitation-free and low-water-absorption halogen-free flame-retardant reinforced nylon 66 to electric, electronic and electrical equipment components.
The invention has the following beneficial effects:
(1) According to the invention, a high molecular weight flame-retardant synergist, a lubricant, a dispersant with a coupling effect and a polymer with low water absorption and capable of improving a PA66 macromolecular aggregation structure are selected through material composition design, and the obtained non-precipitation low-water-absorption halogen-free flame-retardant reinforced PA66 has the notch impact strength as high as 13.0kJ/m 2 The tensile strength is up to 240MPa, the bending strength is up to 310MPa, the bending modulus is up to 12500MPa, the thermal deformation temperature is up to 260 ℃, the flame retardant grade is V-0 grade, no precipitation exists, the saturated water absorption is as low as 0.25 percent, the size is stable, the halogen-free flame retardant reinforced PA66 composite material is non-toxic and environment-friendly, and the technical problem that the halogen-free flame retardant reinforced PA66 composite material is easy to precipitate is fundamentally solved;
(2) The method has simple process and low cost, and is suitable for industrial production;
(3) The low-water-absorption halogen-free flame-retardant reinforced PA66 without precipitation can be widely applied to electric, electronic and electrical equipment components.
Detailed Description
The present invention will be further described with reference to the following examples.
Nylon 66 resin (relative intrinsic viscosity 2.6) used in the examples or comparative examples of the present invention was purchased from sammSub>A group, OP1400 (particle size 100 nm) used was purchased from clariant, diethyl aluminum hypophosphite (particle size 100 nm) used was purchased from clariant, polymeric polyphosphate amine (molecular weight 18000, 10000) used was purchased from BASF, polysiloxane (molecular weight 5000) was purchased from changzhou coloramSub>A, fiberglass 301HP (fiber length 3.5mm, monofilament diameter 10 μm) used was purchased from chongqing international, PA6T/6I (relative intrinsic viscosity 0.8, melting point 315 ℃) used was purchased from qing chinkung chemical company, LDPE (melt index 1.0, melting point 190 ℃) used was purchased from guangzhou petrochemical, P22 used was purchased from rohm haas, grafted EBS (TAF-Sub>A) used was purchased from tsu optical chemical company, and silicone resin used was purchased from sikawSub>A optical research; the starting materials or chemicals used in the examples of the present invention were obtained by conventional commercial methods unless otherwise specified.
Precipitation-free, low-water-absorption, halogen-free, flame-retardant reinforced nylon 66 examples 1-4
The components and parts by weight of the precipitation-free, low-water-absorption, halogen-free, flame-retardant, reinforced nylon 66 of examples 1-4 and comparative examples 1-3 are shown in Table 1.
TABLE 1 table of components and parts by weight of non-precipitating, low water-absorbing, halogen-free, flame-retardant reinforced nylon 66 of examples 1 to 4 and comparative examples 1 to 3
Note: in the table, "-" indicates no addition.
Preparation methods of precipitation-free, low-water-absorption, halogen-free, flame-retardant and reinforced nylon 66 examples 1 and 2
Respectively adding nylon 66 resin into a main material scale, adding a halogen-free flame retardant, a synergist, a precipitation preventing agent, a nucleating agent, a dispersing agent, a lubricant and an antioxidant into a mixer for mixing according to the components and parts by weight of the embodiments 1 and 2 in the table 1, adding an auxiliary material scale, adding glass fibers into a side feeding metering scale, starting a double-screw extruder, sequentially starting the main material and auxiliary material metering extruder, starting the side feeding metering extruder after discharging, heating, melting, blending and extruding in the double-screw extruder at the partition temperature of 250, 260, 260, 265, 270, 260, 250, 250 and 260 ℃ and the vacuum degree of 0.08MPa and the extrusion rotating speed of 500rpm, cooling strips by water, and cutting the strips into granules at the rotating speed of 900rpm to obtain the flame retardant/flame retardant polypropylene composite material.
Preparation methods of precipitation-free, low-water-absorption, halogen-free, flame-retardant and reinforced nylon 66 and examples 3 and 4
Respectively adding nylon 66 resin into a main material scale, adding a halogen-free flame retardant, a synergist, a precipitation preventing agent, a nucleating agent, a dispersant, a lubricant and an antioxidant into a mixer according to the components and parts by weight in the embodiments 3 and 4 in the table 1, mixing, adding an auxiliary material scale, adding glass fibers into a side feeding metering scale, starting a double-screw extruder, starting the main material metering extruder and the auxiliary material metering extruder in sequence, starting the side feeding metering extruder after discharging, heating, melting, blending and extruding in the double-screw extruder at the partition temperature of 250, 260, 260, 265, 265, 260, 250, 250 and 255 ℃ and the vacuum degree of 0.04MPa and the extrusion rotating speed of 550rpm, cooling strips by water, and cutting the strips into granules at the rotating speed of 1000rpm to obtain the flame retardant.
Comparative examples 1 to 3
The compositions and the parts by weight of comparative examples 1 to 3 in Table 1 were prepared by the methods of examples 1 and 2, respectively. In comparative example 1, no precipitation inhibitor was added.
In order to evaluate the performance of the materials of the precipitation-free, low-water-absorption, halogen-free, flame-retardant, reinforced nylon 66 in examples 1-4 and comparative examples 1-3, a performance test sample strip was injection-molded first, and then performance testing was performed, with the results shown in table 2.
(1) The method for testing the injection molding performance of the sample strip comprises the following steps: after the precipitation-free, low-water-absorption, halogen-free, flame-retardant and reinforced nylon 66 of examples 1 to 4 and comparative examples 1 to 3 were dried at 120 ℃ for 2 hours, injection-molded to form performance test specimens (molding process: melting temperature 250 to 265 ℃, nozzle temperature 270 ℃, molding pressure 75 MPa).
