CN115260696B - Flexible polymer composite material with flame retardance as well as preparation method and application thereof - Google Patents

Flexible polymer composite material with flame retardance as well as preparation method and application thereof Download PDF

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CN115260696B
CN115260696B CN202211014457.9A CN202211014457A CN115260696B CN 115260696 B CN115260696 B CN 115260696B CN 202211014457 A CN202211014457 A CN 202211014457A CN 115260696 B CN115260696 B CN 115260696B
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CN115260696A (en
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陆昶
姚大虎
高喜平
李东雪
阿世伟
李雪原
霍佳乐
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Henan University of Science and Technology
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Abstract

The invention discloses a flexible polymer composite material with flame retardance, and a preparation method and application thereof, wherein the flexible polymer composite material is prepared from the following materials: polymeric elastomeric material: 60-70 parts of a lubricant; the intumescent flame retardant consists of the following raw materials: ammonium polyphosphate: 24-30 parts of pentaerythritol: 5-10 parts of organic montmorillonite, 1-3 parts of organic montmorillonite; expandable graphite: 0.15-1 parts. The preparation method comprises the following specific steps: step one, melt blending an intumescent flame retardant composed of the materials in a certain proportion with the polymer elastomer material, granulating, pressing the obtained plasticized sample into a sheet, and cutting the sheet into flame-retardant splines; and step two, placing the flame-retardant spline obtained in the step one into expandable graphite dispersion liquid with a certain concentration for ultrasonic treatment to obtain the modified polymer elastomer material. The scheme can effectively solve the problems of long response time, non-flame retardance and the like of the conventional fire alarm.

Description

Flexible polymer composite material with flame retardance as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of flame-retardant composite materials, and particularly relates to a flexible polymer composite material with flame retardance, and a preparation method and application thereof.
Background
In the prior art, in order to reduce the threat of fire to human life and property safety, a fire alarm is usually installed in a building, so as to achieve the effects of early fire discovery, early escape, early fire extinguishment and the like. The fire sensor commonly used at present is a smoke alarm, and the smoke alarm realizes fire prevention by monitoring the concentration of smoke. The fire sensor is often separated from building materials and is at a certain distance from a fire point, and alarms are usually given after a large amount of smoke is generated after the fire sensor burns for a period of time, so that the response time of a fire alarm is often more than 100 seconds, and the optimal time cannot be provided for timely putting out the fire and evacuating people; meanwhile, the smoke alarm may have the possibility of false alarm; in addition, because such sensors cannot face severe external environments such as heavy rain, heavy wind, dust, corrosive moisture and the like, the application of the sensors in the outdoor and open public places is greatly limited, and materials (such as plastics, rubber, fibers, wood, paper and the like) of the existing fire sensors have the problem of inflammability in use, so that the sensors pollute the environment.
The expandable graphite is an expansion flame retardant, and when heated, the intercalation between the graphite layers is decomposed or gasified, so that the sheets are expanded to form a worm-shaped expanded carbon layer, and the heat insulation, oxygen insulation, smoke suppression and anti-dripping functions are realized.
Disclosure of Invention
The invention aims to provide a flexible polymer composite material with flame retardance, and a preparation method and application thereof. The fire disaster sensor prepared by the composite material has a good fire disaster early warning function.
The invention aims to provide a flexible polymer composite material with flame retardance, which is prepared from the following materials in parts by weight: polymeric elastomeric material: 60-70 parts of a lubricant; an intumescent flame retardant which is composed of the following raw materials: ammonium polyphosphate: 24-30 parts of pentaerythritol: 5-10 parts of organic montmorillonite, 1-3 parts of organic montmorillonite; expandable graphite: 0.15-1 parts.
Preferably, the polymer elastomer material is one of polyurethane elastomer, styrene-butadiene-styrene block copolymer or ethylene octene copolymer.
