CN112210168A - 柔性复合吸声材料、制备方法及其应用 - Google Patents
柔性复合吸声材料、制备方法及其应用 Download PDFInfo
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- CN112210168A CN112210168A CN202011139503.9A CN202011139503A CN112210168A CN 112210168 A CN112210168 A CN 112210168A CN 202011139503 A CN202011139503 A CN 202011139503A CN 112210168 A CN112210168 A CN 112210168A
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- flexible composite
- sound absorption
- composite sound
- absorption material
- aluminum hydrotalcite
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 44
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 62
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 62
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 62
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 8
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- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
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- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 claims description 3
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- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 3
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- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开柔性复合吸声材料、制备方法及其应用,包括以下质量份原料:聚丙烯100份、乙烯‑醋酸乙烯共聚物25~35份、改性层状镁铝水滑石20~25份、二氧化硅气凝胶5~10份、发泡剂4~8份、乙烯基硅烷偶联剂0.5~2份、阻燃剂0.5~1份、抗老化剂0.5~1份;所述改性层状镁铝水滑石的粒径为1~10μm,层间距为是由碳源溶液浸渍后,干燥、炭化而成;所述二氧化硅气凝胶的粒径为0.5~10μm;柔性复合吸声材料在隔音装饰板中的应用。本发明首次利用改性层状镁铝水滑石、二氧化硅气凝胶协同掺杂改性,联合发泡剂造孔,降低柔性复合吸声材料的密度,提高其比表面积,且泡孔结构细密均匀,收缩率小,闭孔型和开孔型孔结构兼有,吸声范围广,显著提高了吸声系数。
Description
技术领域
本发明属于吸声材料制备技术领域,具体涉及柔性复合吸声材料、制备方法及其应用。
背景技术
吸声材料借自身的多孔性、薄膜作用或共振作用而对入射声能具有吸收作用,与周围的传声介质的声特性阻抗匹配,使声能无反射地进入吸声材料,并使入射声能绝大部分被吸收。吸声材料按吸声机理分为:(1)靠从表面至内部许多细小的敞开孔道使声波衰减的多孔材料,以吸收中高频声波为主,如有纤维状聚集组织的各种有机或无机纤维及其制品以及多孔结构的开孔型泡沫塑料和膨胀珍珠岩制品;(2)靠共振作用吸声的材料,如吸收中频的闭孔型泡沫塑料,吸收低中频的塑料膜或布、帆布、漆布和人造革等膜状材料,吸收低频的胶合板、硬质纤维板、石棉水泥板和石膏板等板状材料,吸收中频的穿孔板。上述吸声材料本质上都是利用多孔型或闭孔型泡孔结构进行吸声隔音,而关于微观层状结构物质在吸声材料中的应用尚未被现有专利和文献所公开,仍是国内建筑材料行业的空白,因此,开发一种利用层状化合物吸声降噪的新类型柔性复合吸声材料具有开拓性意义。
