CN107629288B - Polyethylene/metal hydroxide/ketjen black flame-retardant material and preparation method thereof - Google Patents
Polyethylene/metal hydroxide/ketjen black flame-retardant material and preparation method thereof Download PDFInfo
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- CN107629288B CN107629288B CN201710799263.7A CN201710799263A CN107629288B CN 107629288 B CN107629288 B CN 107629288B CN 201710799263 A CN201710799263 A CN 201710799263A CN 107629288 B CN107629288 B CN 107629288B
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Abstract
A polyethylene/metal hydroxide/Ketjen black flame retardant material and a preparation method thereof are disclosed, wherein the material is prepared from the following components in parts by weight (phr): 100phr of polyethylene, 140phr of metal hydroxide 125-140phr and 1-5phr of Ketjen black. The Ketjen black of the invention is in a branched chain state, has large specific surface area, and is easy to form a network structure in a high polymer matrix; adding Ketjen black into a polyethylene/metal hydroxide material, wherein a network structure formed by the Ketjen black is used as a physical barrier layer to block the transfer of heat and mass in the combustion process, so that the combustion process is delayed; under the condition that the flame retardant is added in the same parts, the vertical burning grade and the limit oxygen index value of the polyethylene/metal hydroxide/ketjen black composite material are improved, the peak heat release rate and the total smoke release amount are reduced, and the metal hydroxide and the ketjen black can play a synergistic action when being used for flame-retardant polyethylene.
Description
Technical Field
The invention relates to a process for preparing, treating or batching a high-molecular flame-retardant material, in particular to a polyethylene/metal hydroxide/ketjen black flame-retardant material and a preparation method thereof.
Technical Field
Polyethylene is widely used in various aspects of daily life due to its excellent mechanical properties, chemical stability, easy processability, and the like. However, polyethylene itself is extremely flammable, has a large calorific value, and has a high burning speed and drops during burning, so that the application of polyethylene in the field with high requirements on flame retardant level is limited. With the gradual enhancement of global consciousness of skillful safety and environmental protection, the traditional halogen flame retardant is increasingly limited, and halogen-free, low-smoke, low-toxicity and environment-friendly flame-retardant high polymer materials become the targets pursued by people. Metal hydroxides were one of the earliest environmentally friendly flame retardant systems, but the lower flame retardant efficiency has seriously affected the expansion of its application range.
Keqin black is prepared by a special original production process, and has high purity and high performance. Ketjen black has a branched form, has a relatively large area, and is easily brought into sufficient contact with an active material. Ketjen black is filled into a polymer matrix as a filler, and a network structure is easily formed due to the branched chain form of the Ketjen black. Based on the advantages, the Ketjen black is introduced into the polyethylene/metal hydroxide system, and a network structure formed by the Ketjen black can form a physical barrier layer in the combustion process so as to hinder the transfer of heat and mass and improve the flame retardant efficiency of the metal hydroxide.
Disclosure of Invention
Aiming at the defects in the prior art, the Ketjen black is introduced into a polyethylene/metal hydroxide system to prepare the polyethylene/metal hydroxide/Ketjen black composite material with excellent flame retardant property, thermal stability and mechanical property.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a polyethylene/metal hydroxide/Ketjen black flame retardant material is prepared from the following components in parts by weight (phr):
polyethylene 100phr
Metal hydroxide 125-140phr
Ketjen black 1-5 phr.
The polyethylene of the invention is high density polyethylene.
The metal hydroxide is aluminum hydroxide or magnesium hydroxide; the metal hydroxide is environment-friendly, cheap and easy to obtain.
The ketjen black has the purity of more than 99 percent, has a branched chain shape, and has the appearance shown in figure 1. Ketjen black is different from carbon black in that it is branched and has a branched network structure in comparison with the spherical structure of carbon black; the mechanism of the nano carbon black is to capture radicals, and the influence of particle size is large, and the capture efficiency may be higher when the size is smaller.