The second object of the invention is to provide a method for preparing a flexible polymer composite material with flame retardance: firstly, carrying out melt blending on an expansion flame retardant composed of the materials in a certain proportion and the polymer elastomer material in a double-screw extruder at a temperature of 150-200 ℃, granulating, and carrying out high-temperature plasticization on a granulated sample in an injection molding machine at a temperature of 150-200 ℃ to obtain a plasticized sample; then placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and cutting the sheet into sample pieces with certain specification to obtain flame retardant sample strips modified by the intumescent flame retardant; and step two, placing the flame-retardant spline obtained in the step one into expandable graphite dispersion liquid with a certain concentration for ultrasonic treatment to obtain the flame-retardant modified polymer elastomer material with the surface loaded with the expandable graphite.
In a preferred embodiment, in the second step, the solvent of the expandable graphite dispersion liquid is one or more of cyclohexane, N-hexane, ethanol, tetrahydrofuran, toluene, acetone, chloroform, N-dimethylformamide, and petroleum ether.
In the first step, the plasticized sample is placed in a flat vulcanizing machine to be pressed into a sheet at the temperature of 120-150 ℃.
In the second step, the flame-retardant spline obtained in the first step is placed in expandable graphite dispersion liquid with a certain concentration to be subjected to ultrasonic treatment for 2 s-3 min.
It is a further object of the present invention to provide the use of a flexible polymer composite with flame retardancy, which can be applied to a fire sensor with fire pre-alarm and fire alarm functions.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the invention adopts self-assembly technology to coat conductive material on the surface of polymer to prepare the flexible fire sensor with flame retardant property. The fire-retardant material can effectively solve the problems of long response time, non-flame retardance and the like when the fire-retardant material is applied to a fire sensor at present through improving components and a preparation method, and meanwhile, the fire sensor adopting the material has good fire early warning function and pre-warning function.
The flexible polymer material with the surface loaded with the expandable graphite has good flame retardant property, can also enable the flame retardant composite material to have good mechanical property, has the conductivity, and rapidly reduces the resistance in a short time when the SBS flame retardant composite material with the surface loaded with the expandable graphite is subjected to high temperature, and has sensitive sensing capability. The sensor prepared by the materials has good flame retardance; the fire sensor has a grading alarm function, so that false alarm can be reduced; the composite material can be directly used as a product of a fire sensor; meanwhile, the sensor made of the material can resist the influence of natural environments such as wind, rain and the like. Therefore, the fire sensor has a wider application prospect in the aspect of fire early warning.
Drawings
FIG. 1 is a graph of the thermal release rate (HRR) versus a composite of expandable graphite;
FIG. 2 is a plot of the composite smoke generation rate (SPR) versus expandable graphite;
FIG. 3 is a DTG plot of EG\IFR\SBS;
FIG. 4 is a TG plot of EG\IFR\SBS;
FIG. 5 is a scanning electron microscope image of a sample with EG embedded on the surface thereof after 2s combustion in a flame;
FIG. 6 is a scanning electron microscope image of a graphite worm formed by pure EG volume expansion;
FIG. 7 is a scanning electron microscope image of a sample with EG embedded on the surface thereof, burned in a flame for 10 seconds, and then the graphite worms were removed;
FIG. 8 is a graph of resistance change of EG flake at different temperatures;
FIG. 9 is a graph of real-time resistance change of the sensor at a temperature below 300 ℃;
FIG. 10 is a graph of real-time resistance change of the sensor at a temperature above 300 ℃;
FIG. 11 is a graph of the resistance change of a sample after combustion in different types of flames;
FIG. 12 is a scanning electron microscope image of EG flakes becoming graphite worms after a sample being burned in a flame for 2 seconds.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement of the purposes and the beneficial effects of the present invention easy to understand, the present invention is further described below in connection with the specific embodiments.
The embodiment provides a flame-retardant flexible polymer composite material, which is prepared from the following materials in parts by weight: polymeric elastomeric material: 60-70 parts of a lubricant; the intumescent flame retardant consists of the following raw materials: ammonium polyphosphate: 24-30 parts of pentaerythritol: 5-10 parts of organic montmorillonite, 1-3 parts of organic montmorillonite; expandable graphite: 0.15-1 parts. The polymer elastomer material is one of polyurethane elastomer, styrene-butadiene-styrene block copolymer or ethylene octene copolymer.
