CN116589860B - Intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene, preparation method and application - Google Patents

Intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene, preparation method and application Download PDF

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CN116589860B
CN116589860B CN202310840777.8A CN202310840777A CN116589860B CN 116589860 B CN116589860 B CN 116589860B CN 202310840777 A CN202310840777 A CN 202310840777A CN 116589860 B CN116589860 B CN 116589860B
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flame retardant
cyclotriphosphazene
polyamino
piperazine pyrophosphate
intumescent flame
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CN116589860A (en
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杨喜生
郭秀安
郭建树
柴家启
赵震
辛建卫
袁训刚
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Shandong Meite New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application provides an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene, a preparation method and application thereof, and belongs to the field of intumescent flame retardants. The intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following components in percentage by mass: 57.5-66% of piperazine pyrophosphate, 28.5-36% of polyamino cyclotriphosphazene, 3-9% of UiO-66, 1-3% of coupling agent and 0.3-0.8% of anti-dripping agent. The intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene can realize good flame retardant effect on polyolefin materials, effectively improve flame retardant efficiency, reduce the addition amount in the flame retardant materials and reduce the influence on the processability and mechanical properties of the materials.

Description

Intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene, preparation method and application
Technical Field
The application relates to the field of intumescent flame retardants, in particular to an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene, a preparation method and application thereof.
Background
The Intumescent Flame Retardant (IFR) is a composite flame retardant system consisting of an acid source (dehydrating agent), a carbon source (char forming agent) and a gas source (foaming agent), and has the advantages of high flame retardant efficiency, low smoke yield during combustion, low toxicity and corrosiveness of smoke and the like; especially, the flame retardant has incomparable advantages with other flame retardants in solving the problem that flame retardant polyolefin materials are easy to drip when being burnt. Intumescent flame retardants are recognized as one of the most promising green flame retardants.
The acid source is the most important component in the IFR and is a key substance affecting the flame retardant effect of the IFR. The currently used IFR mainly uses ammonium polyphosphate (APP) as an acid source (abbreviated as APP-based IFR). Because APP has the defects of large water solubility, easy moisture absorption, poor compatibility with matrix materials and the like, the existing APP-based IFR has the following defects: 1) Poor compatibility with the polymer, easy migration and great influence on the physical properties of the polymer; 2) The aging resistance, the thermal stability and the hydrolytic stability are poor, and the prepared flame retardant material has poor water resistance and durability: 3) The flame retardant efficiency is lower, the application range is narrow, and the flame retardant is mainly used for flame retardant treatment of polypropylene (PP). Therefore, developing a more efficient IFR is a research hotspot in the flame retardant field.
Piperazine Pyrophosphate (PAPP) is a novel phosphorus-nitrogen flame retardant, which not only has good dehydration effect, but also has char formation and foaming effects. The intumescent flame retardant (PAPP-based IFR for short) prepared from the piperazine pyrophosphate has good flame retardant effect, is not easy to absorb moisture and not sticky, has good hydrolysis stability and wide application range, and has good flame retardant effect on materials such as polypropylene (PP), polyethylene (PE), epoxy resin, acrylonitrile-butadiene-styrene copolymer (ABS), unsaturated polyester, thermoplastic elastomer and the like. Although PAPP is a phosphorus-nitrogen flame retardant integrating an acid source, a carbon source and an air source, the foaming capacity of PAPP is low, so that the flame retardant effect is not ideal when piperazine pyrophosphate is used alone, and the PAPP is generally used in combination with a foaming agent. In the prior art, piperazine pyrophosphate is usually used in combination with melamine polyphosphate (MPP) or Melamine Cyanurate (MCA), wherein the flame retardant effect of PAPP/MPP is better, because MPP can have dehydration effect. However, although the flame retardant efficiency of PAPP/MPP and PAPP/MCA is significantly higher than that of APP-based IFR, the addition amount is still large to obtain good flame retardant effect, for example, when 3.2mm PP reaches UL 94V-0, the minimum addition amounts of PAPP/MPP and PAPP/MCA are 18wt% and 20wt%, respectively, and the flame retardant efficiency still needs to be further improved. The higher addition of PAPP/MPP and PAPP/MCA not only increases the production cost of the flame retardant material, but also can seriously reduce the processability and mechanical properties of the material, thereby affecting the popularization and application of PAPP-based IFR. Therefore, the flame retardant efficiency of the PAPP-based IFR is further improved, and the flame retardant efficiency of the PAPP-based IFR has important practical significance for popularization and application of the PAPP-based IFR.
