Flame-retardant thermoplastic resin composite material and preparation method thereof
By adding iron oxide as a synergistic flame retardant to the thermoplastic resin composite, the problem of insufficient flame retardant performance of the existing thermoplastic resin composite is solved, and a better flame retardant effect is achieved.
Patent Information
- Application Number
- CN202411972021.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-30
- Publication Date
- 2025-05-13
AI Technical Summary
Existing thermoplastic resin composites are limited in some specific fields due to insufficient flame retardant properties.
A composite material including thermoplastic resin, octabromobenzene bisphenol S ether, synergistic flame retardant and antioxidant is used. The synergistic flame retardant is iron oxide with a particle size of 50 nm to 100 nm, and is prepared by mixing and granulating process.
The flame retardant performance of thermoplastic resin composite materials is significantly improved, and the small particle size of iron oxide effectively isolates oxygen and heat, and prevents the expansion of combustion.
Smart Images
Figure CN119978612A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of polymer materials, and in particular to a flame retardant thermoplastic resin composite material and a preparation method thereof. Background Art
[0002] Thermoplastic resin is a widely used polymer polyester resin. Thermoplastic resin has the advantages of excellent fatigue resistance, good heat resistance, excellent dimensional stability, etc. However, in some specific application fields, very high flame retardant properties of thermoplastic resin are required, which limits the application of thermoplastic resin composites in some specific fields. Summary of the invention
[0003] The main purpose of the present application is to provide a flame retardant thermoplastic resin composite material and a preparation method thereof, aiming to solve the above-mentioned technical problems existing in the prior art.
[0004] In order to solve the above technical problems, the first technical solution adopted in the present application is: to provide a flame retardant thermoplastic resin composite material, which includes components in parts by weight: 90 to 110 parts of thermoplastic resin, 12 to 18 parts of octabromobisphenol S ether, 3 to 5 parts of synergistic flame retardant, and 0.1 to 0.5 parts of antioxidant; wherein the synergistic flame retardant includes iron oxide, and the particle size of the iron oxide is 50nm to 100nm.
[0005] In one embodiment, among the synergistic flame retardants, the synergistic flame retardants having a particle size of 60 nm to 90 nm account for more than 90%.
[0006] In one embodiment, among the synergistic flame retardants, the synergistic flame retardants having a particle size of 60 nm to 80 nm account for more than 75%.
[0007] In one embodiment, the thermoplastic resin includes at least one of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyamide 6 (PA6).
[0008] In one embodiment, the antioxidant is at least one of 2,6-di-tert-butyl-4-methylphenol and 4,4'-thiobis(6-tert-butyl-o-cresol).
[0009] The second technical solution adopted in the present application is: to provide a method for preparing a flame-retardant thermoplastic resin composite material, the preparation method comprising: mixing the following components in parts by weight to obtain a mixture: 90 to 110 parts of thermoplastic resin, 12 to 18 parts of octabromobisphenol S ether, 3 to 5 parts of synergistic flame retardant, and 0.1 to 0.5 parts of antioxidant, wherein the synergistic flame retardant includes iron oxide, and the particle size of the iron oxide is 50nm to 100nm; granulating the mixture to obtain a flame-retardant thermoplastic resin composite material.
[0010] In one embodiment, the preparation method of the synergistic flame retardant includes: mixing ammonium ferric oxalate, sodium bicarbonate, ethanol and deionized water and performing a thermal reaction to obtain an intermediate product; and calcining the intermediate product to obtain the synergistic flame retardant.
[0011] In one embodiment, the mass ratio of ammonium ferric oxalate, sodium bicarbonate, ethanol and deionized water is (20-24):(16-18):(60-80):(80-100).
[0012] In one embodiment, the temperature of the thermal reaction is 70° C. to 90° C., and the time of the thermal reaction is 8 h to 12 h.
[0013] In one embodiment, the calcination temperature is 700° C. to 780° C., and the calcination time is 16 h to 20 h.
[0014] In one embodiment, in the step of granulating the mixed material, the mixed material passes through six melting zones arranged in sequence from discharging to discharging of the extruder, the temperature of the first melting zone is 120℃~240℃, the temperature of the second melting zone is 180℃~280℃, the temperature of the third melting zone is 180℃~280℃, the temperature of the fourth melting zone is 180℃~280℃, the temperature of the fifth melting zone is 180℃~280℃, the temperature of the sixth melting zone is 180℃~280℃, the head temperature of the extruder is 180℃~280℃, and the speed of the screw of the extruder is 220r / min~320r / min.