The embodiment also provides a flexible polymer composite material with flame retardance, which specifically comprises the following steps: firstly, carrying out melt blending on an expansion flame retardant composed of the materials in a certain proportion and the polymer elastomer material in a double-screw extruder at a temperature of 150-200 ℃, granulating, and carrying out high-temperature plasticization on a granulated sample in an injection molding machine at a temperature of 150-200 ℃ to obtain a plasticized sample; then, at the temperature of 120-150 ℃, placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and cutting the sheet into a sample piece with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; and step two, placing the flame-retardant spline obtained in the step one in a cyclohexane dispersion liquid of 3-5 g/100ml expandable graphite, and carrying out ultrasonic treatment for 2 s-3 min to obtain the flame-retardant modified polymer elastomer material with the surface loaded with the expandable graphite.
In extrusion modification, the processing temperatures of different polymers are respectively as follows: polyurethane elastic materials (180-210 ℃), styrene-butadiene-styrene block copolymers SBS (150-200 ℃) and ethylene octene copolymers POE (150-200 ℃), wherein the materials can meet the melting requirement of an extruder in respective temperature ranges; when plasticizing in the injection molding machine, the temperature range percentages are: polyurethane elastic material (180-210 ℃), styrene-butadiene-styrene block copolymer SBS (150-200 ℃), ethylene octene copolymer POE (150-200 ℃); when the press molding is carried out on the press vulcanizer, the setting temperature ranges are as follows: 120-150 ℃.
In this embodiment, the dispersion of expandable graphite may be replaced with one or more of N-hexane, ethanol, tetrahydrofuran, toluene, acetone, chloroform, N-dimethylformamide, and petroleum ether.
Example 1
Firstly, preparing an SBS/IFR/OMMT flame-retardant composite material, which comprises the following components in parts by weight: 69 parts of SBS (styrene-butadiene-styrene block copolymer), 24 parts of APP (ammonium polyphosphate), 6 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite), carrying out melt blending in a twin-screw extruder at 150-200 ℃, granulating, plasticizing the granulated sample at 150-200 ℃ in an injection molding machine to obtain a plasticized sample, and setting the temperature range to be: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; then the prepared SBS/IFR/OMMT flame-retardant sample strip is subjected to ultrasonic treatment in cyclohexane solution with the concentration of 3g/100ml for 2s, and is dried to prepare the SBS flame-retardant composite material with the surface loaded with expandable graphite (0.15 part). Through flame retardant property test, the Limiting Oxygen Index (LOI) is 31.0%, the UL 94 vertical burning grade can reach V-0 level, and the flame retardant property is good. And the SBS flame-retardant composite material with the surface loaded with the expandable graphite has good mechanical property, the tensile strength is 6.92 MPa, and the elongation at break is 838%.
Example 2
Firstly, preparing an SBS/IFR/OMMT flame-retardant composite material, which comprises the following components in parts by weight: 69 parts of SBS (styrene-butadiene-styrene block copolymer), 26 parts of APP (ammonium polyphosphate), 6 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite), carrying out melt blending in a twin-screw extruder at 150-200 ℃, granulating, plasticizing the granulated sample at 150-200 ℃ in an injection molding machine to obtain a plasticized sample, and setting the temperature range to be: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; and then the prepared SBS/IFR/OMMT flame-retardant composite material is subjected to ultrasonic treatment in cyclohexane solution with the concentration of 3g/100ml for about 3 seconds, and the SBS flame-retardant composite material with the expandable graphite loaded on the surface can be prepared by drying. Through flame retardant property test, the Limiting Oxygen Index (LOI) is 32.7%, the UL 94 vertical burning grade can reach V-0 level, and the flame retardant property is good. And the SBS flame-retardant composite material with the surface loaded with the expandable graphite (about 0.2 part) still has good mechanical property, the tensile strength is 6.58MPa, and the elongation at break is 781%.
