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    • 专利摘要:
    The disclosure provides a flame-retardant epoxy resin based on iron-containing nickel silicate 5 and a method for preparing the same, belonging to the technical field of halogen-free flame- retardant epoxy resins. The flame-retardant epoxy resin comprises 93~99.9% by mass of epoxy resin and 0.1~7% of iron-containing nickel silicate; the epoxy resin consists of an epoxy resin monomer and a curing agent, the epoxy resin monomer is 70~80% by mass, and the epoxy curing agent is 20~30% by mass. According to the disclosure, the addition amount of the flame retardant 10 is reduced to the greatest extent while ensuring high-efficiency flame retardancy, no dripping and a low smoke effect, so as to weaken the adverse effect caused by introduction of the flame retardant into the epoxy resin, and production cost is reduced.
    公开号:NL2025962A
    申请号:NL2025962
    申请日:2020-06-30
    公开日:2021-09-01
    发明作者:Yang Wei；Jin Die；Yang Jinian；Xu Yuxuan；Nie Shibin
    申请人:Univ Anhui Sci & Technology；
    IPC主号:
    专利说明:

    FLAME-RETARDANT EPOXY RESIN BASED ON IRON-CONTAINING NICKELSILICATE AND METHOD FOR PREPARING THE SAME
    TECHNICAL FIELD The disclosure belongs to the technical field of halogen-free flame-retardant epoxy resins, and particularly relates to a flame-retardant epoxy resin based on iron-containing nickel silicate and a method for preparing the same.
    BACKGROUND An epoxy resin, as one of traditional thermosetting plastics, is widely applied to the fields of chemistry, architecture, electrical engineering, transport, aerospace, military and the like due to its excellent mechanical performance, high adhesion to multiple base materials, good heat resistance and good chemical resistance. However, the epoxy resin is easily burnable, and has a limit oxygen index of only about 21%, which strictly restricts application of the epoxy resin in the fields having high flame-retardant requirements. In general, the flame retardancy of the epoxy resin is improved by adding a halogen-free flame retardant containing phosphorous, nitrogen, silicon, boron and the like. In addition, it is reported that layered silicate such as montmorillonoid can also be used for preparing the flame-retardant epoxy resin. According to “Materials and Design” (Materials & Design 178(15), 107834, 2019), when montmorillonoid accounts for 2% of total mass of the system and a nano composite flame retardant accounts for 8% of total mass of the system, although the oxygen index of the prepared flame-retardant epoxy resin is higher than that of pure epoxy resin by 11.1%, the prepared flame-retardant epoxy resin still can not meet the high flame-retardant requirement, and compared with the pure epoxy resin, the bending strength and breaking strain of the prepared flame-retardant epoxy resin are reduced. According to “Fire Disaster Science Magazine” (Journal of Fire Sciences 34(3): 212-225, 2016), when 10% by mass of ammonium polyphosphate-montmorillonoid composite is added, other properties of an epoxy matrix are influenced due to much addition amount of the needed flame retardant although the flame retardancy of the epoxy resin can be improved. In order to solve the problems that epoxy resin is easy to drop and high in combustibility, methods where nitrogen and phosphorus-containing flame retardants are added to the epoxy matrix are adopted in most cases, which can well improve the flame retardancy of the epoxy resin but other properties of the epoxy matrix are correspondingly reduced due to large addition amount of the flame retardant, and production cost is higher. At present, preparing environmental-friendly flame retardants and allowing the epoxy resin to achieve the efficient flame-retardant effect in a smaller addition amount have become a research hotspot.
    SUMMARY The disclosure provides a flame-retardant epoxy resin based on iron-containing nickel silicate and a method for preparing the same. According to the disclosure, the addition amount of the flame retardant is reduced to the greatest extent while ensuring high-efficiency flame retardancy, no dripping and a low smoke effect, so as to weaken the adverse effect caused by introduction of the flame retardant into the epoxy resin, and production cost is reduced. In order to achieve the above objective, the disclosure is realized through the following technical solution: A flame-retardant epoxy resin based on iron-containing nickel silicate, comprising 93~99.9% by mass of epoxy resin and 0.1~7% of iron-containing nickel silicate, wherein the epoxy resin consists of an epoxy resin monomer and a curing agent, the epoxy resin monomer is 70~80% by mass, and the epoxy curing agent is 20~30% by mass.
