CN114806072A - Low-VOC flame-retardant filler, flame-retardant ABS composite material and preparation method thereof - Google Patents

Low-VOC flame-retardant filler, flame-retardant ABS composite material and preparation method thereof Download PDF

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Publication number
CN114806072A
CN114806072A CN202210684470.9A CN202210684470A CN114806072A CN 114806072 A CN114806072 A CN 114806072A CN 202210684470 A CN202210684470 A CN 202210684470A CN 114806072 A CN114806072 A CN 114806072A
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temperature
flame
zone
retardant filler
solution
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王俊
林兴旺
赵立伟
宋鑫
朱提允
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Shandong Haike Innovation Research Institute Co Ltd
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Shandong Haike Innovation Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

The invention provides a low-VOC flame-retardant filler, a flame-retardant ABS composite material and a preparation method thereof, belonging to the technical field of high polymer materials. The low-VOC flame-retardant filler is prepared by the following steps: (1) mixing ammonium ceric sulfate, ammonium bicarbonate, isopropanol and water, and reacting to obtain a solution A; (2) calcining the solution A to obtain mesoporous cerium oxide; (3) mixing iron dichloride, ferric trichloride, water, mesoporous cerium oxide and boehmite, and reacting to obtain a solution B; (4) filtering and drying the solution B to obtain a solid C; (5) and mixing the solid C and melamine polyphosphate to obtain the low-VOC flame-retardant filler. The low-VOC flame-retardant filler provided by the invention can effectively improve the flame-retardant effect and reduce the VOC content when being added into an ABS material.

Description

Low-VOC flame-retardant filler, flame-retardant ABS composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-VOC flame-retardant filler, a flame-retardant ABS composite material and a preparation method thereof.
Background
ABS plastic is terpolymer of acrylonitrile (A) -butadiene (B) -styrene (S), and is a widely used polymer plastic. The ABS plastic integrates the performances of three components, and the characteristics of the three components enable the ABS plastic to become thermoplastic plastic with good comprehensive performances of 'hardness, toughness, high rigidity, good strength, glossiness, heat resistance and excellent dimensional stability'. The ABS plastic has the advantages of excellent dimensional stability and the like, so that the ABS plastic is widely applied to the fields of household appliances, electronic appliances, automobiles and the like. However, in some specific application fields, the requirements on the flame retardant performance and VOC content of ABS are strict, and the common ABS material cannot meet the requirements, so that the application of the ABS composite material in some specific fields is limited.
In the prior art, flame retardant MPP and low VOC flame retardant filler zinc borate are adopted to improve the flame retardant property of ABS, but the flame retardant property is poor. Patent CN101048450A discloses the use of boehmite as a flame retardant material, but requires seeding of the boehmite and does not reduce the VOC content.
Disclosure of Invention
The invention provides a low-VOC flame-retardant filler, a flame-retardant ABS composite material and a preparation method thereof. The low VOC flame-retardant filler provided by the invention is matched with a flame retardant MPP, so that the flame-retardant effect can be improved, and the low VOC flame-retardant filler is added into an ABS composite material, so that the ABS composite material has high-efficiency flame-retardant performance.
In order to achieve the purpose, the invention provides a low VOC flame-retardant filler which is prepared by the following steps:
(1) mixing ammonium ceric sulfate, ammonium bicarbonate, isopropanol and water, and reacting to obtain a solution A;
(2) calcining the solution A to obtain mesoporous cerium oxide;
(3) mixing iron dichloride, ferric trichloride, water, mesoporous cerium oxide and boehmite, and reacting to obtain a solution B;
(4) filtering and drying the solution B to obtain a solid C;
(5) and mixing the solid C and melamine polyphosphate to obtain the low-VOC flame-retardant filler.
Preferably, in the step (1), the reaction temperature is 40-60 ℃ and the reaction time is 6-8 h.
Preferably, the temperature of the calcination in the step (2) is 720-780 ℃ and the time is 12-16 h.