[0015] In the technical solution of the present application, the flame retardant thermoplastic resin composite material is prepared from 90 to 110 parts of thermoplastic resin, 12 to 18 parts of octabromobisphenol S ether, 3 to 5 parts of synergistic flame retardant, and 0.1 to 0.5 parts of antioxidant. Among them, the synergistic flame retardant includes iron oxide, and the particle size of iron oxide is 50nm to 100nm. Octabromobisphenol S ether and the synergistic flame retardant cooperate with each other to improve the flame retardant properties of thermoplastic materials, wherein the synergistic flame retardant includes iron oxide, which is in direct contact with the combustible thermoplastic resin, and the iron oxide can separate the combustible thermoplastic resin and oxygen, thereby having a significant flame retardant effect on the thermoplastic material. In addition, the particle size of iron oxide is relatively small, which is 50nm to 100nm. Smaller iron oxide particles can more effectively isolate oxygen and heat, and prevent the spread of combustion. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 is a particle size distribution histogram of a synergistic flame retardant according to an embodiment of the present application;
[0017] Figure 2 is the particle size distribution histogram of commercially available synergistic flame retardant iron oxide;
[0018] Figure 3 is a transmission electron microscope image of a synergistic flame retardant according to an embodiment of the present application;
[0019] Figure 4 This is a transmission electron microscope image of iron oxide, a commercially available synergistic flame retardant. DETAILED DESCRIPTION
[0020] Below, the battery cells, batteries and electrical equipment of the present application are described in detail with appropriate reference to the accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.
[0021] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
[0022] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.
[0023] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.
[0024] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, a method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, a method may also include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
[0025] If there is no special explanation, the "include" and "comprising" mentioned in this application represent open-ended or closed-ended expressions. For example, "include" and "comprising" may represent that other components not listed may also be included or only listed components may be included or only listed components may be included.
[0026] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
[0027] Thermoplastic resin is a widely used polymer polyester resin. Thermoplastic resin has the advantages of excellent fatigue resistance, good heat resistance, excellent dimensional stability, etc. However, thermoplastic materials tend to soften and melt when heated, and produce dripping or flow. This characteristic allows the flame to spread rapidly through these flowing liquids, thereby expanding the scope of the fire and aggravating the severity of the fire. Therefore, this limits the application of thermoplastic materials in some fields that require high flame retardant properties.
[0028] Based on the above problems, the first aspect of the present application provides a flame retardant thermoplastic resin composite material.
[0029] The flame retardant thermoplastic resin composite material includes the following components in parts by weight: 90 to 110 parts of thermoplastic resin, 12 to 18 parts of octabromobisphenol S ether, 3 to 5 parts of synergistic flame retardant, and 0.1 to 0.5 parts of antioxidant; wherein the synergistic flame retardant includes iron oxide, and the particle size of the iron oxide is 50 nm to 100 nm.
[0030] In the technical solution of the present application, octabromobisphenol S ether and a synergistic flame retardant cooperate with each other to improve the flame retardant properties of thermoplastic materials, wherein the synergistic flame retardant includes iron oxide, which is in direct contact with the combustible thermoplastic resin, and the iron oxide can also separate the combustible thermoplastic resin and oxygen, thereby having a significant flame retardant effect on the thermoplastic material. In addition, the particle size of the iron oxide is relatively small, ranging from 50nm to 100nm, and the iron oxide particles with a smaller particle size can more effectively isolate oxygen and heat, thereby better preventing the spread of combustion.
[0031] In some embodiments, in the flame retardant thermoplastic resin composite material, the weight proportion of the thermoplastic resin can be 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, etc., or a range consisting of any of the above values, for example, 90 parts to 100 parts, 100 parts to 110 parts, etc.
[0032] In some embodiments, in the flame retardant thermoplastic resin composite material, the weight proportion of octabromobisphenol S ether can be 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, etc., or a range consisting of any of the above values, for example, 12 parts to 15 parts, 15 parts to 18 parts, etc.
[0033] In some embodiments, in the flame-retardant thermoplastic resin composite material, the weight percentage of the synergistic flame retardant can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc., or a range consisting of any of the above values, for example, 3 parts to 4 parts, 4 parts to 5 parts, etc.
[0034] In some embodiments, in the flame retardant thermoplastic resin composite material, the weight proportion of the antioxidant can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, etc., or a range consisting of any of the above values, for example, 0.1 part to 0.3 part, 0.3 part to 0.5 part, etc.
[0035] In some embodiments, based on the flame retardant thermoplastic resin composite material, the mass percentage of the thermoplastic resin is greater than or equal to 70% and less than 88%. Wherein, based on the flame retardant thermoplastic resin composite material, the mass percentage of the thermoplastic resin can be 70%, 72%, 72.5%, 75%, 79%, 79.3%, 82%, 85%, 87%, 87.9%, 87.93%, etc., or a range composed of any of the above values, for example, 70% to 79%, 75% to 82%, 85% to 87.93%, etc.
