CN114316594B - Composite material with low combustion heat release and smoke release and preparation method thereof - Google Patents
Composite material with low combustion heat release and smoke release and preparation method thereof Download PDFInfo
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- CN114316594B CN114316594B CN202210034112.3A CN202210034112A CN114316594B CN 114316594 B CN114316594 B CN 114316594B CN 202210034112 A CN202210034112 A CN 202210034112A CN 114316594 B CN114316594 B CN 114316594B
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Abstract
A composite material with low combustion heat release and smoke release and a preparation method thereof, wherein the preparation method comprises the following steps: taking a G-Fe2O3 composite nano material with the content of 30% -85% of dried Fe2O3, and drying after secondary dispersion; mixing PPS, a silane coupling agent and the G-Fe2O3 composite nano material treated in the step S1 according to the content of the G-Fe2O3 composite nano material of 0.3-3 percent and the content of the silane coupling agent of 10-30 percent of the G-Fe2O3, and then carrying out melt blending at the temperature of 200-350 ℃ to prepare composite master batch; drying the composite master batch to make the water content less than 50ppm; and extruding and injection molding the dried composite master batch to obtain the PPS/G-Fe2O3 composite material with low combustion heat release and smoke release. The PPS/G-Fe2O3 composite material prepared by the method has the advantages that the thermal stability is obviously improved, the thermal weight loss curve pyrolysis stage moves to a high temperature region, the carbon residue is increased, and the thermal and smoke barrier is facilitated; and the heat release and smoke release of combustion are obviously improved, and the heat release rate, total heat release, smoke release rate and total smoke release are obviously reduced.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a composite material with low combustion heat release and smoke release and a preparation method thereof.
Background
There are often a number of high temperature risks in engineering production, for example, susceptibility to combustion, thermal and smoke injuries, and the like. For such environments, it is important to develop a lightweight thermal protective material that is resistant to heat and has low heat and smoke release during combustion. The general polymer material has lower heat-resistant temperature, and the heat permeation is high and quick along with the melting and collapsing in the combustion process, and simultaneously generates a large amount of smoke, which is not beneficial to the safety protection. The PPS material has good thermal stability, the thermal decomposition temperature is up to 400 ℃, the limiting oxygen index is up to UL-94-V0 level, and the PPS material is hopeful to be developed into a light thermal protection article. However, the carbon layer is still at risk, mainly because the carbon layer is a thermoplastic material, although the carbon layer can be cyclized and crosslinked in the combustion process, the cyclized and crosslinked efficiency is low, and the formed carbon layer is loose in structure, so that the heat of the carbon layer rapidly permeates, and a large amount of pyrolysis products are separated out of a matrix to form smoke under the impact of the heat, so that the smoke is released more.
Therefore, it is necessary to improve the flame retardant and fire resistance of PPS and prepare polymer composites doped with PPS as a matrix.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a composite material with low combustion heat release and smoke release and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing a composite material having low heat release under combustion and smoke release, comprising the steps of:
s1, taking a G-Fe2O3 composite nano material with the content of 30% -85% of dried Fe2O3, and drying after secondary dispersion;
s2, mixing PPS, a silane coupling agent and the G-Fe2O3 composite nano material treated in the step S1 according to the content of the G-Fe2O3 composite nano material of 0.3-3% and the content of the silane coupling agent of 10-30% of the G-Fe2O3, and then carrying out melt blending at 200-350 ℃ to prepare a composite master batch;
s3, drying the composite master batch to enable the water content to be less than 50ppm;
s4, preparing the PPS/G-Fe2O3 composite material with low combustion heat release and smoke release by extrusion injection molding of the dried composite master batch, wherein the PPS/G-Fe2O3 composite material with low combustion heat release and smoke release manufactured by the step can be abbreviated as a composite material with low combustion heat release and smoke release.