Preferably, the reaction temperature of the step (3) is 30-40 ℃ and the reaction time is 4-6 h.
Preferably, the mass ratio of the ammonium cerium sulfate, the ammonium bicarbonate, the isopropanol and the water in the step (1) is (40-50): (36-40): (60-80): (70-80).
Preferably, in the step (3), the mass ratio of the ferric dichloride, the ferric trichloride, the water, the mesoporous cerium oxide and the boehmite is (30-50): (6-10): (72-80): (30-40): (70-80); the mass ratio of the solid C to the melamine polyphosphate in the step (5) is (30-50): (12-16).
The invention also provides a flame-retardant ABS composite material, which comprises the following components in parts by weight:
80-100 parts of ABS and 14-18 parts of low VOC flame-retardant filler; the low-VOC flame-retardant filler is the low-VOC flame-retardant filler in any one of the above schemes.
Preferably, 0.1-0.5 weight part of antioxidant is also included.
Preferably, the antioxidant is one or more of tris (2, 4-di-tert-butyl) phenyl phosphite, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
The invention also provides a preparation method of the flame-retardant ABS composite material, which comprises the following steps:
mixing the materials, and extruding and granulating the obtained mixed material to obtain the flame-retardant ABS composite material;
the extrusion granulation is carried out in a double-screw extruder, and the double-screw extruder adopts six temperature zones which are sequentially arranged when carrying out the extrusion granulation, and the six temperature zones sequentially respectively comprise: the temperature of the first zone is 180-210 ℃, the temperature of the second zone is 200-230 ℃, the temperature of the third zone is 200-230 ℃, the temperature of the fourth zone is 200-230 ℃, the temperature of the fifth zone is 200-230 ℃, and the temperature of the sixth zone is 200-230 ℃; the head temperature of the double-screw extruder is 200-230 ℃, and the screw rotating speed is 200-280 r/min.
Compared with the prior art, the invention has the advantages and positive effects that:
the mesoporous cerium oxide in the low-VOC flame-retardant filler provided by the invention can well improve the VOC content of ABS, and boehmite can generate water and Al in the thermal decomposition process 2 O 3 Water dilutes combustible gases, Al 2 O 3 Ferroferric oxide can be used as a synergistic flame retardant of melamine polyphosphate (MPP) serving as a main flame retardant to cover the surface of a polyolefin matrix to block and delay the combustion rate, so that the flame-retardant and smoke-suppression effects are achieved, and the flame-retardant property of ABS is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a low VOC flame-retardant filler, which is prepared by the following steps:
(1) mixing ammonium ceric sulfate, ammonium bicarbonate, isopropanol and water, and reacting to obtain a solution A;
(2) calcining the solution A to obtain mesoporous cerium oxide;
(3) mixing iron dichloride, iron trichloride, water, mesoporous cerium oxide and boehmite, and reacting to obtain a solution B;
(4) filtering and drying the solution B to obtain a solid C;
(5) and mixing the solid C and melamine polyphosphate (MPP) to obtain the low-VOC flame-retardant filler.
The method comprises the steps of mixing cerium ammonium sulfate, ammonium bicarbonate, isopropanol and water, and reacting to obtain a solution A. In the present invention, the mass ratio of the cerium ammonium sulfate, the ammonium bicarbonate, the isopropyl alcohol and the water is preferably (40-50): (36-40): (60-80): (70-80). It is understood that the skilled person can select suitable reaction ratios within the above preferred ratio ranges, such as 40:36:60:70, 50:40:80:80, 50:38:70:75, etc. In the present invention, the reaction temperature is preferably 40 to 60 ℃ and the reaction time is preferably 6 to 8 hours.
After the solution A is obtained, the solution A is calcined to obtain the mesoporous cerium oxide. In the present invention, the calcination temperature is preferably 720-780 ℃, and the calcination time is preferably 12-16 h. In the present invention, it is preferable to filter, wash and dry the solution a before calcining. In the present invention, washing with water is preferred. In the invention, the drying temperature is preferably 60-80 ℃, and the time is preferably 2-4 h.