Disclosure of Invention
In order to solve the technical problems in the prior art, the application provides an intumescent flame retardant, a preparation method and application thereof, which can realize good flame retardant effect on polyolefin materials, effectively improve flame retardant efficiency, reduce the addition amount in the flame retardant materials and reduce the influence on the processability and mechanical properties of the materials.
In order to solve the technical problems, the technical scheme adopted by the application is as follows:
an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene is characterized by comprising the following components in percentage by mass: 57.5-66% of piperazine pyrophosphate, 28.5-36% of polyamino cyclotriphosphazene, 3-9% of UiO-66, 1-3% of coupling agent and 0.3-0.8% of anti-dripping agent.
The P content in the polyamino cyclotriphosphazene is 42.5-44.0wt%; the N content is 50.5-51.5wt%; the H content is 3.5-3.9wt%; the Cl content is 1.8-2.3wt%.
The UiO-66 is prepared by the following method, zrCl 4 Adding into N, N-dimethylformamide, ultrasonic dispersing until completely dissolved, adding terephthalic acid, ultrasonic dispersing until completely dissolved, adding hydrochloric acid and acetic acid, mixingHomogenizing to obtain a mixed solution; heating the mixed solution to 148-152 ℃, reacting for 1.8-2.5h at a temperature, naturally cooling to room temperature, centrifugally separating, washing the centrifugally separated solids with N, N-dimethylformamide and methanol for three times respectively, and then drying in vacuum to obtain the UIO-66.
In the preparation of the UIO-66, zrCl 4 And terephthalic acid in a molar ratio of 1:1.3 to 1.7;
ZrCl 4 the mass ratio of the N, N-dimethylformamide to the hydrochloric acid to the acetic acid is 1:20-30:0.5-1.0:30-40.
In the preparation of the UiO-66, the dosage of the N, N-dimethylformamide for washing the centrifugal solid is ZrCl 4 5-10 times of the weight of the centrifugal solid, and the methanol consumption for washing the centrifugal solid is ZrCl 4 5-10 times of the weight.
The coupling agent is silane coupling agent KH-550;
the anti-dripping agent is polytetrafluoroethylene anti-dripping agent.
The preparation method of the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the steps of uniformly mixing the piperazine pyrophosphate, the polyamino cyclotriphosphazene, UIO-66, a coupling agent and an anti-dripping agent of the intumescent flame retardant to prepare the intumescent flame retardant.
The preparation method of the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the steps of putting piperazine pyrophosphate, polyamino cyclotriphosphazene, UIO-66, a coupling agent and an anti-dripping agent into a high-speed mixer, controlling the mixing temperature to be 90-130 ℃, controlling the mixing rotating speed to be 1500-2000rpm, mixing time to be 20-60min, and cooling to obtain the intumescent flame retardant.
A polyolefin flame retardant material adopts the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene.
The polyolefin flame-retardant material is characterized in that the polyolefin is polypropylene or polyethylene.
Compared with the prior art, the application has the beneficial effects that:
(1) The intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene takes piperazine pyrophosphate as a carbon source with dehydration function (acid source), and takes polyamino cyclotriphosphazene as an acid source with foaming function (air source); simultaneously, uiO-66 (Zr) with high synergistic effect on piperazine pyrophosphate and polyamino cyclotriphosphazene is pertinently arranged, and an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene is prepared, wherein the intumescent flame retardant has excellent flame retardant effect on polyolefin materials (such as polypropylene and polyethylene) and can effectively improve flame retardant efficiency while having flame retardant effect; meanwhile, the flame retardant efficiency is improved, the addition amount of the intumescent flame retardant in the flame retardant material can be effectively reduced, the problem that the intumescent flame retardant with higher addition amount reduces the processability and mechanical properties of the material is effectively avoided, and the influence of the intumescent flame retardant on the processability and mechanical properties of the material is effectively reduced.