[0036] The particle size of the synergistic flame retardant may be 50 nm, 60 nm, 80 nm, 90 nm, 100 nm, etc., or a range consisting of any of the above values, for example, 50 nm to 80 nm, 80 nm to 100 nm, etc.
[0037] In one embodiment, among the synergistic flame retardants, the synergistic flame retardants having a particle size of 60 nm to 90 nm account for more than 90%.
[0038] The particle size of the synergistic flame retardant is within the above range, which can make the synergistic flame retardant more effectively isolate oxygen and heat and prevent the spread of combustion. The proportion of synergistic flame retardant particles with a particle size of 60nm to 90nm is greater than 90%, indicating that the particle size of the synergistic flame retardant is relatively uniform, and the dispersibility of the synergistic flame retardant particles is good, so that the synergistic flame retardant can be more evenly dispersed in the thermoplastic resin, and the flame retardant effect is more significant.
[0039] In one embodiment, among the synergistic flame retardants, the synergistic flame retardants having a particle size of 60 nm to 80 nm account for more than 75%.
[0040] The particle size of the synergistic flame retardant is within the above range, which can make the synergistic flame retardant more effectively isolate oxygen and heat and prevent the spread of combustion. The proportion of synergistic flame retardant particles with a particle size of 60nm to 80nm is greater than 75%, indicating that the particle size of the synergistic flame retardant is relatively uniform, and the dispersibility of the synergistic flame retardant particles is good, so that the synergistic flame retardant can be more evenly dispersed in the thermoplastic resin, and the flame retardant effect is more significant.
[0041] In one embodiment, the thermoplastic resin includes at least one of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyamide 6 (PA6).
[0042] The thermoplastic resin includes at least one of the above-mentioned polymer materials, so that the prepared flame-retardant thermoplastic resin composite material can have good flame retardancy and better mechanical properties.
[0043] In one embodiment, the antioxidant is at least one of 2,6-di-tert-butyl-4-methylphenol and 4,4'-thiobis(6-tert-butyl-o-cresol).
[0044] The antioxidant is at least one of 2,6-di-tert-butyl-4-methylphenol and 4,4'-thiobis(6-tert-butyl-o-cresol), which can capture free radicals generated during the aging process of the thermoplastic material to reduce the reaction between the free radicals and oxygen, thereby slowing down the oxidation and aging of the thermoplastic material and improving the service life of the flame-retardant thermoplastic material composite material.
[0045] It should be noted that the flame retardant thermoplastic resin composite material may also include a colorant (pigment and pearlescent powder, etc.) 、 Lubricants (stearate and paraffin, etc.), fillers (calcium carbonate and bamboo powder, etc.) and other substances are used to match the requirements of actual usage scenarios for visual effects, processing, strength, etc.
[0046] The second technical solution adopted in the present application is: to provide a method for preparing a flame-retardant thermoplastic resin composite material, the preparation method comprising: mixing the following components in parts by weight to obtain a mixture: 90 to 110 parts of thermoplastic resin, 12 to 18 parts of octabromobisphenol S ether, 3 to 5 parts of synergistic flame retardant, and 0.1 to 0.5 parts of antioxidant, wherein the synergistic flame retardant includes iron oxide, and the particle size of the iron oxide is 50nm to 100nm; granulating the mixture to obtain a flame-retardant thermoplastic resin composite material.
[0047] In the technical solution of the present application, a thermoplastic resin, octabromobisphenol S ether, a synergistic flame retardant, and an antioxidant are uniformly mixed according to the above weight proportions to obtain a mixture, and the mixture is melted by an extruder and granulated to obtain a flame-retardant thermoplastic resin composite material. The weight proportion of the thermoplastic resin, octabromobisphenol S ether, the synergistic flame retardant, and the antioxidant within the above range can make the flame-retardant thermoplastic resin composite material have good flame retardancy. In addition, the synergistic flame retardant includes iron oxide, and the particle size of the iron oxide is in the range of 50nm to 100nm, which can make the iron oxide more effectively isolate oxygen and heat, thereby better preventing the spread of combustion.
[0048] In one embodiment, the preparation method of the synergistic flame retardant includes: mixing ammonium ferric oxalate, sodium bicarbonate, ethanol and deionized water and then performing a thermal reaction to obtain an intermediate product; calcining the intermediate product to obtain a synergistic flame retardant. Ammonium ferric oxalate and sodium bicarbonate are dissolved in ethanol and deionized water to perform a thermal reaction to obtain an intermediate product, and then the intermediate product is calcined to pyrolyze the intermediate product, and the nitrogen and carbon elements in the intermediate product are removed in the form of ammonia and carbon dioxide, and finally iron oxide is produced. The iron oxide prepared by this method has a smaller particle size and better dispersion, which is beneficial to improve the flame retardant properties of flame-retardant thermoplastic resin composites. The specific chemical reaction equation is as follows:
[0049] Chemical reaction equation 1:
[0050]
[0051] Chemical reaction equation 2:
[0052]
[0053] In one embodiment, the mass ratio of ammonium ferric oxalate, sodium bicarbonate, ethanol and deionized water is (20-24):(16-18):(60-80):(80-100).