After the mesoporous cerium oxide is obtained, the invention mixes iron dichloride, ferric trichloride, water, the mesoporous cerium oxide and boehmite to react to obtain a solution B. In the present invention, the reaction temperature is preferably 30 to 40 ℃ and the reaction time is preferably 4 to 6 hours. In the invention, the mass ratio of the iron dichloride, the ferric trichloride, the water, the mesoporous cerium oxide and the boehmite is preferably (30-50): (6-10): (72-80): (30-40): (70-80). It is understood that the skilled person can select suitable reaction ratios within the above preferred ratio ranges, such as 30:10:72:40:80, 40:10:80:35:80 or 50:8:80:40:70, etc.
After the solution B is obtained, the invention dries the solution B to obtain a solid C. In the invention, the drying temperature is preferably 60-80 ℃, and the drying time is preferably 2-4 h. In the present invention, the solution B is preferably filtered and washed before being calcined. In the present invention, washing with water is preferred.
After the solid C is obtained, the solid C and melamine polyphosphate (MPP) are mixed to obtain the low-VOC flame-retardant filler. In the invention, the mass ratio of the solid C to the melamine polyphosphate (MPP) is (30-50): (12-16). It is understood that one skilled in the art can select a suitable reaction ratio within the above-mentioned preferred ratio range, such as 30:12, 50:12 or 50: 16.
The reaction mechanism for preparing the low VOC flame retardant filler is as follows:
(NH 4 ) 4 Ce(SO 4 ) 4 +4NH 4 HCO 3 →(NH 4 ) 4 CeO(HCO 3 ) 6 +4(NH 4 ) 2 SO 4 +2CO 2 +H 2 O
(NH 4 ) 4 CeO(HCO 3 ) 6 →CeO 2 +4NH 3 +5H 2 O+6CO 2
NH 3 ·H 2 O→NH 4+ +OH -
2Fe 3+ +Fe 2+ +8OH - →Fe 3 O 4 +4H 2 O。
the invention also provides a flame-retardant ABS composite material, which comprises the following components in parts by weight: 80-100 parts of ABS and 14-18 parts of low VOC flame-retardant filler; the low-VOC flame-retardant filler is the low-VOC flame-retardant filler in any one of the above schemes.
The flame-retardant ABS composite material provided by the invention comprises ABS. Comprises 80 to 100 portions by weight. It is understood that the ABS content may be 80, 81, 85, 90, 95, 100 parts or any value within the above range. The source of the ABS is not particularly limited in the invention, and the ABS can be obtained by adopting conventional commercial products in the field.
The flame retardant ABS composite material provided by the invention comprises a low VOC flame retardant filler. Comprises 14 to 18 portions by weight. It is understood that the low VOC flame retardant filler content may be 14, 15, 16, 17, 18 parts or any point within the above ranges.
The flame-retardant ABS composite material also comprises 0.1-0.5 weight part of antioxidant. It is understood that the antioxidant may be present in an amount of 0.1, 0.2, 0.3, 0.4, 0.5 parts or any value within the above range. In the present invention, the antioxidant is preferably one or more of tris (2, 4-di-tert-butyl) phenyl phosphite, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
In the invention, the mechanism of the flame retardant ABS composite material for performing flame retardance is as follows: low VOC flame-retardant fillerThe mesoporous cerium oxide in the material can well improve the VOC content of ABS, and boehmite can generate water and Al in the thermal decomposition process 2 O 3 Water dilutes combustible gases, Al 2 O 3 The ferroferric oxide can be used as a synergistic flame retardant of the main flame retardant MPP to cover the surface of the polyolefin matrix to block and delay the combustion rate, thereby achieving the effects of flame retardance and smoke suppression and improving the flame retardance of ABS.
