CN112746384A - 真空绝热板复合膜用改性玻纤布及其制备方法 - Google Patents

真空绝热板复合膜用改性玻纤布及其制备方法 Download PDF

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CN112746384A
CN112746384A CN202011553456.2A CN202011553456A CN112746384A CN 112746384 A CN112746384 A CN 112746384A CN 202011553456 A CN202011553456 A CN 202011553456A CN 112746384 A CN112746384 A CN 112746384A
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glass fiber
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vacuum insulation
insulation panel
panel composite
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马汝军
柳永忠
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Suzhou Junyue New Material Technology Co ltd
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    • D04CBRAIDING OR MANUFACTURE OF LACE, INCLUDING BOBBIN-NET OR CARBONISED LACE; BRAIDING MACHINES; BRAID; LACE
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    • B32B15/00Layered products comprising a layer of metal
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03C25/16Dipping
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    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
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    • C03GLASS; MINERAL OR SLAG WOOL
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    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
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    • C03C25/24Coatings containing organic materials
    • C03C25/26Macromolecular compounds or prepolymers
    • C03C25/32Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/323Polyesters, e.g. alkyd resins
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    • C03C25/10Coating
    • C03C25/465Coatings containing composite materials
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03C25/10Coating
    • C03C25/48Coating with two or more coatings having different compositions
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    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04CBRAIDING OR MANUFACTURE OF LACE, INCLUDING BOBBIN-NET OR CARBONISED LACE; BRAIDING MACHINES; BRAID; LACE
    • D04C1/00Braid or lace, e.g. pillow-lace; Processes for the manufacture thereof
    • D04C1/02Braid or lace, e.g. pillow-lace; Processes for the manufacture thereof made from particular materials
    • BPERFORMING OPERATIONS; TRANSPORTING
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Abstract

本发明涉及一种真空绝热板复合膜用改性玻纤布及其制备方法,真空绝热板复合膜用改性玻纤布的制备方法,包括以下步骤:将玻璃纤维在450‑500℃下煅烧1‑1.5h,得到预处理后的玻璃纤维,然后与硅烷偶联剂浸渍于改性蒙脱土分散液中,然后在110‑120℃下加热,使得改性蒙脱土沉积至玻璃纤维表面;然后将处理后的玻璃纤维浸于含有金属离子的多巴胺水溶液中,震荡30‑36h后干燥,将处理后的玻璃纤维在氧化剂的水溶液中处理完全;将处理后的玻璃纤维与聚乳酸混合后,通过双螺杆密炼机挤出制成改性玻璃纤维,然后编织成型,得到所述真空绝热板复合膜用改性玻纤布。本发明提高了玻纤布的耐温性和力学强度,提高了真空绝热板复合膜的抗冲击性。

