首页 | 官方网站   微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 46 毫秒
1.
Iron alginate is chosen as an eco-friendly synergist to improve the flame retardancy, smoke suppression, and mechanical properties of epoxy resin/ammonium polyphosphate composites (EP/APP). The suitable additive amount of iron alginate further enhances the char-forming ability in the higher-temperature range and flame retardancy of EP/APP. EP/APP9.0-iron alginate1.0 retains a char residue of 33.3% at 700 °C and obtains a limiting oxygen index value of 28.4% and vertical burning test (UL-94) V-0 rating, while EP/APP10 has no UL-94 rating. The burning behaviors of EP/APP9.0-iron alginate1.0 are also suppressed; and the total smoke production value is much lower than that of EP/APP10. EP/APP9.0-iron alginate1.0 releases less smoke and flammable fragments. The suitable additive amount of iron alginate boosts the mechanical properties of EP/APP, while APP destroys the mechanical properties of EP. Therefore, the addition of suitable amount of iron alginates can further reduce the fire hazard, and improve the mechanical properties of EP/APP composites.  相似文献   

2.
In this work, an efficient approach to improving the fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene (PP) composites is developed via incorporating functionalized sepiolite (organo‐modified sepiolite [ONSep]). The PP composites with different amounts of intumescent flame retardants and ONSep were prepared by melt compounding. The morphology, thermal behavior, fire retardancy, smoke suppression, and mechanical property of flame‐retardant PP composites were studied. The results indicate an appropriate amount of ONSep in the flame‐retardant PP composites can increase thermal degradation temperature and char formation as well as a reduction of the peak heat release rate and total heat release; moreover, the addition of ONSep significantly decreases the CO production, total smoke production, smoke production rate, and smoke temperature. Simultaneously, the impact strength of intumescent flame‐retardant PP composite is also maintained by introducing an appropriate amount of ONSep as compared with that without ONSep.  相似文献   

3.
A novel functionalized graphene oxide (f‐GO) decorated with phosphorus/nitrogen (P/N)‐containing molecules is fabricated using a facile water‐based procedure. The chemical structure and micro‐morphology are well characterized by a combination of experimental and theoretical methods. Reactive force field‐based molecular dynamics simulations reveal at the atomic level that the GO sheets are successfully functionalized with P‐N flame‐retardant molecules by means of hydrogen bonds. Subsequently, f‐GO with extremely low loading is introduced into epoxy resin (EP) for reducing its flammability. Thermogravimetric analysis suggests that f‐GO significantly reduces the maximum mass loss rate of EP and enhances the char‐yield during heating. Combined with the results of a microscale combustion calorimeter and limiting oxygen index, EP/f‐GO2 shows better flame retardancy than the other nanocomposites. Furthermore, the presence of 2 wt% f‐GO substantially reduces the fire hazard of EP, resulting in 29.3% decline in the peak heat release rate, as well as 73% and 65% reduction in total smoke production and rate of smoke release, respectively, according to cone calorimetric tests. Based on the analyses of the char layers, f‐GO is determined to promote the formation of a more protective phosphorus‐containing char barrier for EP during combustion, indicating an effective condensed phase flame‐retardant mechanism.  相似文献   

4.
Diatomite (DIA) particles are commonly employed as flame-retardant additives for polymers, yet their intrinsic inefficiency requires substantial quantities for optimal efficacy. To address this issue, we proposed a novel approach involving the microencapsulation of DIA with polyethylene glycol phosphate (PEGP) to enhance the flame retardancy of epoxy resin (EP). Characterization of the prepared DIA@PEGP utilized scanning electron microscopy with energy-dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The resulting EP composite, DIA@PEGP-4/EP, achieved a limiting oxygen index of 33.2% and achieved a V-0 level in vertical combustion tests. Compared to EP, DIA@PEGP-4/EP demonstrated significantly improved fire performance, with 38.6%, 47.8%, 25.0%, 41.3%, and 60.4% reduction in peak heat release rate, total heat release, peak smoke production rate, total smoke production, and CO yield. Furthermore, the highest FPI value of 0.080 m2·s/kW for DIA@PEGP-1/EP and the lowest FGI value of 8.734 kW/m2·s for DIA@PEGP-4/EP, indicate that the incorporation of DIA@PEGP into EP enhances its fire safety. The flame retardancy mechanism of DIA@PEGP-4 involves the formation of a phosphorus-containing aromatic carbon layer during EP char formation, capturing radicals in the gas phase during combustion.  相似文献   