本发明首次将碳层改性层状镁铝水滑石用于吸声材料领域,利用具有粘性的碳源溶液浸渍层状镁铝水滑石,碳源插入镁铝水滑石层间,同时,在炭化过程中,碳源热解产生CO、H2O(g)、NH3等气体,热解气体进一步充盈扩大镁铝水滑石层间距,使层状结构的间距膨胀增大,同时,水滑石层间及表面碳源炭化后,在其表面形成大量不规则、不均一的碳层微孔和中孔结构,声音的本质是波,在具有层状结构及多孔结构的镁铝水滑石介质中发生多次传播,在多次传播过程中,声波不断衰减,进而达到吸声降噪的作用;此外,镁铝水滑石还能提高吸声材料的硬度、机械强度及阻燃性、耐火性。
发明内容
针对现有技术的不足之处,本发明的目的在于提供柔性复合吸声材料、制备方法及其应用。
本发明的技术方案概述如下:
柔性复合吸声材料,包括以下质量份原料:
所述二氧化硅气凝胶的粒径为0.5~10μm。
优选的是,所述碳源溶液中碳源浓度为0.2~2%。
优选的是,所述碳源溶液为壳聚糖溶液、羧甲基纤维素溶液、聚乙烯醇溶液、葡甘聚糖溶液、淀粉分散液中的一种。
优选的是,所述发泡剂由碳酸氢铵、对甲苯磺酰肼、4,4'-氧代双苯磺酰肼按照1:(0.5~1.5):(0.5~2)的质量比混合而成。
优选的是,所述乙烯基硅烷偶联剂包括乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三乙酰氧基硅烷中的一种或多种。
优选的是,所述阻燃剂为聚硅硼氧烷。
优选的是,所述抗老化剂包括2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、2-(2-羟基-3,5-二叔丁基苯基)5-氯代苯并三唑、2-羟基-4-辛氧基二苯甲酮中的一种或多种。
本发明还提供柔性复合吸声材料的制备方法,包括以下步骤:
S1:制备改性层状镁铝水滑石:将层状镁铝水滑石加入碳源溶液中,控制固液比为1g/5mL,超声浸渍1~3h,固液分离后,80℃干燥固化,于氮气气氛下,220~280℃炭化6~12h,即得改性层状镁铝水滑石;
S2:制备混合料A:将改性层状镁铝水滑石、二氧化硅气凝胶混合均匀后,加入乙烯基硅烷偶联剂,搅拌处理0.5~1h,得到混合料A;
S3:制备熔体B:将聚丙烯与乙烯-醋酸乙烯共聚物混合后,165~200℃加热熔融2~3h,得到熔体B;
S4:制备预成品:165~180℃下,将混合料A加入熔体B中,搅拌均匀,再与阻燃剂、抗老化剂混合均匀后,并迅速降温至155~165℃,加入发泡剂并注入模具中,模压发泡成型15~30min,脱模、冷却后,得到预成品;
S5:制备柔性复合吸声材料:110~130℃下,将预成品二次发泡3~6h,即得所述柔性复合吸声材料。
本发明还进一步提供柔性复合吸声材料在隔音装饰板中的应用。
本发明的有益效果:
1、本发明首次将碳层改性层状镁铝水滑石用于吸声材料领域,利用具有粘性的碳源溶液浸渍层状镁铝水滑石,碳源插入镁铝水滑石层间,同时,在炭化过程中,碳源热解产生CO、H2O(g)、NH3等气体,热解气体进一步充盈扩大镁铝水滑石层间距,使层状结构的间距膨胀增大,同时,水滑石层间及表面碳源炭化后,在其表面形成大量不规则、不均一的碳层微孔和中孔结构,声音的本质是波,在具有层状结构及多孔结构的镁铝水滑石介质中发生多次传播,在多次传播过程中,声波不断衰减,进而达到吸声降噪的作用;此外,镁铝水滑石还能提高吸声材料的硬度、机械强度及阻燃性、耐火性。
2、本发明首次利用改性层状镁铝水滑石、二氧化硅气凝胶协同掺杂改性,联合发泡剂造孔手段,降低柔性复合吸声材料的密度,提高其比表面积,且泡孔结构细密均匀,收缩率小,闭孔型和开孔型泡孔结构兼有,可同时吸收低中频和中高频声波,吸声范围广,显著提高了吸声系数。
3、本发明制备出的柔性复合吸声材料具有良好的隔音降噪、保温隔热作用,可作室内装饰板使用。
4、本发明以聚硅硼氧烷作为阻燃剂,在高温燃烧条件,迁移到柔性复合吸声材料表面的聚硅硼氧烷裂解生成含有Si键、Si-C键的无机隔氧保护碳层,阻止了燃烧热解产物外逸,又抑制了聚丙烯、乙烯-醋酸乙烯共聚物的热分解,达到阻燃、低烟和低毒等效果。
附图说明
图1为柔性复合吸声材料制备方法流程图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
实施例1
柔性复合吸声材料,包括以下质量份原料:
2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑0.5份;
