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    • 专利摘要:
    The present invention discloses a flame-retardant charring agent and a preparation process thereof, and a structural formula is shown as follows: , 5 wherein n=1-3. The preparation process includes the following steps: 1) weighing phosphoric acid and NiCO3`2Ni(OH)2`4H2O according to the substance amount ratio of 1:6, adding deionized water and stirring and mixing the substances for dissolution until no bubble is generated, so as to obtain a mixed solution A; and 2) mixing the mixed solution A and pentaerythritol and adding an obtained mixture into a methylbenzene solution for 10 reaction, after heating and reacting for 9 h at the temperature of 100 °C, continuing the reaction by increasing the temperature to 110 °C until methylbenzene is completely removed, then increasing the temperature of the system to 150 °C, adding tris(2-hydroxyethyl)isocyanurate and a catalyst, continuously stirring and reacting for 12 h to obtain a thick product, and crystallizing the thick product into a solid product so as to 15 obtain a finished product PECN. The novel intumescent flame-retardant charring agent provided by the present invention is used for flame retardance of polypropylene, and compared with a traditional APP/PER system, the flame-retardant efficiency is obviously improved.
    公开号:NL2024549A
    申请号:NL2024549
    申请日:2019-12-20
    公开日:2021-07-30
    发明作者:Dong Xiang；Kong Fanbei；Nie Shibin
    申请人:Univ Anhui Sci & Technology；
    IPC主号:
    专利说明:

    NR. P100379NL00 | FLAME-RETARDANT CHARRING AGENT AND PREPARATIONPROCESS THEREOF
    BACKGROUND Technical Field The present invention belongs to the technical field of intumescent flame retardants, and particularly relates to a flame-retardant charring agent and a preparation process thereof. Related Art An intumescent flame retardant (IFR) technology is an efficient and environment-friendly polymer flame retardant technology and has good application prospects. A typical intumescent flame retardant is composed of an acid source, a gas source and a charring agent. At present, since ammonium polyphosphate (APP) can have the effects of an efficient acid source and an efficient gas source simultaneously and has been widely accepted in research and application, further exploratory space of the APP is limited. Therefore, in order to further improve the efficiency of the flame-retardant effect of an IFR, designing and synthesizing of an efficient charring agent of a novel structure become an important breakthrough of the field.
    The IFR composed of the APP and pentaerythritol (PER) is a traditional and classic IFR system, and effects and principles of the IFR in different polymers have been widely researched. However, as higher requirements are continuously proposed for the flame-retardant efficiency of the IFR in application, the flame-retardant efficiency of the APP/PER system cannot meet the requirements, and the overall flame-retardant effect is not satisfied.
    Tris(2-hydroxyethyl)isocyanurate (THEIC) is a relatively new substance structure for synthesizing of the charring agent in recent years, quasi-thiotriazinone in the structure of the THEIC has relatively high thermal stability and a relatively good flame-retardant effect, meanwhile, the chemical structure of the THEIC also has relatively good expansibility, and thus the THEIC 1s suitable for structural design and synthesis. However, there is no report about a novel charring agent with the PER and the THEIC structure combined.
    SUMMARY The present invention aims to provide a flame-retardant charring agent and a preparation process thereof in order to overcome the defects in the prior art, and the technical problem of the non-obvious flame-retardant effect of a flame retardant of an APP/PER system in the prior art is solved. The aims of the present invention can be realized through the following technical scheme: a structural formula of the flame-retardant charring agent is shown as follows: TEER Le GH OHO SNOR : OH HO DH od Da zD o / YT a , ( a Ong) OD iH i ! wo } Po HOHENGN. RCH OHO Pi’ QP OREN NGR GPR DN, NOH OHON I 5 o wit I Je Sue YT 5 ò a a wherein n=1-3.