    Preferably, the epoxy resin monomer is one or more of a glycidyl ether epoxy resin, glycidyl ester epoxy resin, a glycidyl amine epoxy resin, a linear aliphatic epoxy resin and an alicyclic epoxy resin. The glycidyl ether epoxy resin is one or more of bisphenol A, bisphenol F, bisphenol S and hydrogenated bisphenol A.
    Preferably, the epoxy curing agent is one or more of an aliphatic amine curing agent, an aromatic amine curing agent (diaminodiphenyl sulfone DDS and 4,4'-diaminodiphenylmethane DDM), an amino amine curing agent and a latent curing amine curing agent.
    Preferably, raw materials for synthesizing iron-containing nickel silicate comprise 10~50% by mass of nickel silicate and 50%~90% by mass of iron compounds, based on 100% total amount of nickel silicate and iron compounds.
    Preferably, raw material components for synthesizing nickel silicate comprise 10~40% by mass of silicon source and 60~90% by mass of nickel source, based on 100% total amount of silicon source and nickel source.
    Preferably, a method for preparing the silicon source comprises: preparing NHs HO, C:HsOH and deionized water which are in a volume ratio of (1-4): 80:30 into a solution, slowly dropping a mixed solution prepared from a silane compound and C:H50OH which are in a volume ratio of (1-4): 80 under the condition of stirring, and continuously stirring for 6-12 h so that the silane compound is sufficiently hydrolyzed, then centrifuging the product, washing with ethanol and then drying to obtain the silicon source.
    Preferably, the silane compound is one or more of TMOS, TEOS, KH550, KH560 and KH570.
    Preferably, the nickel source is one or more of NiClz, Ni(NO3)2 and Ni(CH3COO):.
    Preferably, the iron compound is one or more of FeCls, Fe (NO3)s and Fe (POa)a.
    A method for preparing a flame-retardant epoxy resin based on iron-containing nickel silicate, comprising the following steps: (1) mixing a silicon source with deionzied water in a mass ratio of (0.02~0.09):20, carrying out ultrasound treatment until uniform suspension is formed to obtain a silicon source solution; preparing a nickel source, NH4Cl and deionized water which are in a mass ratio of
    (0.14~0.18): (0.5~1):30 into a solution, adjusting the pH of the mixed solution to 8-10 with NH:3:H2O, and then mixing the solution with the above silicon source solution to be poured into a stainless steel reaction kettle with a teflon lining for hydrothermal reaction with the reaction temperature of 80~100°C and the reaction time of 8~14 h; and then centrifuging the product in the reaction kettle, washing with ethanol, and then drying to obtain nickel silicate; (2) preparing nickel silicate, an iron compound and deionized water which are in a mass ratio of (0.23~1.15): (1.15~2.07): 50 into a mixed solution, adjusting the pH of the mixed solution to 7-9 with NHs:H2O after stirring for a while, and continuing to stir for 4~8 h; and subsequently, centrifuging and drying the product to obtain iron-containing nickel silicate; and (3) heating and stirring an epoxy resin monomer at 80-100°C, meanwhile ultrasonically mixing iron-containing nickel silicate and acetone which are in a mass ratio of (0.1~7). (30-50) for 20~30 min, then adding the obtained mixture into the epoxy resin monomer, and continuously stirring for 1.5~2.5 h; subsequently, adding a molten epoxy curing agent, pouring the obtained mixture into a mould after removing bubbles, and curing in an oven for 2 h at the curing temperature of 90~120°C and for 2 h at the curing temperature of 140~180°C, so as to obtain the flame-retardant epoxy resin based on iron-containing nickel silicate.
