High polyphosphoric acid antimony-magnesium borate composite flame-retardant synergist and ABS flame-retardant master batch

Abstract

The invention relates to a high polyphosphoric acid antimony-magnesium borate composite flame-retardant synergist and ABS flame-retardant masterbatch, and the composite flame-retardant synergist is prepared by the following steps: (1) putting raw materials of high polyphosphoric acid antimony and magnesium borate into a high-speed mixer, uniformly stirring and mixing, heating, preserving heat, and cooling to normal temperature; (2) adding a modifier into the mixture of the high-poly-antimony phosphate and the magnesium borate, and uniformly stirring and mixing at a high speed; then, adding a halogen-containing flame retardant, and continuously stirring uniformly at a high speed to prepare a modified premix; and (3) heating, activating and modifying the premix in a kneading machine to obtain the high polyphosphoric acid antimony-magnesium borate composite flame-retardant synergist. And adding a carrier ABS master batch into the composite flame-retardant synergist, kneading, extruding, and pelletizing to obtain the composite flame-retardant synergist ABS flame-retardant master batch. The flame-retardant material prepared from the flame-retardant master batch has a good flame-retardant effect, the smoke density can be reduced by more than 35%, and no molten drop exists; compared with a halogen-antimony trioxide system, the antimony addition amount is reduced by 50% or above, and the cost is greatly reduced.

Description

Technical Field

[0001] The present invention relates to a composite flame retardant synergist, in particular to a high-polymer antimony phosphate-magnesium borate composite flame retardant synergist and a preparation method thereof, as well as an ABS flame retardant masterbatch containing the high-polymer antimony phosphate-magnesium borate composite flame retardant synergist. Background Art

[0002] The function of a flame retardant should not only be "flame retardant" but also "smoke suppression".

[0003] Smoke generation is a basic characteristic of polymer combustion. Excessive smoke density will not only reduce the visibility at the fire scene, bringing great difficulties to the escape of personnel and fire fighting and rescue, but also be the most fatal factor during a fire. According to statistics, 80% of the deaths in fires are caused by smoke asphyxiation. Therefore, in flame retardant technology, "flame retardancy" and "smoke suppression" are two key elements that need to be solved simultaneously.

[0004] Antimony-halogen flame retardants are the most classic, have the best flame retardant effect and are the most widely used flame retardants. However, their existing defects such as large smoke, "antimony toxicity" and high price have also attracted much attention. Reducing the smoke during the combustion of flame retardant materials and reducing the amount of antimony used or even completely replacing antimony-halogen systems have become the forefront of flame retardant scientific research.

[0005] However, due to the unique flame retardant effect of antimony-halogen flame retardants and the many defects of halogen-free flame retardants, it still takes a long process to completely replace antimony-halogen flame retardants. The most commonly used halogen-containing flame retardants are bromine compounds, mainly including decabromodiphenyl ether (DBDPO), decabromodiphenylethane (DBDPE), brominated triazine (TR-245), octabromo, hexabromo, tetrabromo and other brominated organic compounds. Among them, DBDPO was the earliest flame retardant used for flame retardancy, but it has been gradually phased out because the flame retardant material containing DBDPO produces carcinogenic dioxins during the fire combustion process and contains free bromine that corrodes production and processing equipment. Currently, the more commonly used halogen-containing flame retardants on the market mainly include DBDPE, TR-245 and environmentally friendly brominated organic compounds such as octabromo and hexabromo that do not contain free bromine.

[0006] The safety of antimony phosphate has passed the SGS certification and meets multiple environmental protection requirements such as RoHS, REACH, PAHs, etc. It is an environmentally friendly flame retardant synergist. In flame retardant applications, it can replace more than 50% of antimony trioxide. It can simultaneously exert the effects of phosphorus-based flame retardants and antimony-halogen synergistic flame retardants during the flame retardant process. It conforms to the development trend of reducing antimony in the flame retardant system. However, when used alone, the addition amount and smoke reduction effect still cannot meet the ideal requirements.

[0007] Magnesium borate is also a flame retardant and smoke suppressant that is pollution-free and has low toxicity. It can react with a variety of polymers, and the resulting composite materials have excellent mechanical properties, high temperature resistance, corrosion resistance, etc. In a fire scene, it can generate structural water that reduces the temperature around the combustible material, and can also generate boron trioxide that prevents the combustible material from contacting the atmosphere and prevents the intense melting of the combustible substrate at high temperatures, improving the carbon formation property and carbon formation stability, and significantly improving the anti-dripping effect, thereby reducing the occurrence of secondary fires. However, when used alone, it has the disadvantage of a large addition amount, and the large addition of inorganic powder will deteriorate some mechanical properties of the organic matrix material.