所述改性层状镁铝水滑石的粒径为1~10μm,是由碳源溶液浸渍后,干燥、炭化而成;
所述二氧化硅气凝胶的粒径为0.5~10μm。
柔性复合吸声材料的制备方法,包括以下步骤:
S1:制备改性层状镁铝水滑石:将层状镁铝水滑石加入0.2%羧甲基纤维素溶液中,控制固液比为1g/5mL,超声浸渍1h,固液分离后,80℃干燥固化,于氮气气氛下,220℃炭化6h,即得改性层状镁铝水滑石;
S2:制备发泡剂:将碳酸氢铵、对甲苯磺酰肼、4,4'-氧代双苯磺酰肼按照1:0.5:0.5的质量比混合均匀,得到发泡剂;
S3:制备混合料A:将改性层状镁铝水滑石、二氧化硅气凝胶混合均匀后,加入乙烯基硅烷偶联剂,搅拌处理0.5h,得到混合料A;
S4:制备熔体B:将聚丙烯与乙烯-醋酸乙烯共聚物混合后,170℃加热熔融2~3h,得到熔体B;
S5:制备预成品:165℃下,将混合料A加入熔体B中,搅拌均匀,再与阻燃剂、抗老化剂混合均匀后,并迅速降温至155℃,加入发泡剂并注入模具中,模压发泡成型15min,脱模、冷却后,得到预成品;
S6:制备柔性复合吸声材料:110℃下,将预成品二次发泡3h,即得所述柔性复合吸声材料。
实施例2
柔性复合吸声材料,包括以下质量份原料:
2-(2-羟基-3,5-二叔丁基苯基)5-氯代苯并三唑0.8份;
所述改性层状镁铝水滑石的粒径为1~10μm,是由碳源溶液浸渍后,干燥、炭化而成;
所述二氧化硅气凝胶的粒径为0.5~10μm。
柔性复合吸声材料的制备方法,包括以下步骤:
S1:制备改性层状镁铝水滑石:将层状镁铝水滑石加入1%聚乙烯醇溶液中,控制固液比为1g/5mL,超声浸渍2h,固液分离后,80℃干燥固化,于氮气气氛下,250℃炭化8h,即得改性层状镁铝水滑石;
S2:制备发泡剂:将碳酸氢铵、对甲苯磺酰肼、4,4'-氧代双苯磺酰肼按照1:1:1.5的质量比混合均匀,得到发泡剂;
S3:制备混合料A:将改性层状镁铝水滑石、二氧化硅气凝胶混合均匀后,加入乙烯基三乙氧基硅烷,搅拌处理1h,得到混合料A;
S4:制备熔体B:将聚丙烯与乙烯-醋酸乙烯共聚物混合后,180℃加热熔融3h,得到熔体B;
S5:制备预成品:170℃下,将混合料A加入熔体B中,搅拌均匀,再与聚硅硼氧烷、2-(2-羟基-3,5-二叔丁基苯基)5-氯代苯并三唑混合均匀后,并迅速降温至160℃,加入发泡剂并注入模具中,模压发泡成型30min,脱模、冷却后,得到预成品;
S6:制备柔性复合吸声材料:120℃下,将预成品二次发泡6h,即得所述柔性复合吸声材料。
实施例3
柔性复合吸声材料,包括以下质量份原料:
所述改性层状镁铝水滑石的粒径为1~10μm,是由碳源溶液浸渍后,干燥、炭化而成;
所述二氧化硅气凝胶的粒径为0.5~10μm。
柔性复合吸声材料的制备方法,包括以下步骤:
S1:制备改性层状镁铝水滑石:将层状镁铝水滑石加入2%葡甘聚糖溶液中,控制固液比为1g/5mL,超声浸渍3h,固液分离后,80℃干燥固化,于氮气气氛下,280℃炭化12h,即得改性层状镁铝水滑石;
S2:制备发泡剂:将碳酸氢铵、对甲苯磺酰肼、4,4'-氧代双苯磺酰肼按照1:1.5:2的质量比混合均匀,得到发泡剂;
S3:制备混合料A:将改性层状镁铝水滑石、二氧化硅气凝胶混合均匀后,加入乙烯基三乙酰氧基硅烷,搅拌处理1h,得到混合料A;
S4:制备熔体B:将聚丙烯与乙烯-醋酸乙烯共聚物混合后,200℃加热熔融2~3h,得到熔体B;
S5:制备预成品:180℃下,将混合料A加入熔体B中,搅拌均匀,再与聚硅硼氧烷、2-羟基-4-辛氧基二苯甲酮混合均匀后,并迅速降温至165℃,加入发泡剂并注入模具中,模压发泡成型30min,脱模、冷却后,得到预成品;
S6:制备柔性复合吸声材料:130℃下,将预成品二次发泡6h,即得所述柔性复合吸声材料。
对比例1与实施例1相同,区别在于:以层状镁铝水滑石代替实施例1中的改性层状镁铝水滑石。
表1列出实施例1~3改性层状镁铝水滑石和对比例1层状镁铝水滑石层间距的对比:
表1:
对比例2与实施例1相同,区别在于:无实施例1中的改性层状镁铝水滑石。
对实施例1~3及对比例1~2制备的柔性复合吸声材料进行性能对比,试验结果如表2所示:
表2:
降噪系数/NRC | 导热系数W/(m·K) | 硬度/HA | |
实施例1 | 0.89 | 0.084 | 8 |
实施例2 | 0.92 | 0.059 | 10 |
实施例3 | 0.96 | 0.043 | 10 |
对比例1 | 0.81 | 0.106 | 8 |