    The disclosure has the beneficial effects: Nickel silicate (Ni3Si2O05(OH)s) is of a 1:1 layered structure, which is composed of a Si-O tetrahedron and a Ni-O (OH) octahedron by sharing oxygen atoms on the vertexes of the Si-O tetrahedron. Nickel silicate not only has the advantages of layered compounds, but also contains flame-retardant elements silicon and nickel, so nickel silicate has a relatively good fire-retardant effect. In addition, the transition metal iron element has an excellent catalytic carbon formation effect and a smoke suppression effect. The iron element is introduced into nickel silicate to form iron-containing nickel silicate. The prepared iron-containing nickel silicate can further improve the flame retardancy of the epoxy resin.
    For the halogen-free flame-retardant epoxy resin based on iron-containing nickel silicate, the oxygen index of the flame-retardant epoxy resin based on 4% iron-containing nickel silicate can reach 28.9% due to the iron element having the catalytic carbon formation effect contained in the system. When a vertical combustion test is performed, an ignition source can be self- extinguished after leaving for 12s, thereby overcoming the disadvantages that the existing flame- retardant epoxy resin is large in flame retardant addition amount, low in flame-retardant effect and the like. However, when SiO: is only used to modify the epoxy resin, based on total mass percentage of the epoxy system, the oxygen index of the epoxy resin containing 4% SiO: is
    25.3% which is only higher than that of pure epoxy resin by 0.9%, and thus the flame-retardant effect is not significantly improved.
    The flame-retardant epoxy resin based on iron-containing nickel silicate not only greatly improves the oxygen index flame retardancy of the epoxy resin, but also significantly improves the vertical combustion performance, has obvious smoke suppression and dropping-free effects, can completely retain the epoxy matrix, is convenient for processing and production and is low in cost.
    BRIEF DESCRIPTION OF THE DRAWINGS For more clearly describing embodiments of the disclosure or technical solution in the prior art, drawings required to be used in embodiments or in the prior art will be simply described below. Obviously, drawings described below are only some embodiments of the disclosure. Those of ordinary skill in the art can also obtain other drawings according to these drawings without creative efforts.
    Fig.1 is an SEM image of nickel silicate in example 1.
    DESCRIPTION OF THE EMBODIMENTS In order to make the objective, technical solution and advantages of the embodiments of the disclosure more clear, the technical solution will be clearly and completely described in combination with embodiments of the disclosure. Obviously, described embodiments are one part of embodiments of the disclosure but not all the embodiments The disclosure provides a flame-retardant epoxy resin based on iron-containing nickel silicate, comprising 93~99.9% by mass of epoxy resin and 0.1~7% of iron-containing nickel silicate, wherein the epoxy resin consists of an epoxy resin monomer and a curing agent, the epoxy resin monomer is 70~80% by mass, and the epoxy curing agent is 20~30% by mass.
    The epoxy resin monomer is one or more of a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, a linear aliphatic epoxy resin and an alicyclic epoxy resin, wherein the glycidyl ether epoxy resin is one or more of bisphenol A, bisphenol F, bisphenol Sand hydrogenated bisphenol A.
    The epoxy curing agent is one or more of an aliphatic amine curing agent, an aromatic amine curing agent (diaminodiphenyl sulfone DDS and 4,4’-diaminodiphenylmethane DDM), an amino amine curing agent and a latent curing amine curing agent.
    Raw materials for synthesizing iron-containing nickel silicate comprise 10~50% by mass of nickel silicate and 50%-90% by mass of iron compounds, based on 100% total amount of nickel silicate and iron compounds.
    The iron compound is one or more of FeCls, Fe (NOs); and Fe (POs)a.
    Raw material components for synthesizing nickel silicate comprise 10~40% by mass of silicon source and 60~90% by mass of nickel source, based on 100% total amount of silicon source and nickel source.
    A method for preparing the silicon source specifically comprises: preparing NH3:Hz0, C:HsOH and deionized water which are in a volume ratio of (1-4): 80:30 into a solution, slowly dropping a mixed solution prepared from a silane compound and C;HsOH which are in a volume ratio of (1-4): 80 under the condition of stirring, continuously stirring for 6-12 h so that the silane compound is sufficiently hydrolyzed, then centrifuging the product, washing with ethanol and then drying to obtain the silicon source.