Example 3
Firstly, preparing an SBS/IFR/OMMT flame-retardant composite material, which comprises the following components in parts by weight: 69 parts of SBS (styrene-butadiene-styrene block copolymer), 24 parts of APP (ammonium polyphosphate), 6 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite), carrying out melt blending in a twin-screw extruder at 150-200 ℃, granulating, plasticizing the granulated sample at 150-200 ℃ in an injection molding machine to obtain a plasticized sample, and setting the temperature range to be: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; and then the prepared SBS/IFR/OMMT flame-retardant composite material is subjected to ultrasonic treatment in cyclohexane solution with the concentration of 5g/100ml for a plurality of seconds, and the SBS flame-retardant composite material with the expandable graphite loaded on the surface can be prepared by drying. Through flame retardant property test, the Limiting Oxygen Index (LOI) is 34.6%, the UL 94 vertical burning grade can reach V-0 level, and the flame retardant property is good. And the SBS flame-retardant composite material with the surface loaded with the expandable graphite (about 0.8 part) still has good mechanical property, the tensile strength is 6.38 MPa, and the elongation at break is 796 percent.
Example 4
Firstly, preparing an SBS/IFR/OMMT flame-retardant composite material, which comprises the following components in parts by weight: 60 parts of SBS (styrene-butadiene-styrene block copolymer), 30 parts of APP (ammonium polyphosphate), 8 parts of PER (pentaerythritol) and 2 parts of OMMT (organic montmorillonite), carrying out melt blending in a twin-screw extruder at 150-200 ℃, granulating, plasticizing the granulated sample at 150-200 ℃ in an injection molding machine to obtain a plasticized sample, and setting the temperature range to be: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; then the SBS/IFR/OMMT flame-retardant sample strip prepared above is put into normal hexane solution with the concentration of 5g/100ml for ultrasonic treatment for several seconds, and is dried to obtain the SBS flame-retardant composite material with expandable graphite loaded on the surface (about 0.2 part of expandable graphite loaded on the surface). Through flame retardant property test, the Limiting Oxygen Index (LOI) is 35.8%, the UL 94 vertical burning grade can reach V-0 level, and the flame retardant property is good.
Example 5
Firstly, preparing an SBS/IFR/OMMT flame-retardant composite material, which comprises the following components in parts by weight: 70 parts of SBS (styrene-butadiene-styrene block copolymer), 24 parts of APP (ammonium polyphosphate), 5 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite), carrying out melt blending in a twin-screw extruder at 150-200 ℃, granulating, plasticizing the granulated sample at 150-200 ℃ in an injection molding machine to obtain a plasticized sample, and setting the temperature range to be: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; then the SBS/IFR/OMMT flame-retardant sample strip prepared above is put into cyclohexane solution with the concentration of 3g/100ml for ultrasonic treatment for several seconds, and is dried to obtain the SBS flame-retardant composite material with expandable graphite loaded on the surface (about 1 part of expandable graphite loaded on the surface). Through flame retardant property test, the Limiting Oxygen Index (LOI) is 34.9%, the UL 94 vertical burning grade can reach V-0 level, and the flame retardant property is good.
Example 6
Firstly, preparing an SBS/IFR/OMMT flame-retardant composite material, which comprises the following components in parts by weight: 67 parts of SBS (styrene-butadiene-styrene block copolymer), 24 parts of APP (ammonium polyphosphate), 6 parts of PER (pentaerythritol) and 3 parts of OMMT (organic montmorillonite), carrying out melt blending in a twin-screw extruder at 150-200 ℃, granulating, plasticizing the granulated sample at 150-200 ℃ in an injection molding machine to obtain a plasticized sample, and setting the temperature range to be: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; and then the prepared SBS/IFR/OMMT flame-retardant composite material is subjected to ultrasonic treatment in cyclohexane solution with the concentration of 3g/100ml for a few seconds, and is dried to obtain the SBS flame-retardant composite material with the surface loaded with the expandable graphite (about 0.2 part of the surface loaded with the expandable graphite). Through flame retardant property test, the Limiting Oxygen Index (LOI) is 33.3%, the UL 94 vertical burning grade can reach V-0 level, and the flame retardant property is good.
