CN112812366A - Flame-retardant composition and application thereof, PBT composite material and preparation method thereof - Google Patents
Flame-retardant composition and application thereof, PBT composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant composition, application thereof, a PBT composite material and a preparation method thereof. Wherein, the components of the flame-retardant composition comprise: 55-65 wt% of diethyl aluminum phosphinate, 15-26 wt% of melamine polyphosphate, 10-15 wt% of melamine cyanurate, 4-8 wt% of organic modified montmorillonite and 0-5 wt% of aluminum phosphite. When the flame-retardant composition is mixed with main materials such as PBT and the like in a melting way to prepare the flame-retardant material, the prepared flame-retardant material can be decomposed to form a coke layer in the combustion process, the coke layer has the function of a heat-insulating and oxygen-blocking protective layer, meanwhile, a nitrogen-containing compound in the flame-retardant composition also has the functions of foaming and coke reinforcement, and the aluminum phosphite can play a synergistic flame-retardant and whitening effect, so that the prepared flame-retardant material has good flame retardance and can keep better mechanical property.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a flame-retardant composition and application thereof, and a PBT composite material and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) is a thermoplastic engineering plastic with wide sources and low price, but has low mechanical property and flame retardant property, so that the application of the polybutylene terephthalate in the engineering field is limited. One technique attempts to modify polybutylene terephthalate with flame retardants to improve its flame retardant properties. The flame retardant used in the method is generally a halogen-free flame retardant, for example, a halogen-free flame retardant resorcinol bis (diphenyl phosphate) or hypophosphite is used, and the flame retardant is low-smoke and halogen-free and can improve the flame retardant property of the polybutylene terephthalate. However, these halogen-free flame retardants still have some disadvantages, such as the resorcinol bis (diphenyl phosphate) flame retardant being liquid, inconvenient to use, low thermal decomposition temperature, low flame retardant efficiency, low flame retardant drip resistance; the hypophosphite flame retardant is easy to decompose in the using process, has explosion risk and can cause the mechanical property of the PBT material to be seriously reduced.
Therefore, it is urgently needed to develop a flame retardant which can improve the flame retardance of PBT and does not adversely affect the mechanical properties of PBT materials.
Disclosure of Invention
Based on the flame retardant composition, the invention provides a flame retardant composition, application of the flame retardant composition, a PBT composite material and a preparation method of the PBT composite material. The flame-retardant composition can improve the flame retardance of the PBT, and simultaneously cannot generate adverse effects on the mechanical properties of the PBT material.
The technical scheme of the invention is as follows.
One aspect of the present invention provides a flame retardant composition comprising the components of: 55-65 wt% of diethyl aluminum phosphinate, 15-26 wt% of melamine polyphosphate, 10-15 wt% of melamine cyanurate, 4-8 wt% of organic modified montmorillonite and 0-5 wt% of aluminum phosphite.
In some of these embodiments, the components of the flame retardant composition include: 60-65 wt% of aluminum diethylphosphinate, 15-18 wt% of melamine polyphosphate, 10-14 wt% of melamine cyanurate, 4-7 wt% of organic modified montmorillonite and 1-5 wt% of aluminum phosphite.
In some embodiments, the organic modified montmorillonite is at least one of inorganic montmorillonite modified by alkyl ammonium salt with 8-30 carbon atoms.
In some of these embodiments, the aluminum diethylphosphinate has a particle size D50 from 10nm to 30nm and a particle size D95 from 20nm to 45 nm.
In another aspect of the invention, the application of the flame-retardant composition in preparing a flame-retardant material is provided.
The invention further provides a PBT composite material, and the preparation raw materials of the PBT composite material comprise: 13 to 25 weight percent of flame-retardant composition, 45 to 65 weight percent of polybutylene terephthalate, 20 to 40 weight percent of glass fiber and 0.3 to 0.8 weight percent of coupling agent;
wherein the flame retardant composition is as described above.
In some of these embodiments, the glass fibers are long glass fibers; and/or the coupling agent is a silane coupling agent.
The invention also provides a preparation method of the PBT composite material, which comprises the following steps:
according to the raw material proportion of the PBT composite material, mixing the flame-retardant composition, the polybutylene terephthalate and the coupling agent to obtain a mixture;
and heating the mixture to be molten, mixing the mixture with the glass fiber, and performing melt extrusion to obtain the PBT composite material.