[0054] The weight ratio of ammonium ferric oxalate to sodium bicarbonate is within the above range, so that the two can react fully and thus the intermediate product has a higher yield. The ratio of ammonium ferric oxalate, sodium bicarbonate, ethanol and deionized water is within the above range, so that the ammonium ferric oxalate and sodium bicarbonate have a suitable concentration in the solution system, which is beneficial to the reaction between the ammonium ferric oxalate and sodium bicarbonate, and the intermediate product has a better grain size.
[0055] The mass ratio of ammonium ferric oxalate, sodium bicarbonate, ethanol and deionized water can be 20:16:60:80, 20.5:16.8:64.5:83.5, 22:17:70:90, 23.5:17.5:62.5:91.5, 24:18:80:100, etc., or a range consisting of any of the above numerical values, for example, (20-22):(16-17):(60-70):(80-90), (22-24):(17-18):(70-80):(90-100), etc.
[0056] In one embodiment, the temperature of the thermal reaction is 70° C. to 90° C., and the time of the thermal reaction is 8 h to 12 h.
[0057] The temperature and time of the thermal reaction in the chemical reaction equation 1 within the above ranges can make the ammonium ferric oxalate and sodium bicarbonate have a suitable reaction rate and make the generated intermediate product have a better grain size.
[0058] The temperature of the thermal reaction may be 70°C, 75°C, 80°C, 85°C, 90°C, etc., or any range thereof, for example, 70°C to 80°C, 80°C to 90°C, etc. The time of the thermal reaction may be 8h, 9h, 10h, 11h, 12h, etc., or any range thereof, for example, 8h to 10h, 10h to 12h, etc.
[0059] In one embodiment, the calcination temperature is 700° C. to 780° C., and the calcination time is 16 h to 20 h.
[0060] The calcination temperature and time in the chemical reaction equation 2 are within the above ranges, which can effectively decompose the nitrogen and carbon elements in the intermediate product in the form of gas, only generate the required iron oxide, and the generated iron oxide can have a better particle size. In addition, the preparation method does not require the use of strong acid or strong base for dissolution.
[0061] The calcination temperature may be 700°C, 720°C, 740°C, 760°C, 780°C, etc., or any range thereof, for example, 700°C to 740°C, 740°C to 780°C, etc. The calcination time may be 16h, 17h, 18h, 19h, 20h, etc., or any range thereof, for example, 16h to 18h, 18h to 20h.
[0062] In one embodiment, in the step of granulating the mixed material, the mixed material passes through six melting zones arranged in sequence from discharging to discharging of the extruder, the temperature of the first melting zone is 120℃~240℃, the temperature of the second melting zone is 180℃~280℃, the temperature of the third melting zone is 180℃~280℃, the temperature of the fourth melting zone is 180℃~280℃, the temperature of the fifth melting zone is 180℃~280℃, the temperature of the sixth melting zone is 180℃~280℃, the head temperature of the extruder is 180℃~280℃, and the speed of the screw of the extruder is 220r / min~320r / min.
[0063] After the thermoplastic resin, octabromobisphenol S ether, synergistic flame retardant and antioxidant are uniformly mixed, the mixture is put into the extruder and blended through six melting zones. The temperatures of the first melting zone to the sixth melting zone and the extruder head are respectively within the above ranges, which can preheat the mixture well and make the mixture melt evenly and gradually, reducing the possibility of material decomposition or deterioration due to local overheating. The speed of the screw of the extruder can control the residence time and shear rate of the mixture in the melting zone within the above range, thereby making the mixture fully melted and mixed in the melting zone, reducing the situation of local overheating or incomplete melting, and finally making the prepared flame-retardant thermoplastic resin composite material have better flame retardant properties.
[0064] The temperature of the first melting zone may be 120°C, 150°C, 180°C, 210°C, 240°C, etc., or any range of the above values, for example, 120°C to 180°C, 180°C to 240°C, etc. The temperatures of the second melting zone to the sixth melting zone and the die head of the extruder may be 180°C, 205°C, 230°C, 255°C, 280°C, etc., or any range of the above values, for example, 180°C to 230°C, 230°C to 280°C, etc. The speed of the screw of the extruder may be 220r / min, 250r / min, 275r / min, 300r / min, 320r / min, etc., or any range of the above values, for example, 220r / min to 275r / min, 275r / min to 320r / min, etc.
[0065] In one embodiment, the first to sixth melting zones may be sequentially arranged along a direction from feeding to discharging of the extruder.