对比例2 | 0.47 | 0.142 | 5 |
实施例1~3首次将碳层改性层状镁铝水滑石用于吸声材料领域,利用具有粘性的碳源溶液浸渍层状镁铝水滑石,碳源插入镁铝水滑石层间,同时,在炭化过程中,碳源热解产生CO、H2O(g)、NH3等气体,热解气体进一步充盈扩大镁铝水滑石层间距,使层状结构的间距膨胀增大,同时,水滑石层间及表面碳源炭化后,在其表面形成大量不规则、不均一的碳层微孔和中孔结构,声音的本质是波,在具有层状结构及多孔结构的镁铝水滑石介质中发生多次传播,在多次传播过程中,声波不断衰减,进而达到吸声降噪的作用;此外,镁铝水滑石还能提高吸声材料的硬度、机械强度及阻燃性、耐火性。
实施例1~3首次利用改性层状镁铝水滑石、二氧化硅气凝胶协同掺杂改性,联合发泡剂造孔手段,降低柔性复合吸声材料的密度,提高其比表面积,且泡孔结构细密均匀,收缩率小,闭孔型和开孔型泡孔结构兼有,可同时吸收低中频和中高频声波,吸声范围广,显著提高了吸声系数。
实施例1~3制备出的柔性复合吸声材料具有良好的隔音降噪、保温隔热作用,可作室内隔音装饰板、保温装饰板使用。
实施例1~3以聚硅硼氧烷作为阻燃剂,在高温燃烧条件,迁移到柔性复合吸声材料表面的聚硅硼氧烷裂解生成含有Si键、Si-C键的无机隔氧保护碳层,阻止了燃烧热解产物外逸,又抑制了聚丙烯、乙烯-醋酸乙烯共聚物的热分解,达到阻燃、低烟和低毒等效果。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。
Claims (9)
2.根据权利要求1所述柔性复合吸声材料,其特征在于,所述碳源溶液中碳源浓度为0.2~2%。
3.根据权利要求1或2任意一项所述柔性复合吸声材料,其特征在于,所述碳源溶液为壳聚糖溶液、羧甲基纤维素溶液、聚乙烯醇溶液、葡甘聚糖溶液、淀粉分散液中的一种。
4.根据权利要求1所述柔性复合吸声材料,其特征在于,所述发泡剂由碳酸氢铵、对甲苯磺酰肼、4,4'-氧代双苯磺酰肼按照1:(0.5~1.5):(0.5~2)的质量比混合而成。
5.根据权利要求1所述柔性复合吸声材料,其特征在于,所述乙烯基硅烷偶联剂包括乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三乙酰氧基硅烷中的一种或多种。
6.根据权利要求1所述柔性复合吸声材料,其特征在于,所述阻燃剂为聚硅硼氧烷。
7.根据权利要求1所述柔性复合吸声材料,其特征在于,所述抗老化剂包括2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、2-(2-羟基-3,5-二叔丁基苯基)5-氯代苯并三唑、2-羟基-4-辛氧基二苯甲酮中的一种或多种。
8.柔性复合吸声材料的制备方法,其特征在于,包括以下步骤:
S1:制备改性层状镁铝水滑石:将层状镁铝水滑石加入碳源溶液中,控制固液比为1g/5mL,超声浸渍1~3h,固液分离后,80℃干燥固化,于氮气气氛下,220~280℃炭化6~12h,即得改性层状镁铝水滑石;
S2:制备混合料A:将改性层状镁铝水滑石、二氧化硅气凝胶混合均匀后,加入乙烯基硅烷偶联剂,搅拌处理0.5~1h,得到混合料A;
S3:制备熔体B:将聚丙烯与乙烯-醋酸乙烯共聚物混合后,165~200℃加热熔融2~3h,得到熔体B;
S4:制备预成品:165~180℃下,将混合料A加入熔体B中,搅拌均匀,再与阻燃剂、抗老化剂混合均匀后,并迅速降温至155~165℃,加入发泡剂并注入模具中,模压发泡成型15~30min,脱模、冷却后,得到预成品;
S5:制备柔性复合吸声材料:110~130℃下,将预成品二次发泡3~6h,即得所述柔性复合吸声材料。
9.柔性复合吸声材料在隔音装饰板中的应用。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100828630B1 (ko) * | 2007-05-09 | 2008-05-09 | 월드메카텍(주) | 난연성 알루미늄 복합패널 및 이를 제조하기 위한 장치 |
CN102505820A (zh) * | 2011-09-30 | 2012-06-20 | 德阳金路高新材料有限公司 | 柔性内墙保温装饰材料及其生产方法 |
CN102504426A (zh) * | 2011-10-26 | 2012-06-20 | 重庆巨翁塑料制造有限公司 | 发泡聚丙烯复合板材及其制备方法 |
CN105440420A (zh) * | 2014-08-07 | 2016-03-30 | 中国石油化工股份有限公司 | 纳米级镁铝水滑石阻燃eva发泡材料及其制备方法 |