[0008] Both high-polymer antimony phosphate and magnesium borate products are inorganic powders. When they are added to high-molecular polymers, there are adverse factors such as interfacial energy and uneven dispersion, which deteriorate the physical properties of the flame-retardant materials. At present, the method to solve the interfacial energy and dispersibility of inorganic powders in organic compounds is to carry out surface activation modification on the inorganic powders. The activation modification methods mainly include mechanical force modification; high-energy modification; chemical modification and physicochemical modification, etc. Mechanical force modification is to use mechanical grinding, impact, friction and other effects to change the physical structure and morphology of the powder surface and increase the surface active sites. High-energy modification is further divided into plasma method and corona method. The plasma method is to introduce new functional groups on the powder surface through plasma treatment to change the surface chemical properties. The high-energy particles in the plasma can activate the molecules on the powder surface and initiate chemical reactions. The corona method is a method to improve the surface activity of the powder through electric shock treatment. Chemical modification is divided into two methods: uniformly coating a layer of substance on the powder surface to form a core-shell structure surface coating and chemically grafting specific functional groups onto the powder surface through chemical reactions. Physicochemical modification includes the coupling agent method that uses coupling agents to build a bridge between the powder and other materials to enhance the interfacial bonding force and the surfactant method that uses the adsorption of surfactants on the powder surface to change its surface energy and wettability. Each activation modification has its own advantages and disadvantages.

[0009] Powder activation modifiers are mainly divided into two categories: coupling agents and surfactants. Among them, the most widely used coupling agents include silanes, titanates, aluminate esters, borate esters, etc. These coupling agents couple organic molecules and inorganic molecules through hydrophilic and lipophilic groups in the molecule. However, due to the differences in elements and their own molecular structures, they each have advantages and defects. Summary of the Invention

[0010] The technical problem to be solved by the present invention is to overcome the above-mentioned defects existing in the prior art and provide a high-polymer antimony phosphate-magnesium borate composite flame retardant synergist that is low in antimony, low in toxicity, has a smoke suppression function, low in cost, and meets environmental protection requirements.

[0011] A further technical problem to be solved by the present invention is to provide an ABS flame retardant masterbatch containing the above-mentioned antimony polyphosphate-magnesium borate composite flame retardant synergist.

[0012] The technical solution adopted by the present invention to solve its technical problems is an antimony polyphosphate-magnesium borate composite flame retardant synergist, which is prepared by the following method:

[0013] (1) Put the raw materials of antimony polyphosphate and magnesium borate into a high-speed mixer, stir and mix evenly, then heat, keep warm, and then cool to room temperature to obtain a mixture of antimony polyphosphate and magnesium borate;

[0014] (2) Add the mixture of antimony polyphosphate and magnesium borate obtained in step (1) to a dry modification machine, add a modifier, and stir and mix evenly at high speed to obtain a semi-finished product of a modified antimony polyphosphate-magnesium borate-modifier flame retardant synergist; then, add a halogen-containing flame retardant to the semi-finished product of the flame retardant synergist, and continue to stir evenly at high speed to obtain a modified premix of the flame retardant-synergist;

[0015] (3) Put the flame retardant-synergist premix prepared in step (2) into a kneader, knead and heat to carry out the activation modification of antimony polyphosphate-magnesium borate, and obtain the antimony polyphosphate-magnesium borate composite flame retardant synergist.

[0016] Further, in step (1), the mass ratio of the antimony polyphosphate to the magnesium borate is 1:0.7-1.2; preferably 1:0.85-1.1. By adopting the above technical solution, the prepared composite flame retardant synergist has better flame retardant and smoke suppression effects.

[0017] Further, the antimony polyphosphate is a white powdery antimony polyphosphate product with a whiteness ≥ 92%, a degree of polymerization of 50-65, a particle size ≤ 2 μm, a moisture absorption rate ≤ 0.6 in the air for 72 h, and a purity (i.e., the content of antimony polyphosphate) ≥ 98%, which is prepared by a solid-phase reaction in a microwave field. Compared with the antimony polyphosphate products prepared by the liquid-phase method and the ordinary high-temperature sintering method, the antimony polyphosphate product prepared by the microwave solid-phase reaction method has a greatly increased degree of polymerization and a greatly reduced moisture absorption rate, and is extremely suitable for the flame retardation of polymer composite materials. The specific operation method can refer to a method for preparing antimony polyphosphate at low temperature by solid phase disclosed in CN117003213A).

[0018] Further, in step (1), the magnesium borate is preferably magnesium borate whiskers. Magnesium borate whiskers are not only a good inorganic flame retardant synergist, but also a material reinforcement when added in an appropriate amount, and can enhance the mechanical properties of polymer matrix (such as plastics, resins) materials.