[0066] In order to make the technical problems, technical solutions and beneficial effects solved by the embodiments of the present application clearer, the following will be further described in detail with reference to the embodiments and the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present application and its applications. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present application.
[0067] Preparation Example 1
[0068] (1) Weigh 200 g of ammonium ferric oxalate, 160 g of sodium bicarbonate, 600 g of ether, and 800 g of deionized water, place them in a reaction vessel, and stir and react at 70° C. for 8 h to prepare a mixed liquid containing an intermediate product precipitate;
[0069] (2) The mixed liquid was cooled, filtered, washed, dried in a vacuum oven at 30° C. for 6 h, and then calcined in a muffle furnace at 700° C. for 16 h to obtain an iron oxide type synergistic flame retardant M1.
[0070] Example 1
[0071] (1) Weigh 90 parts of polypropylene (PP), 12 parts of octabromobisphenol S ether, 3 parts of synergistic flame retardant M1, and 0.1 parts of 2,6-di-tert-butyl-4-methylphenol, mix and stir to obtain a mixture.
[0072] (2) The mixed material obtained in step (1) is extruded and granulated from a twin-screw extruder to obtain a PP composite material P1.
[0073] Among them, the twin-screw extruder includes six melting zones arranged in sequence, the temperature of the first melting zone is 170°C, the temperature of the second melting zone is 230°C, the temperature of the third melting zone is 230°C, the temperature of the fourth melting zone is 230°C, the temperature of the fifth melting zone is 230°C, the temperature of the sixth melting zone is 230°C, the head temperature of the twin-screw extruder is 230°C, and the screw speed is 220r / min.
[0074] Comparative Example 1-1
[0075] (1) Weigh 90 parts of PP, 12 parts of octabromobisphenol S ether, 3 parts of synergistic flame retardant antimony trioxide, and 0.1 parts of 2,6-di-tert-butyl-4-methylphenol, mix and stir to obtain a mixture.
[0076] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PP composite material D1-1. The rest is the same as in Example 1 and will not be described in detail here.
[0077] Comparative Example 1-2
[0078] (1) Weigh 90 parts of PP, 12 parts of octabromobisphenol S ether, 3 parts of commercially available iron oxide as a synergistic flame retardant, and 0.1 parts of 2,6-di-tert-butyl-4-methylphenol, mix and stir to obtain a mixture.
[0079] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PP composite material D1-2. The rest is the same as in Example 1 and will not be described in detail here.
[0080] The PP composite materials prepared in the above Example 1 and Comparative Example 1-1 and Comparative Example 1-2 were made into strips by injection molding machine for testing. The test data are shown in Table 1:
[0081] Table 1 Flame retardant properties of PP composite materials prepared in Example 1, Comparative Examples 1-1 and 1-2
[0082] Test items Test Standards P1 D1-1 D1-2 Flame retardant performance (1.6mm) UL-94 V-0 V-1 V-1
[0083] It can be seen from the above table that the flame retardant properties of the PP composite material prepared in Example 1 are better than those of the PP composite materials prepared using commercially available antimony trioxide and iron oxide in Comparative Example 1-1 and Comparative Example 1-2.
[0084] Among them, V-2 means: after two 10-second combustion tests on the sample, the flame goes out within 60 seconds, and the burning objects can fall. V1 means: after two 10-second combustion tests on the sample, the flame goes out within 60 seconds, and no burning objects can fall. V-0 means: after two 10-second combustion tests on the sample, the flame goes out within 30 seconds, and no burning objects can fall.
[0085] See the attached manual Figure 1 and Figure 2 , Figure 1 1 is a particle size distribution histogram of the synergistic flame retardant according to one embodiment of the present application. Figure 2 It is the particle size distribution histogram of commercially available synergistic flame retardant iron oxide. Figure 1 and Figure 2 It can be seen that compared with the commercially available iron oxide used in Comparative Examples 1-2, the particle size range of the commercially available iron oxide is 90nm to 140nm, and the particle size range of the iron oxide prepared in Preparation Example 1 of the present application is 60nm to 100nm. The particle size of the iron oxide prepared in the present application is smaller, thereby more effectively isolating oxygen and heat, and having better flame retardancy. In addition, Figure 1 The proportion of iron oxide particles in the range of 60nm to 80nm is greater than 75%, while Figure 2 The particle size of the iron oxide in the present invention has more particle size segments and a wider particle size distribution. Therefore, the particle size of the iron oxide prepared in the present invention is more uniform. The uniform particle size can make the iron oxide more evenly distributed in the thermoplastic material, and the flame retardant effect is more significant. Figure 3 and Figure 4 , Figure 3 This is a transmission electron microscope image of a synergistic flame retardant according to one embodiment of the present application. Figure 4 This is a transmission electron microscope image of the commercially available synergistic flame retardant iron oxide. Figure 3 and Figure 4 It can also be seen intuitively that Figure 4 Compared with the commercially available iron oxide Figure 3 The particle size distribution of the iron oxide prepared in the present application is wider and the dispersibility is worse.