The invention also provides a preparation method of the polyethylene/metal hydroxide/ketjen black flame-retardant material, which comprises the following specific processes: drying the metal hydroxide and the ketjen black in an oven at 70-90 ℃ for 4-8h, then stirring the polyethylene, the metal hydroxide and the ketjen black according to the formula proportion, adding the mixture into a torque rheometer for melt blending: the reaction temperature is 170-190 ℃, the rotating speed is 50-70r/min, and the reaction time is 8-12 min; thus obtaining the black blocky flame-retardant polyethylene/metal hydroxide/ketjen black composite material with metallic luster.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the Ketjen black of the invention is in a branched chain state, has large specific surface area, and is easy to form a network structure in a high polymer matrix; adding Ketjen black into a polyethylene/metal hydroxide material, wherein a network structure formed by the Ketjen black is used as a physical barrier layer to block the transfer of heat and mass in the combustion process, so that the combustion process is delayed; under the condition that the flame retardant is added in the same parts, the vertical burning grade and the limit oxygen index value of the polyethylene/metal hydroxide/ketjen black composite material are improved, the peak heat release rate and the total smoke release amount are reduced, and the metal hydroxide and the ketjen black can play a synergistic action when being used for flame-retardant polyethylene.
(2) The metal hydroxide and the ketjen black are compounded and added into polyethylene, and the flame-retardant polyethylene material is prepared by melt blending. Compared with the method of simply adding metal hydroxide, under the condition of achieving the same vertical combustion grade, the metal hydroxide and the ketjen black are jointly used, so that the addition amount of the flame retardant can be reduced, and the thermal stability and the mechanical property of the flame retardant material are improved.
(3) According to the invention, the Ketjen black, the polyethylene and the metal hydroxide material are mixed for use for the first time, the mixture ratio is simple, other substances are not required to be added, and the branched chain morphological structure of the Ketjen black is fully utilized, so that the formed network structure can form a physical barrier layer in the combustion process, further, the heat and mass transfer is hindered, and the flame retardant efficiency of the metal hydroxide is improved.
Drawings
FIG. 1 is a transmission electron micrograph of Ketjen black.
FIG. 2 thermogravimetric curve of polyethylene/aluminum hydroxide/Ketjen black material.
FIG. 3 cone calorimetry curves for polyethylene/aluminum hydroxide/Ketjen black material.
Detailed Description
The present invention will be described in further detail below with reference to specific examples, but the present invention is not limited to only the following examples. The invention is not limited to the embodiments described herein, but is capable of numerous modifications and variations within the spirit and scope of the invention as defined by the appended claims.
Examples
In the embodiment of the invention, aluminum hydroxide (ATH) and Ketjen Black (KB) are dried in an oven at 85 ℃ for 5 hours, then high-density polyethylene (HDPE), aluminum hydroxide and Ketjen black are stirred and added into a torque rheometer for melt blending, the reaction temperature is 180 ℃, the rotation speed is 60r/min, and the reaction time is 8min, so that a uniformly mixed composite material, namely polyethylene/aluminum hydroxide/Ketjen black flame retardant material is obtained, and the specific formula is shown in Table 1.
After the flame-retardant composite material is melted and blended, preheating the prepared sample in a flat vulcanizing machine at 180 ℃ for 5min, boosting the pressure to 15MPa, preserving the heat for 7min, and carrying out pressure maintaining and natural cooling molding for various performance tests.
TABLE 1 formulation, thermal stability and flame retardancy of the examples of the invention
aT20％Expressed as the temperature at which the sample loses 20 wt% by heat;
Tmaxexpressed as the temperature at the maximum rate of thermal weight loss, Tmax1、Tmax2Corresponding to the first and second maximum thermal decomposition rates, respectively.
Thermal stability test of this example: taking 5-10mg of powder sample, and adopting a thermogravimetric analyzer to measure in a nitrogen atmosphere, wherein the heating rate is 20 ℃/min, and the temperature range is 50-700 ℃. The test results are shown in table 1, and the specific curves are shown in fig. 3. Under the condition of the same addition amount of the flame retardant, the addition of the Ketjen black can improve the thermal decomposition temperature and the carbon residue amount of the polyethylene/aluminum hydroxide material, and the thermal stability is improved along with the increase of the content of the Ketjen black. With the improved thermal stability, the range of applications for the material will be expanded.