[0019] Furthermore, in step (1), the magnesium borate whiskers are white powdery magnesium borate whisker products with a diameter of 0.5 - 1 μm, an aspect ratio of 20 - 30, a purity of ≥98.0%, a water content of ≤0.3%, and a whiteness of ≥98%. In flame retardant applications, they can improve carbon formation and carbon formation stability. While significantly improving the flame retardant efficiency, they have a good reinforcing effect on the flame retardant substrate, obtaining good physical and mechanical properties and processing properties, excellent electrical insulation properties, and being non-toxic, harmless, and pollution-free. They can be produced by using Mg(OH)2, H3BO3 as raw materials, NaCl as a flux, and ZnO as a heating medium, and adopting the microwave solid-phase method.

[0020] Furthermore, in step (1), during mixing, the rotational speed of the high-speed mixer is 700 - 950 r / min, preferably 750 - 900 r / min.

[0021] Furthermore, in step (1), the time for high-speed stirring and mixing of antimony polyphosphate and magnesium borate in the high-speed mixer is 5 - 10 min.

[0022] Furthermore, in step (1), the heating temperature is 80°C - 100°C, preferably 85°C - 95°C; the heat preservation time is 5 - 15 min, preferably 8 - 12 min. To remove the trace physical moisture in the two raw materials and ensure better modification effect in the next step.

[0023] Furthermore, in step (2), the modifier is one or more composites of titanate, aluminate, and borate coupling agents; preferably borate coupling agent LD-100P. The borate coupling agent is a white powdery product, which does not need to be dissolved in a solvent and can directly activate and modify antimony polyphosphate - magnesium borate with inorganic powder in a dry modification machine, simplifying the activation and modification process of antimony polyphosphate - magnesium borate.

[0024] Furthermore, the addition amount of the modifier is 0.6 - 1.5% of the total mass of antimony polyphosphate - magnesium borate; preferably 0.8 - 1.2%.

[0025] Furthermore, in step (2), the halogen-containing flame retardant is one or two composites of halogen-containing flame retardant brominated triazine (TR-245) or decabromodiphenylethane (DBDPE); preferably brominated triazine. Brominated triazine is a new type of environmentally friendly flame retardant with bromine / nitrogen synergy and no free bromine. It has excellent anti-ultraviolet radiation and light resistance performance, overcoming the disadvantages of poor light resistance and easy yellowing of tetrabromide and decabromide, and is an upgraded alternative product to tetrabromide and decabromide.

[0026] Furthermore, the brominated triazine (TR-245) is a white powdery product with a bromine content of ≥66.7% and a main component (i.e., brominated triazine) content of ≥99%. Its decomposition temperature is usually 310°C.

[0027] Further, in step (2), the addition amount of the halogen-containing flame retardant is 3.0 - 4.0 times, preferably 3.2 - 3.8 times, of the total mass of the antimony polyphosphate - magnesium borate.

[0028] Further, in step (2), the time for high-speed stirring and mixing after adding the modifier is 5 - 10 min; the time for continuous high-speed stirring and mixing after adding the halogen-containing flame retardant is 3 - 8 min.

[0029] Further, in step (3), the heating temperature is 60°C - 90°C, preferably 70°C - 85°C; the kneading time is 10 - 30 min, preferably 15 - 25 min.

[0030] In step (2), the dry modification machine is a device similar to a high-speed mixer. The difference is that the materials in the high-speed mixer move at a high speed in a swirling flow, and it is modified from the high-speed mixer by itself by modifying the blades. While the materials in the dry modification machine move at a high speed in a vortex flow under the action of its three special "C"-shaped blades. The materials in this vortex flow can be mixed evenly in a relatively short time and also have the function of crushing agglomerated particles. Dry modification is a process with simple process, energy conservation and environmental protection, and is most suitable for the physical and chemical modification of powdery materials and powdery modifiers. It is especially suitable for the modification process where the free water on the surface of the material to be modified is ≤ 0.3% when using borate coupling agent for modification.

[0031] In step (3), preferably, the chemical name of the borate coupling agent LD-100P is diisopropyl stearoyl borate; it is a white powder with an effective ingredient ≥ 99%, and is a small molecule organic compound with a low melting point, non-toxic and antibacterial properties, and with a boron atom as the central atom, and is a coupling agent with boric acid as the main functional group. Its functional groups can bind to inorganic fillers at a relatively low temperature; its chemical structure contains boron-oxygen bonds, integrating a coupling agent, a dispersant and a modifier, and has multiple functions. Its unique boron-oxygen skeleton is used for the surface modification of boron-containing inorganic fillers, improving the compatibility between boron-containing inorganic fillers and polymers, and can produce good physical adsorption with borate whiskers, and has a good modification effect on the modification of borate whiskers. It also has a strong affinity for inorganic powders, can prevent the agglomeration of inorganic powder particles, make the inorganic powder particles more evenly dispersed into the polymer structure, and better improve the influence on the mechanical properties of the matrix material.