[0086] Preparation Example 2
[0087] (1) Weigh 240 g of ammonium ferric oxalate, 180 g of sodium bicarbonate, 800 g of ether, and 1.0 kg of deionized water, place them in a reaction vessel, and stir and react at 90° C. for 12 h to prepare a mixed liquid containing an intermediate product precipitate.
[0088] (2) The mixed liquid was cooled, filtered, washed, dried in a vacuum drying oven at 50° C. for 8 h, and then calcined in a muffle furnace at 780° C. for 20 h to obtain an iron oxide type synergistic flame retardant M2.
[0089] Example 2
[0090] (1) Weigh 110 parts of polybutylene terephthalate (PBT), 18 parts of octabromobisphenol S ether, 5 parts of synergistic flame retardant M2, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.4 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture.
[0091] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PBT composite material P2.
[0092] The twin-screw extruder includes six melting zones arranged in sequence, the temperature of the first melting zone is 200°C, the temperature of the second melting zone is 230°C, the temperature of the third melting zone is 240°C, the temperature of the fourth melting zone is 240°C, the temperature of the fifth melting zone is 240°C, the temperature of the sixth melting zone is 240°C, the head temperature of the twin-screw extruder is 240°C, and the screw speed is 300r / min.
[0093] Comparative Example 2-1
[0094] (1) Weigh 110 parts of PBT, 18 parts of octabromobisphenol S ether, 5 parts of synergistic flame retardant antimony trioxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.4 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture.
[0095] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PBT composite material D2-1. The rest is the same as in Example 2 and will not be described in detail here.
[0096] Comparative Example 2-2
[0097] (1) Weigh 110 parts of PBT, 18 parts of octabromobisphenol S ether, 5 parts of commercially available synergistic flame retardant iron oxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.4 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture.
[0098] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PBT composite material D2-2. The rest is the same as in Example 2 and will not be described in detail here.
[0099] The PBT composite materials prepared in the above Example 2 and Comparative Example 2-1 and Comparative Example 2-2 were made into strips by injection molding machine for testing. The test data are shown in Table 2:
[0100] Table 2 Flame retardant properties of PBT composite materials prepared in Example 2, Comparative Examples 2-1 and 2-2
[0101] Test items Test Standards P2 D2-1 D2-2 Flame retardant performance (1.6mm) UL-94 V-0 V-1 V-1
[0102] It can be seen from the above table that the flame retardant properties of the PBT composite material prepared in Example 2 are better than those of the PBT composite materials prepared using commercially available antimony trioxide and iron oxide in Comparative Example 2-1 and Comparative Example 2-2.
[0103] Preparation Example 3
[0104] (1) Weigh 220 g of ammonium ferric oxalate, 170 g of sodium bicarbonate, 700 g of ether, and 900 g of deionized water, place them in a reaction vessel, and stir and react at 80° C. for 10 h to prepare a mixed liquid containing an intermediate product precipitate;
[0105] (2) The mixed liquid was cooled, filtered, washed, dried in a vacuum oven at 40° C. for 7 h, and then calcined in a muffle furnace at 740° C. for 18 h to obtain an iron oxide type synergistic flame retardant M3.
[0106] Example 3
[0107] (1) Weigh 100 parts of polyethylene (PE), 15 parts of octabromobisphenol S ether, 4 parts of synergistic flame retardant M3, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0108] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PE composite material P3.
[0109] The twin-screw extruder includes six melting zones arranged in sequence, the temperature of the first melting zone is 120°C, the temperature of the second melting zone is 180°C, the temperature of the third melting zone is 180°C, the temperature of the fourth melting zone is 180°C, the temperature of the fifth melting zone is 180°C, the temperature of the sixth melting zone is 180°C, the head temperature of the twin-screw extruder is 180°C, and the screw speed is 300r / min.
[0110] Comparative Example 3-1
[0111] (1) Weigh 100 parts of PE, 15 parts of octabromobisphenol S ether, 4 parts of synergistic flame retardant antimony trioxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0112] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PE composite material D3-1. The rest is the same as in Example 3 and will not be described in detail here.
[0113] Comparative Example 3-2
[0114] (1) Weigh 100 parts of PE, 15 parts of octabromobisphenol S ether, 4 parts of commercially available synergistic flame retardant iron oxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0115] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PE composite material D3-2. The rest is the same as in Example 3 and will not be described again.