As a further preferable technical scheme of the present invention, in step S1, the secondary dispersion includes the following specific operations:
firstly, dissolving a G-Fe2O3 composite nano material in a solvent to obtain a mixed solution;
then, carrying out ultrasonic dispersion on the mixed solution for 2-5h at the frequency of 20-50 Hz by an ultrasonic breaker;
finally, the sonicated suspension is centrifuged and the supernatant removed.
As a further preferable technical scheme of the invention, the solvent is one or a mixture of more of ethanol, water and acetone.
In a further preferable embodiment of the present invention, in step S1, the secondary dispersion is followed by drying with a freeze dryer for a drying time of not less than 24 hours.
As a further preferable embodiment of the present invention, the melt blending operation is performed by a twin screw extruder in step S2.
As a further preferable technical scheme of the invention, in the step S3, a drum drying device is adopted for drying treatment, and the process conditions in the drying process are as follows: firstly, heating to 95 ℃ at 10 ℃/h, preserving heat for 15h, then heating to 130 ℃ at 10 ℃/h, preserving heat for 15h, then heating to 160 ℃ at 10 ℃/h, preserving heat for 4h, and finally cooling to normal temperature at 25 ℃/h.
As a further preferable embodiment of the present invention, the temperature at the time of extrusion injection molding in step S4 is 300 to 350 ℃.
According to another aspect of the present invention, there is provided a composite material having low heat and smoke release from combustion, wherein the composite material is prepared by the method of any one of the above.
The composite material with low combustion heat release and smoke release and the preparation method thereof can achieve the following beneficial effects by adopting the technical scheme:
1) According to the invention, the G-Fe2O3 composite nano material with iron oxide loaded on the surface of graphene is adopted, and when the G-Fe2O3 composite nano material is positioned in a PPS matrix, fe2O3 has good dispersibility, and because the barriers of Fe2O3 cannot be mutually aggregated, the optimization of heat release performance is realized;
2) According to the PPS/G-Fe2O3 composite material prepared by the invention, when Fe2O3 is loaded on the surface of graphene and mixed with PPS, the graphitized structure of a carbon layer is further optimized, so that the thermal stability is remarkably improved, the thermal weight loss curve pyrolysis stage moves to a high temperature region, the carbon residue is increased, and the thermal and smoke barrier is facilitated;
3) Compared with pure PPS material, the PPS/G-Fe2O3 composite material prepared by the invention has the advantages that the combustion heat release and smoke release are obviously improved, the heat release rate, total heat release, smoke release rate and total smoke release are obviously reduced, and the PPS/G-Fe2O3 composite material is a light heat protection material with excellent performance.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a graph comparing the thermal stability of pure PPS material and the composite material prepared in example 2;
FIG. 2 is a graph comparing the heat of combustion release rate and the total heat release curve of pure PPS material and the composite material prepared in example 2;
FIG. 3 is a plot of smoke production rate and total smoke production for pure PPS material and the composite material prepared in example 2;
FIG. 4 is a graphical representation of the carbon residue of the pure PPS material and the composite material prepared in example 2 after combustion.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The invention will be further described with reference to the drawings and detailed description. The terms such as "upper", "lower", "left", "right", "middle" and "a" in the preferred embodiments are merely descriptive, but are not intended to limit the scope of the invention, as the relative relationship changes or modifications may be otherwise deemed to be within the scope of the invention without substantial modification to the technical context.
Both iron oxide and graphene can be introduced into the polymer through mixed doping, wherein the iron oxide has a good catalytic char formation effect, and is widely applied to researches on polymer combustion, such as good effects in PET and PVC systems, and the graphene can form a substance barrier in a polymer matrix by constructing a good barrier network, so that the combustion performance of the polymer is improved. Based on the principle, the invention provides a preparation method of a composite material with low combustion heat release and smoke release, iron oxide is loaded on the surface of graphene, the dispersibility of dopants in a PPS matrix is improved through secondary dispersion, and then the composite material is prepared through melt blending, extrusion and injection molding.
The present invention will be further described in detail below with reference to specific examples in order to enable those skilled in the art to better understand and realize the technical aspects of the present invention.