5.
Previously, it was reported that epoxy resin (EP) filled with ammonium polyphosphate (APP) and copper (I) oxide (Cu2O) at a mass ratio of 8/2 (APP8-Cu2O2) as a self-intumescent system demonstrated promising fire retardancy. To further improve the flame retardant efficiency, the possibility of expandable graphite (EG) as an effective synergist for the self-intumescent EP system was revealed by limiting oxygen index (LOI) test. The results showed that the incorporation of EG increased the LOI value of EP/APP8-Cu2O2 obviously. The highest LOI value was obtained at the EG/APP8-Cu2O2 mass ratio of 3/7, indicating the optimal synergistic effect being achieved. Furthermore, UL-94 test results showed that the excellent synergistic effect resulted in the addition of 13 wt% EG/APP8-Cu2O2 of 3/7 not only endowed EP a relatively high LOI value of 34.3%, but also made it pass UL-94 V-0 rating. Moreover, the main fire hazard parameters obtained from cone calorimeter tests, such as peak heat release rate, total smoke production, and peak CO production were reduced 40.3%, 30.3%, and 46.2%, respectively by the combination effect of EG/APP8-Cu2O2 with mass ratio of 3/7, suggesting the excellent improvement in the fire safety of EP significantly. Finally, a possible action mode, which would be beneficial for developing other flame retardant polymers with high fire safety, was proposed.  相似文献   

6.
Ultrathin nickel phenylphosphate (NiPP) nanosheets with layered structure are successfully synthesized through a mixed solvothermal method. The results indicate that NiPP is Ni(O3PC6H5)·H2O and has good thermal stability. To ameliorate the thermal stability and flame ratardancy of epoxy resin (EP), EP/NiPP nanocomposites are prepared by incorporating NiPP into EP matrix. The results show that adding NiPP can availably enhance thermal stability at high temperature due to the remarkable catalytic char performance of NiPP, and the residues yield of EP/NiPP nanocomposites with 6 wt% NiPP is 24.1% while the pure EP had only 14.2% at 700°C. In contrast with pure EP, the peak heat release rate, total heat release, smoke production rate, CO production, and CO2 production of EP/6wt%NiPP nanocomposites reduced by 35.2%, 20.2%, 27.1%, 45.8%, and 35.5%. The synergistic effect of catalytic char performance and fire retardancy of NiPP make the EP/NiPP nanocomposites possess prominent flame retardancy, smoke suppression, and thermal stability.  相似文献   

7.
To improve the compatibility and flame retardance of kaolinite (Kaol) in polymeric materials, ammonium dihydrogen phosphate (ADP) was intercalated into kaolinite to obtain a novel intercalated kaolinite (K-ADP) for enhancing thermal stability, flame retardance, smoke suppression, and mechanical performance of epoxy resins (EPs). The results show that the presence of K-ADP exerts a more positive effect on reducing the heat release and smoke generation of EPs than the same addition of Kaol. Condensed phase analysis shows that EP/K-ADP composite generates more aromatic cross-links in the condensed phase to reinforce the compactness and intumescence of char compared to EP/Kaol composite. Especially, 5 wt% K-ADP confers a 43.7% reduction in peak heat release rate value and a 36.3% reduction in peak smoke production rate value to EP. Toxic gases analysis shows that K-ADP conduces to inhibiting the release of combustible gases including isocyanates and aromatic volatiles, and generating incombustible gases including ammonia and carbon dioxide to reduce the intensity of EP combustion. The mechanical test shows that K-ADP imparts less adverse impact on mechanical behavior to EP composites than Kaol due to the good dispersion and compatibility between K-ADP with EP matrix.  相似文献   