[0116] The PE composite materials prepared in the above Example 3 and Comparative Example 3-1 and Comparative Example 3-2 were made into test strips by injection molding machine. The test data are shown in Table 3:
[0117] Table 3 Flame retardant properties of PE composite materials prepared in Example 3, Comparative Examples 3-1 and 3-2
[0118] Test items Test Standards P3 D3-1 D3-2 Flame retardant performance (1.6mm) UL-94 V-0 V-1 V-1
[0119] It can be seen from the above table that the flame retardant properties of the PE composite material prepared in Example 3 are better than those of the PE composite materials prepared using commercially available antimony trioxide and iron oxide in Comparative Example 3-1 and Comparative Example 3-2.
[0120] Preparation Example 4
[0121] (1) Weigh 235 g of ammonium ferric oxalate, 175 g of sodium bicarbonate, 625 g of ether, and 915 g of deionized water, place them in a reaction vessel, and stir and react at 85° C. for 11 h to prepare a mixed liquid containing an intermediate product precipitate.
[0122] (2) The mixed liquid was cooled, filtered, washed, dried in a vacuum oven at 45° C. for 7.5 h, and then calcined in a muffle furnace at 745° C. for 17 h to obtain an iron oxide type synergistic flame retardant M4.
[0123] Example 4
[0124] (1) Weigh 96.8 parts of PA6, 15.4 parts of octabromobisphenol S ether, 4.5 parts of synergistic flame retardant M4, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0125] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PA6 composite material P4.
[0126] The twin-screw extruder includes six melting zones arranged in sequence, the temperature of the first melting zone is 210°C, the temperature of the second melting zone is 260°C, the temperature of the third melting zone is 260°C, the temperature of the fourth melting zone is 260°C, the temperature of the fifth melting zone is 260°C, the temperature of the sixth melting zone is 260°C, the head temperature of the twin-screw extruder is 260°C, and the screw speed is 320r / min.
[0127] Comparative Example 4-1
[0128] 1) Weigh 96.8 parts of polyamide 6 (PA6), 15.4 parts of octabromobisphenol S ether, 4.5 parts of synergistic flame retardant antimony trioxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir evenly to obtain a mixture;
[0129] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PA6 composite material D4-1. The rest is the same as in Example 4 and will not be described in detail here.
[0130] Comparative Example 4-2
[0131] (1) Weigh 96.8 parts of PA6, 15.4 parts of octabromobisphenol S ether, 4.5 parts of commercially available synergistic flame retardant iron oxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0132] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PA6 composite material D4-2. The rest is the same as in Example 4 and will not be described in detail here.
[0133] The PA6 composite materials prepared in the above Example 4 and Comparative Example 4-1 and Comparative Example 4-2 were made into strips by injection molding machine for testing. The test data are shown in Table 4:
[0134] Table 4 Flame retardant properties of PA6 composite materials prepared in Example 4, Comparative Examples 4-1 and 4-2
[0135] Test items Test Standards P4 D4-1 D4-2 Flame retardant performance (1.6mm) UL-94 V-0 V-1 V-1
[0136] It can be seen from the above table that the flame retardant properties of the PA6 composite material prepared in Example 4 are better than those of the PA6 composite materials prepared using commercially available antimony trioxide and iron oxide in Comparative Example 4-1 and Comparative Example 4-2.
[0137] Preparation Example 5
[0138] (1) Weigh 205 g of ammonium ferric oxalate, 168 g of sodium bicarbonate, 645 g of ether, and 835 g of deionized water, place them in a reaction vessel, and stir and react at 78° C. for 11.5 h to prepare a mixed liquid containing an intermediate product precipitate;
[0139] (2) The mixed liquid was cooled, filtered, washed, dried in a vacuum oven at 48° C. for 6.5 h, and then calcined in a muffle furnace at 735° C. for 19.5 h to obtain an iron oxide type synergistic flame retardant M5.
[0140] Example 5
[0141] (1) Weigh 107.5 parts of polyethylene terephthalate (PET), 15.5 parts of octabromobisphenol S ether, 3.8 parts of synergistic flame retardant M5, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.1 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0142] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material P5.
[0143] The twin-screw extruder includes six melting zones arranged in sequence, the temperature of the first melting zone is 240°C, the temperature of the second melting zone is 280°C, the temperature of the third melting zone is 280°C, the temperature of the fourth melting zone is 280°C, the temperature of the fifth melting zone is 280°C, the temperature of the sixth melting zone is 280°C, the head temperature of the twin-screw extruder is 280°C, and the screw speed is 280r / min.
[0144] Comparative Example 5-1
[0145] (1) Weigh 107.5 parts of PET, 15.5 parts of octabromobisphenol S ether, 3.8 parts of synergistic flame retardant antimony trioxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.1 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0146] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material D5-1. The rest is the same as in Example 5 and will not be described in detail here.