[0032] The technical solution adopted by the present invention to further solve its technical problems is an ABS flame retardant masterbatch containing the high-polymer antimony phosphate-magnesium borate composite flame retardant synergist, which is prepared by the following method: adding a carrier ABS masterbatch to the high-polymer antimony phosphate-magnesium borate flame retardant synergist, and then kneading, extruding and pelletizing to obtain the ABS flame retardant masterbatch; the mass ratio of the added carrier ABS masterbatch to the high-polymer antimony phosphate-magnesium borate composite flame retardant synergist is 80-85:20-15, preferably 81-84:19-16.

[0033] The magnesium borate whiskers used as the raw material for manufacturing the product of the present invention can be prepared by the following method:

[0034] Prepared by microwave solid-phase method using magnesium hydroxide [Mg(OH)2] and boric acid as raw materials, ZnO as the heating medium, and NaCl+KCl (1:1) as the flux. The process flow is shown in the attached Figure 1 .

[0035] Process conditions: Microwave calcination temperature: 850°C - 900°C; Calcination time 20 - 30 min; Drying temperature: 100 - 120°C; Drying time: 90 - 120 min.

[0036] Product indexes: Mg2B2O5 ≥ 98%; Particle size 0.5 - 1.5 μm, aspect ratio 20 - 30; Water content ≤ 0.3%; Whiteness ≥ 98%.

[0037] Chemical reaction formula: Mg(OH)2 + H3B2O3 → Mg2B2O5 + H2O

[0038] The high-polymer antimony phosphate-magnesium borate composite flame retardant synergist of the present invention is composed of 2 flame retardant components and 2 flame retardant and smoke suppression components in combination, realizing the reduction of antimony, reduction of toxicity, smoke suppression, reduction of addition amount and enhancement of flame retardant performance of the flame retardant. Also, due to the significant reduction of antimony, the production cost of the flame retardant material is greatly reduced; the ABS flame retardant masterbatch containing the high-polymer antimony phosphate-magnesium borate flame retardant synergist of the present invention, compared with existing types of flame retardants (including flame retardant synergists), has better flame retardant performance, more significant antimony reduction, smoke reduction and toxicity reduction effects, is more environmentally friendly, convenient to use, has lower cost, and has less impact on the physical and mechanical properties of the flame retardant material.

[0039] The present invention has the following beneficial effects: 1) The present invention selects two flame retardant synergists, antimony polyphosphate and magnesium borate, as raw materials for compounding, and activates and modifies antimony polyphosphate and magnesium borate by using modifiers such as borate coupling agent, so that the flame retardant performance is improved compared with that of any single halogen-antimony flame retardant material, and the antimony addition amount is reduced by more than 50%. Under the condition of not reducing or even enhancing the flame retardant effect, the production cost is reduced by more than 35%; 2) When the prepared ABS sample bar with a size of 2-3 mm is subjected to a vertical burning test, it extinguishes immediately after leaving the fire, without dripping, and fully meets the requirements of the V-0 level of the UL94 standard, with excellent flame retardant effect; 3) The OI value of the sample piece (100×1×4 mm) measured by an oxygen index instrument is 29-33%; which is greatly improved compared with the oxygen index (18-20%) of the unflame-retarded ABS; 4. The sample piece (75×75×20 mm) is tested in a smoke density meter; the specific optical density is 453-467, compared with the maximum specific optical density of 720 of the control ABS, the optical density is reduced by 35%-37%; the smoke amount can be reduced by up to 37% during combustion; 4) Through the two-stage activation modification of mixing and melt kneading of antimony polyphosphate-magnesium borate, the activation coupling agent is more firmly adsorbed to antimony polyphosphate and magnesium borate, with better coupling and less influence on the physical properties of the matrix resin; 5) Research shows that the preferred raw material magnesium borate whisker is not only a good inorganic flame retardant synergist, but also another main use can be used as a material reinforcing body to enhance and toughen the mechanical properties of polymer matrix materials (such as plastics and resins); through the activation modification of the Sb2O3-Mg2B2O5 composite, the mechanical properties of the ABS flame retardant material are greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 It is a process flow diagram for preparing the magnesium borate whisker, which is one of the raw materials used in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0041] The present invention will be further described in detail below with reference to specific embodiments.

[0042] One of the main raw materials used in the following embodiments of the present invention, antimony polyphosphate, is prepared by the method for preparing antimony polyphosphate at low temperature in solid phase disclosed in CN 117003213 A.