The invention also provides a preparation method of the flame-retardant ABS composite material, which comprises the following steps:
mixing the materials, and extruding and granulating the obtained mixed material to obtain the flame-retardant ABS composite material;
the extrusion granulation is carried out in a double-screw extruder, and the double-screw extruder adopts six temperature zones which are sequentially arranged when carrying out the extrusion granulation, and the six temperature zones sequentially respectively comprise: the temperature of the first zone is 180-210 ℃, the temperature of the second zone is 200-230 ℃, the temperature of the third zone is 200-230 ℃, the temperature of the fourth zone is 200-230 ℃, the temperature of the fifth zone is 200-230 ℃, and the temperature of the sixth zone is 200-230 ℃; the head temperature of the double-screw extruder is 200-230 ℃, and the screw rotating speed is 200-280 r/min.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
The raw materials used in the following examples are as follows:
ABS (model PA-757K), Zhenjiangqi beautifier, Inc.; cerium ammonium sulfate, Shandonghao Yao New materials Co., Ltd; isopropanol, denna guangyu chemical ltd; iron dichloride, chemical ltd, denrunford; ferric chloride, juan color chemical ltd; boehmite, Shandong Yulong New Material Co., Ltd; deionized water, beijing baiolai bock technologies ltd; antioxidants (type Irganox168, Irganox1010, Irganox1330), Pasteur Germany, MPP, Winhamen New rubber and Plastic Material Ltd.
Example 1
(1) Weighing 80 parts of ABS, 14 parts of low VOC flame-retardant filler M1 and 0.1 part of antioxidant Irganox1010, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P1.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 180 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 200 ℃, the temperature of a machine head is 200 ℃, and the rotating speed of a screw is 200 r/min.
The low VOC flame-retardant filler M1 is prepared by the following steps:
(1) weighing 400g of ammonium ceric sulfate, 360g of ammonium bicarbonate, 600g of isopropanol and 700g of deionized water, placing the materials in a reaction vessel, and reacting for 6 hours at 40 ℃ to obtain a solution A.
(2) And filtering, washing and drying the solution A (the drying temperature is 60 ℃ and the drying time is 2 hours), and calcining the solution A in a muffle furnace at the temperature of 720 ℃ for 12 hours to obtain the mesoporous cerium oxide.
(3) Weighing 300g of iron dichloride, 60g of ferric trichloride, 720g of deionized water, 300g of mesoporous cerium oxide and 700g of boehmite, placing the materials into a reaction vessel, and stirring and reacting for 4 hours at 30 ℃ to obtain a solution B.
(4) And filtering, washing and drying the solution B (the drying temperature is 60 ℃ and the drying time is 2 hours) to obtain a solid C.
(5) 300g of solid C and 120g of melamine polyphosphate (MPP) were mixed to give a low VOC flame retardant filler M1.
Example 2
(1) Weighing 100 parts of ABS, 18 parts of low VOC flame retardant filler M2, 0.1 part of Irganox1010, 0.2 part of Irganox168 and 0.2 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (2) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 210 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 230 ℃, the temperature of a machine head is 230 ℃, and the rotating speed of a screw is 280 r/min.
The low VOC flame-retardant filler M2 is prepared by the following steps:
(1) weighing 500g of ammonium ceric sulfate, 400g of ammonium bicarbonate, 800g of isopropanol and 800g of deionized water, placing the materials in a reaction vessel, and reacting for 8 hours at 60 ℃ to obtain a solution A.
(2) And filtering, washing and drying the solution A (the drying temperature is 80 ℃ and the drying time is 4h), and calcining the solution A in a muffle furnace at 780 ℃ for 16h to obtain the mesoporous cerium oxide.
(3) Weighing 500g of iron dichloride, 100g of ferric trichloride, 800g of deionized water, 400g of mesoporous cerium oxide and 800g of boehmite, placing the materials into a reaction vessel, and stirring and reacting for 6 hours at 40 ℃ to obtain a solution B.
(4) And filtering, washing and drying the solution B (the drying temperature is 80 ℃ and the drying time is 4 hours) to obtain a solid C.
(5) 500g of solid C and 160g of melamine polyphosphate (MPP) were mixed to give a low VOC flame retardant filler M2.
