CN111319332A - 一种多层复合膜 - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 229920001721 polyimide Polymers 0.000 claims abstract description 49
- 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 36
- 239000003063 flame retardant Substances 0.000 claims abstract description 36
- 239000004642 Polyimide Substances 0.000 claims abstract description 33
- 150000004985 diamines Chemical class 0.000 claims abstract description 24
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 7
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 7
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- 238000009833 condensation Methods 0.000 claims abstract description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
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- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 2
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
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- 206010000369 Accident Diseases 0.000 description 1
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- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- SCDFUIZLRPEIIH-UHFFFAOYSA-N dichlorine heptoxide Inorganic materials O=Cl(=O)(=O)OCl(=O)(=O)=O SCDFUIZLRPEIIH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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Abstract
本发明公开了一种多层复合膜,由外到内依次为阻燃聚酰亚胺层、聚对苯二甲酸丁二酯层、PVDC层、阻燃聚酰亚胺层,所述的阻燃聚酰亚胺层是由均苯四甲酸酐和改性二胺经缩合制备得到的阻燃聚酰亚胺膜。在聚酰亚胺本体结构上进行了改进,引入了阻燃成分,在燃烧时,N原子燃烧生成一氧化氮和二氧化氮,覆盖在膜表面,隔绝空气,阻止其进一步然后;P原子燃烧呈磷酸等化合物覆盖在聚合物表面,使得聚合物脱水形成致密碳层,且在持续燃烧中,磷酸等化合物脱水形成一种富磷的玻璃态物质,并且包围在聚合物表面,起到将聚合材料保护隔离起来,形成隔离膜并且阻拦基材中可燃气体的释放量,从而达到阻燃目的。
Description
技术领域
本发明属于膜技术领域,具体涉及一种多层复合膜。
背景技术
随着高分子材料技术科学的飞速发展,以及其成型加工技术的进步,高分子材料的产品档次、产品质量不断提高,并且被广泛应用于多种领域,如:包装、军工、建筑、电子电气和日常生活用品中。但是,高分子材料很大程度属于易燃材质,尤其是使用在包装、建筑材料、日常生活用品上的高分子材料,一旦意外发生失火情况就会造成极其惨重的损失。因此对高分子材料实施阻燃化的研究,开发及生产利用难燃材料,具有与时俱进的重要性。
大多数高分子聚合材料在遇到火源的情况下,都会在空气中被点燃然后燃烧,燃烧时大多还会产生熔融的滴落物质,从而引燃其他可燃物造成火灾。由于高分子材料组成成分的特殊性,燃烧时会产生极大地热量并产生高温度,燃烧时速度蔓延较快,由于燃烧过程中会出现不完全燃烧现象,继而产生大量的黑烟,并且产生一些有害气体,例如氯化氢、氟化氢、氰化氢、苯乙烯等。因此在这种情况下,会给逃难、消防、就生等工作带来困难。