(2) When the vertical combustion performance of the PP flame retardant material reaches UL 94V-0 level, the minimum addition amount of the intumescent flame retardant can be as low as 14-15wt%, the flame combustion time t1 of the first ignition is 1.2s in a vertical combustion test, the flame combustion time t2 of the second ignition is 2.1s, no molten drop exists in the combustion process, the LOI of the PP flame retardant material can reach 31.3%, good flame retardant effect on PP can be realized, the consumption of the intumescent flame retardant is reduced, and the flame retardant efficiency is effectively improved.
(3) When the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene is used for carrying out flame retardant treatment on PE materials, the minimum addition amount of the intumescent flame retardant can be as low as 16-17wt% when the vertical combustion performance of the prepared PE flame retardant reaches UL 94V-0 level, the flame combustion time t1 of the first ignition in a vertical combustion test is 1.6s, the flame combustion time t2 of the second ignition is 2.3s, no molten drop exists in the combustion process, the LOI of the PE flame retardant can reach 30.6%, good flame retardant effect on PE can be realized, the consumption of the intumescent flame retardant is reduced, and the flame retardant efficiency is effectively improved.
(4) In the preparation process of the intumescent flame retardant and the active ingredient containing piperazine pyrophosphate and polyamino cyclotriphosphazene, the synthesis process is simple, no potential safety hazard exists, the production cost is low, and the flame retardant is suitable for large-scale industrial production.
Detailed Description
Specific embodiments of the present application will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present application. It should be understood that the detailed description is of the preferred embodiment, which is presented by way of illustration and explanation only and is not intended to limit the application.
The polypropylene resin used in the application is PPH8020 produced by Lanzhou petrochemical company, and the polyethylene resin is 2426H type Low Density Polyethylene (LDPE) produced by the Mao petrochemical company; piperazine pyrophosphate PAPP is supplied by the institute of fine chemical industry, tetrachuan; hexachlorocyclotriphosphazene and liquid ammonia are supplied by the Wilkiginer chemical industry liability Co., ltd; the silane coupling agent is provided by Jiangxi Chenling New Material Co., ltd; anti-drip agents are provided by new material technology limited of Guangzhou tiger sources; other reagents were supplied by the national pharmaceutical group chemical company, inc.
For performance detection of the intumescent flame retardant prepared in the subsequent embodiment, the intumescent flame retardant prepared in each embodiment is firstly adopted to prepare a PP flame retardant material and a PE flame retardant material respectively, and then the flame retardant performance of the PP flame retardant material and the PE flame retardant material is detected respectively. The method comprises the following steps:
the preparation method of the PP flame-retardant material comprises the steps of firstly adding PP and an expansion type flame retardant IFR into powder mixing equipment with the volume of 1L, and mixing for 3min to obtain a mixture; and feeding the mixture into a double screw extruder (Lab-20 type double screw extruder of Nanjing Kowei extrusion machinery Co., ltd., L/D=30:1), controlling the rotation speed of the double screw extruder to be 150rpm, carrying out melt mixing extrusion granulation at the extrusion temperature of 195+/-5 ℃, and finally pressing the dried granules into a plate with the thickness of 100mm multiplied by 3.2mm by an automatic tablet press (Dongguan Koku) at the temperature of 200+/-5 ℃ and 5MPa, cooling at room temperature for 4 hours, and cutting into standard test bars for subsequent relevant performance detection.
The preparation method of the PE flame retardant material is basically the same as that of the PP flame retardant material, and the difference is that: 1) Mixing LDPE and an expansion type flame retardant IFR, and then carrying out melt mixing, extrusion and granulation by a double-screw extruder, wherein the extrusion temperature is controlled to be 175+/-5 ℃; 2) Tabletting the dried granules, wherein the tabletting temperature is controlled to be 180+/-5 ℃.
Flame retardant performance test: limiting Oxygen Index (LOI) is measured by adopting a JF-3 oxygen index measuring instrument (Nanjing Jiang Ning analytical instrument Co., ltd.) according to the relevant regulations of GB/T2406.1-2008 "measuring combustion behavior by oxygen index method for plastics", and the size of a test sample is 100mm multiplied by 6.5mm multiplied by 3.2mm; the vertical burning test was carried out by using a CZF-3 horizontal vertical burning tester in accordance with GB/T2408-2021 (measuring horizontal method and vertical method for burning property of plastics) and the dimensions of the sample were 100 mm. Times.13 mm. Times.3.2 mm.