Example 3
(1) Weighing 90 parts of ABS, 16 parts of low VOC flame-retardant filler M3, 0.1 part of Irganox168 and 0.2 part of Irganox1010, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P3.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 215 ℃, the temperature of the third zone is 215 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of a machine head is 220 ℃, and the rotating speed of a screw is 240 r/min.
The low VOC flame-retardant filler M3 is prepared by the following steps:
(1) weighing 450g of ammonium ceric sulfate, 380g of ammonium bicarbonate, 700g of isopropanol and 750g of deionized water, placing the materials in a reaction vessel, and reacting for 7 hours at 50 ℃ to obtain a solution A.
(2) And filtering, washing and drying the solution A (the drying temperature is 70 ℃ and the drying time is 3h), and calcining the solution A in a muffle furnace at 750 ℃ for 14h to obtain the mesoporous cerium oxide.
(3) 400g of iron dichloride, 80g of ferric trichloride, 760g of deionized water, 350g of mesoporous cerium oxide and 750g of boehmite are weighed and placed in a reaction vessel to be stirred and reacted for 5 hours at the temperature of 35 ℃ to obtain a solution B.
(4) And filtering, washing and drying the solution B (the drying temperature is 70 ℃, and the drying time is 3 hours) to obtain a solid C.
(5) 400g of solid C and 140g of melamine polyphosphate (MPP) were mixed to give a low VOC flame retardant filler M3.
Example 4
(1) Weighing 85 parts of ABS, 15 parts of low VOC flame-retardant filler M4 and 0.1 part of Irganox1010, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P4.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 205 ℃, the temperature of the second zone is 218 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃, the temperature of the sixth zone is 225 ℃, the temperature of a machine head is 225 ℃ and the rotating speed of a screw is 230 r/min.
The low VOC flame-retardant filler M4 is prepared by the following steps:
(1) 415g of ammonium ceric sulfate, 395g of ammonium bicarbonate, 625g of isopropanol and 735g of deionized water are weighed and placed in a reaction vessel to react for 7 hours at 45 ℃ to obtain a solution A.
(2) And filtering, washing and drying the solution A (the drying temperature is 65 ℃ and the drying time is 2.5h), and calcining the solution A in a muffle furnace at 765 ℃ for 15h to obtain the mesoporous cerium oxide.
(3) 325g of iron dichloride, 95g of ferric trichloride, 765g of deionized water, 355g of mesoporous cerium oxide and 725g of boehmite are weighed and placed in a reaction vessel to be stirred and reacted for 6 hours at 35 ℃ to obtain a solution B.
(4) And filtering, washing and drying the solution B (the drying temperature is 65 ℃ and the drying time is 2.5 hours) to obtain a solid C.
(5) 480g of solid C and 150g of melamine polyphosphate (MPP) were mixed to obtain a low VOC flame retardant filler M4.
Example 5
(1) Weighing 85 parts of ABS, 17 parts of low VOC flame-retardant filler M5 and 0.1 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P5.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃ and the temperature of the sixth zone is 225 ℃; the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 225 r/min.
The low VOC flame-retardant filler M5 is prepared by the following steps:
(1) 495g of ammonium ceric sulfate, 385g of ammonium bicarbonate, 675g of isopropanol and 735g of deionized water are weighed and placed in a reaction vessel to react for 7 hours at the temperature of 45 ℃ to obtain a solution A.
(2) And filtering, washing and drying the solution A (the drying temperature is 75 ℃ and the drying time is 3.5h), and calcining the solution A in a muffle furnace at 765 ℃ for 15h to obtain the mesoporous cerium oxide.
(3) 385g of iron dichloride, 75g of ferric trichloride, 785g of deionized water, 335g of mesoporous cerium oxide and 745g of boehmite are weighed and placed in a reaction vessel, and stirred and reacted for 6 hours at the temperature of 35 ℃ to obtain a solution B.
(4) And filtering, washing and drying the solution B (the drying temperature is 75 ℃, and the drying time is 3.5 hours) to obtain a solid C.