    The forming reaction of the flame-retardant charring agent is shown as follows: the reaction equation in S1, Oe ea HOw Xa iN Q J {Q NF { 3 AR NA i A “pe orion ee $e Pee Coed QE OH Ho OH ee A & oO ne
    NE the reaction equation in S2, HO fo (Hn [er Hom, 70H xk 0 Go Ae 0 hom Oi ox ko Hom, 08 on KD (3 3 0 | X i YY PHO YY | X I YY i he | YY Hop ie + HOREHESN, NCH AHH me HOEN Jo} 0 en NCO jo OOH CHC News CH,CH,OB ! oN Y T 0 i T 0 ON T & 0 0 5 0 wherein n=1-3. The preparation process of the flame-retardant charring agent includes the following steps: 1) weighing phosphoric acid and NiCOs2Ni(OH)2>4H:0 according to the substance amount ratio of 1:6, adding deionized water, and stirring and mixing the substances for dissolution until no bubble is generated, so as to obtain a mixed solution A; and 2) mixing the mixed solution A and pentaerythritol and adding an obtained mixture into a methylbenzene solution for reaction, after heating and reacting for 9 h at the temperature of 100 °C, continuing the reaction by increasing the temperature to 110 °C until methylbenzene is completely removed, then increasing the temperature of the system to 150 °C, adding tris(2-hydroxyethyl)isocyanurate and a catalyst, continuously stirring and reacting for 12 h to obtain a thick product, and crystallizing the thick product into a solid product so as to obtain a finished product PECN. Further, the mass concentration of the phosphoric acid selected in the step 1) is 98%. Further, the substance amount of the pentaerythritol added in the step 2) is 1/2 of that that of the phosphoric acid added in S1. Further, reactants are continuously stirred during the heating reaction in the step 2). Further, the substance amount ratio between the tris(2-hydroxyethyl)isocyanurate in the step 2) and the phosphoric acid in S1 is 0.75-0.84. Further, the catalyst in the step 2) is tetrabutyl titanate. Further, the crystallized solid product in the step 2) is immersed in ethyl alcohol to be recrystallized, then the product is dried, and the dried solid product is ground. The present invention has the following beneficial effects: the novel intumescent flame-retardant charring agent provided by the present invention is used for flame retardance of polypropylene, and the flame-retardant efficiency is obviously improved compared with traditional APP/PER system.
    BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a Fourier infrared comparison diagram of an embodiment of the present invention and synthetic raw materials. Fig. 2 is a schematic diagram of a nuclear magnetic resonance H spectrum in an embodiment of the present invention. Fig. 3 is a schematic diagram of a nuclear magnetic resonance P spectrum in an embodiment of the present invention, Fig. 4 is a variation diagram of limiting oxygen index values of a flame-retardant charring agent of an embodiment of the present invention. Fig. 5 is heat release rate curves of a part of flame-retardant charring agents in an embodiment of the present invention.
    DETAILED DESCRIPTION As shown in Fig. 1, a structural formula of a flame-retardant charring agent provided by the present invention is shown as follows: THRON he on FHOMON om on Shea Te XE NY KENT HOREN Te or REEL ok SOE Aches 3 & 3 Ia DN 8 wherein n=1-3; and the following two-step forming chemical equations are included:
    Hwy on FS STH ‘ oO “ oi 0 TE Xs (oo me LA we I I § w | ve] wherein n=1-3. A preparation process of the flame-retardant charring agent includes the following steps: 1) selecting and weighing 55.0 ml of H:PO, with the mass concentration being 98% and 25.0 g of NiCO:32Ni(OH):4H:0 according to the substance amount ratio of 1:6 and mixing the substances, then adding a small amount of deionized water for mixing and dissolving under the assistance thereof until no bubble is generated, so as to obtain a mixed solution A; and 2) adding 120 ml of methylbenzene into a 500 ml four-neck flask at first, then adding the mixed solution A and 28.3 g of pentaerythritol into the flask (the substance amount of the added pentaerythritol is 1/2 of that of phosphoric acid), stirring the substances at the temperature of 100 °C for heating reaction for 9 h, then increasing the temperature to 110 °C to continue the reaction until the methylbenzene is completely removed, then increasing the temperature of the system to 150 °C, adding tris(2-hydroxyethyl)isocyanurate (the substance amount ratio between the tris(2-hydroxyethyl)isocyanurate and the phosphoric acid 1s 0.75-0.84) and 0.5 ml of a tetrabutyl titanate catalyst, continuously stirring and reacting for 12 h to obtain a thick product, crystallizing the thick product into a solid product, then immersing the solid product in ethyl alcohol for recrystallization, then drying the product, and grinding the dried solid product to obtain a finished product PECN.