In some of these embodiments, the step of melt extruding is carried out in a twin-screw extruder, the temperature of which, in the direction of advance of the material, is in the order: 200-210 ℃, 210-220 ℃, 220-230 ℃, 230-240 ℃, 235-245 ℃, 225-235 ℃ and 225-230 ℃, and the temperature of a machine head is 220-225 ℃.
In some of these embodiments, the flame retardant composition, the polybutylene terephthalate, and the coupling agent are mixed under the conditions of: mixing for 10-15 min at 80-120 ℃.
Advantageous effects
In the flame-retardant composition, the special components and the proportion are adopted, and the aluminum diethylphosphinate, the melamine polyphosphate, the melamine cyanurate, the organic modified montmorillonite and the aluminum phosphite in specific mass percentage act together, so that the flame-retardant property of the material is improved, and the mechanical property of the main material is not adversely affected. The flame retardant composition is prepared by compounding diethyl aluminum phosphinate serving as a main flame retardant with melamine phosphate, melamine cyanurate, organic modified montmorillonite and aluminum phosphite in a specific ratio, wherein the melamine phosphate and the melamine cyanurate are nitrogen-containing flame retardants, and the compound with diethyl aluminum phosphinate has an excellent coordination flame retardant effect. When the flame-retardant composition is mixed with PBT and other main materials in a melting way to prepare the flame-retardant material, the prepared flame-retardant material can be decomposed to form a coke layer in the combustion process, the coke layer has the function of a heat-insulating and oxygen-blocking protective layer, meanwhile, a nitrogen-containing compound in the flame-retardant composition also has the functions of foaming and coke reinforcement, and the aluminum phosphite can play a role in synergistic flame retardance, so that the prepared flame-retardant material has good flame retardance and can keep better mechanical properties.
The invention also provides a PBT composite material, and the preparation raw materials of the PBT composite material comprise the flame-retardant composition, polybutylene terephthalate, glass fiber and a coupling agent in a specific ratio. The composite material has good flame retardant property, and simultaneously keeps good mechanical property and surface finish. Compared with the traditional flame retardant modified polybutylene terephthalate, the flame retardant composition has lower content when the polybutylene terephthalate is modified by the flame retardant composition.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the prior art, a plurality of schemes of enhancing PBT by adopting a halogen-free flame retardant are adopted, the halogen-free flame retardant is low in smoke and halogen, and the prepared halogen-free flame-retardant enhanced PBT material has better flame retardant property. However, after a great deal of research and experiments on the traditional flame retardant used for the modified PBT, the technicians of the invention find that the traditional halogen-free flame retardant has some defects, such as that the resorcinol bis (diphenyl phosphate) flame retardant is liquid, inconvenient to use, low in thermal decomposition temperature, low in flame retardant efficiency and low in flame retardant anti-dripping property; the hypophosphite flame retardant is easy to decompose in the using process, has explosion risk and can cause the mechanical property of the PBT material to be seriously reduced, for example, the diethyl aluminum phosphinate flame retardant has good thermal stability and good flame retardant effect, but the diethyl aluminum phosphinate flame retardant can cause the mechanical property of the PBT material to be seriously reduced.
Based on the above, after long-term research and numerous creative experiments, the technicians of the invention obtain the flame retardant composition which can improve the flame retardance of the PBT and simultaneously can not generate adverse effect on the mechanical property of the PBT material.
One embodiment of the present invention provides a flame retardant composition comprising the components of: 55-65 wt% of diethyl aluminum phosphinate, 15-26 wt% of melamine polyphosphate, 10-15 wt% of melamine cyanurate, 4-8 wt% of organic modified montmorillonite and 0-5 wt% of aluminum phosphite.
In some embodiments, the aluminum diethylphosphinate is 60 wt% to 65 wt%.
In some embodiments, the melamine polyphosphate is 15 wt% to 18 wt%.
In some embodiments, the melamine cyanurate is 10 wt% to 14 wt%.
In some embodiments, the weight percentage of the organic modified montmorillonite is 4 wt% -7 wt%
In some embodiments, the aluminum phosphite is 1 wt% to 5 wt%.