Example 7
Firstly, preparing an SBS/IFR/OMMT flame-retardant composite material, which comprises the following components in parts by weight: 63 parts of SBS (styrene-butadiene-styrene block copolymer), 26 parts of APP (ammonium polyphosphate), 10 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite), carrying out melt blending in a twin-screw extruder at 150-200 ℃, granulating, plasticizing the granulated sample at 150-200 ℃ in an injection molding machine to obtain a plasticized sample, and setting the temperature range to be: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; and then the prepared SBS/IFR/OMMT flame-retardant spline material is subjected to ultrasonic treatment in a cyclohexane solution with the concentration of 3g/100ml for a few seconds, and is dried to obtain the SBS flame-retardant composite material with the surface loaded with the expandable graphite (about 0.2 part of the surface loaded expandable graphite). Through flame retardant property test, the Limiting Oxygen Index (LOI) is 34.3%, the UL 94 vertical burning grade can reach V-0 level, and the flame retardant property is good.
The flame retardant spline prepared in the above examples 1 to 7 has good flame retardance and mechanical properties, wherein the ultrasonic time of examples 3 to 7 is 3 to 10 seconds, and the surface loading of the expandable graphite enables the flame retardant spline to have conductivity, and the resistance of the type of flame retardant elastomer spline is correspondingly changed due to the change of the ambient temperature, so that the material can be applied as a fire sensor for fire early warning.
Comparative example 1
The SBS (styrene-butadiene-styrene block copolymer) has an oxygen limiting index (LOI) of 14.5% when no flame retardant is added, is no grade when subjected to an UL 94 vertical burning test, and has the characteristic of being extremely easy to burn. In the absence of any flame retardant, the tensile strength of the pure SBS elastomer was 4.47 MPa and the elongation at break was 1141%.
Comparative example 2
The SBS/IFR/OMMT flame-retardant composite material is prepared by adopting a melt blending method, and comprises the following components in parts by weight: 69 parts of SBS (styrene-butadiene-styrene block copolymer), 24 parts of APP (ammonium polyphosphate), 6 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite). Under the condition of 150-200 ℃, carrying out melt blending in a double-screw extruder, granulating, carrying out high-temperature plasticization on a granulated sample in an injection molding machine at 150-200 ℃ to obtain a plasticized sample, and setting the temperature range as follows when a vulcanizing press is used for compression molding: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; through flame retardant property test, the Limiting Oxygen Index (LOI) is 23.1%, and the UL 94 vertical burning test is no grade, which shows that the SBS/IFR/OMMT flame retardant composite material shows poor flame retardant property when the IFR consumption is 30 parts and the OMMT consumption is 1 part. At this time, the tensile strength of the flame retardant composite material was 5.77 MPa, and the elongation at break was 752%.
Comparative example 3
The SBS/IFR/OMMT flame-retardant composite material is prepared by adopting a melt blending method, and comprises the following components in parts by weight: 59 parts of SBS (styrene-butadiene-styrene block copolymer), 32 parts of APP (ammonium polyphosphate), 8 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite). Under the condition of 150-200 ℃, carrying out melt blending in a double-screw extruder, granulating, carrying out high-temperature plasticization on a granulated sample in an injection molding machine at 150-200 ℃ to obtain a plasticized sample, and setting the temperature range as follows when a vulcanizing press is used for compression molding: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; through flame retardant property test, the Limiting Oxygen Index (LOI) is 27.5%, and the UL 94 vertical burning test is no grade, which shows that the SBS/IFR/OMMT flame retardant composite material has poorer flame retardant property when the IFR consumption is 40 parts and the OMMT consumption is 1 part.
Comparative example 4
The SBS/IFR/OMMT flame-retardant composite material is prepared by adopting a melt blending method and comprises the following components in parts by weight: 54 parts of SBS (styrene-butadiene-styrene block copolymer), 36 parts of APP (ammonium polyphosphate), 9 parts of PER (pentaerythritol) and 1 part of OMMT (organic montmorillonite). Under the condition of 150-200 ℃, carrying out melt blending in a double-screw extruder, granulating, carrying out high-temperature plasticization on a granulated sample in an injection molding machine at 150-200 ℃ to obtain a plasticized sample, and setting the temperature range as follows when a vulcanizing press is used for compression molding: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; through flame retardant property test, the Limiting Oxygen Index (LOI) is 28.9%, and the UL 94 vertical burning can reach V-0 level, which shows that when the IFR consumption is 45 parts and the OMMT consumption is 1 part, the SBS/IFR/OMMT flame retardant composite material shows better flame retardant property. At this time, the tensile strength of the SBS/IFR/OMMT flame retardant composite material was 4.19 MPa, and the elongation at break was 480%. Compared with the mechanical property of the SBS flame-retardant composite material with the expandable graphite loaded on the surface, the tensile strength is obviously reduced, and the elongation at break is greatly reduced. This is due to the addition of a large amount of intumescent flame retardant which is unevenly distributed in the SBS composite material, thus leading to a significant decrease in mechanical properties. Meanwhile, compared with the prepared SBS/IFR/OMMT flame-retardant composite material with EG loaded on the surface, the flame-retardant performance has lower LOI.