聚酰亚胺材料具有优异的热稳定性能、高机械强度、低介电常数、强耐化学性等诸多其他材料无法企及的性能,因而在航空、微电子、包装等领域备受青睐;其中,聚酰亚胺薄膜最早商品的应用类型之一,其中介电常数小的薄膜使用于电机的绝缘槽及电缆绕包材料等方面,透明的聚酰亚胺薄膜可作为柔软的太阳能电池底板,线膨胀系数低的聚酰亚胺薄膜可以使用在柔性印刷线路板上;聚酰亚胺本身为自熄型聚合物,但是其阻燃性能还达不到难燃,因此,提升其阻燃性能有助于聚酰亚胺的进一步应用和拓展应用领域。
发明内容
本发明的目的在于提供一种多层复合膜,由外到内依次为阻燃聚酰亚胺层、聚对苯二甲酸丁二酯层、PVDC层、阻燃聚酰亚胺层,该多层复合膜具有良好的阻燃耐高温的性能,可适用于航空航天、电子领域和耐高温包装领域,拓展了复合膜的使用范围,具有潜在的商业价值。
本发明的目的可以通过以下技术方案实现:
一种多层复合膜,由外到内依次为阻燃聚酰亚胺层、聚对苯二甲酸丁二酯层、PVDC层、阻燃聚酰亚胺层;
所述的阻燃聚酰亚胺层是由均苯四甲酸酐和改性二胺经缩合制备得到的阻燃聚酰亚胺膜。
进一步,所述的改性二胺的制备方法为:
S1、在反应瓶中加入50-52mmol二甘油,通入氮气10-15min,置换掉反应瓶中的空气,在氮气氛围中,逐滴滴加105-110mmol三氯氧磷,加入完毕后,关闭氮气通道,边搅拌边升温至95-100℃,保温反应4-5h,反应结束后,自然冷却到室温,采用无水乙醚洗涤3-5次,干燥后即得到中间体A1;
S2、向步骤S1制备的中间体A1中加入100-110mmol对羟基苯胺、115-130mmol无机碱、干燥剂和400-500ml干燥的溶剂甲苯,通入氮气保护,边搅拌边升温至135-140℃,保温搅拌反应8-10h,反应结束后,趁热过滤,滤液自然冷却到室温,然后将滤液加入到1L蒸馏水中,缓慢搅拌20-30min,过滤,滤渣经去离子水水洗、干燥后即得到粗产物A2,最后经柱层析分离,即得到式A2所示的改性二胺。
进一步,所述的无机碱为碳酸铯。
进一步,所述的干燥剂为无水硫酸钠,无水硫酸钠的加入量为120-130mmol。
进一步,柱层析所用层析液为石油醚:二氯甲烷:乙酸乙酯=10:1:2。
进一步,所述的阻燃聚酰亚胺膜的制备方法为:
第一步、在反应瓶中加入20-22mmol改性二胺和120-150ml溶剂DMF,通入氮气保护,搅拌使得改性二胺溶解完全,接着逐滴滴加10mmol均苯四甲酸二酐,放置与水浴锅中,水浴温度为45-50℃,保温搅拌反应6-7h,即得到聚酰胺酸预聚体乳液,冷藏于温度为0-5℃的环境中,备用;
第二步、将第一步制备的聚酰胺酸预聚体乳液平铺在洁净的玻璃板上,放置于烘箱中,以0.5-0.7℃/min的速度升温至170-175℃,在最高温保温30-45min,除去溶剂DMF,接着关闭加热,自然冷却到室温后转移至真空干燥箱中,以5-10℃/min速率升温至150℃,接着以1℃/min速率升温至300℃,在300℃保温30-45min,热亚胺化成聚酰亚胺,即得到透明的阻燃聚酰亚胺膜。
本发明的有益效果:
(1)本发明提供的一种多层复合膜,由外到内依次为阻燃聚酰亚胺层、聚对苯二甲酸丁二酯层、PVDC层、阻燃聚酰亚胺层,该多层复合膜具有良好的阻燃耐高温的性能,可适用于航空航天、电子领域和耐高温包装领域,拓展了复合膜的使用范围,具有潜在的商业价值;
(2)阻燃聚酰亚胺层是由均苯四甲酸酐和改性二胺经缩合制备得到的阻燃聚酰亚胺膜,首先研制出原料改性二胺,以二甘油和三氯氧磷为原料,在无溶剂下发生取代环合反应,得到了中间体A1,接着,在碱性环境中,中间体A1与羟基苯胺发生取代反应,得到了含有对称结构和双氨基的改性二胺A2,对称结构的改性二胺A2为原料,可以更有效的与均苯四甲酸二酐进行缩合,另外改性二胺不同于现有的制备聚酰亚胺的原料,改性二胺中引入了双分子的磷元素,且以醚键相连,最后改性二胺与均苯四甲酸二酐首先进行开环缩合得到聚酰胺酸预聚体乳液,然后在高温下经热亚胺化成聚酰亚胺,制备的聚酰亚胺是由C、H、O、N、P五种元素组成,在聚酰亚胺本体结构上进行了改进,引入了阻燃成分,在燃烧时,N原子燃烧生成一氧化氮和二氧化氮,覆盖在膜表面,隔绝空气,阻止其进一步然后;P原子燃烧呈磷酸等化合物覆盖在聚合物表面,使得聚合物脱水形成致密碳层,且在持续燃烧中,磷酸等化合物脱水形成一种富磷的玻璃态物质,并且包围在聚合物表面,起到将聚合材料保护隔离起来,形成隔离膜并且阻拦基材中可燃气体的释放量,从而达到阻燃目的。
当然,实施本发明的任一产品并不一定需要同时达到以上所述的所有优点。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明中间体A1的反应式;
图2为本发明改性二胺A2的反应式;
图3为本发明阻燃聚酰亚胺A的反应式。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
请参阅图1-2所示,改性二胺的制备方法为:
S1、在反应瓶中加入52mmol二甘油,通入氮气15min,置换掉反应瓶中的空气,在氮气氛围中,逐滴滴加106mmol三氯氧磷,加入完毕后,关闭氮气通道,边搅拌边升温至95℃,保温反应5h,反应结束后,自然冷却到室温,采用无水乙醚洗涤3-5次,干燥后即得到中间体A1,收率为88.4%;