    The silane compound is one or more of TMOS, TEOS, KH550, KH560 and KH570. 5 The nickel source is one or more of NiClz, Ni(NO:3)2 and Ni(CH3COO)2. A method for preparing a flame-retardant epoxy resin based on iron-containing nickel silicate comprises the following steps: (1) mixing a silicon source with deionzied water in a mass ratio of (0.02-0.09):20, carrying ultrasound treatment until uniform suspension is formed to obtain a silicon source solution; preparing a nickel source, NH.Cl and deionized water which are in a mass ratio of (0.14~0.18): (0.5~1):30 into a solution, adjusting the pH of the mixed solution to 8-10 with NHs:H2O, and then mixing the solution with the above silicon source solution to be poured into a stainless steel reaction kettle with a teflon lining for hydrothermal reaction with the reaction temperature of 80~100°C and the reaction time of 8~14 h; and then centrifuging the product in the reaction kettle, washing with ethanol, and then drying to obtain nickel silicate; (2) preparing nickel silicate, an iron compound and the deionized water which are in a mass ratio of (0.23-1.15): (1.15~2.07): 50 into a mixed solution, adjusting the pH of the mixed solution to 7-9 with NH3:H2O after stirring for a while, and continuing to stir for 4~8 h; and subsequently, centrifuging and drying the product to obtain iron-containing nickel silicate; and (3) heating and stirring an epoxy resin monomer at 60~100°C, meanwhile ultrasonically mixing iron-containing nickel silicate and acetone which are in a mass ratio of (0.1~7). (30~50) for 20~30 min, then adding the obtained mixture into the epoxy resin monomer, and continuously stirring for 1.5~2.5 h; and subsequently, adding a molten epoxy curing agent, pouring into a mould after removing bubbles, and curing in an oven for 2 h at the curing temperature of 90~120°C and for 2 h at the curing temperature of 140~180°C, so as to obtain the flame-retardant epoxy resin based on iron-containing nickel silicate.
    Examples
    Example 1 A method for preparing a flame-retardant epoxy resin matrix based on iron-containing nickel silicate comprises the following steps: (1) 30 mL of deionzied water, 80 mL of absolute ethanol and 2 mL of NH3:H2O were mixed and stirred, the mixed solution of 1 mL TEOS, 1 mL KH550 and 80 mL absolute ethanol was slowly dropped to the above alkaline solution at a slow dropping speed as much as possible and stirred for 12 h, and then white muddy solution was then centrifuged, washed with ethanol and then dried for 12 h in an oven of 80 °C, so as to obtain white SiO, microsphere powder.
    Subsequently, 0.05g of SiO. microsphere powder and 20 mL of deionized water were ultrasonically mixed for 30 min to obtain SiO; solution; in addition, 1 mL of NHs-H2O, 30 mL of deionized water, 0.18 g of NiClz-6H>O and 0.53 g of NH4CI were prepared into a solution and then mixed with SiO: solution to be poured into a stainless steel reaction kettle with a teflon lining for hydrothermal reaction at a reaction temperature of 90°C for 10 h. After cooling to room temperature, the product in the reaction kettle was centrifuged to obtain a green precipitate, the precipitate was washed with ethanol and then dried for 12 h in an oven of 120°C to obtain light green nickel silicate powder.
    (2) 0.3 g of nickel silicate, 2 g of Fe (NO1)3-9H20 and 50 mL of deionized water were mixed and stirred for 2 h, the pH value of the mixed solution was adjusted to about 8 with NH3-H»O, and the mixed solution was further stirred for 4 h. Subsequently, the mixed solution was centrifuged and then put into an oven of 120°C for 12 h. Yellow brown iron-containing nickel silicate was finally obtained for later use.
    (3) 30 g of E-51 was stirred in an oil bath of 70°C, meanwhile 1.5 g of iron-containing nickel silicate was added into 30 mL of acetone, ultrasonic treatment was conducted for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h. in addition, 7.74 g of 4,4’-diaminodiphenylmethane was molten for 1 h at 100°C and then added into a mixture of iron-containing nickel silicate and E-51 epoxy resin to be violently stirred for 5 min, and then the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain the halogen-free flame-retardant epoxy resin based on iron-containing nickel silicate.