Comparative example 5
Adding EG into a preparation SBS, IFR, OMMT system by adopting a melt blending method, and then preparing the SBS/IFR/EG/OMMT flame-retardant composite material, wherein the EG comprises the following components in parts by weight: 64 parts of SBS (styrene-butadiene-styrene block copolymer), 24 parts of APP (ammonium polyphosphate), 6 parts of PER (pentaerythritol), 1 part of OMMT (organic montmorillonite) and 5 parts of EG (expandable graphite). Under the condition of 150-200 ℃, carrying out melt blending in a double-screw extruder, granulating, carrying out high-temperature plasticization on a granulated sample in an injection molding machine at 150-200 ℃ to obtain a plasticized sample, and setting the temperature range as follows when a vulcanizing press is used for compression molding: 120-150 ℃; placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and then cutting the sheet into a sample wafer with a certain specification to obtain an intumescent flame retardant modified flame retardant spline; through flame retardant property tests, the Limiting Oxygen Index (LOI) of the flame retardant composite material is 31.3%, and the V-0 grade of the flame retardant composite material can be achieved through UL94 vertical burning, which shows that the SBS/IFR/OMMT flame retardant composite material has better flame retardant property when the IFR consumption is 30 parts, the OMMT consumption is 1 part and the EG is 5 parts. At this time, the tensile strength of the SBS/IFR/OMMT flame retardant composite material was 5.16 MPa, and the elongation at break was 633%. Compared with the mechanical property of the SBS flame-retardant composite material with the expandable graphite loaded on the surface, when EG is added into the SBS/IFR/OMMT flame-retardant composite material by adopting a melt blending method, the flame-retardant property is almost similar to that of EG with 0.15 part of the surface loaded when the addition amount is 5 parts. But the mechanical properties are obviously reduced, such as obviously reduced tensile strength and greatly reduced elongation at break. This is due to the addition of large amounts of EG, which makes its distribution in SBS flame retardant composites uneven, resulting in significant decrease in mechanical properties.
By comparing the above examples with the comparative examples, it was found that the SBS flexible polymer material having EG (expandable graphite) supported on the surface has both good flame retardant property and good mechanical property. Meanwhile, the SBS flame-retardant composite material with the expandable graphite loaded on the surface has the conductivity, and the resistance rapidly drops in a short time when the SBS flame-retardant composite material is subjected to high temperature, so that the SBS flame-retardant composite material has the sensitive sensing capability. For example, the initial resistance of the flame-retardant composite material is 10M Ω, and under the condition that the surface is burnt by a spray gun for 0.2 to a few seconds, the resistance can be rapidly reduced to about one percent of the initial resistance, and excellent sensing performance is shown; and the sample is not easy to burn, and has excellent flame retardant property. Therefore, the flame-retardant, electrically conductive composite material can be applied as a fire sensor.
As shown in fig. 1, the cone calorimeter test results show that (expandable graphite) EG can significantly reduce the Heat Release Rate (HRR) of the sample at the initial stage of combustion, and especially EG can reduce the HRR of the sample by nearly 40% at the very beginning of ignition. In LOI and UL-94 tests of samples with EG embedded in the surface layer, the flame retardance is better and the effect is better, which shows that EG obviously improves the flame retardance of the samples in early combustion. Fig. 2 shows that SPR is the rate of smoke generation and EG (expandable graphite) reduces smoke emissions at the beginning of combustion. Therefore, EG can obviously reduce the burning intensity of the sample in the early stage of burning, reduce the release of smoke and provide precious time for escaping from a fire scene.