Example 1
The preparation of the polyaminocyclotriphosphazene used in the subsequent examples may be carried out with reference to the disclosure of chinese patent CN 103524885B. Specifically, 174g (0.5 mol) of hexachlorocyclotriphosphazene and 1.5L of toluene are added into a 5L three-neck flask, the mixture is cooled to about 0 ℃ by an ice salt bath, ammonia gas is introduced under stirring to react for 12 hours, and then the mixture is filtered, and a white powdery solid (a mixture of hexaaminocyclotriphosphazene and by-product ammonium chloride) is obtained after a filter cake is dried. Placing the white powdery solid in a drying box, polycondensing at 180 ℃ for 0.5h, taking out, placing in air, cooling to room temperature, adding 300mL of deionized water, dissolving for 10min, press-filtering, washing a filter cake twice with 150mL of deionized water, and drying at 110 ℃ to constant weight to obtain the polyamino cyclotriphosphazene.
According to detection, the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, the content of chlorine is 2.01%, and the solubility is 1.05g/100mL of water.
Example 2
The preparation method of the UiO-66 comprises the following specific preparation processes:
9.32g (0.04 mol) of ZrCl 4 Dissolving in 240mL of N, N-dimethylformamide, dispersing by ultrasonic until the mixture is completely dissolved, adding 9.97g (0.06 mol) of terephthalic acid, continuing dispersing by ultrasonic until the mixture is completely dissolved, adding 7.72g of hydrochloric acid (concentration of 37 wt%) and 300g of acetic acid, and uniformly mixing; transferring the mixed solution into a 1000mL polytetrafluoroethylene reaction kettle, and placing the reaction kettleIn a microwave hydrothermal parallel synthesizer, the temperature is programmed to 150 ℃ at the speed of 10 ℃/min, and the reaction is carried out for 2 hours after heat preservation, and then the natural cooling is carried out. After the material was cooled to room temperature, it was centrifuged, and the centrifuged solid was washed three times with 80mLN, N-dimethylformamide and 80mL methanol, respectively, and dried in a vacuum oven at 150℃for 24 hours to give UiO-66.5 g as a white powder.
Example 3
The preparation method of the UiO-66 comprises the following specific preparation processes:
9.32g (0.04 mol) of ZrCl 4 Dissolving in 197mL of N, N-dimethylformamide, dispersing by ultrasonic until the mixture is completely dissolved, adding 8.65g (0.052 mol) of terephthalic acid, continuing dispersing by ultrasonic until the mixture is completely dissolved, adding 4.66g of hydrochloric acid (concentration of 37 wt%) and 279.6g of acetic acid, and uniformly mixing; transferring the mixed solution into a 1000mL polytetrafluoroethylene reaction kettle, placing the reaction kettle into a microwave hydrothermal parallel synthesizer, programming the temperature to 148 ℃ at the speed of 8 ℃/min, preserving heat for reaction for 1.8h, and naturally cooling. After the material was cooled to room temperature, it was centrifuged, and the centrifuged solid was washed three times with 50mLN, N-dimethylformamide and 59mL methanol, respectively, and dried in a vacuum oven at 145℃for 22 hours to give UiO-66.1 g as a white powder.
Example 4
The preparation method of the UiO-66 comprises the following specific preparation processes:
9.32g (0.04 mol) of ZrCl 4 Dissolving in 295mL of N, N-dimethylformamide, dispersing by ultrasonic until the mixture is completely dissolved, adding 11.31g (0.068 mol) of terephthalic acid, continuing dispersing by ultrasonic until the mixture is completely dissolved, adding 9.32g of hydrochloric acid (concentration of 37 wt%) and 372.8g of acetic acid, and uniformly mixing; transferring the mixed solution into a 1000mL polytetrafluoroethylene reaction kettle, placing the reaction kettle into a microwave hydrothermal parallel synthesizer, programming the temperature to 152 ℃ at the speed of 12 ℃/min, preserving heat for 2.5h, and naturally cooling. After the material was cooled to room temperature, it was centrifuged, and the centrifuged solid was washed three times with 98mLN, N-dimethylformamide and 118mL methanol, respectively, and dried in a vacuum oven at 155℃for 26 hours to give UIO-66.4 g as a white powder.