Example 1
S1, preparing a G-Fe2O3 composite nano material with the Fe2O3 content of 30 percent (the Fe2O3 content refers to the loading amount of Fe2O3 in the G-Fe2O3 composite nano material) by a high-temperature thermal reduction method, and precipitating the obtained G-Fe2O3 composite nano material in a freeze drying device for drying for 48 hours; the G in the G-Fe2O3 composite nanomaterial represents graphene, that is, the G-Fe2O3 composite nanomaterial refers to a composite nanomaterial formed by loading ferric oxide on the surface of graphene.
S2, dissolving the G-Fe2O3 composite nano material in ethanol, carrying out ultrasonic treatment for 5 hours at the frequency of 20Hz by an ultrasonic breaker, centrifuging the suspension after ultrasonic treatment, removing the supernatant, and drying in freeze drying equipment for 48 hours;
s3, mixing PPS, a silane coupling agent and the G-Fe2O3 composite nano material treated in the step S2 according to the content of the G-Fe2O3 composite nano material of 0.3 percent and the content of the silane coupling agent of 20 percent of the G-Fe2O3, and then carrying out melt blending granulation at 295 ℃ by a double-screw extruder to prepare composite master batch;
s4, transferring the composite master batch into drum drying equipment, heating to 95 ℃ at 10 ℃/h, preserving heat for 15h, continuously heating to 130 ℃ at 10 ℃/h, preserving heat for 15h, heating to 160 ℃ at 10 ℃/h, preserving heat for 4h, and finally drying by a process of cooling to normal temperature at 25 ℃/h.
S5, preparing the composite master batch treated by the S4 into a PPS/G-Fe2O3 composite material at 320 ℃ through extrusion injection molding.
Example 2
S1, preparing a G-Fe2O3 composite nano material with the Fe2O3 content of 83 percent (the Fe2O3 content refers to the loading amount of Fe2O3 in the G-Fe2O3 composite nano material) by a high-temperature thermal reduction method, and precipitating the obtained G-Fe2O3 composite nano material in a freeze drying device for drying for 48 hours;
s2, dissolving the G-Fe2O3 composite nano material in ethanol, carrying out ultrasonic treatment for 5 hours at the frequency of 20Hz by an ultrasonic breaker, centrifuging the suspension after ultrasonic treatment, removing the supernatant, and drying in freeze drying equipment for 48 hours;
s3, mixing PPS, a silane coupling agent and the G-Fe2O3 composite nano material treated in the step S2 according to the content of the G-Fe2O3 composite nano material of 1.8 percent and the content of the silane coupling agent of 25 percent of the G-Fe2O3, and then carrying out melt blending granulation at 295 ℃ by a double-screw extruder to prepare composite master batch;
s4, transferring the composite master batch into drum drying equipment, heating to 95 ℃ at 10 ℃/h, preserving heat for 15h, continuously heating to 130 ℃ at 10 ℃/h, preserving heat for 15h, heating to 160 ℃ at 10 ℃/h, preserving heat for 4h, and finally drying by a process of cooling to normal temperature at 25 ℃/h.
S5, preparing the composite master batch treated by the S4 into a PPS/G-Fe2O3 composite material at 320 ℃ through extrusion injection molding.
Example 3
S1, preparing a G-Fe2O3 composite nano material with the Fe2O3 content of 83 percent (the Fe2O3 content refers to the loading amount of Fe2O3 in the G-Fe2O3 composite nano material) by a high-temperature thermal reduction method, and precipitating the obtained G-Fe2O3 composite nano material in a freeze drying device for drying for 48 hours;
s2, dissolving the G-Fe2O3 composite nano material in ethanol, carrying out ultrasonic treatment for 5 hours at the frequency of 20Hz by an ultrasonic breaker, centrifuging the suspension after ultrasonic treatment, removing the supernatant, and drying in freeze drying equipment for 48 hours;
s3, mixing PPS, a silane coupling agent and the G-Fe2O3 composite nano material treated in the step S2 according to the content of the G-Fe2O3 composite nano material of 3%, wherein the content of the silane coupling agent is 20% of that of the G-Fe2O3, and then carrying out melt blending granulation at 295 ℃ by a double-screw extruder to prepare composite master batch;
s4, transferring the composite master batch into drum drying equipment, heating to 95 ℃ at 10 ℃/h, preserving heat for 15h, continuously heating to 130 ℃ at 10 ℃/h, preserving heat for 15h, heating to 160 ℃ at 10 ℃/h, preserving heat for 4h, and finally drying by a process of cooling to normal temperature at 25 ℃/h.