(5) 390g of solid C and 130g of melamine polyphosphate (MPP) were mixed to obtain a low VOC flame retardant filler M5.
Comparative example 1
(1) Weighing 85 parts of ABS and 0.1 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material D1.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃ and the temperature of the sixth zone is 225 ℃; the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 225 r/min.
Comparative example 2
(1) Weighing 85 parts of ABS, 17 parts of low VOC flame retardant filler N1 and 0.1 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material D2.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃ and the temperature of the sixth zone is 225 ℃; the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 225 r/min.
The low VOC flame-retardant filler N1 is prepared by the following steps:
(1) 785g of deionized water and 745g of boehmite are weighed and placed in a reaction vessel, and stirred and reacted for 6 hours at 35 ℃ to obtain a solution B1.
(2) The solution B1 was filtered, washed and dried (drying temperature 75 ℃ C., time 3.5h) to give solid C1.
(3) 390g of solid C1, 130g of melamine polyphosphate (MPP) were mixed to give a low VOC flame retardant filler N1.
Comparative example 3
(1) Weighing 85 parts of ABS, 17 parts of low VOC flame retardant filler N2 and 0.1 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material D3.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃ and the temperature of the sixth zone is 225 ℃; the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 225 r/min.
The low VOC flame-retardant filler N2 is prepared by the following steps:
(1) 385g of iron dichloride, 75g of ferric trichloride, 785g of deionized water and 745g of boehmite are weighed and placed in a reaction vessel, and stirred and reacted for 6 hours at the temperature of 35 ℃ to obtain a solution B2.
(2) The solution B2 was filtered, washed and dried (drying temperature 75 ℃ C., time 3.5h) to give solid C2.
(3) 390g of solid C2, 130g of melamine polyphosphate (MPP) were mixed to give a low VOC flame retardant filler N2.
Comparative example 4
(1) Weighing 85 parts of ABS, 17 parts of low VOC flame retardant filler N3 and 0.1 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material D4.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃ and the temperature of the sixth zone is 225 ℃; the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 225 r/min.
The low VOC flame-retardant filler N3 is prepared by the following steps:
(1) 495g of ammonium ceric sulfate, 385g of ammonium bicarbonate, 675g of isopropanol and 735g of deionized water are weighed and placed in a reaction vessel to react for 7 hours at the temperature of 45 ℃ to obtain a solution A.
(2) And filtering, washing and drying the solution A (the drying temperature is 75 ℃ and the drying time is 3.5h), and calcining the solution A in a muffle furnace at 765 ℃ for 15h to obtain the mesoporous cerium oxide.
(3) 785g of deionized water, 335g of mesoporous cerium oxide and 745g of boehmite are weighed and placed in a reaction vessel, and stirred and reacted for 6 hours at the temperature of 35 ℃ to obtain a solution B3.
(4) The solution B3 was filtered, washed and dried (drying temperature 75 ℃ C., time 3.5h) to give solid C3.
(5) 390g of solid C3, 130g of melamine polyphosphate (MPP) were mixed to give a low VOC flame retardant filler N3.
Comparative example 5
(1) Weighing 85 parts of ABS, 17 parts of low VOC flame retardant filler N4 and 0.1 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material D5.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃ and the temperature of the sixth zone is 225 ℃; the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 225 r/min.
The low VOC flame-retardant filler N4 is prepared by the following steps:
(1) 495g of ammonium ceric sulfate, 385g of ammonium bicarbonate, 675g of isopropanol and 735g of deionized water are weighed and placed in a reaction vessel to react for 7 hours at the temperature of 45 ℃ to obtain a solution A.
(2) And filtering, washing and drying the solution A (the drying temperature is 75 ℃ and the drying time is 3.5h), and calcining the solution A in a muffle furnace at 765 ℃ for 15h to obtain the mesoporous cerium oxide.