(2) Performance test standard:
notched impact strength kJ/m 2 ：ASTM D756；
Tensile strength MPa: ASTM D638;
bending strength MPa: ASTM D790;
flexural modulus MPa: ASTM D790;
thermal deformation temperature ℃: ASTM D648;
flame retardant rating: UL94;
precipitation property: humidity 80%, temperature 120 ℃, standing time: taking out the product for 7 days, and visually observing whether the surface of the product is separated out or not;
saturated water absorption: GB/T6284-2006.
TABLE 2 comparison table of material properties of precipitation-free, low water-absorbing, halogen-free, flame-retardant reinforced nylon 66 of examples 1-4 and comparative examples 1-3
As can be seen from Table 2, the notched impact strength of the low water absorption halogen-free flame retardant reinforced nylon 66 without precipitation in the embodiment of the invention is as high as 13.0kJ/m 2 The tensile strength is up to 240MPa, the bending strength is up to 310MPa, the bending modulus is up to 12500MPa, the thermal deformation temperature is up to 260 ℃, the flame retardant grade is V-0 grade, no precipitation exists, the saturated water absorption is as low as 0.21 percent, the size is stable, the composite material is non-toxic and environment-friendly, and the technical problem that the halogen-free flame retardant reinforced nylon 66 composite material is easy to precipitate is fundamentally solved; wherein, PA6T/6I has obvious effect on improving the water absorption and precipitation performance of the halogen-free flame-retardant reinforced nylon 66, the mechanical property and the thermal property are optimal, and the molecular weight of the ammonium polyphosphate has obvious influence on the flame retardance, the precipitation resistance and the water absorption performance of the composite material.
Application examples 1-4 of precipitation-free, low-water-absorption, halogen-free, flame-retardant and reinforced nylon 66
The precipitation-free, low-water-absorption, halogen-free, flame-retardant reinforced nylon 66 of examples 1 to 4 were applied to electrical, electronic, and electrical equipment parts, respectively.
Through detection, the electrical, electronic and electric equipment parts have excellent mechanical property, flame retardance, insulativity and dimensional stability.
Claims (5)
1. A precipitation-free low-water-absorption halogen-free flame-retardant reinforced nylon 66 is characterized by comprising the following components in parts by weight: 100 parts of nylon 66 resin, 10-16 parts of halogen-free flame retardant, 4-8 parts of synergist, 30-50 parts of glass fiber, 5-20 parts of anti-precipitation agent, 0.1-0.5 part of nucleating agent, 0.3-1.0 part of dispersant, 0.3-0.6 part of lubricant and 0.4-0.8 part of antioxidant; the synergist is a compound of macromolecular poly-amine phosphate and polysiloxane resin in a mass ratio of 1-3; the molecular weight of the high-molecular poly phosphoric acid amine is more than or equal to 18000; the glass fiber is alkali-free chopped fiber; the length of the fiber is 3.5-4.5 mm, and the diameter of the monofilament is 7-13 mu m; the dispersing agent is grafted ethylene double-hard amide.
2. The no-precipitation, low-water-absorption, halogen-free, flame-retardant reinforced nylon 66 according to claim 1, which is characterized in that: the relative intrinsic viscosity of the nylon 66 resin is 2.4-3.2; the particle size of the halogen-free flame retardant is 50-150 nm; the halogen-free flame retardant is alkyl phosphate; the alkyl phosphate is one or more of diethyl aluminum hypophosphite, diethyl calcium hypophosphite or diethyl sodium hypophosphite; the anti-precipitation agent is PA6T/6I and/or low-density polyethylene; the relative intrinsic viscosity of the PA6T/6I is 0.8-1.2; the melt index of the low-density polyethylene is 0.5-2.0; the nucleating agent is organic nano montmorillonite and/or ionic polymer/metal oxide mixture; the lubricant is silicone resin and/or pentaerythritol ester; the antioxidant is a hindered phenol compound and/or a high molecular weight phosphate.
3. The preparation method of the precipitation-free low-water-absorption halogen-free flame-retardant reinforced nylon 66 according to claim 1 or 2, which is characterized by comprising the following steps: adding nylon 66 resin into a main material scale, adding a halogen-free flame retardant, a synergist, a precipitation-proof agent, a nucleating agent, a dispersant, a lubricant and an antioxidant into a mixer, mixing, adding an auxiliary material scale, adding glass fibers into a side feeding metering scale, starting a double-screw extruder, sequentially starting the main material metering extruder and the auxiliary material metering extruder, after discharging, starting the side feeding metering extruder, heating, melting, blending and extruding in the double-screw extruder, cooling strips with water, and granulating in a granulator to obtain the glass fiber reinforced plastic composite material.
4. The preparation method of the no-precipitation, low-water-absorption, halogen-free and flame-retardant reinforced nylon 66 according to claim 3, wherein the method comprises the following steps: the temperature of the heating, melting, blending and extruding is 250-270 ℃, the vacuum degree is-0.06-0.09 MPa, and the extrusion rotating speed is 400-600 rpm; the rotating speed of the grain cutting is 800-1000 rpm.
5. The use of the no-precipitation, low water absorption, halogen-free, flame retardant reinforced nylon 66 according to claim 1 or 2, wherein: the precipitation-free, low-water-absorption, halogen-free, flame-retardant reinforced nylon 66 according to claim 1 or 2 is applied to electric, electronic and electronic equipment parts.
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| CN115433456A (en) * | 2022-09-14 | 2022-12-06 | 广东聚石化学股份有限公司 | High-flame-retardant and high-impact-resistant melamine cyanurate flame-retardant nylon composition as well as preparation method and application thereof |
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