As shown in fig. 3 and 4, EG (expandable graphite) or IFR (intumescent flame retardant) improves the flame retardant properties of the matrix by forming graphite worms or an expanded carbon layer, respectively. DTG and TG results as shown, the thermal decomposition temperatures of IFR and EG were very close, both well below that of SBS, indicating that either EG (expandable graphite) or IFR (intumescent flame retardant) can protect the matrix by forming a char layer before thermal degradation of the SBS (styrene-butadiene-styrene block copolymer) matrix.
As shown in FIGS. 5-7, the morphology change of the carbon layer of the flame-retardant composite material with EG supported on the combustion surface was observed by studying the flame-retardant composite material. The samples with EG embedded in their surface layers were burned in the flame of an alcohol burner 2 s, and the flaky EG became vermicular (FIG. 5). The worm structure is consistent with the graphite worms formed by the volumetric expansion of EG (FIG. 6), indicating that EG embedded in the skin layer can rapidly expand and transform into graphite worms when heated in a flame. After combustion in the flame 10 s, the graphite worms were carefully removed from the sample surface, which showed a morphology of porous structure. The appearance characterization of the carbon layer shows that the SBS/IFR/OMMT flame-retardant composite material with EG loaded on the surface has better flame-retardant performance, because EG loaded on the surface has good oxygen and heat insulation effect when being heated to become vermiform graphite, and further assists the flame-retardant effect of the intumescent flame retardant mainly comprising ammonium polyphosphate.
The early warning mode (temperature below 300 ℃) triggered by the fire detection sensor before the material is ignited is defined as early warning of the fire. A warning mode in which a sensor is triggered by contact with a flame or a temperature above the ignition temperature of the material is defined as fire detection or fire alarm.
We tested the early warning and detection capabilities of EG embedded samples in the skin. The electrical resistance of the carbon material decreases with increasing temperature, i.e. a negative temperature effect is produced. EG may expand to graphite worms at a temperature of 270 ℃. Thus, EG (expandable graphite) has a more complex temperature response than other carbon materials. The resistance change of pure EG flakes prepared by evaporation-induced self-assembly was tested at different temperatures, as shown in fig. 8, at temperatures of 200 ℃ and 250 ℃ the resistance of EG decreased with increasing temperature, i.e. negative temperature effect. According to the scheme, the early fire early warning and fire detection capabilities of the sample strip with EG loaded on the surface layer at different temperatures are shown in figure 8. When the temperature is lower than 300 ℃, the sample shows a phenomenon of negative temperature effect (fig. 8). The higher the temperature, the faster the resistance of the sample decreases. At 200 ℃, the resistance of the sample can be reduced to 1/10 of the initial resistance. The resistance of the sample at room temperature is about 10M Ω, in order to avoid the false alarm triggered by the fluctuation of the resistance, 1/10 of the initial value of the resistance of the sample, namely 1M Ω is taken as the early alarm resistance value to trigger the fire alarm. Under the constraint condition, the fire early-warning temperature of the sample is 200 ℃, and the early-warning response time is 21.5 s. When the temperature is increased to 300 ℃, the early warning response time is reduced to 5.5 s. By increasing the temperature above the ignition temperature of SBS, i.e. 450 ℃ and 550 ℃, the resistance of the fire sensor drops rapidly twice (fig. 9). At temperatures of 450 ℃ and 550 ℃, the resistance of the sensor is reduced to 1MΩ within 5s and 2.5 s respectively, thereby triggering fire early warning. The resistance drops rapidly below 0.1mΩ, i.e. the time point of the second rapid drop in resistance occurs at about 28s and 8s, respectively. Since the temperature is already higher than the ignition temperature of the material, a resistance value of 0.1mΩ can be set as a detection resistance for the occurrence of fire (i.e., fire alarm resistance). Therefore, the sample can perform fire early warning (resistance value is reduced to one tenth of the original value) and fire detection (or fire alarm) in hot air (resistance value is reduced to one hundredth of the original value). Thereby playing the role of early warning function (when the temperature is lower, the material is heated but does not burn) and fire warning function (when the temperature is higher, the material is burned).