8.
Traditional curing agents have only a single property, while traditional synthetic organic flame‐retardant hardeners often show poor tolerance to oxidants, strongly acidic or alkaline reagents, and organic solvents and have toxicity problems. Here, a novel and multifunctional flame‐retardant curing agent of the inorganic substrate multifunctional curing agent of the inorganic substrate (FCIN) was proposed first and successfully prepared, and then an intrinsically flame‐retardant epoxy resin (EP) was prepared by covalently incorporating FCIN nanoparticles (FCINs) into the EP. The curing behavior of the FCINs was investigated, showing that FCIN/EP expresses a higher global activation energy than tetraethylenepentamine (TEPA)/EP and that the FCINs had strong interfacial adhesion to the EP matrix. Additionally, the FCINs were well dispersed and provided a remarkable improvement in mechanical and flame‐retardant properties of the intrinsically flame‐retardant EP. With the incorporation of 9 wt % FCINs into the EP, dramatic enhancements in the strength, modulus under bending, and toughness (~36%, ~109%, and ~586%, respectively) were observed, along with 85.2%, 46.4%, 98.3%, and 77.26% decreases in the peak heat release rate, total heat release, smoke production rate peak, and total smoke production, respectively, with respect to that of TEPA/EP. The mechanisms of its flame‐retardant, smoke‐suppression, and failure behaviors were investigated. The development of this unconventional, multifunctional flame‐retardant curing agent based on an inorganic substrate showed promise for enabling the preparation of a variety of new high‐performance materials (such as intrinsically flame‐retardant EP and functional modified polyesters). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46410.  相似文献   

9.
DOPO based flame retardants demonstrate exceptional flame retardancy efficiency when applied to epoxy resins. However, the crosslinking degree of epoxy resin may decrease due to the addition of DOPO, leading to a deterioration in flame retardancy and mechanical properties. Herein, a reactive DOPO derivative flame retardant 6-((1H-benzo[d]imidazol-2-yl) amino) dibenzo oxaphosphinine 6-oxide (BADO) was successfully synthesized, which contains multiple reactive sites, thus ensuring a higher degree of crosslinking in the system. As a result, the modified epoxy resin exhibits excellent flame retardancy. The limiting oxygen index value of the modified epoxy resins increased from 19.8% to 29.7% by adding 7.5 wt% BADO, and its UL-94 test passed V-0. Flame retardancy mechanism analysis reveals that BADO exhibits both gas-phase and condensed-phase flame retardant effects. In particular, the formation of a porous inside-char layer is a significant factor in reducing smoke release. The 7.5% BADO/EP composite exhibited a 43.2% reduction in total smoke production and a 43.6% reduction in total smoke rate compared to neat epoxy resins (EP). Furthermore, the addition of BADO slightly deteriorates the mechanical properties of the modified epoxy resin.  相似文献   

10.
A high-efficiency DOPO-based reactive flame retardant (DPE) with bi-hydroxyl was successfully synthesized via reacting DOPO with imine obtained from the condensation of ethanolamine and 1,4-phthalaldehyde, and used as co-curing agent to improve the fire safety of epoxy resin (EP). Its chemical structure was characterized by Fourier transform infrared (FTIR) spectra, 1H, 31P nuclear magnetic resonance (NMR) spectra and elemental analysis. The curing behavior, thermal properties, flame-retardant properties of EP/DPE systems were investigated. The results revealed that DPE slightly decreased the glass transition temperature (Tg), but accelerated the curing cross-linking reaction of EP. Furthermore, DPE decreased thermal degradation rate of epoxy matrix and promoted the formation of residual char at high temperature. After adding DPE, the flame retardant of epoxy thermosets was greatly improved. Especially, the thermoset modified with 5 wt% DPE achieved limiting oxygen index (LOI) value of 33.6% and V-0 rating in UL-94 test, demonstrating the highly efficient flame retardancy. While its peak heat release rate (PHRR), total heat release (THR) and total smoke production (TSP) were respectively decreased by 32.6%, 17.8%, and 13.9% compared with neat EP. Moreover, the research on flame retardant mechanism disclosed that DPE played dual flame-retardant effect in the gaseous and condensed phases.  相似文献   