[0147] Comparative Example 5-2
[0148] (1) Weigh 107.5 parts of PET, 15.5 parts of octabromobisphenol S ether, 3.8 parts of commercially available synergistic flame retardant iron oxide, 0.1 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.1 parts of antioxidant 4,4'-thiobis(6-tert-butyl-o-cresol), mix and stir to obtain a mixture;
[0149] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain a PET composite material D5-2. The rest is the same as in Example 5 and will not be described in detail here.
[0150] The PET composite materials prepared in the above Example 5 and Comparative Example 5-1 and Comparative Example 5-2 were made into strips by injection molding machine for testing. The test data are shown in Table 5:
[0151] Table 5 Flame retardant properties of PET composite materials prepared in Example 5, Comparative Examples 5-1 and 5-2
[0152] Test items Test Standards P4 D5-1 D5-2 Flame retardant performance (1.6mm) UL-94 V-0 V-1 V-1
[0153] It can be seen from the above table that the flame retardant properties of the PET composite material prepared in Example 5 are better than those of the PET composite materials prepared using commercially available antimony trioxide and iron oxide in Comparative Example 5-1 and Comparative Example 5-2.
[0154] The above are only implementation methods of the present application, and are not intended to limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly used in other related technical fields, are also included in the patent protection scope of the present application.
Claims
1. A flame retardant thermoplastic resin composite material, characterized in that: The flame retardant thermoplastic resin composite material comprises the following components in parts by weight: Thermoplastic resin is 90 to 110 parts, octabromobisphenol S ether is 12 to 18 parts, synergistic flame retardant is 3 to 5 parts, antioxidant is 0.1 to 0.5 parts; Wherein, the synergistic flame retardant includes iron oxide, and the particle size of the iron oxide is 50nm to 100nm.
2. The flame retardant thermoplastic resin composite material according to claim 1, characterized in that: Among the synergistic flame retardants, the synergistic flame retardants with a particle size of 60 nm to 90 nm account for more than 90%.
3. The flame retardant thermoplastic resin composite material according to claim 1 or 2, characterized in that: Among the synergistic flame retardants, the synergistic flame retardants with a particle size of 60 nm to 80 nm account for more than 75%.
4. The flame retardant thermoplastic resin composite material according to claim 1, characterized in that: The thermoplastic resin includes at least one of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyamide 6 (PA6).
5. The flame retardant thermoplastic resin composite material according to claim 1, characterized in that: The antioxidant is at least one of 2,6-di-tert-butyl-4-methylphenol and 4,4'-thiobis(6-tert-butyl-o-cresol).
6. A method for preparing a flame retardant thermoplastic resin composite material, characterized in that: The preparation method of the synergistic flame retardant comprises: Mix the following components in parts by weight to obtain a mixture: 90 to 110 parts of a thermoplastic resin, 12 to 18 parts of octabromobisphenol S ether, 3 to 5 parts of a synergistic flame retardant, and 0.1 to 0.5 parts of an antioxidant, wherein the synergistic flame retardant comprises iron oxide, and the particle size of the iron oxide is 50 nm to 100 nm; The mixed material is granulated to obtain the flame retardant thermoplastic resin composite material.
7. The method for preparing a flame retardant thermoplastic resin composite material according to claim 6, characterized in that: The preparation method of the synergistic flame retardant comprises: ammonium ferric oxalate, sodium bicarbonate, ethanol and deionized water are mixed and then subjected to a thermal reaction to obtain an intermediate product; The intermediate product is calcined to obtain the synergistic flame retardant.
8. The method for preparing a flame-retardant thermoplastic resin composite material according to claim 7, characterized in that: The mass ratio of the ammonium ferric oxalate, the sodium bicarbonate, the ethanol and the deionized water is (20-24):(16-18):(60-80):(80-100).
9. The method for preparing a flame-retardant thermoplastic resin composite material according to claim 7, characterized in that: The temperature of the thermal reaction is 70° C. to 90° C., and the time of the thermal reaction is 8 h to 12 h.
10. The method for preparing a flame retardant thermoplastic resin composite material according to claim 7, characterized in that: The calcination temperature is 700° C. to 780° C., and the calcination time is 16 h to 20 h.
11. The method for preparing a flame retardant thermoplastic resin composite material according to claim 9, characterized in that: In the step of granulating the mixed material, the mixed material passes through six melting zones arranged in sequence from material discharge to material discharging of an extruder, the temperature of the first melting zone is 120°C to 240°C, the temperature of the second melting zone is 180°C to 280°C, the temperature of the third melting zone is 180°C to 280°C, the temperature of the fourth melting zone is 180°C to 280°C, the temperature of the fifth melting zone is 180°C to 280°C, the temperature of the sixth melting zone is 180°C to 280°C, the head temperature of the extruder is 180°C to 280°C, and the speed of the screw of the extruder is 220r / min to 320r / min.