To further demonstrate that the fire sensor using the material has a fire alarm (detection) function, different types of flames are used to apply the sample combustion and observe the resistance change condition. After burning 1.6 s, 2.2 s, and 0.6 s in candles, ethanol, and butane flames, the sample resistance was reduced to 0.1M Ω, respectively, causing fire detection. This illustrates the ability of the sample to quickly detect fire from different flames (as in fig. 11, the various sample combustion patterns are shown in fig. 11 at the same time, and therefore the abscissa indicates that they are not shown). After the sample was burned in a flame 2 s a surface of the sample was covered with graphite worms (fig. 12), indicating that the fire detection mechanism was caused by the conversion of sheet EG into graphite worms. The sample can trigger fire detection rapidly when butane flame burns even after bending the sample 300 times repeatedly. The product may undergo multiple deformations during installation, transportation and use. However, after 300 repeated bending and stretching cycles, the mechanical properties, flame retardance and fire detection capability of the sample are maintained, which shows that the product based on the corresponding sample can meet the requirements of practical application. The test results show that the fire alarm function can be realized by setting the alarm resistance value. If the initial resistance value is 10M Ω, when the resistance value is reduced to 1/100 (one percent), the fire alarm is realized.
Meanwhile, the fire sensor prepared from the composite material has the function of preventing false alarm. Based on the Seebeck effect, when a sample is heated to a certain temperature, a corresponding voltage value is generated, the measured voltage of the sample is increased along with the increase of the heating temperature, and high temperature difference and conductivity can generate high voltage. The significant difference in voltage caused by the significant change in temperature before and after ignition of the sample is utilized, thereby being applicable to fire detection based on the Seebeck effect. The means for detecting the auxiliary voltage and the electric measurement can avoid false alarm generated by the fire sensor due to the decrease of resistance value caused by external water, conductor contact and the like.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.

Claims (5)

1. The preparation method of the flexible polymer composite material with flame retardance is characterized by comprising the following steps: the material is prepared from the following materials in parts by weight:
polymeric elastomeric material: 60-70 parts of a lubricant;
An intumescent flame retardant which is composed of the following raw materials: ammonium polyphosphate: 24-30 parts of pentaerythritol: 5-10 parts of organic montmorillonite: 1-3 parts;
Expandable graphite: 0.15-1 parts;
The polymer elastomer material is one of polyurethane elastomer, styrene-butadiene-styrene block copolymer or ethylene octene copolymer;
The preparation method of the flexible polymer composite material with flame retardance comprises the following steps: firstly, carrying out melt blending on an expansion flame retardant consisting of a certain proportion of the materials and the polymer elastomer material in a double-screw extruder at the temperature of 150-200 ℃, granulating, and carrying out high-temperature plasticization on a granulated sample in an injection molding machine at the temperature of 150-200 ℃ to obtain a plasticized sample; then placing the obtained plasticized sample in a flat vulcanizing machine to press into a sheet, and cutting the sheet into sample pieces with certain specification to obtain flame retardant sample strips modified by the intumescent flame retardant;
And step two, placing the flame-retardant spline obtained in the step one into expandable graphite dispersion liquid with a certain concentration for ultrasonic treatment to obtain the flame-retardant modified polymer elastomer material with the surface loaded with the expandable graphite.
2. A method of preparing a flexible polymer composite having flame retardancy as claimed in claim 1, wherein: in the second step, the solvent of the expandable graphite dispersion liquid is one or more of cyclohexane, normal hexane, ethanol, tetrahydrofuran, toluene, acetone, chloroform, N-dimethylformamide and petroleum ether.
3. A method of preparing a flexible polymer composite having flame retardancy as claimed in claim 1, wherein: in the first step, the obtained plasticized sample is placed in a flat vulcanizing machine to be pressed into a sheet at the temperature of 120-150 ℃.
4. A method of preparing a flexible polymer composite having flame retardancy as claimed in claim 1, wherein: and in the second step, the flame-retardant spline obtained in the first step is placed in expandable graphite dispersion liquid with a certain concentration to be subjected to ultrasonic treatment for 2 s-3 min.
5. Use of a flexible polymer composite with flame retardancy as claimed in claim 1, wherein: the flexible polymer composite material can be applied to a fire sensor with fire pre-alarm and fire alarm functions.
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