    According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx86.5 mmx3.2 mm was subjected to oxygen index test on an TTech-GBT2406 type oxygen index instrument, and its limit oxygen index value reached 28.9%.
    According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester. The flame was combusted only for 12 s and then self-extinguished after the first ignition for 10 s, and the flame was instantly self-extinguished after the second ignition.
    Furthermore, little of smoke was generated when in combustion without dropping. Example 2 A method for preparing a flame-retardant epoxy resin matrix based on iron-containing nickel silicate comprises the following steps: Iron-containing nickel silicate was prepared according to the method in example 1. 30 g of E-51 epoxy resin was stirred in an oil bath of 70°C, meanwhile 0.9 g of iron-containing nickel silicate was added into 30 mL of acetone, ultrasonic treatment was conducted for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h. In addition, 7.74 g of 4,4’-diaminodiphenylmethane was molten at 100°C and then added into a mixture of iron-containing nickel silicate and E-51 epoxy resin to be violently stirred for 5 min, and then the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain the halogen-free flame-retardant epoxy resin based on iron-containing nickel silicate. According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx8.5 mmx3.2 mm was subjected to oxygen index test on a TTech-GBT2406 type oxygen index instrument, and its limit oxygen index value reached 27.1%. According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester. The flame was combusted only for 35.9 s and self-extinguished after the first ignition for 10s, and the flame was self-extinguished after the second ignition for 10.4s.
    Example 3 A method for preparing a flame-retardant epoxy resin matrix based on iron-containing nickel silicate comprises the following steps: Iron-containing nickel silicate was prepared according to the method in example 1. 30 g of E-51 epoxy resin was stirred in an oil bath of 70°C, meanwhile 1.35 g of iron-containing nickel silicate was added into 30 mL of acetone, ultrasonic treatment was conducted for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h. In addition, 7.74 g of 4, 4’-diaminodiphenylmethane was molten for 1 h at 100°C and then added into a mixture of iron-containing nickel silicate and E-51 epoxy resin to be violently stirred for 5 min, and the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain the halogen-free flame-retardant epoxy resin based on iron-containing nickel silicate (its limit oxygen index value reached 28.4%). According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx86.5 mmx3.2 mm was subjected to oxygen index text on a TTech-GBT2406 type oxygen index instrument (its limit oxygen index value reached 28.4%). According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester. The flame was combusted only for 17.6 s and self-extinguished after the first ignition for 10 s, and the flame was instantly self-extinguished after the second ignition. Example 4 A method for preparing a flame-retardant epoxy resin matrix based on iron-containing nickel silicate comprises the following steps: iron-containing nickel silicate was prepared according to the method in example 1. 30 g of E-51 epoxy resin was stirred in oil bath of 70°C, meanwhile 1.65 g of iron-containing nickel silicate was added into 30 mL of acetone, ultrasonic treatment was conducted for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h. In addition,
    7.74 g of 4,4’-diaminodiphenylmethane was molten for 1 h at 100°C and then added into a mixture of iron-containing nickel silicate and E-51 epoxy resin to be violently stirred for 5 min, and then the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain the halogen-free flame-retardant epoxy resin based on iron-containing nickel silicate. According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx8.5 mmx3.2 mm was subjected to oxygen index test on a TTech-GBT2406 type oxygen index instrument, and its limit oxygen index value reached 28.5%. According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester. The flame was combusted only for 7.0 s and self-extinguished after the first ignition for 10 s, and the flame was instantly self-extinguished after the second ignition 15.4s. Example 5 A method for preparing a flame-retardant epoxy resin matrix based on iron-containing nickel silicate comprises the following steps: Iron-containing nickel silicate was prepared according to the method in example 1. 30 g of E-51 epoxy resin was stirred in oil bath of 70°C, meanwhile 2.1 g of iron-containing nickel silicate was added into 30 mL of acetone to undergo ultrasonic treatment for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h. In addition, 7.74 g of 4,4’-diaminodiphenylmethane was molten for 1 h at 100°C and then added into a mixture of iron-containing nickel silicate and E-51 epoxy resin to be violently stirred for 5 min, and the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain the halogen-free flame-retardant epoxy resin based on iron-containing nickel silicate. According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx86.5 mmx3.2 mm was subjected to oxygen index test on a TTech-GBT2406 type oxygen index instrument, and its limit oxygen index value reached 27.3%. According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on the CZF-2 type horizontal and vertical combustion tester. The flame was combusted only for 46.7 s and self-extinguished after the first ignition for 10 s, and the flame was self-extinguished after the second ignition 1.0 s.