[0043] Refer to Figure 1, another main raw material used in the embodiments of the present invention, magnesium borate whiskers, is prepared by the following method: Add 1.5 Kg of Mg(OH)2, H3BO3 and a flux of NaCl+KCl (1:1) in a molar mass ratio of Mg:B:Na of 2:3:7 to a high-speed crusher with mixing function, crush and mix for 10 min. Put the uniformly mixed mixture into a corundum crucible, then place the crucible in a mullite crucible containing a heating medium ZnO, and send it into a box-type microwave oven. The heating rate is 10 °C / min. When the temperature rises to 850 °C, start timing, and react at this temperature for 25 min. Stop heating and cool. After the reactant is cooled to room temperature, take it out and put it into a high-speed crusher to crush it into powder. Send the powdered material into a leaching tank equipped with a stirring device and deionized water at 40-50 °C, stir and leach for 45 min, vacuum filter, wash the filter cake 3 times with deionized water at 40-50 °C, and microwave-dry the washed filter cake at 120 °C for 20 min to obtain a magnesium borate whisker product with a water content of ≤0.3%.

[0044] The halogen-containing flame retardant brominated triazine (TR-245) used is produced by Jiangsu Xinzhou Chemical Technology Co., Ltd.

[0045] The borate coupling agent LD-100P used is produced by Shandong Suihua Biotechnology Co., Ltd.

[0046] The ABS masterbatch DG-4117 used is produced by Tianjin Dagu Chemical Industry Co., Ltd.

[0047] The performance of the products in each embodiment is detected according to the following national standard specified methods:

[0048] 1) Oxygen index: Detected according to the method specified in GB / T 2406.2;

[0049] 2) Smoke density: Detected according to the method specified in GB / 8323.2-2008;

[0050] 3) Vertical burning rating: Detected according to the method specified in GB / T 2408;

[0051] 4) Tensile strength: Detected according to the method specified in GB / T 1040.2;

[0052] 5) Elongation at break: Detected according to the method specified in GB / T 1040.2;

[0053] 6) Izod notched impact strength: Detected according to the method specified in GB / T 1843-2008.

[0054] Example 1

[0055] The high-polymer antimony phosphate-magnesium borate composite flame retardant synergist in this example is made by the following method:

[0056] (1) Weigh 350 g of antimony polyphosphate (degree of polymerization ≥ 60) and 330 g of magnesium borate whiskers, put them into a high-speed mixer with heating function, raise the temperature while stirring at low speed, raise the temperature to 90 °C, adjust the stirring speed to 800 r / min, keep for 8 min at this temperature and stirring speed, stop heating, and cool to room temperature by stirring at low speed to obtain a mixture of antimony polyphosphate and magnesium borate whiskers;

[0057] (2) Put the mixture of antimony polyphosphate and magnesium borate whiskers obtained in step (1) into a dry modification machine, and add 6.8 g of borate coupling agent LD-100P. The rotation speed of the dry modification machine is 950 r / min, and the modification time is 10 min. Then add 2289 g of TR-245 (bromotriazine), and stir and mix at a high speed at a rotation speed of 850 r / min for 3 min to obtain a flame retardant-synergist premix;

[0058] (3) Feed the premix obtained in step (2) into a kneader, knead at 75 °C for 25 min to obtain an antimony polyphosphate-magnesium borate composite flame retardant synergist product; and retain it in the kneader for subsequent preparation of ABS flame retardant masterbatch.

[0059] The ABS flame retardant masterbatch in this example is made according to the following method:

[0060] Weigh 13380 g of ABS masterbatch and put it into the kneader that retains the antimony polyphosphate-magnesium borate composite flame retardant synergist product in the above step (3), knead with the antimony polyphosphate-magnesium borate composite flame retardant synergist at the same temperature for 20 min, and then extrude, draw into strips and cut into pellets according to the conventional process to obtain the ABS flame retardant masterbatch containing the antimony polyphosphate-magnesium borate composite flame retardant synergist.

[0061] Performance test of the ABS flame retardant masterbatch:

[0062] Mold the ABS flame retardant masterbatch into standard vertical combustion test strips of 3 mm and 2 mm, and standard specimens of 100×1×4 mm for oxygen index determination and 75×75×20 mm for smoke density test; mold 1A dumbbell-shaped standard specimens for detecting tensile strength and elongation at break according to GB / T 1040.2 standard and standard specimens for cantilever beam notched impact strength according to GB / T 1843-2008 standard. In addition, use the same system, the same amount of main flame retardant and antimony trioxide compounded flame retardant system to prepare flame retardant ABS for physical property comparison and detection. The detected data are shown in Table 1 and Table 2 below.

[0063] Example 2

[0064] The antimony polyphosphate-magnesium borate flame retardant synergist in this example is made by the following method:

[0065] (1) Weigh 368 g of antimony polyphosphate (degree of polymerization ≥ 63) and 328 g of magnesium borate whiskers, and put them into a high-speed mixer with a heating function. While stirring at a low speed, raise the temperature to 85 °C. Adjust the stirring speed to 850 r / min, and maintain for 10 min at this temperature and stirring speed. Stop heating and low-speed stirring, and cool to room temperature to obtain a mixture of antimony polyphosphate and magnesium borate whiskers;

[0066] (2) Put the mixture of antimony polyphosphate and magnesium borate whiskers obtained in step (1) into a dry modification machine, and add 6.2 g of borate coupling agent LD-100P. The rotation speed of the dry modification machine is 1000 r / min, and the modification time is 9 min. Then add 2262 g of TR-245 (bromotriazine), and mix at a high speed at a rotation speed of 1000 r / min for 3 min to obtain a flame retardant-synergist modified premix;

[0067] (3) Feed the modified premix prepared in step (2) into a kneader, and knead at 80 °C for 20 min to obtain an antimony polyphosphate-magnesium borate composite flame retardant synergist; and retain it in the kneader for subsequent preparation of ABS flame retardant masterbatch.