S5, preparing the composite master batch treated by the S4 into a PPS/G-Fe2O3 composite material at 320 ℃ through extrusion injection molding.
The PPS/G-Fe2O3 composite materials prepared in examples 1-3 were used as test groups, and the commercially pure PPS materials were used as control groups, and the combustion performance test (cone calorimetric analysis) was performed, and the data are shown in Table 1, wherein the pure PPS material was designated PPS for convenience of explanation, and the PPS/G-Fe2O3 composite material prepared in the present invention was designated PPS/G-Fe2O3.
TABLE 1 PHRR, THR, PSPR and TSP parameters for PPS and PPS/G-Fe2O3 nanocomposites
Analysis of the data in Table 1 shows that: the composite nano material prepared by loading Fe2O3 with graphene is doped in a PPS matrix,can effectively improve the combustion performance of PPS, and the Peak Heat Release Rate (PHRR) is 100.41Kw/m 2 Down to 5.12Kw/m 2 Total Heat Release (THR) is defined by 28.41MJ/m 2 Down to 0.58MJ/m 2 Peak smoke rate of 0.028m 3 The/s drops to 0.004m 3 Per second, the total smoke yield is 2.61m 3 Down to 0.43m 3 。
To further investigate the combustion performance of the composite material prepared according to the present invention, the following is an example of the preparation product of example 2, and the thermal stability studies were performed in combination with the pure PPS material of the control group, respectively, and fig. 1 to 4 are thermal weight loss curves of the pure PPS material and the PPS/G-Fe2O3 nanocomposite material of example 2 in nitrogen, and the data related thereto are shown in table 2.
TABLE 2 PPS and PPS/G-Fe 2 O 3 Thermal decomposition parameters in nanocomposite nitrogen
Referring to FIG. 1, which is a graph comparing the thermal stability of pure PPS material and the composite material prepared in example 2, the data are shown in Table 2, and it is found that G-Fe2O3 has a significant effect on the thermal stability of PPS in combination with FIG. 1 and Table 2. The temperature when the mass loss of pure PPS reaches 1% is 435 ℃, the temperature of the highest pyrolysis is 535 ℃, the temperature when the mass loss of the PPS/G-Fe2O3 composite material reaches 1% is 461 ℃, the temperature of the highest pyrolysis is 557 ℃, the temperature is 26 ℃ and 22 ℃ respectively higher than that of pure PPS, and the carbon residue is increased by about 3%. As can be seen from FIG. 1, the mass loss rate curve of PPS/G-Fe2O3 is significantly shifted to a high temperature region compared with pure PPS, the pyrolysis temperature is increased, and the peak value of the mass loss rate curve is significantly reduced, so that the pyrolysis is slowed down. The above indicated a significant improvement in thermal stability.
Referring to FIG. 2, a graph is shown showing the comparison of the heat of combustion release rate and the total heat release curve of the pure PPS material and the composite material prepared in example 2. The graph shows that the pure PPS has high heat release rate and high total heat release, and is easy to cause fire hazard, the peak value of the heat release rate of the PPS/G-Fe2O3 composite material is obviously slowed down, the total heat release amount is obviously reduced, the open flame time is obviously shortened, and the G-Fe2O3 can inhibit the heat release of combustion, so that the material has higher fireproof safety.