CN106745117A (zh) * | 2016-12-16 | 2017-05-31 | 武汉工程大学 | 一种片状生物碳/水滑石复合纳米材料及其制备方法和用途 |
CN107354267A (zh) * | 2017-06-27 | 2017-11-17 | 常州市协旺纺织品有限公司 | 一种钢水保温剂 |
CN108117700A (zh) * | 2017-11-29 | 2018-06-05 | 国网湖南省电力有限公司 | 阻燃柔性吸声材料及其制备方法和应用 |
CN108658507A (zh) * | 2018-05-31 | 2018-10-16 | 兰军亚 | 一种建筑室内用复合功能材料及其制备工艺 |
JP2019112631A (ja) * | 2018-12-21 | 2019-07-11 | 積水化学工業株式会社 | 防火防音パネル |
CN111662506A (zh) * | 2020-06-28 | 2020-09-15 | 浙江农林大学 | 一种具有电磁屏蔽功能的隔音材料及制备方法和电子设备 |
-
2020
- 2020-10-22 CN CN202011139503.9A patent/CN112210168B/zh active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100828630B1 (ko) * | 2007-05-09 | 2008-05-09 | 월드메카텍(주) | 난연성 알루미늄 복합패널 및 이를 제조하기 위한 장치 |
CN102505820A (zh) * | 2011-09-30 | 2012-06-20 | 德阳金路高新材料有限公司 | 柔性内墙保温装饰材料及其生产方法 |
CN102504426A (zh) * | 2011-10-26 | 2012-06-20 | 重庆巨翁塑料制造有限公司 | 发泡聚丙烯复合板材及其制备方法 |
CN105440420A (zh) * | 2014-08-07 | 2016-03-30 | 中国石油化工股份有限公司 | 纳米级镁铝水滑石阻燃eva发泡材料及其制备方法 |
CN106745117A (zh) * | 2016-12-16 | 2017-05-31 | 武汉工程大学 | 一种片状生物碳/水滑石复合纳米材料及其制备方法和用途 |
CN107354267A (zh) * | 2017-06-27 | 2017-11-17 | 常州市协旺纺织品有限公司 | 一种钢水保温剂 |
CN108117700A (zh) * | 2017-11-29 | 2018-06-05 | 国网湖南省电力有限公司 | 阻燃柔性吸声材料及其制备方法和应用 |
CN108658507A (zh) * | 2018-05-31 | 2018-10-16 | 兰军亚 | 一种建筑室内用复合功能材料及其制备工艺 |
JP2019112631A (ja) * | 2018-12-21 | 2019-07-11 | 積水化学工業株式会社 | 防火防音パネル |
CN111662506A (zh) * | 2020-06-28 | 2020-09-15 | 浙江农林大学 | 一种具有电磁屏蔽功能的隔音材料及制备方法和电子设备 |
Non-Patent Citations (2)
Title |
---|
HAO KAI PENG ET AL.: "Effects of hydrotalcite on rigid polyurethane foam composites containing a fire retarding agent: compressive stress, combustion resistance, sound absorption, and electromagnetic shielding effectiveness", 《RSC ADVANCE》 * |
公晋芳: "硅藻土/聚丙烯复合材料的吸声性能研究", 《建筑材料学报》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116218201A (zh) * | 2023-02-02 | 2023-06-06 | 广州誉鑫精密部件有限公司 | 一种自结皮发泡料及其制备方法 |
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