[0068] The ABS flame retardant masterbatch in this example is prepared according to the following method:

[0069] Weigh 14440 g of ABS flame retardant masterbatch and put it into the kneader in the above step (3). Knead with the antimony polyphosphate-magnesium borate flame retardant synergist at the same temperature for 20 min, and then extrude, draw and pellet according to the conventional process to obtain the ABS flame retardant masterbatch containing the antimony polyphosphate-magnesium borate composite flame retardant synergist.

[0070] Performance test of the ABS flame retardant masterbatch:

[0071] Mold the ABS flame retardant masterbatch into standard vertical combustion test strips of 3 mm and 2 mm, and standard specimens of 100×1×4 mm for oxygen index determination and 75×75×20 mm for smoke density test; mold 1A dumbbell-shaped standard specimens for detecting tensile strength and elongation at break according to GB / T 1040.2 standard and standard specimens for cantilever beam notched impact strength according to GB / T 1843-2008 standard. In addition, use the same system, the same amount of main flame retardant and antimony trioxide compound flame retardant system to prepare flame retardant ABS for physical property comparison detection. The detected data are shown in Table 1 and Table 2 below.

[0072] Example 3

[0073] The antimony polyphosphate-magnesium borate flame retardant synergist in this example is prepared by the following method:

[0074] (1) Weigh 353 g of antimony polyphosphate (degree of polymerization ≥ 63) and 353 g of magnesium borate whiskers prepared in step (1), put them into a high-speed mixer with heating function, heat while stirring at low speed, after heating to 95 °C, adjust the stirring speed to 900 r / min, keep at this temperature and stirring speed for 12 min, stop heating and low-speed stirring, and cool to room temperature for standby;

[0075] (2) Put the standby product in step (1) into a dry modification machine, and add 8.5 g of borate coupling agent LD-100P. The rotation speed of the dry modification machine is 900 r / min, and the modification time is 12 min. Then add 2278 g of TR-245 (bromotriazine) and mix at a high speed of 900 r / min for 3 min to obtain a flame retardant-synergist modified premix.

[0076] (3) Feed the modified premix prepared in step (2) into a kneader and knead at 85 °C for 18 min to obtain an antimony polyphosphate-magnesium borate composite flame retardant synergist; and keep it in the kneader for subsequent preparation of ABS flame retardant masterbatch.

[0077] The ABS flame retardant masterbatch in this example is prepared according to the following method:

[0078] Weigh 13635 g of ABS masterbatch and put it into the kneader used in step (3) above, knead with the antimony polyphosphate-magnesium borate flame retardant synergist at the same temperature for 20 min, and then extrude, draw and pellet according to the conventional process to obtain the ABS flame retardant masterbatch containing the antimony polyphosphate-magnesium borate composite flame retardant synergist.

[0079] Performance test of the ABS flame retardant masterbatch:

[0080] Mold the ABS flame retardant masterbatch into standard vertical combustion test strips of 3 mm and 2 mm and standard specimens of 100×1×4 mm for oxygen index determination and 75×75×20 mm for smoke density test; mold 1A dumbbell-shaped standard specimens for detecting tensile strength and elongation at break according to GB / T 1040.2 standard and standard specimens for notched Izod impact strength according to GB / T 1843-2008 standard. Another flame retardant ABS is prepared using the same system, the same amount of main flame retardant and antimony trioxide compound flame retardant system for comparative detection of physical properties, and the detected data are shown in Table 1 and Table 2 below.

[0081] Example 4

[0082] The antimony polyphosphate-magnesium borate flame retardant synergist in this example is prepared by the following method:

[0083] (1) Weigh 287 g of antimony polyphosphate (degree of polymerization ≥ 63) and 315.5 g of magnesium borate whiskers prepared in step (1), put them into a high-speed mixer with heating function, heat up while stirring at low speed, after heating up to 90 °C, adjust the stirring speed to 850 r / min, keep at this temperature and stirring speed for 15 min, stop heating and low-speed stirring, and cool to room temperature for standby.

[0084] (2) Put the standby product in step (1) into a dry modification machine, add 5.5 g of borate coupling agent LD-100P, the rotation speed of the dry modification machine is 850 r / min, the modification time is 15 min, then add 2272 g of TR-245 (bromotriazine), and mix at a high speed of 850 r / min for 3 min to obtain a flame retardant-synergist modified premix.