Example 5
A preparation method of an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following specific preparation processes:
accurately weighing the following raw material components in percentage by weight: 305g (mass fraction 61.0 wt%) of piperazine pyrophosphate, 150g (mass fraction 30.0 wt%) of polyamino cyclotriphosphazene prepared in example 1, 28.5g (mass fraction 5.7 wt%) of UiO-66 prepared in example 2, 15g (mass fraction 3.0 wt%) of silane coupling agent KH-550 g (mass fraction 0.3%) of anti-dripping agent, and charging into a high-speed mixer with a volume of 1L, controlling the mixing temperature to be 110 ℃, mixing rotational speed to be 1800rpm, mixing time to be 20min, and naturally cooling to obtain the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene.
Wherein the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, and the content of chlorine is 2.01%.
The anti-dripping agent is polytetrafluoroethylene anti-dripping agent F-201.
The flame retardant performance test result of the PP flame retardant material is as follows: when the vertical combustion performance of the PP flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 14wt%, the flame combustion time t1 of the first ignition in the vertical combustion test is 1.4s, the flame combustion time t2 of the second ignition is 3.8s, no molten drop exists in the combustion process, and the LOI of the PP flame retardant material is 30.2%.
The flame retardant performance test result of the PE flame retardant material is as follows: when the vertical combustion performance of the LDPE flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 16wt%, the flame combustion time t1 of the first ignition in the vertical combustion test is 2.6s, the flame combustion time t2 of the second ignition is 3.8s, no molten drop exists in the combustion process, and the LOI of the LDPE sample is 29.7%.
Example 6
A preparation method of an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following specific preparation processes:
accurately weighing the following raw material components in percentage by weight: 311g (mass fraction 62.2 wt%) of piperazine pyrophosphate, 160g (mass fraction 32.0 wt%) of polyamino cyclotriphosphazene prepared in example 1, 20g (mass fraction 4.0 wt%) of UiO-66 prepared in example 2, 4g (mass fraction 0.8 wt%) of silane coupling agent KH-550 g (mass fraction 1.0 wt%) of anti-dripping agent, and adding into a high-speed mixer with a volume of 1L, controlling mixing temperature to 90 ℃, mixing rotating speed to 1500rpm, mixing time to 60min, and naturally cooling to obtain the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene.
Wherein the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, and the content of chlorine is 2.01%.
The anti-dripping agent is polytetrafluoroethylene anti-dripping agent F-201.
The flame retardant performance test result of the PP flame retardant material is as follows: when the vertical combustion performance of the PP flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 14wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 1.8s, the flame combustion time t2 of the second ignition is 4.1s, no molten drop exists in the combustion process, and the LOI of the PP flame retardant material is 29.9%.
The flame retardant performance test result of the PE flame retardant material is as follows: when the vertical combustion performance of the LDPE flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 16wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 2.8s, the flame combustion time t2 of the second ignition is 4.2s, no molten drop exists in the combustion process, and the LOI of the LDPE sample is 29.5%.
Example 7
A preparation method of an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following specific preparation processes:
accurately weighing the following raw material components in percentage by weight: 330g (mass fraction 66.0 wt%) of piperazine pyrophosphate, 142.5g (mass fraction 28.5 wt%) of polyamino cyclotriphosphazene prepared in example 1, 15g (mass fraction 3.0 wt%) of UiO-66 prepared in example 3, 2.5g (mass fraction 0.5%) of silane coupling agent KH-550 (mass fraction 2.0 wt%) of anti-dripping agent, and adding into a high-speed mixer with a volume of 1L, controlling the mixing temperature to 100 ℃ and mixing rotating speed to 2000rpm, mixing time to 30min, and naturally cooling to obtain the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene.
Wherein the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, and the content of chlorine is 2.01%.
The anti-dripping agent is polytetrafluoroethylene anti-dripping agent F-201.
The flame retardant performance test result of the PP flame retardant material is as follows: when the vertical combustion performance of the PP flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 14wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 1.2s, the flame combustion time t2 of the second ignition is 2.1s, no molten drop exists in the combustion process, and the LOI of the PP flame retardant material is 31.3%.