    Comparative example 1 30 g of E-51 epoxy resin was stirred in an oil bath of 70°C, meanwhile 7.74 g of 4,4- diaminodiphenylmethane was molten for 1 h at 100°C and then added into the E-51 epoxy resin to be violently stirred for 5 min, and then the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain a pure epoxy resin.
    According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx6.5 mmx3.2 mm was subjected to oxygen index test on a TTech-GBT2406 type oxygen index instrument, and its limit oxygen index value reached 24.4%.
    According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester. The flame was combusted for 142.7 s and completely combusted after the first ignition for 10s, accompanying with a large amount of black smoke.
    Comparative example 2 SiO; was prepared according to the method in example 1. 30 g of E-51 epoxy resin was stirred in an oil bath of 70°C, meanwhile 1.5 g of SiO, was added into 30 mL of acetone, ultrasonic treatment was conducted for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h. In addition, 7.74 g of 4,4'-diaminodiphenylmethane was molten for 1 h at 100°C and then added into a mixture of SiO, and E-51 epoxy resin to be violently stirred for 5 min, and then the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain a halogen-free flame-retardant epoxy resin containing SiOx.
    According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx86.5 mmx3.2 mm was subjected to oxygen index test on a TTech-GBT2406 type oxygen index instrument, and its limit oxygen index value reached 25.3%.
    According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester. The flame was combusted for 151.3 s and completely combusted after the first ignition for 10 s.
    Comparative example 3 Nickel silicate was prepared according to the method in example 1. 30 g of E-51 epoxy resin was stirred in an oil bath of 70°C, meanwhile 1.5 g of nickel silicate was added into 30 mL of acetone, ultrasonic treatment was conducted for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h. In addition, 7.74 g of 4,4- diaminodiphenylmethane was molten for 1 h at 100°C and then added into a mixture of nickel silicate and E-51 epoxy resin to be violently stirred for 5 min, and the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain a halogen-free epoxy resin containing nickel silicate.
    According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx8.5 mmx3.2 mm was subjected to oxygen index test on a TTech-GBT2406 type oxygen index instrument, and its limit oxygen index value reached 27.2%. According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester.
    The flame was combusted only for 50.1 s and self-extinguished after the first ignition for 10 s, and the flame was self-extinguished after undergoing second ignition for 12.0 s.
    Comparative example 4 2 g of Fe (NOs3)3-9H20 and 50 mL of deionized water were mixed and stirred for 2 h, the pH value of the mixed solution was then adjusted to about 8 with NH3:H2O and then continued to be stirred for 4 h.
    Subsequently, the mixed solution was centrifuged, and the centrifuged product was dried for 12 h in an oven of 120 °C.
    The yellow brown iron-containing compound was finally obtained for later use. 30 g of E-51 epoxy resin was stirred in an oil bath of 70°C, meanwhile 1.5 g of iron- containing compound was added into 30 mL of acetone, ultrasonic treatment was conducted for 30 min, and then the mixed solution was poured into E-51 epoxy resin to be continuously stirred for 2 h.
    In addition, 7.74 g of 4,4’-diaminodiphenylmethane was molten for 1 h at 100°C and then added into a mixture of iron-containing compound and E-51 epoxy resin to be violently stirred for 5 min, and the obtained mixture was put into a vacuum oven, poured into a mould after removing bubbles and then put into the oven to be cured for 2 h at 100°C and further cured for 2 h at 150°C, so as to obtain a halogen-free flame-retardant epoxy resin containing the iron compound.