Preferably, the components of the flame retardant composition comprise: 60 to 65 weight percent of diethyl aluminum phosphinate, 15 to 18 weight percent of melamine polyphosphate, 10 to 14 weight percent of melamine cyanurate, 4 to 7 weight percent of organic modified montmorillonite and 1 to 5 weight percent of aluminum phosphite.
In the flame-retardant composition, the special components and the proportion are adopted, and the aluminum diethylphosphinate, the melamine polyphosphate, the melamine cyanurate, the organic modified montmorillonite and the aluminum phosphite in specific mass percentage act together, so that the flame-retardant property of the material is improved, and the mechanical property of the material is not adversely affected. The flame retardant composition is prepared by compounding diethyl aluminum phosphinate serving as a main flame retardant with melamine phosphate, melamine cyanurate, organic modified montmorillonite and aluminum phosphite in a specific ratio, wherein the melamine phosphate and the melamine cyanurate are nitrogen-containing flame retardants, and the compound with diethyl aluminum phosphinate has an excellent coordination flame retardant effect. When the flame-retardant composition is mixed with main materials such as PBT and the like in a melting way to prepare the flame-retardant material, the prepared flame-retardant material can be decomposed to form a coke layer in the combustion process, the coke layer has the function of a heat-insulating and oxygen-blocking protective layer, meanwhile, a nitrogen-containing compound in the flame-retardant composition also has the functions of foaming and coke reinforcement, and the aluminum phosphite can play a synergistic flame-retardant and whitening effect, so that the prepared flame-retardant material has good flame retardance and can keep better mechanical property and surface finish. Compared with the traditional flame retardant, the flame retardant composition disclosed by the invention has the advantage that the required amount is reduced when the main material such as polybutylene terephthalate is modified by the flame retardant composition.
In some of these examples, the aluminum diethylphosphinate has a particle size D50 of 10nm to 30nm and a particle size D95 of 20nm to 45 nm.
In the flame-retardant composition, diethyl aluminum phosphinate flame retardant is taken as a main component and is compounded with melamine phosphate, melamine cyanurate, organic modified montmorillonite and aluminum phosphite in a specific ratio. Compared with other hypophosphorous acid metal salts, the salt composed of the aluminum chloride ions, the diethyl phosphinic acid groups and the phosphorous acid groups in the flame-retardant combination can promote the carbon formation of the flame-retardant composition and improve the flame-retardant efficiency of the flame-retardant composition.
The organic modified montmorillonite is at least one of inorganic montmorillonite modified by alkyl ammonium salt with 8-30 carbon atoms.
The organic modified montmorillonite has a 2:1 layered structure unit, the structure unit consists of two layers of silica tetrahedral crystal wafers and a layer of aluminum octahedral wafer in the middle, the thickness of a unit lamella is about 1nm, the width and the length are both about 100nm, and the interlayer distance is effectively expanded after the organic modified montmorillonite is modified by alkyl ammonium salt with 8-30 carbon atoms, so that the compatibility of the organic modified montmorillonite with a PBT matrix is improved, and the functions of coordinating flame retardance and toughening and enhancing are achieved.
Specifically, the organic modified montmorillonite is selected from, but not limited to, the following commercially available types of organic montmorillonite: DK1, DK2, DK3, DK4, DK5 and DK 1N.
An embodiment of the present invention further provides an application of the flame retardant composition in preparing a flame retardant material.
When the flame-retardant composition is mixed with the main materials such as PBT and the like in a melting way to prepare the flame-retardant material, the prepared flame-retardant material can be decomposed to form a coke layer in the combustion process, the coke layer has the function of a heat-insulating and oxygen-blocking protective layer, the nitrogen-containing compound in the flame-retardant composition also has the functions of foaming and coke reinforcement, and the aluminum phosphite can play a synergistic flame-retardant and whitening effect, so that the prepared flame-retardant material has good flame retardance and can keep good mechanical property and surface smoothness.
Such host materials include, but are not limited to, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and Polyarylate (PAR).