The flame retardant performance test result of the PE flame retardant material is as follows: when the vertical combustion performance of the LDPE flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 17wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 1.9s, the flame combustion time t2 of the second ignition is 2.3s, no molten drop exists in the combustion process, and the LOI of the LDPE sample is 30.5%.
Example 8
A preparation method of an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following specific preparation processes:
accurately weighing the following raw material components in percentage by weight: 287.5g (mass fraction 57.5 wt%) of piperazine pyrophosphate, 155g (mass fraction 31.0 wt%) of polyamino cyclotriphosphazene prepared in example 1, 45.0g (mass fraction 9.0 wt%) of UiO-66 prepared in example 4, 2.5g (mass fraction 0.5%) of anti-dripping agent (KH-550) of silane coupling agent (2.0 wt%) and adding into a high-speed mixer with a volume of 1L, controlling mixing temperature to 130 ℃ and mixing rotating speed to 2000rpm, mixing time to 20min, and naturally cooling to obtain the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene.
Wherein the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, and the content of chlorine is 2.01%.
The anti-dripping agent is polytetrafluoroethylene anti-dripping agent F-201.
The flame retardant performance test result of the PP flame retardant material is as follows: when the vertical combustion performance of the PP flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 15wt%, the flame combustion time t1 of the first ignition in the vertical combustion test is 1.6s, the flame combustion time t2 of the second ignition is 3.2s, no molten drop exists in the combustion process, and the LOI of the PP flame retardant material is 30.9%.
The flame retardant performance test result of the PE flame retardant material is as follows: when the vertical combustion performance of the LDPE flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 17wt%, the flame combustion time t1 of the first ignition in the vertical combustion test is 1.6s, the flame combustion time t2 of the second ignition is 2.5s, no molten drop exists in the combustion process, and the LOI of the LDPE sample is 30.6%.
Comparative example 1
A preparation method of an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following specific preparation processes:
the Uio-66 components adopted in the previous embodiment are omitted, and the following raw material components in percentage by weight are accurately weighed: 325.0g (mass fraction 65.0 wt%) of piperazine pyrophosphate, 162.5g (mass fraction 32.5 wt%) of polyamino cyclotriphosphazene prepared in example 1, 2.5g (mass fraction 2.0 wt%) of silane coupling agent KH-550 and anti-dripping agent (mass fraction 0.5%), placing into a high-speed mixer with a volume of 1L, controlling mixing temperature to 110 ℃, mixing rotating speed to 1800rpm, mixing time to 30min, and naturally cooling to obtain the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene.
Wherein the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, and the content of chlorine is 2.01%.
The anti-dripping agent is polytetrafluoroethylene anti-dripping agent F-201.
The flame retardant performance test result of the PP flame retardant material is as follows: when the vertical combustion performance of the PP flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 18.5wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 2.6s, the flame combustion time t2 of the second ignition is 4.9s, no molten drop exists in the combustion process, and the LOI of the PP flame retardant material is 28.6%.
The flame retardant performance test result of the PE flame retardant material is as follows: when the vertical combustion performance of the LDPE flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 19wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 3.4s, the flame combustion time t2 of the second ignition is 5.0s, no molten drop exists in the combustion process, and the LOI of the LDPE sample is 28.3%.
It can be seen that the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene takes piperazine pyrophosphate as a carbon source with dehydration function (acid source), and takes polyamino cyclotriphosphazene as an acid source with foaming function (air source); simultaneously, uiO-66 (Zr) with high synergistic effect on piperazine pyrophosphate and polyamino cyclotriphosphazene is pertinently arranged, and an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene is prepared, wherein the intumescent flame retardant has excellent flame retardant effect on polyolefin materials (such as polypropylene and polyethylene) and can effectively improve flame retardant efficiency while having flame retardant effect; meanwhile, the flame retardant efficiency is improved, the addition amount of the intumescent flame retardant in the flame retardant material can be effectively reduced, the problem that the intumescent flame retardant with higher addition amount reduces the processability and mechanical properties of the material is effectively avoided, and the influence of the intumescent flame retardant on the processability and mechanical properties of the material is effectively reduced. The inventor finds that, as UiO-66 (Zr) is a porous material composed of metal-containing nodes and organic connecting ligands, unsaturated metal centers and uncoordinated active groups exist, the porous material has a catalytic carbonizing effect and a smoke suppression effect on piperazine pyrophosphate and polyaminocyclotriphosphazene, and can realize an effective synergistic flame retardant effect and a smoke suppression effect by being matched with the piperazine pyrophosphate and the polyaminocyclotriphosphazene. After UiO-66 (Zr) with high synergistic effect of piperazine pyrophosphate and polyaminocyclotriphosphazene is omitted in comparative example 1, the prepared intumescent flame retardant has obvious degradation of flame retardant performance on polypropylene and polyethylene, and obviously reduces flame retardant efficiency.