(3) 385g of iron dichloride, 75g of ferric trichloride, 785g of deionized water and 335g of mesoporous cerium oxide are weighed and placed in a reaction vessel, and stirred and reacted for 6 hours at the temperature of 35 ℃ to obtain a solution B4.
(4) The solution B4 was filtered, washed and dried (drying temperature 75 ℃ C., time 3.5h) to give solid C4.
(5) 390g of solid C4, 130g of melamine polyphosphate (MPP) were mixed to give a low VOC flame retardant filler N4.
Performance testing
The flame retardant performance of the ABS composite materials prepared in the examples and comparative examples was tested, and the specific test standard was UL94, and the specific results are shown in table 1.
TABLE 1 ABS composite Properties
Figure BDA0003699558240000121
As can be seen from Table 1, the flame retardant filler prepared by the invention can effectively improve the flame retardant property and reduce the VOC content when being added into an ABS material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The low-VOC flame-retardant filler is characterized by being prepared by the following steps:
(1) mixing ammonium ceric sulfate, ammonium bicarbonate, isopropanol and water, and reacting to obtain a solution A;
(2) calcining the solution A to obtain mesoporous cerium oxide;
(3) mixing iron dichloride, ferric trichloride, water, mesoporous cerium oxide, melamine polyphosphate (MPP) and boehmite, and reacting to obtain a solution B;
(4) filtering and drying the solution B to obtain a solid C;
(5) and mixing the solid C and melamine polyphosphate to obtain the low-VOC flame-retardant filler.
2. The low VOC flame retardant filler according to claim 1, characterized in that in step (1), the reaction temperature is 40-60 ℃ and the reaction time is 6-8 h.
3. The low VOC flame retardant filler in claim 1, wherein the calcination in step (2) is carried out at 720-780 ℃ for 12-16 h.
4. The low VOC flame retardant filler according to claim 1, characterized in that the temperature of the reaction of step (3) is 30-40 ℃ and the time is 4-6 h.
5. The low VOC flame retardant filler according to claim 1, characterized in that the mass ratio of cerium ammonium sulfate, ammonium bicarbonate, isopropyl alcohol and water in step (1) is (40-50): (36-40): (60-80): (70-80).
6. The low VOC flame retardant filler according to claim 1, wherein the mass ratio of iron dichloride, iron trichloride, water, mesoporous ceria and boehmite in step (3) is (30-50): (6-10): (72-80): (30-40): (70-80);
the mass ratio of the solid C to the melamine polyphosphate in the step (5) is (30-50): (12-16).
7. The flame-retardant ABS composite material is characterized by comprising the following components in parts by weight:
80-100 parts of ABS and 14-18 parts of low VOC flame-retardant filler; the low VOC flame-retardant filler is the low VOC flame-retardant filler described in any one of claims 1-6.
8. The flame retardant ABS composite material of claim 7 further comprising 0.1 to 0.5 parts by weight of an antioxidant.
9. The flame retardant ABS composite material of claim 8 wherein the antioxidant is one or more of tris (2, 4-di-tert-butyl) phenyl phosphite, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
10. The preparation method of the flame-retardant ABS composite material as claimed in any of claims 7 to 9, characterized by comprising the following steps:
mixing the materials, and extruding and granulating the obtained mixed material to obtain the flame-retardant ABS composite material;
the extrusion granulation is carried out in a double-screw extruder, and the double-screw extruder adopts six temperature zones which are sequentially arranged when carrying out the extrusion granulation, and the six temperature zones sequentially respectively comprise: the temperature of the first zone is 180-210 ℃, the temperature of the second zone is 200-230 ℃, the temperature of the third zone is 200-230 ℃, the temperature of the fourth zone is 200-230 ℃, the temperature of the fifth zone is 200-230 ℃, and the temperature of the sixth zone is 200-230 ℃; the head temperature of the double-screw extruder is 200-230 ℃, and the screw rotating speed is 200-280 r/min.
CN202210684470.9A 2022-06-17 2022-06-17 Low-VOC flame-retardant filler, flame-retardant ABS composite material and preparation method thereof Pending CN114806072A (en)

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