11.
In this article, a novel flame retardant (coded as BNP) was successfully synthesized through the addition reaction between triglycidyl isocyanurate, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and phenylboronic acid. BNP was blended with diglycidyl ether of bisphenol‐A to prepare flame‐retardant epoxy resin (EP). Thermal properties, flame retardancy, and combustion behavior of the cured EP were studied by thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the flame retardancy and smoke suppressing properties of EP/BNP thermosets were significantly enhanced. The LOI value of EP/BNP‐3 thermoset was increased to 32.5% and the sample achieved UL94 V‐0 rating. Compared with the neat EP sample, the peak of heat release rate, average of heat release rate, total heat release, and total smoke production of EP/BNP thermosets were decreased by 58.2%–66.9%, 27.1%–37.9%, 25.8%–41.8%, and 21.3%–41.7%, respectively. The char yields of EP/BNP thermosets were increased by 46.8%–88.4%. The BNP decomposed to produce free radicals with quenching effect and enhanced the charring ability of EP matrix. The multifunctional groups of BNP with flame retardant effects in both gaseous and condensed phases were responsible for the excellent flame retardancy of the EP/BNP thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45291.  相似文献   

12.
Ammonium polyphosphate (APP)–polystyrene (PSt) core–shell microspheres (CSPs) were synthesized via in situ radical polymerization. The core–shell structure was confirmed by transmission electron microscope (TEM). The results of optical contact angle measurements demonstrated a significant improvement in hydrophobicity of the modified APP. The obtained APP–PSt CSPs were added into epoxy (EP) system with various loadings. Effects of CSP on flame retardancy, thermal properties, heat release rate (HRR), smoke production, and mechanical properties of EP/CSP composites were investigated by limiting oxygen index (LOI), UL‐94 tests, thermogravimetric analysis (TGA), cone calorimeter, and tensile test. LOI and UL‐94 indicated that CSP remarkably improved the flame retardancy of EP composites. TGA showed that the initial decomposition temperature and the maximum‐rate decomposition temperature decreased, whereas residue yields at high temperature increased with the incorporation of microspheres. Cone calorimetry gave evidence that HRR, peak release rate, average HRR, and smoke production rate of EP/CSP composites decreased significantly. The morphology of char residues suggested that CSP could effectively promote EP to form high‐quality char layer with compact outer surface and swollen inner structure. Tensile strength of EP was enhanced with the addition of CSP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40218.  相似文献   

13.
Epoxy resin (EP) is extremely flammable, and smoke release during combusting is considered toxic and harmful for human health. Mesoporous materials offer reliable desorption performance due to their large specific surface area. Therefore, the construction of mesoporous nanocomposites is a novel method for enhanced smoke suppression effect of EP. In this work, zinc hydroxystannate (ZHS)‐mesoporous silica (SBA‐15 and MCM‐41) modified reduced graphene oxide (RGO) is successfully prepared and used to enhance the fire safety of EP. SBA‐15‐RGO‐ZHS/EP exhibits the lowest total smoke production (22.8 m2) and peak heat release rate (416 kW m?2), which are reduced by 55% and 37% compared with pure EP, respectively. Furthermore, the effect of mesoporous nanoparticles is also investigated. Apparently, the smoke suppression effect and flame retardancy of SBA‐15‐RGO‐ZHS/EP is even more remarkable than that of MCM‐41‐RGO‐ZHS/EP, which indicates that the pore size and structure of mesoporous are important factors for reducing the smoke toxicity of EP. Finally, it is verified that its enhanced fire safety is attributed to the synergistic action of physical barrier properties of RGO, “labyrinth” effect of SBA‐15, and catalytic ability of ZHS.  相似文献   