    According to standard ASTM D 2863-2017a, a standard specimen of 127 mmx6.5 mmx3.2 mm was subjected to oxygen index test on a TTech-GBT2406 type oxygen index instrument and its limit oxygen index value reached 26.5%. According to standard ASTM D3801-2010, a standard specimen of 127mmx12.7 mmx3.2 mm was subjected to UL-94 vertical combustion test on a CZF-2 type horizontal and vertical combustion tester.
    The flame was combusted only for 98 s and self-extinguished after the first ignition for 10 s, and combusted for 19 s and then self-extinguished after the second ignition for 10 s.
    It can be seen from examples 1~5 and comparative example 1 that compared with the pure epoxy resin, the limit oxygen index of the halogen-free flame-retardant epoxy resin based on iron-containing nickel silicate is significantly improved, and the flame combustion time of vertical combustion test is obviously shortened, meaning that introduction of iron-containing nickel silicate into the epoxy resin can well overcome the defect that the pure epoxy resin is prone to combustion, can greatly improve the flame retardancy of the epoxy matrix. It can be seen from example 1 and comparative examples 2-4 that when 4% by mass of SiO, nickel silicate and the iron-containing compound are added, the flame retardancy of the epoxy resin can be improved to a certain extent but improvement amplitude is relatively small. However, under the same addition amount, the iron-containing nickel silicate epoxy resin exhibits better flame-retardant effect, suggesting that iron-containing nickel silicate can obviously promote the flame retardancy of the epoxy resin. It can be seen from examples 1~5 that with the increase of iron-containing nickel silicate content, the flame-retardant effect of the epoxy resin can be improved, however, after a certain addition amount is reached, the flame-retardant effect of the epoxy resin can be reduced if the addition amount of the flame retardant is further increased Accordingly, it is summarized that when the content of iron-containing nickel silicate is 4%, the flame-retardant effect of the epoxy resin is the best, and the limit oxygen index can reach
    28.9%; in the vertical combustion test, the flame is combusted only for 12 s and self-extinguished after the first ignition for 10 s, the flame is instantly self-extinguished after second ignition, and the smoke produced during the combustion is very little without dropping. In conclusion, iron- containing nickel silicate can successfully give the epoxy resin excellent flame-retardant effect. The disclosure provides a halogen-free flame-retardant epoxy resin based on iron- containing nickel silicate and a method for preparing the same thereof. The epoxy resin can achieve excellent flame-retardant effect due to the good thermal stability of the silicon element and the excellent catalytic carbon formation effect of nickel and iron elements, the epoxy resin can reach excellent flame-retardant effect when only one additive is used without compounding with other flame retardants and iron-containing nickel silicate accounts for 4% by mass of total amount of the epoxy resin system, so as to overcome the defects that the existing nitrogen and phosphorus flame retardant is low in flame-retardant efficiency, large in addition amount and high in cost and various flame retardants are needed, thereby reducing the adverse effects of flame retardants on other performances of epoxy resin and facilitating production and use. The above embodiments are only used to explain the technical solution of the disclosure but not limiting the disclosure; although the disclosure is described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that they can still make modifications to the technical solutions in the above embodiments, or make equivalent substitutions to partial technical features therein; and these modifications or substitutions do not allow the essence of the corresponding technical solution to depart from the spirit and scope of the technical solutions of various embodiments of the disclosure.
    权利要求:
    Claims (10)
    [1]
    1. A flame-retardant epoxy resin based on ferrous nickel silicate, comprising 93-99.9 wt% epoxy resin and 0.1~7% ferrous nickel silicate, wherein the epoxy resin is composed of an epoxy resin monomer and a curing agent wherein the content of the epoxy resin monomer is 70-80 wt. .% and of the epoxy curing agent is 20-30% by weight.
    [2]
    The ferrous nickel silicate-based flame retardant epoxy resin according to claim 1, wherein the epoxy resin monomer is one or more of a glycidyl ether epoxy resin, glycidyl ether epoxy resin, a glycidylamine epoxy resin, a linear aliphatic epoxy resin and an alicyclic epoxy resin.