The invention also provides a PBT composite material, which comprises the following raw materials in part by weight: 13 to 25 weight percent of flame-retardant composition, 45 to 65 weight percent of polybutylene terephthalate, 20 to 40 weight percent of glass fiber and 0.3 to 0.8 weight percent of coupling agent; wherein the flame retardant composition is as described above.
The PBT composite material has good flame retardant property, and simultaneously keeps good mechanical property and surface finish. The amount required when using the flame retardant composition of the invention to modify polybutylene terephthalate is reduced relative to modifying polybutylene terephthalate with conventional flame retardants. The dosage of the flame-retardant composition is reduced to 13-16 wt% from 20 wt% and above in the traditional technology.
In some of these embodiments, the glass fibers are long glass fibers; specifically, the diameter of the glass fiber is 10um to 12 um.
In some of these embodiments, the coupling agent is a silane coupling agent.
The embodiment of the invention also provides a preparation method of the PBT composite material, which comprises the following steps S10-S20.
And step S10, mixing the flame-retardant composition, the polybutylene terephthalate and the coupling agent according to the raw material proportion of the PBT composite material to obtain a mixture.
In some of these embodiments, the flame retardant composition, polybutylene terephthalate, and coupling agent are mixed in step S10 under the conditions of: mixing for 10-15 min at 80-120 ℃.
It will be appreciated that the mixing step can be carried out in any apparatus known in the art for mixing substances, and in particular, the mixing step is carried out in a high speed mixer operating at a speed of 600 to 900 rmp.
In some of these embodiments, prior to the step of mixing the flame retardant composition, the polybutylene terephthalate, and the coupling agent, there is further included a step of drying the polybutylene terephthalate; further, the polybutylene terephthalate is dried to a moisture content of less than 0.4 wt%.
And S20, heating the mixture obtained in the S10 to be molten, mixing the mixture with glass fibers, and performing melt extrusion to obtain the PBT composite material.
In some of these embodiments, the step of performing melt extrusion is performed in a twin screw extruder in step S20; further, the mixture was fed from the feed port of the twin-screw extruder, and the glass fiber was fed from the vent port of the twin-screw extruder.
Further, the glass fiber is fed from a vent located in the middle section of the twin-screw extruder, and specifically, the distance from the vent where the feeding is performed to the feeding port is 0.5m to 0.9 m.
In some of the embodiments, the temperature of the twin-screw extruder is, in order of the material advancing direction: 200-210 ℃, 210-220 ℃, 220-230 ℃, 230-240 ℃, 235-245 ℃, 225-235 ℃ and 225-230 ℃, and the temperature of a machine head is 220-225 ℃.
Specifically, the temperature of the double-screw extruder is provided with 9 temperature distribution areas according to the advancing direction of the material, wherein the temperature distribution areas are T1-T9: t1-200 ℃, T2-210 ℃, T3-220-230 ℃, T4-230-240 ℃, T5-235-245 ℃, T6-225-235 ℃, T7-225-235 ℃, T8-225-230 ℃, T9-225-230 ℃.
In some embodiments, step S20 includes cooling the composite material; further, the cooled composite material is cut and granulated according to actual needs.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
1) Putting 57.5kg of PBT, 11kg of aluminum diethylphosphinate, 3kg of melamine polyphosphate, 2kg of melamine cyanurate, 0.8kg of organic montmorillonite (DK2 type), 0.2kg of aluminum phosphite and 0.5kg of silane coupling agent into a high-speed mixer, mixing for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, uniformly mixing the materials under the action of a stirring paddle to obtain a mixture, and discharging for later use.
2) Adding the uniformly mixed mixture obtained in the step 1) into a feeding hopper of a double-screw extruder which is preheated to a set temperature, conveying the materials to the front side by rotating a screw rod, heating and melting the materials, simultaneously adding 25kg of long glass fibers quantitatively from an exhaust port in the middle of the extruder, mixing the long glass fibers with a melt, extruding the mixture through an extruder opening die into strips, cooling the strips through a water tank, and then granulating the strips through a granulator to obtain the modified composite material.
The double-screw extruder is sequentially provided with a heating temperature distribution zone T1-T9 according to the flowing direction of the material: t1 ═ 205 ℃, T2 ═ 215 ℃, T3 ═ 225 ℃, T4 ═ 235 ℃, T5 ═ 245 ℃, T6 ═ 235 ℃, T7 ═ 235 ℃, T8 ═ 230 ℃, T9 ═ 230 ℃, T nose ═ 220 ℃.