14.
将含镍金属有机框架材料(Ni-MOF)与焦磷酸哌嗪(PPAP)复配后添加到环氧树脂(EP)中,通过极限氧指数(LOI)、垂直燃烧(UL 94)及锥形量热(CONE)测试研究了材料的阻燃性能及烟释放行为。结果表明,添加6%(质量分数,下同)的PPAP时,材料的LOI值为27.9%,垂直燃烧测试通过了UL 94 V-0级;当PPAP与Ni-MOF以质量比99∶1混合,总添加量为5%时,材料的LOI值达到29.3%并通过了UL 94 V-0级;极少量Ni-MOF的加入,有效提高了材料的阻燃效率。CONE测试表明,在相同阻燃剂添加量下,EP/PPAP/Ni-MOF材料的热释放速率、总热释放量、烟释放速率及总烟释放量,与EP/PPAP材料相比均得到了明显降低;Ni-MOF的引入,降低了材料的燃烧强度,减少了烟气的释放;Ni离子与PPAP受热分解形成的磷酸及多聚磷酸发生交联,将更多的磷留在了凝聚相中,促进了材料形成更加丰富、强度更高的炭层,有效抑制EP燃烧过程中热量和烟气的释放,从而提高了EP材料的火安全性能。  相似文献   

15.
To reduce the flammability of epoxy resin (EP), a flame retardant (designated as D-POSS) containing diphenylphosphinyl and polyhedral oligomeric silsesquioxane (POSS) was constructed by aminopropyl-isobutyl POSS and diphenylphosphinyl chloride. The chemical structure of D-POSS was fully characterized, then it was used to enhance the flame retardancy of EP. When the flame-retardant EP composite contained 4 wt% D-POSS, its limiting oxygen index value was 29.0% and it achieved UL 94 V-1 rating. Also, its peak of heat release rate (pk-HRR), total heat release (THR) and total smoke production were decreased by 35.3%, 30.3%, and 38.3%, respectively. Moreover, the results from cone calorimeter disclosed that diphenylphosphinyl group and POSS group in D-POSS showed a strong synergistic effect in inhibiting pk-HRR, THR, and smoke production, promoting the charring formation of EP material, and forming an intumescent char layer. Additionally, the theoretical THR reduction of flame-retardant EP composite was calculated by the equation deduced from the standard, and it was almost same with the practical THR reduction. Notably, some silicon oxide enriched on the residue's surface. The phenomenon led to form a double-layer residue that consisted of white yarn-like outer char and normal intumescent inner char. This double-layer residue was contributed to enhance EP composite's flame retardancy.  相似文献   

16.
以来自自然界储量第二的木质素作为膨胀型阻燃剂的基体,通过接枝氮、磷元素成功合成碳源、酸源、气源三位一体的木质素基膨胀型阻燃剂(Lig-T),实现了良好的阻燃性能。将Lig?T按照不同含量添加到环氧树脂(EP)中制备EP/Lig-T复合材料,以锥形量热测试考察复合材料的热稳定性能和阻燃性能,并重点考察复合材料在接近真实火灾事故时的热释放和烟释放规律。结果表明,当Lig-T含量为20 %(质量分数,下同)时,复合材料的热释放速率峰值为1 374 kW/m2、热释放总量为41.63 MJ/m2、烟释放总量为1 634 m2/m2,与EP参比试样的数值相比,均呈现下降的趋势,燃烧结束的残炭率从4.26 %增至10.01 %。基于气相和凝聚相的协效阻燃机理,木质素作为膨胀型阻燃剂的碳源使得复合材料在高温条件下具备更好的成炭效果,在燃烧过程中形成稳定且致密的炭层结构,在实现高效阻燃的同时减少有毒烟气的释放,降低火灾的危害。  相似文献   

17.
For effectively strengthening the comprehensive properties of intumescent flame-retardant epoxy resins (EPs), a microencapsulating γ-Fe2O3 by polypyrrole (PPy) named PPy-Fe2O3 was synthesized and used as a synergist to simultaneously enhance the flame retardancy, smoke toxicity suppression and mechanical strength of EP composites containing diaminodiphenylmethane modified ammonium polyphosphate (DDP). The results demonstrate that the mixture of PPy-Fe2O3 and DDP exhibits a surprising synergistic effect on strengthening the comprehensive properties of EP composites. Specifically, EP composite containing 0.2 wt% PPy-Fe2O3 and 9.8 wt% DDP achieves the UL94 V-0 rating with a limiting oxygen index (LOI) value of 35.5%, while 10 wt% DDP only imparts a UL94 V-1 rating and a LOI value of 34.0% to EP. Furthermore, 0.2 wt% PPy-Fe2O3 shows a 11.0% reduction in peak smoke production rate and a 12.3% reduction in peak heat release rate of the EP/DDP system. The enhanced fire security of EP/DDP/PPy-Fe2O3 is attributed to the formation of more phosphorus-rich structures retained in the char, thus reducing the release of harmful gases including NH3, CO, and CO2, and generating more incombustible gases including H2O to weaken burning intensity. Meanwhile, the satisfactory compatibility of PPy-Fe2O3 with epoxy matrix imparts a superior mechanical strength to EP composites.  相似文献   