Comparative example 2
A preparation method of an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following specific preparation processes:
accurately weighing the following raw material components in percentage by weight: 316.5g (mass fraction 63.3 wt%) of piperazine pyrophosphate, 157g (mass fraction 31.4 wt%) of polyamino cyclotriphosphazene prepared in example 1, 10.0g (mass fraction 2.0 wt%) of UiO-66 prepared in example 2, 15g (mass fraction 3.0 wt%) of silane coupling agent KH-550, 1.5g (mass fraction 0.3%) of anti-dripping agent, and adding into a high-speed mixer with a volume of 1L, controlling mixing temperature to 110 ℃, mixing rotating speed to 1800rpm, mixing time to 20min, and naturally cooling to obtain the intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene.
Wherein the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, and the content of chlorine is 2.01%.
The anti-dripping agent is polytetrafluoroethylene anti-dripping agent F-201.
The flame retardant performance test result of the PP flame retardant material is as follows: when the vertical combustion performance of the PP flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 16wt%, the flame combustion time t1 of the first ignition in the vertical combustion test is 1.7s, the flame combustion time t2 of the second ignition is 5.3s, no molten drop exists in the combustion process, and the LOI of the PP flame retardant material is 29.9%.
The flame retardant performance test result of the PE flame retardant material is as follows: when the vertical combustion performance of the LDPE flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 18wt%, the flame combustion time t1 of the first ignition in the vertical combustion test is 2.7s, the flame combustion time t2 of the second ignition is 5.2s, no molten drop exists in the combustion process, and the LOI of the LDPE sample is 29.6%.
It can be seen that, compared with example 7 (the addition amount of UiO-66 is 3 wt%), the intumescent flame retardant of comparative example 2 was reduced to 2wt%, and the addition amount was too low to achieve high synergistic effect of piperazine pyrophosphate and polyaminocyclotriphosphazene, resulting in a significant reduction in flame retardant effect and flame retardant efficiency of the intumescent flame retardant of comparative example 2 on PP and PE, which is manifested by an increase in minimum addition amount of intumescent flame retardant in flame retardant material, deterioration of vertical combustion test results, and reduction of LOI.
Comparative example 3
A preparation method of an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene comprises the following specific preparation processes:
accurately weighing the following raw material components in percentage by weight: 286.5g (mass fraction 57.3 wt.%), 142g (mass fraction 28.4 wt.%) of polyamino cyclotriphosphazene prepared in example 1, 55.0g (mass fraction 11 wt.%) of UiO-66 prepared in example 2, 15g (mass fraction 3.0 wt.%) of silane coupling agent KH-550, 1.5g (mass fraction 0.3%) of anti-dripping agent are put into a high-speed mixer with a volume of 1L, the mixing temperature is controlled to be 110 ℃, the mixing rotating speed is 1800rpm, the mixing time is 20min, and natural cooling is carried out to prepare the intumescent flame retardant containing the piperazine pyrophosphate and the polyamino cyclotriphosphazene.
Wherein the content of phosphorus in the polyamino cyclotriphosphazene is 43.15%, the content of nitrogen is 51.09%, the content of hydrogen is 3.65%, and the content of chlorine is 2.01%.
The anti-dripping agent is polytetrafluoroethylene anti-dripping agent F-201.
The flame retardant performance test result of the PP flame retardant material is as follows: when the vertical combustion performance of the PP flame retardant material reaches UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 16.6wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 2.5s, the flame combustion time t2 of the second ignition is 5.8s, no molten drop exists in the combustion process, and the LOI of the PP flame retardant material is 29.5%.