3) The flame retardant test and the mechanical property test were carried out on the prepared composite material, and the specific results are shown in table 1.
Example 2
1) Putting 55.5kg of PBT, 12kg of aluminum diethylphosphinate, 4kg of melamine polyphosphate, 2kg of melamine cyanurate, 1kg of organic montmorillonite (DK2 type) and 0.5kg of silane coupling agent into a high-speed mixer, mixing for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, uniformly mixing the materials under the action of a stirring paddle to obtain a mixture, and discharging for later use.
2) Adding the uniformly mixed mixture obtained in the step 1) into a feeding hopper of a double-screw extruder which is preheated to a set temperature, conveying the materials to the front side by rotating a screw rod, heating and melting the materials, simultaneously adding 25kg of long glass fibers quantitatively from an exhaust port in the middle of the extruder, mixing the long glass fibers with a melt, extruding the mixture through an extruder opening die into strips, cooling the strips through a water tank, and then granulating the strips through a granulator to obtain the modified composite material.
The double-screw extruder is sequentially provided with a heating temperature distribution zone T1-T9 according to the flowing direction of the material: t1 ═ 205 ℃, T2 ═ 215 ℃, T3 ═ 225 ℃, T4 ═ 235 ℃, T5 ═ 245 ℃, T6 ═ 235 ℃, T7 ═ 235 ℃, T8 ═ 230 ℃, T9 ═ 230 ℃, T nose ═ 220 ℃.
3) The flame retardant test and the mechanical property test were carried out on the prepared composite material, and the specific results are shown in table 1.
Example 3
1) 51.5kg of PBT, 14kg of aluminum diethylphosphinate, 3.5kg of melamine polyphosphate, 3kg of melamine cyanurate, 1.5kg of organic montmorillonite (DK2 type), 1kg of aluminum phosphite and 0.5kg of silane coupling agent are placed in a high-speed mixer, mixed for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, and the materials are uniformly mixed under the action of a stirring paddle to obtain a mixture which is discharged for later use.
2) Adding the uniformly mixed mixture obtained in the step 1) into a feeding hopper of a double-screw extruder which is preheated to a set temperature, conveying the materials to the front side by rotating a screw rod, heating and melting the materials, simultaneously adding 25kg of long glass fibers quantitatively from an exhaust port in the middle of the extruder, mixing the long glass fibers with a melt, extruding the mixture through an extruder opening die into strips, cooling the strips through a water tank, and then granulating the strips through a granulator to obtain the modified composite material.
The double-screw extruder is sequentially provided with a heating temperature distribution zone T1-T9 according to the flowing direction of the material: t1 ═ 205 ℃, T2 ═ 215 ℃, T3 ═ 225 ℃, T4 ═ 235 ℃, T5 ═ 245 ℃, T6 ═ 235 ℃, T7 ═ 235 ℃, T8 ═ 230 ℃, T9 ═ 230 ℃, T nose ═ 220 ℃.
3) The flame retardant test and the mechanical property test were carried out on the prepared composite material, and the specific results are shown in table 1.
Example 4
1) 51.5kg of PBT, 12.7kg of aluminum diethylphosphinate, 4.3kg of melamine polyphosphate, 2.5kg of melamine cyanurate, 0.95kg of organic montmorillonite (DK2 type), 2.55kg of aluminum phosphite and 0.5kg of silane coupling agent are placed in a high-speed mixer, mixed for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, and the materials are uniformly mixed under the action of a stirring paddle to obtain a mixture which is discharged for later use.
Other steps and conditions were the same as in example 1.
Example 5
1) 51.5kg of PBT, 14kg of aluminum diethylphosphinate, 4.5kg of melamine polyphosphate, 2.5kg of melamine cyanurate, 1.2kg of organic montmorillonite (DK2 type), 0.8kg of aluminum phosphite and 0.5kg of silane coupling agent are placed in a high-speed mixer, mixed for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, and the materials are uniformly mixed under the action of a stirring paddle to obtain a mixture which is discharged for later use.