Referring to fig. 3, there is shown a plot of smoke rate and total smoke yield for pure PPS material and the composite material prepared in example 2. From the figure, the smoke release phenomenon during the combustion of pure PPS is quite remarkable. The peak value of the smoke production rate in the combustion is up to 0.028m < 3 >/s, the total smoke production amount is up to 2.61m < 3 >, and the high-risk hidden danger exists in practical application. The PPS/G-Fe2O3 composite material has lower values in the aspects of the smoke production rate and the total smoke production amount, the peak value of the smoke production rate is only 0.0053/s, the total smoke production amount is 0.061m3, and the good smoke suppression effect is shown.
Referring to fig. 4, G-Fe2O3 combines the good barrier of graphene and the efficient catalytic char formation of Fe2O3 to promote densification of the char layer structure, and the macroscopic char layer structure formed by combustion shows a dense structure, which inhibits heat release and smoke release.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (5)
1. A method for preparing a composite material having low heat and smoke release, comprising the steps of:
s1, taking G-Fe with the content of 30-85% of dry Fe2O3 2 O 3 Drying the composite nano material by using a freeze dryer after secondary dispersion, wherein the drying time is not less than 24 hours, and the G-Fe 2 O 3 G in the composite nanomaterial refers to graphene;
s2, taking PPS, a silane coupling agent and the G-Fe treated in the step S1 2 O 3 Composite nano material according to G-Fe 2 O 3 The content of the composite nano material is 0.3-3%, and the content of the silane coupling agent is G-Fe 2 O 3 Is mixed at 10-30% of the total weight of the mixture, and thenMelting and blending at 200-350 ℃ to prepare composite master batch;
s3, drying the composite master batch by adopting rotary drum drying equipment to ensure that the water content is less than 50ppm, wherein the process conditions in the drying process are as follows: firstly, heating to 95 ℃ at 10 ℃/h, preserving heat for 15h, then heating to 130 ℃ at 10 ℃/h, preserving heat for 15h, then heating to 160 ℃ at 10 ℃/h, preserving heat for 4h, and finally cooling to normal temperature at 25 ℃/h;
s4, preparing the dried composite master batch into PPS/G-Fe with low combustion heat release and smoke release through extrusion injection molding 2 O 3 A composite material;
in step S1, the secondary dispersion includes the following specific operations:
first, G-Fe 2 O 3 The composite nano material is dissolved in a solvent to obtain a mixed solution;
then, carrying out ultrasonic dispersion on the mixed solution for 2-5h at the frequency of 20-50 Hz by an ultrasonic breaker;
finally, the sonicated suspension is centrifuged and the supernatant removed.
2. The method for preparing a composite material with low combustion heat release and smoke release according to claim 1, wherein the solvent is one or more of ethanol, water and acetone.
3. The method for producing a composite material having low heat and smoke release according to claim 1, wherein the melt blending operation is performed by a twin screw extruder in step S2.
4. The method for preparing a composite material with low heat and smoke release according to claim 1, wherein the temperature at the time of extrusion injection molding in step S4 is 300-350 ℃.
5. A composite material having low heat and smoke release, wherein the composite material is prepared by the preparation method of any one of claims 1 to 4.
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| CN106243388A (en) * | 2016-07-27 | 2016-12-21 | 华南理工大学 | A kind of metal oxide-loaded nano-particle of graphite phase carbon nitride with flame-retardant smoke inhibition function and preparation method and application |
| CN112795191A (en) * | 2020-12-29 | 2021-05-14 | 上海日之升科技有限公司 | High CTI polyphenylene sulfide composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243388A (en) * | 2016-07-27 | 2016-12-21 | 华南理工大学 | A kind of metal oxide-loaded nano-particle of graphite phase carbon nitride with flame-retardant smoke inhibition function and preparation method and application |
| CN112795191A (en) * | 2020-12-29 | 2021-05-14 | 上海日之升科技有限公司 | High CTI polyphenylene sulfide composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 刘世乡 ; 杨俊龙 ; 黄亚江 ; 李光宪 ; .石墨烯在聚合物阻燃与防老化应用中的研究进展.中国材料进展.(第11期),第843-848页. * |
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