经GC-MS检测得到:中间体A1(C6H10Cl2O7P2)的分子量为327.162;
S2、向步骤S1制备的中间体A1中加入105mmol对羟基苯胺、120mmol碳酸铯、130mmol无水硫酸钠干燥剂和500ml干燥的溶剂甲苯,通入氮气保护,边搅拌边升温至135℃,保温搅拌反应10h,反应结束后,趁热过滤,滤液自然冷却到室温,然后将滤液加入到1L蒸馏水中,缓慢搅拌30min,过滤,滤渣经去离子水水洗、干燥后即得到粗产物A2,最后经柱层析分离,层析液为石油醚:二氯甲烷:乙酸乙酯=10:1:2,即得到式A2所示的改性二胺,收率为75.9%。
经GC-MS检测得到:改性二胺A2(C18H22N2O9P2)的分子量为473.082。
实施例2
请参阅图3所示,阻燃聚酰亚胺膜的制备方法为:
第一步、在反应瓶中加入22mmol改性二胺和140ml溶剂DMF,通入氮气保护,搅拌使得改性二胺溶解完全,接着逐滴滴加10mmol均苯四甲酸二酐,放置与水浴锅中,水浴温度为45℃,保温搅拌反应6h,即得到聚酰胺酸预聚体乳液,冷藏于温度为0-5℃的环境中,备用;
第二步、将第一步制备的聚酰胺酸预聚体乳液平铺在洁净的玻璃板上,放置于烘箱中,以0.5℃/min的速度升温至175℃,在最高温保温40min,除去溶剂DMF,接着关闭加热,自然冷却到室温后转移至真空干燥箱中,以8℃/min速率升温至150℃,接着以1℃/min速率升温至300℃,在300℃保温40min,热亚胺化成聚酰亚胺,即得到透明的阻燃聚酰亚胺膜。
对制备的阻燃聚酰亚胺膜进行红外检测:
实施例3
一种多层复合膜,由外到内依次为阻燃聚酰亚胺层、聚对苯二甲酸丁二酯层、PVDC层、阻燃聚酰亚胺层。
对比例1
一种多层复合膜,由外到内依次为聚酰亚胺层、聚对苯二甲酸丁二酯层、PVDC层、聚酰亚胺层。
所述的聚酰亚胺层由聚酰亚胺薄膜制备得到;
聚酰亚胺薄膜购自东莞市美鑫绝缘材料有限公司。
对制备的多层复合膜进行性能测试
由上表可知,本发明制备的阻燃聚酰亚胺膜和多层复合膜极限氧指数均大于32%,属于难燃材料,可适用于航空航天、电子领域和耐高温包装领域,拓展了复合膜的使用范围,具有潜在的商业价值。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (6)
1.一种多层复合膜,其特征在于:由外到内依次为阻燃聚酰亚胺层、聚对苯二甲酸丁二酯层、PVDC层、阻燃聚酰亚胺层;
所述的阻燃聚酰亚胺层是由均苯四甲酸酐和改性二胺经缩合制备得到的阻燃聚酰亚胺膜。
2.根据权利要求1所述的一种多层复合膜,其特征在于:所述的改性二胺的制备方法为:
S1、在反应瓶中加入50-52mmol二甘油,通入氮气10-15min,置换掉反应瓶中的空气,在氮气氛围中,逐滴滴加105-110mmol三氯氧磷,加入完毕后,关闭氮气通道,边搅拌边升温至95-100℃,保温反应4-5h,反应结束后,自然冷却到室温,采用无水乙醚洗涤3-5次,干燥后即得到中间体A1;
S2、向步骤S1制备的中间体A1中加入100-110mmol对羟基苯胺、115-130mmol无机碱、干燥剂和400-500ml干燥的溶剂甲苯,通入氮气保护,边搅拌边升温至135-140℃,保温搅拌反应8-10h,反应结束后,趁热过滤,滤液自然冷却到室温,然后将滤液加入到1L蒸馏水中,缓慢搅拌20-30min,过滤,滤渣经去离子水水洗、干燥后即得到粗产物A2,最后经柱层析分离,即得到式A2所示的改性二胺。
3.根据权利要求1所述的一种多层复合膜,其特征在于:所述的无机碱为碳酸铯。
4.根据权利要求1所述的一种多层复合膜,其特征在于:所述的干燥剂为无水硫酸钠,无水硫酸钠的加入量为120-130mmol。
5.根据权利要求1所述的一种多层复合膜,其特征在于:柱层析所用层析液为石油醚:二氯甲烷:乙酸乙酯=10:1:2。
6.根据权利要求1所述的一种多层复合膜,其特征在于:所述的阻燃聚酰亚胺膜的制备方法为:
第一步、在反应瓶中加入20-22mmol改性二胺和120-150ml溶剂DMF,通入氮气保护,搅拌使得改性二胺溶解完全,接着逐滴滴加10mmol均苯四甲酸二酐,放置与水浴锅中,水浴温度为45-50℃,保温搅拌反应6-7h,即得到聚酰胺酸预聚体乳液,冷藏于温度为0-5℃的环境中,备用;
第二步、将第一步制备的聚酰胺酸预聚体乳液平铺在洁净的玻璃板上,放置于烘箱中,以0.5-0.7℃/min的速度升温至170-175℃,在最高温保温30-45min,除去溶剂DMF,接着关闭加热,自然冷却到室温后转移至真空干燥箱中,以5-10℃/min速率升温至150℃,接着以1℃/min速率升温至300℃,在300℃保温30-45min,热亚胺化成聚酰亚胺,即得到透明的阻燃聚酰亚胺膜。
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