The flame retardant performance test result of the PE flame retardant material is as follows: when the vertical combustion performance of the LDPE flame retardant material reaches the UL 94V-0 level, the minimum addition amount of the intumescent flame retardant prepared in the embodiment is 18.7wt%, the flame combustion time t1 of the first ignition in a vertical combustion test is 2.8s, the flame combustion time t2 of the second ignition is 5.4s, no molten drop exists in the combustion process, and the LOI of the LDPE sample is 29.5%.
It can be seen that, compared with example 8 (9 wt% of UiO-66) in which the addition amount of UiO-66 in the intumescent flame retardant was increased to 11wt%, the addition amount of piperazine pyrophosphate and polyaminocyclotriphosphazene in the intumescent flame retardant was insufficient due to the excessively high addition amount, and the high synergistic effect could not be achieved by the mutual combination, resulting in a remarkable decrease in the flame retardant effect and flame retardant efficiency of the intumescent flame retardant of comparative example 3 on PP and PE, which is manifested as an increase in the minimum addition amount of the intumescent flame retardant in the flame retardant material, deterioration of the vertical combustion test result, and decrease in LOI.
The percentages used in the present application are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (9)

1. An intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene is characterized by comprising the following components in percentage by mass: 57.5-66% of piperazine pyrophosphate, 28.5-36% of polyamino cyclotriphosphazene, 3-9% of UiO-66, 1-3% of coupling agent and 0.3-0.8% of anti-dripping agent;
the UiO-66 is prepared by the following method, zrCl 4 Adding into N, N-dimethylformamide, dispersing by ultrasonic until the terephthalic acid is completely dissolved, continuing dispersing by ultrasonic until the terephthalic acid is completely dissolved, adding hydrochloric acid and acetic acid, and uniformly mixing to obtain a mixed solution; heating the mixed solution to 148-152 ℃, preserving heat for 1.8-2.5h, naturally cooling to room temperature, centrifuging, and separating the centrifuged solid by using N, N-dimethylformamide and methanol respectivelyAfter three washes, vacuum drying, uiO-66 was obtained.
2. The intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene according to claim 1, characterized in that the content of P in the polyamino cyclotriphosphazene is 42.5-44.0 wt.%; the N content is 50.5-51.5wt%; the H content is 3.5-3.9wt%; the Cl content is 1.8-2.3wt%.
3. The intumescent flame retardant containing piperazine pyrophosphate and polyaminocyclotriphosphazene according to claim 1 characterized in that in the preparation of said UiO-66 ZrCl 4 And terephthalic acid in a molar ratio of 1:1.3 to 1.7;
ZrCl 4 the mass ratio of the N, N-dimethylformamide to the hydrochloric acid to the acetic acid is 1:20-30:0.5-1.0:30-40.
4. The intumescent flame retardant containing piperazine pyrophosphate and polyaminocyclotriphosphazene according to claim 1, characterized in that in the preparation of said UiO-66, the amount of N, N-dimethylformamide used for washing the centrifuged solid is ZrCl 4 5-10 times of the weight of the centrifugal solid, and the methanol consumption for washing the centrifugal solid is ZrCl 4 5-10 times of the weight.
5. The intumescent flame retardant containing piperazine pyrophosphate and polyaminocyclotriphosphazene according to claim 1, characterized in that said coupling agent is a silane coupling agent KH-550;
the anti-dripping agent is polytetrafluoroethylene anti-dripping agent.
6. A method for preparing an intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene as claimed in any one of claims 1 to 5, characterized in that piperazine pyrophosphate, polyamino cyclotriphosphazene, uiO-66, coupling agent and anti-dripping agent are uniformly mixed to prepare the intumescent flame retardant.
7. The method for preparing intumescent flame retardant containing piperazine pyrophosphate and polyamino cyclotriphosphazene according to claim 6, characterized in that piperazine pyrophosphate, polyamino cyclotriphosphazene, UIO-66, coupling agent and anti-dripping agent are put into a high-speed mixer, mixing temperature is controlled to be 90-130 ℃, mixing rotating speed is controlled to be 1500-2000rpm, mixing time is controlled to be 20-60min, and the intumescent flame retardant is prepared by cooling.
8. A polyolefin flame retardant material, characterized in that the intumescent flame retardant comprising piperazine pyrophosphate and polyaminocyclotriphosphazene according to any one of claims 1 to 5 is used.
9. The polyolefin flame retardant material of claim 8, wherein the polyolefin is polypropylene or polyethylene.
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