[0085] (3) Feed the modified premix prepared in step (2) into a kneader and knead at 80 °C for 18 min to obtain an antimony polyphosphate-magnesium borate composite flame retardant synergist; and keep it in the kneader for subsequent preparation of ABS flame retardant masterbatch.

[0086] The ABS flame retardant masterbatch in this example is prepared according to the following method:

[0087] Weigh 13119 g of ABS masterbatch and put it into the kneader used in step (3) above, knead with the antimony polyphosphate-magnesium borate flame retardant synergist at the same temperature for 20 min, then extrude, draw and pellet according to the conventional process to obtain the ABS flame retardant masterbatch containing the antimony polyphosphate-magnesium borate composite flame retardant synergist.

[0088] Performance test of the ABS flame retardant masterbatch:

[0089] Mold the ABS flame retardant masterbatch into standard vertical combustion test strips of 3 mm and 2 mm, and standard specimens of 100×1×4 mm for oxygen index determination and 75×75×20 mm for smoke density test; mold 1A dumbbell-shaped standard specimens for detecting tensile strength and elongation at break according to GB / T 1040.2 standard and standard specimens for cantilever beam notched impact strength according to GB / T 1843-2008 standard. In addition, a flame retardant ABS is prepared using the same system, the same amount of main flame retardant and antimony trioxide compound flame retardant system for comparative detection of physical properties, and the detected data are shown in Table 1 and Table 2 below.

[0090] Example 5

[0091] The antimony polyphosphate-magnesium borate flame retardant synergist in this example is prepared by the following method:

[0092] (1) Weigh 378 g of antimony polyphosphate (degree of polymerization ≥ 63) and 321 g of magnesium borate whiskers, put them into a high-speed mixer with heating function, heat up while stirring at low speed, after heating up to 85 °C, adjust the stirring speed to 800 r / min, keep at this temperature and stirring speed for 9 min, stop heating and low-speed stirring, and cool to room temperature for standby;

[0093] (2) Put the standby product from step (1) into a dry modification machine, and add 8.0 g of borate coupling agent LD-100P. The rotation speed of the dry modification machine is 900 r / min, and the modification time is 18 min. Then add 2279 g of TR-245 (bromotriazine) and mix at a high speed of 900 r / min for 3 min to obtain a flame retardant-synergist modified premix;

[0094] (3) Feed the modified premix obtained in step (2) into a kneader and knead at 75 °C for 20 min to obtain an antimony polyphosphate-magnesium borate composite flame retardant synergist; and retain it in the kneader for subsequent preparation of ABS flame retardant masterbatch.

[0095] The ABS flame retardant masterbatch in this example is made according to the following method:

[0096] Weigh 12731 g of ABS masterbatch and put it into the kneader used in the above step (3). At the same temperature, knead with the antimony polyphosphate-magnesium borate flame retardant synergist for 20 min, and then extrude, draw and pellet according to the conventional process to obtain the ABS flame retardant masterbatch containing the antimony polyphosphate-magnesium borate flame retardant synergist.

[0097] Performance test of the ABS flame retardant masterbatch:

[0098] Mold the ABS flame retardant masterbatch into standard vertical combustion test strips of 3 mm and 2 mm, and standard specimens of 100×1×4 mm for oxygen index determination and 75×75×20 mm for smoke density test; mold 1A dumbbell-shaped standard specimens for detecting tensile strength and elongation at break according to GB / T 1040.2 standard and standard specimens for cantilever beam notched impact strength according to GB / T 1843-2008 standard. In addition, an ABS flame retardant masterbatch prepared by compounding the same amount of bromine flame retardant and antimony trioxide flame retardant system is used for comparison and detection of physical properties. The detected data are shown in Table 1 and Table 2 below.

[0099] Table 1 Flame retardant performance and smoke density test results of the ABS flame retardant masterbatch of the embodiment of the present invention and the antimony trioxide flame retardant system

[0100]

[0101] Note: 1. The "synergist" in the table refers to the ABS flame retardant masterbatch of the antimony polyphosphate-magnesium borate flame retardant synergist of the present invention;

[0102] 2. "Sb2O3" refers to the bromine flame retardant and antimony trioxide compound flame retardant system;

[0103] 3. "1s and 2s" represent the extinguishing time after leaving the fire during two burns of the same sample.