Other steps and conditions were the same as in example 1
Example 6
1) 60.5kg of PBT, 14kg of aluminum diethylphosphinate, 3.5kg of melamine polyphosphate, 3kg of melamine cyanurate, 1.5kg of organic montmorillonite (DK2 type), 1kg of aluminum phosphite and 0.5kg of silane coupling agent are placed in a high-speed mixer, mixed for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, and the materials are uniformly mixed under the action of a stirring paddle to obtain a mixture, and the mixture is discharged for later use.
2) Adding the uniformly mixed mixture obtained in the step 1) into a feeding hopper of a double-screw extruder which is preheated to a set temperature, conveying the materials to the front side by rotating a screw rod, heating and melting the materials, simultaneously adding 16kg of long glass fibers quantitatively from an exhaust port in the middle of the extruder, mixing the long glass fibers with a melt, extruding the mixture through an extruder opening die into strips, cooling the strips through a water tank, and then granulating the strips through a granulator to obtain the modified composite material.
The other steps were the same as in example 1.
Comparative example 1
1) Placing 57.5kg of PBT, 17kg of aluminum diethylphosphinate and 0.5kg of silane coupling agent in a high-speed mixer, mixing for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, uniformly mixing the materials under the action of a stirring paddle to obtain a mixture, and discharging for later use.
2) Adding the uniformly mixed mixture obtained in the step 1) into a feeding hopper of a double-screw extruder which is preheated to a set temperature, conveying the materials to the front side by rotating a screw rod, heating and melting the materials, simultaneously adding 25kg of long glass fibers quantitatively from an exhaust port in the middle of the extruder, mixing the long glass fibers with a melt, extruding the mixture through an extruder opening die into strips, cooling the strips through a water tank, and then granulating the strips through a granulator to obtain the modified composite material.
The heating temperature distribution of the double-screw extruder is as follows: t1 ═ 205 ℃, T2 ═ 215 ℃, T3 ═ 225 ℃, T4 ═ 235 ℃, T5 ═ 245 ℃, T6 ═ 235 ℃, T7 ═ 235 ℃, T8 ═ 230 ℃, T9 ═ 230 ℃, T nose ═ 220 ℃.
3) The flame retardant test and the mechanical property test were carried out on the prepared composite material, and the specific results are shown in table 1.
Comparative example 2
1) Putting 57.5kg of PBT, 12kg of aluminum hypophosphite, 5kg of resorcinol bis (diphenyl phosphate) and 0.5kg of silane coupling agent into a high-speed mixer, mixing for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, uniformly mixing the materials under the action of a stirring paddle to obtain a mixture, and discharging for later use.
The other steps were the same as in example 1.
Comparative example 3
1) Putting 58kg of PBT, 127kg of aluminum hypophosphite and 0.5kg of silane coupling agent into a high-speed mixer, mixing for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, uniformly mixing the materials under the action of a stirring paddle to obtain a mixture, and discharging for later use.
The other steps were the same as in example 1.
Comparative example 4
1) 51.5kg of PBT, 14kg of aluminum diethylphosphinate, 7kg of melamine polyphosphate, 0.2kg of aluminum phosphite and 0.5kg of silane coupling agent are placed in a high-speed mixer, mixed for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, and the materials are uniformly mixed under the action of a stirring paddle to obtain a mixture, and discharged for later use.
The other steps were the same as in example 1.
Comparative example 5
51.5kg of PBT, 14kg of aluminum diethylphosphinate, 4.5kg of melamine polyphosphate, 2kg of melamine cyanurate, 1.5kg of organic montmorillonite (DK2 type), 1kg of aluminum phosphite and 0.5kg of silane coupling agent are placed in a high-speed mixer, mixed for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, and the materials are uniformly mixed under the action of a stirring paddle to obtain a mixture which is discharged for later use.
The other steps were the same as in example 1.
Comparative example 6
1) Putting 57.5kg of PBT, 11kg of aluminum diethylphosphinate, 3kg of melamine polyphosphate, 2kg of melamine cyanurate, 0.8kg of inorganic montmorillonite, 0.2kg of aluminum phosphite and 0.5kg of silane coupling agent into a high-speed mixer, mixing for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, uniformly mixing the materials under the action of a stirring paddle to obtain a mixture, and discharging for later use.