    [3]
    The flame-retardant nickel silicate ferrous epoxy resin according to claim 1, wherein the epoxy curing agent is one or more of an aliphatic amine curing agent, an aromatic amine curing agent, an amino amine curing agent and a latent curing amine curing agent.
    [4]
    The ferrous nickel silicate-based flame retardant epoxy resin according to claim 1, wherein raw materials for synthesizing ferrous nickel silicate comprise 10-50% by weight of nickel silicate and 50-90% by weight of iron compounds, based on 100% of the total amount of nickel silicate and iron compounds. .
    [5]
    The flame-retardant nickel silicate ferrous epoxy resin according to claim 4, wherein raw materials for synthesizing ferrous nickel silicate contain 10-40% by weight of silicon source and 50-90% by weight of nickel source, based on 100% of the total amount of silicon source and nickel source. .
    [6]
    The ferrous nickel silicate-based flame retardant epoxy resin according to claim 5, wherein a method for preparing the silicon source comprises: preparing a solution of NH:3:H2O, C:HsOH and deionized water in a volume ratio of (1-4 ): 80:30, slowly dropping in a mixed solution prepared from a silane compound and C:HsOH in a volume ratio of (1-4):80 with stirring, followed by continuous stirring for 6-12 hours so that the silane compound sufficiently hydrolyzed, then centrifuging the product, washing with ethanol and then drying to obtain the silicon source.
    [7]
    The ferrous nickel silicate-based flame retardant epoxy resin according to claim 6, wherein the silane compound is one or more of TMOS, TEOS, KH550, KH560 and KH570.
    [8]
    The flame-retardant nickel silicate ferrous epoxy resin according to claim 5, wherein the nickel source is one or more of NiCl 3 , Ni(NO:3) 2 and Ni(CH 3 COO) 2 . is.
    [9]
    The flame-retardant nickel silicate ferrous epoxy resin according to claim 4, wherein the iron compound is one or more of FeCl 3 , Fe(NO:3) 3 and Fe(POa) 3 .
    [10]
    A process for preparing the ferrous nickel silicate-based flame-retardant epoxy resin according to any one of claims 5 to 8, which process comprises the steps of: (1) mixing a silicon source with deionized water in a mass ratio of (0.02~); 0.09):20, wherein an ultrasonic treatment is performed until a uniform slurry is formed to obtain a silicon source solution; Prepare a nickel source, NH4Cl and deionized water with a mass ratio of (0.14-0.18):(0.5-1:30) in a solution, keeping the pH of the mixed solution with NH::H2O at 8-10 is being brought; and then mixing the solution with the above silicon source solution to be poured into a stainless steel reaction vessel having a Teflon liner for a hydrothermal reaction having a reaction temperature of 80-100°C and a reaction time of 8-14 hours; and then centrifuging the product in the reaction vessel, washing with ethanol and then drying to obtain nickel silicate; (2) preparing nickel silicate, an iron compound and deionized water in a mass ratio of {0.23-1.15) : (1.15-2.07) :50 in a mixed solution, adjusting the pH of the mixed solution with NH3:H2O after stirring for some time at 7-9 is stated; stirring for 4-8 hours; and then centrifuging and drying the product to obtain ferrous nickel silicate; and (3) heating and stirring an epoxy resin monomer at 80-100°C while ultrasonically mixing ferrous nickel silicate and acetone in a mass ratio of (0.1-7) : (30-50) for 20-30 minutes; then adding the resulting mixture to the epoxy resin monomer; and stirring continuously for 1.5-2.5 hours and then adding a molten epoxy curing agent; pouring the obtained mixture into a mold after removing air bubbles, and curing in an oven for 2 hours at a curing temperature of 90~120°C and for 2 hours at a curing temperature of 140-180°C to obtain the flame-retardant ferrous epoxy resin nickel silicate available
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    同族专利:
    公开号 | 公开日
    CN111154233A|2020-05-15|
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    CN202010061841.9A|CN111154233A|2020-01-19|2020-01-19|Flame-retardant epoxy resin based on iron-containing nickel silicate and preparation method thereof|
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