The flame retardant performance test of the present example is divided into three parts: the method comprises the following specific implementation processes of limit oxygen index testing, vertical combustion testing and cone calorimetry testing:
(1) limiting Oxygen Index (LOI) according to GB/T2406-1993 standard, on an HC-2 oxygen index apparatus, the sample size is 130X 6X 3mm315 specimens were tested for each sample, and the oxygen index of the material was calculated according to the correction method specified in the national standard. The test results are shown in table 1.
(2) The vertical burning test (UL-94) was carried out according to GB/T2408-1996 on a model CZF-3 horizontal vertical burning tester with test specimen dimensions of 130X 13X 3mm 35 specimens were tested for each sample, the mean value was taken, and the flammability of the material was evaluated according to the regulations in the national standard with reference to the experimental results. The test results are shown in table 1.
(3) Cone calorimetric test (Cone) according to ASTM E1354/ISO 5660, sample size 100 x 3mm3Heat flow 35kW/m2. The test results are shown in table 2, and the specific curves are shown in fig. 2.
TABLE 2 Cone calorimetry test results for the examples of the invention
aPHRR is expressed as peak heat release rate;
THR is expressed as total heat release;
Tignexpressed as the ignition time;
TSP is expressed as total smoke emission
The addition of Ketjen black can reduce the amount of aluminum hydroxide added while maintaining the vertical burning rating of UL-94V0, which shows that Ketjen black can improve the vertical burning rating of polyethylene/aluminum hydroxide systems. Meanwhile, the higher the content of Ketjen black added to aluminum hydroxide systems with different contents, the higher the limit oxygen index value of the flame retardant material. The cone calorimetry test shows that under the condition of the same addition amount of the flame retardant, the addition of the ketjen black can reduce the peak heat release rate and the total smoke release amount of the polyethylene/aluminum hydroxide material. The test result shows that the Ketjen black and the aluminum hydroxide have a synergistic flame retardant effect in a polyethylene system.
The mechanical property test of the embodiment: the method is carried out on a tensile testing machine according to GB/T1040, the tensile speed is 50mm/min, the testing environment temperature is 25 +/-2 ℃, the number of test samples is more than or equal to 5, the data are averaged, and the testing results are shown in Table 3. When the Ketjen black is added into a polyethylene/aluminum hydroxide system, the tensile strength, the tensile modulus and the elongation at break of the material are improved. In summary, the flame retardant, thermal stability and tensile properties of sample PE/ATH136/KB4 are all better than those of sample PE/ATH 160. Ketjen black improves the flame retardant properties of polyethylene without deteriorating its tensile properties, which is of practical significance for polyethylene applications.
TABLE 3 tensile test results for inventive examples
Claims (4)
1. A polyethylene/metal hydroxide/Ketjen black flame retardant material, characterized in that: the composition is prepared from the following components in parts by weight:
polyethylene 100phr
Metal hydroxide 125-140phr
1-5phr of Ketjen black;
the Ketjen black has a purity of >99% and a branched morphology.
2. The polyethylene/metal hydroxide/ketjen black flame retardant material according to claim 1, wherein: the polyethylene is high-density polyethylene.
3. The polyethylene/metal hydroxide/ketjen black flame retardant material according to claim 1, wherein: the metal hydroxide is aluminum hydroxide or magnesium hydroxide.
4. The method for preparing the polyethylene/metal hydroxide/ketjen black flame retardant material according to claim 1, wherein: the preparation method comprises the following steps:
(1) drying the metal hydroxide and the ketjen black in an oven at 70-90 ℃ for 4-8 h;
(2) and then premixing the dried metal hydroxide and the Ketjen black with polyethylene, adding into a Thermal-Haake torque rheometer, and carrying out melt blending for 8-12min at 170-190 ℃ under the condition of 60-80 r/min to obtain the uniformly mixed polyethylene/metal hydroxide/Ketjen black flame retardant material.
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| 纳米碳材料复配氢氧化铝阻燃HDPE的研究;韩黎刚;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170215(第02期);B016-415 * |
| 金属氢氧化物协效阻燃聚烯烃的研究进展;韩黎刚等;《材料科学与工程学报》;20151231;第33卷(第6期);923-926 * |
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