    Fig. 1 is a Fourier infrared comparison diagram of an embodiment of the present invention and synthetic raw materials (wherein THEIC represents the tris(2-hydroxyethyl)isocyanurate, and PER represents the pentaerythritol), and a nuclear magnetic resonance H spectrum and a nuclear magnetic resonance P spectrum shown in Figs. 2-3 are used for proving successful realization of the structure of the present invention.
    Table 1 Compositions of PP/IFR Composite and UL-94 Test Results Table 1 Sample | PP | OS-MCAPP PECN PPO | 100 | 0 | 0 | Noraing | ppt | 70 [30 | 0 | Norating | ppp | 70 0 | 30 | Norating | pee | 70 | 10 | 2 | OVL It can be known from Table 1 that the novel charring agent of the present invention and APP (the APP is wrapped with silicon during implementation and is temporarily 5 named as OS-MCAPP) form an IFR system which is used for flame retardance of polypropylene and is remarkable in effect.
    Compared with a traditional APP/PER system, the flame-retardant efficiency is obviously improved.
    A sample PP4 has a limiting oxygen index value of 28.8 has the best flame retardance in the system, while the limiting oxygen index value of pure polypropylene is only 17.8, which can be seen from Fig. 4 for details.
    The maximum heat release rate of the sample PP4 is also the lowest among samples and is only 885.5, which is lower than the heat release rate of 1200.1 of a sample PPI, and can be seen from Fig. 5 for details.
    权利要求:
    Claims (9)
    [1]
    1. A flame retardant carbon-forming compound having the structural formula: Gron/GHOHon HCH QR 8D OH < 3 f N NM, 0 QG: Rs 0 Ted Te NY le Xe hy HOM GHG N. ROH OHO 0 QE DREHER. HCH Ogee’ Wo Pong NV GHG HOH YT > oN Tr fo Da TT Q a 7 1 © Of which n=1-3.
    [2]
    The flame retardant carbon-forming compound according to claim 1, having the formation reaction: S1 Reaction formula BOT, OH dl # x SAS # rd y 8 od > 3 + ~ a S2 Reaction formula CH, HCHO CHEO ie Hom 0H Lo o Us i Or 0 Lo Hom 0E on A LO A YY YY i YY AL YY Nome ort ROHCH,C=N, N==CH.(H. oH von {HAN denied 0 mon (CN. N~CHOH,0 ls oee SHC AtRCH6H | : | TY „Cl Na TT tht | 2) T EE) | | y T 1 oO ON 0 ONF Q ON 0 9 0 n 0 Of which n=1-3.
    [3]
    A method for forming the flame-retardant carbon-forming compound according to claim 1-2, comprising the steps: 1) Weigh phosphoric acid and NiC O 3 2Ni(OH) 2 4H 2 O according to the amount ratio of 1:6, add deionized water thereto , stir and dissolve until no more bubbles are formed, to obtain mixed solution A, 2) mix solution A with pentaerythritol in a toluene solution for reaction, after heating at 100°C for 9 hours, the temperature is raised to 110°C and the reaction is continued until the toluene is completely removed for 1 sec. Then the system is heated to 150°C and add tris(2-hydroxyethyl)isocyanurate and catalyst, keep stirring for the next 12 hours for thickening, and the thickened product crystallizes into a solid product to obtain the finished PECN.
    [4]
    The method for preparing the flame-retardant carbon-forming compound according to claim 3, wherein the mass concentration of phosphoric acid in step 1) is 98%.
    [5]
    The process for preparing the flame-retardant carbon-forming compound according to claim 4, wherein the amount of added pentaerythritol in step 2) is 1/2 s of the added amount of phosphate in S1.
    [6]
    The process for preparing the flame-retardant carbon-forming compound according to claim 3, wherein the reactants are constantly stirred while the reaction is heated in step 2).
    [7]
    The process for preparing the flame retardant carbon-forming compound according to claim 4, wherein the ratio of the amount of tris(2-hydroxyethyl) isocyanurate in step 1) to the amount of phosphoric acid in S1 is 0.75 to 0.84.
    [8]
    The process for preparing the flame-retardant carbon-forming compound according to claim 3, wherein the catalyst in step 2) is tetrabutyl titanate.
    [9]
    The process for preparing the flame-retardant carbon-forming compound according to claim 3, wherein the crystallized solid product in said step 2 is immersed in ethanol for recrystallization, followed by a drying operation and the dried solid product is ground again.
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