[0104] Table 2 Physical Property Detection Results of ABS Flame Retardant Masterbatch in Each Example

[0105]

[0106] The data in the above Table 1 and Table 2 show that:

[0107] 1. The polyantimony phosphate-magnesium borate composite flame retardant system of the present invention (which can be abbreviated as "bromine-high flame retardant system") has been well improved in terms of flame retardancy, reduction of smoke density, dripping condition, and the influence on the physical properties of the matrix material ABS compared with the bromine-antimony trioxide flame retardant system;

[0108] 2. The bromine-high flame retardant system of the present invention not only significantly enhances the flame retardant effect, but also reduces the dosage of expensive Sb2O3 by more than 50%, greatly reducing the production cost and use cost of the flame retardant material. In the field of use, it can completely replace the bromine-antimony flame retardant system.

[0109] 3. Due to the significant reduction in the antimony content, the smoke density during the combustion of the flame retardant material has been greatly reduced, with the maximum reduction in smoke density reaching 37%. At the same time, the harm caused by "antimony toxicity" has been greatly reduced, achieving the low toxicity, safety, and green environmental protection of the flame retardant.

[0110] The described embodiments are only used to illustrate the preferred embodiments of the present invention and are not limited to the above embodiments. Any changes, substitutions, simplifications, etc. made without departing from the core technical principle of the present invention are regarded as equivalent substitutions and all fall within the protection scope of the present invention.

Claims

1. A high-polymer antimony phosphate-magnesium borate composite flame retardant synergist, characterized in that, It is prepared by the following method: (1) Put the raw materials antimony polyphosphate and magnesium borate into a high-speed mixer, stir and mix evenly, then heat, keep warm, and then cool to room temperature to obtain a mixture of antimony polyphosphate and magnesium borate; (2) Add the mixture of antimony polyphosphate and magnesium borate obtained in step (1) into a dry modification machine, add a modifier, and stir and mix evenly at high speed to obtain a semi-finished product of a modified antimony polyphosphate-magnesium borate-modifier composite flame retardant synergist; then, add a halogen-containing flame retardant to the semi-finished product of the composite flame retardant synergist and continue to stir evenly at high speed to obtain a modified premix of the flame retardant-synergist; (3) Put the flame retardant-synergist premix prepared in step (2) into a kneader, knead, heat, and carry out the activation modification of antimony polyphosphate-magnesium borate to obtain the antimony polyphosphate-magnesium borate composite flame retardant synergist.

2. The high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to claim 1, characterized in that In step (1), the mass ratio of the antimony polyphosphate to the magnesium borate is 1:0.7 - 1.2; preferably 1:0.85 - 1.

1.

3. The high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to claim 2, characterized in that The antimony polyphosphate is a white powdery antimony polyphosphate product with a whiteness ≥ 92%, a degree of polymerization of 50 - 65, a particle size ≤ 2 μm, a moisture absorption rate in air of ≤ 0.6 in 72 h, and a purity ≥ 98%, which is prepared by solid-phase reaction in a microwave field.

4. A high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to any one of claims 1-3, characterized in that In step (1), the magnesium borate is magnesium borate whiskers.

5. The high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to claim 4, characterized in that, In step (1), the magnesium borate whiskers are white powdery magnesium borate whisker products with a diameter of 0.5 - 1 μm, an aspect ratio of 20 - 30, a purity ≥ 98.0%, a water content ≤ 0.3%, and a whiteness ≥ 98%.

6. A high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to any one of claims 1 to 5, characterized in that, In step (1), during mixing, the rotation speed of the high-speed mixer is 700 - 950 r / min, preferably 750 - 900 r / min; the time for high-speed stirring and mixing is 5 - 10 min; the heating temperature is 80°C - 100°C, preferably 85°C - 95°C; the heat preservation time is 5 - 15 min, preferably 8 - 12 min.

7. A high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to any one of claims 1-6, characterized in that In step (2), the modifier is one or more composites of titanate, aluminate, and borate coupling agents; the addition amount of the modifier is 0.6 - 1.5% of the total mass of antimony polyphosphate-magnesium borate; preferably 0.8 - 1.2%.

8. A high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to claim 1 or 2, characterized in that, In step (2), the halogen-containing flame retardant is bromotriazine or decabromodiphenylethane; the addition amount of the halogen-containing flame retardant is 3.0 - 4.0 times the total mass of antimony polyphosphate-magnesium borate, preferably 3.2 - 3.8 times.

9. A high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to any one of claims 1-8, characterized in that, In step (3), the heating temperature is 60°C - 90°C, preferably 70°C - 85°C; the kneading time is 10 - 30 min, preferably 15 - 25 min.

10. An ABS flame retardant masterbatch containing the high-polymer antimony phosphate-magnesium borate composite flame retardant synergist according to any one of claims 1-9, characterized in that, It is prepared by the following method: In the antimony polyphosphate-magnesium borate flame retardant synergist, add a carrier ABS masterbatch, and then knead, extrude, and pelletize to obtain the ABS flame retardant masterbatch; the mass ratio of the added carrier ABS masterbatch to the antimony polyphosphate-magnesium borate composite flame retardant synergist is 80 - 85:20 - 15, preferably 81 - 84:19 - 16.

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