The other steps were the same as in example 1.
Comparative example 7
1) Putting 57.5kg of PBT, 11kg of aluminium hypophosphite, 3kg of melamine polyphosphate, 2kg of melamine cyanurate, 0.8kg of organic montmorillonite (DK2 type), 0.2kg of aluminium phosphite and 0.5kg of silane coupling agent into a high-speed mixer, mixing for 12 minutes at the temperature of 90 ℃ and the stirring speed of 700rmp, uniformly mixing the materials under the action of a stirring paddle to obtain a mixture, and discharging for later use.
The other steps were the same as in example 1.
Performance testing
1) The composite materials prepared in the embodiments 1-6 and the comparative examples 1-7 and the PBT serving as the raw material are subjected to an impact resistance test, an anti-bending test and a tensile property test, and the test standards refer to GB/T1843-2008, GB/T9341-2008 and GB/T1040.2-2006 respectively; the results are shown in Table 1.
2. Testing the combustion grade of the composite materials prepared in the examples 1-6 and the comparative examples 1-7 and the PBT serving as the raw material, and specifically referring to the standard GB/T2408-2008; and specifically referring to the standard GB/T2406.2-2009 for the oxygen index of the tested composite material. The results obtained are shown in table 1 below.
TABLE 1
Note: in the vertical combustion grade, the flame retardant grade is gradually increased from HB, V-2, V-1 to V-0, and the better flame retardant property is shown.
As can be seen from the test data in Table 1, the composite material prepared according to the technical scheme of the invention has high mechanical properties such as bending strength and the like and excellent flame retardant property.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A flame retardant composition, wherein the flame retardant composition comprises the components: 55-65 wt% of diethyl aluminum phosphinate, 15-26 wt% of melamine polyphosphate, 10-15 wt% of melamine cyanurate, 4-8 wt% of organic modified montmorillonite and 0-5 wt% of aluminum phosphite.
2. The flame retardant composition of claim 1, wherein the flame retardant composition comprises the components: 60-65 wt% of aluminum diethylphosphinate, 15-18 wt% of melamine polyphosphate, 10-14 wt% of melamine cyanurate, 4-7 wt% of organic modified montmorillonite and 1-5 wt% of aluminum phosphite.
3. The flame retardant composition of claim 1, wherein the organically modified montmorillonite is at least one selected from inorganic montmorillonite modified with an alkylammonium salt having 8-30 carbon atoms.
4. The flame retardant composition of any one of claims 1 to 3, wherein the aluminum diethylphosphinate has a particle size D50 from 10nm to 30nm and a particle size D95 from 20nm to 45 nm.
5. Use of a flame retardant composition according to any of claims 1 to 4 for the preparation of a flame retardant material.
6. The PBT composite material is characterized in that the preparation raw materials of the PBT composite material comprise: 13 to 25 weight percent of flame-retardant composition, 45 to 65 weight percent of polybutylene terephthalate, 20 to 40 weight percent of glass fiber and 0.3 to 0.8 weight percent of coupling agent;
wherein the flame retardant composition is as defined in any one of claims 1 to 5.
7. The PBT composite of claim 6, wherein the glass fibers are long glass fibers; and/or the coupling agent is a silane coupling agent.
8. The preparation method of the PBT composite material is characterized by comprising the following steps:
according to the raw material proportion of the PBT composite material of any one of claims 6-7, mixing the flame-retardant composition, the polybutylene terephthalate and the coupling agent to obtain a mixture;
and heating the mixture to be molten, mixing the mixture with the glass fiber, and performing melt extrusion to obtain the PBT composite material.
9. The process for the preparation of PBT composite according to claim 8, wherein the step of melt extruding is performed in a twin screw extruder, the temperature of which is, in order of the direction of advance of the material: 200-210 ℃, 210-220 ℃, 220-230 ℃, 230-240 ℃, 235-245 ℃, 225-235 ℃ and 225-230 ℃, and the temperature of a machine head is 220-225 ℃.
10. The process for preparing a PBT composite of claim 9, wherein the flame retardant composition, the polybutylene terephthalate, and the coupling agent are mixed under the conditions of: mixing for 10-15 min at 80-120 ℃.
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