18.
In order to eliminate the negative effect of traditional 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) -based flame retardants on heat resistance, mechanical properties, and curing process of epoxy resin (EP), a DOPO derivative (DST) constructed by sulfaguanidine and thiophene is designed and used as co-cured agent for EP. Compared with EP, the maximum decrease of glass transition temperature (Tg) in all EP/DST samples is less than 5%, indicating EP modified by DST maintains good heat resistance. Encouragingly, DST shows satisfactory flame-retardant efficiency and excellent smoke suppressing effects. EP containing barely 5 wt% of DST (P content: 0.37 wt%) achieves a UL-94 V-0 rating and 32.8% limited oxygen index (LOI) value. Its peak heat release rate (PHRR), total heat release (THR), and total smoke production (TSP) are also decreased by 31.2%, 18.8%, and 30.2% . Further, DST significantly improves mechanical properties of the EP/DDM/DST system. The tensile strength and modulus increase by 37.2% and 14.6%, respectively, as DST content is 7.5 wt%. It is revealed that DST has positive quenching and diluting effects in the gas phase, as well as promoting the formation of a compact char layer in the condensed phase.  相似文献   

19.
In this work, two cross-linked Salen-based polyphosphazenes (Salen-PZNs: Salen-PZN-1 microspheres and layered Salen-PZN-2), which contains Salen-Schiff base and phosphazene components, were synthesized. The results showed that the peak heat release rate and total smoke production of 3% Salen-PZN-1/epoxy resin (EP) (3 wt% addition) were reduced by 23.8% and 87.3%, respectively. Meanwhile, after introducing the layered Salen-PZN-2 into EP, efficient flame resistance was obtained. The results of thermogravimetric analysis/infrared spectrometry proved that the harmful gasses of 5% Salen-PZN-1/EP composites were reduced during the combustion. The possible flame retardancy mechanism was considered to be the synergy of phosphate group catalysis, release of nitrogen-containing noncombustible gasses and gas phase quenching. Therefore, this work provides a method for preparing polymers with highly efficient flame-retardant properties.  相似文献   

20.
王娜  尤家奇  毕晴晴  姚红蕊  张静  姜岩 《精细化工》2020,37(10):2125-2131
用反相乳液法,以卡拉胶(KC)为壳材,聚磷酸铵(APP)和二氧化锰(MnO2)为芯材,制备了KC包覆APP/MnO2阻燃剂(KC-FR)。通过FTIR、 XRD、 SEM和 EDS对KC-FR进行了表征。结果表明:卡拉胶已成功包覆APP和MnO2,合成的样品具有微胶囊结构。将KC-FR应用于水性环氧树脂(EP)中,考察KC、APP、MnO2 三者质量比对EP阻燃、抑烟性能的影响。用极限氧指数(LOI)、垂直燃烧(UL-94)和锥形量热(CCT)测试了涂层的阻燃、抑烟性能。结果发现,当KC/APP/MnO2的质量比为2∶1∶1,并且在EP中添加量为20%时,制备的阻燃涂层EP2的LOI达到29.1%,UL-94达到V-0级,表现出较好的阻燃性能。EP2相比于其它涂层热释放峰值(pHRR)、热释放总量(THR)和烟释放总量(TSP)最低,相比于EP0分别下降了42%、37%和46%,表现出较好的抑烟性能。另外,热重分析(TGA)测试结果显示EP2在800℃残炭量(W800)为33%,表明KC-FR具有促进EP成炭的功能。通过SEM对残炭表面分析发现,EP2表面炭层更加致密,这表明KC-FR对促进形成稳定并且致密的炭层起到至关重要的作用。  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司    京ICP备09084417号-23

京公网安备 11010802026262号