Description

真空绝热板复合膜用改性玻纤布及其制备方法
技术领域
本发明涉及真空绝热板技术领域,尤其涉及一种真空绝热板复合膜用改性玻纤布及其制备方法。
背景技术
真空绝热板(VIP),是真空保温材料中的一种。VIP由填充芯材与保护表层经真空封装设备复合而成,它有效地避免了空气对流引起的热传递,因此其导热系数大幅度降低,甚至小于0.002W/(m.K),VIP不含有任何ODS材料,具有环保和高效节能的特性。是目前世界上最先进的高效保温材料。VIP被广泛应用于冷藏、冷冻及保温行业。
VIP的封装膜材由5-7层较薄的膜材复合而成,通常设有一层玻纤布,虽然目前的玻纤布可以解决常规真空绝热板复合膜存在的怕划伤、怕刺穿和阻燃的问题,但是,玻纤布的韧性较差,在强烈冲击下,可能会发生破裂。因此,如何解决上述问题是当前的重要研究课题之一。
发明内容
为解决上述技术问题,本发明的目的是提供一种真空绝热板复合膜用改性玻纤布及其制备方法,本发明提高了玻纤布的耐温性和力学强度,提高了真空绝热板复合膜的抗冲击性。
本发明的第一个目的是提供一种真空绝热板复合膜用改性玻纤布的制备方法,包括以下步骤:
(1)将玻璃纤维在450-500℃下煅烧1-1.5h,得到预处理后的玻璃纤维,然后将所述预处理后的玻璃纤维与硅烷偶联剂KH550浸渍于改性蒙脱土分散液中,然后在110-120℃下加热,使得改性蒙脱土沉积至玻璃纤维表面;
(2)然后将经步骤(1)处理后的玻璃纤维浸于含有金属离子的多巴胺水溶液中,震荡30-36h后干燥,将处理后的玻璃纤维在氧化剂的水溶液中,于40℃-60℃下处理20min-50min;
(3)将经步骤(2)处理后的玻璃纤维与聚乳酸混合后,通过双螺杆密炼机挤出制成改性玻璃纤维,然后编织成型,得到所述真空绝热板复合膜用改性玻纤布。
进一步地,在步骤(1)中,改性蒙脱土的制备方法包括以下步骤:
将钠基蒙脱土与3-磺丙基十六烷基二甲基铵在70-80℃下反应,反应完全后再与双-[γ-(三乙氧基硅)丙基]四硫化物和气相二氧化硅混合,在90-95℃下反应,反应完全后得到所述改性蒙脱土。
蒙脱土和气相二氧化硅均具有良好的耐热性和隔热性,蒙脱土具有层状结构,用3-磺丙基十六烷基二甲基铵对蒙脱土进行插层,扩大了蒙脱土的层间距并且增加了蒙脱土的非极性,一方面,蒙脱土的层间距扩大,使得气相二氧化硅更容易进入蒙脱土层间,气相二氧化硅上的羟基与层间的羟基发生化学键合,形成蒙脱土和气相二氧化硅夹层,从而大大增加玻璃纤维的耐热性和隔热性。
进一步地,在步骤(1)中,所述玻璃纤维与硅烷偶联剂的质量比为40-60:0.5-0.6。
进一步地,在步骤(1)中,所述金属离子为铁离子、亚铁离子、铜离子和锰离子中的一种或几种。
进一步地,在步骤(1)中,所述氧化剂为过硼酸钠、过硼酸钾、过氧化氢、过硫酸钾、过硫酸钠、过醋酸钠和过醋酸钾中的一种或几种。
进一步地,步骤(1)中的玻璃纤维与步骤(2)中的含有金属离子的多巴胺水溶液中的多巴胺的质量比为100-200:10-50。
进一步地,在步骤(3)中,玻璃纤维与聚乳酸的质量比为40-60:200-250。
本发明的第二个目的是提供一种采用上述制备方法所制备的真空绝热板复合膜用改性玻纤布。
本发明的第三个目的是提供一种真空绝热板复合膜,包括依次设置的聚乙烯层、尼龙层、铝箔层、聚酯层、热固性树脂层和上述真空绝热板复合膜用改性玻纤布。
进一步地,聚酯层为PET层或PU层;所述热固性树脂层为环氧树脂层。
借由上述方案,本发明至少具有以下优点:
在步骤(1)中,在玻璃纤维表面沉积改性蒙脱土,改性蒙脱土具有层状结构,且耐热性好,有助于改善玻璃纤维的界面性能和耐温性。
在步骤(2)中,多巴胺在多价金属离子的催化作用下以氧化剂的氧化下氧化原位聚合形成聚多巴胺,增强玻璃纤维的强度。在氧化聚合后期,随着多巴胺聚合完成,多余的氧化剂氧化金属离子,使其形成纳米金属氧化物颗粒附着在玻璃纤维表面,提高了防潮性。
在步骤(3)中,将改性后的玻璃纤维与聚乳酸混合后制备改性纤维,聚乳酸的加入,改善了玻璃纤维的韧性和强度。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合详细说明如后。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1
将钠基蒙脱土加入水中,以150r/min的速度搅拌1.5h,升温至75℃,滴加3-磺丙基十六烷基二甲基铵水溶液,搅拌反应1h,过滤后,水洗、烘干并粉碎,得到粉末状产物。其中,钠基蒙脱土与3-磺丙基十六烷基二甲基铵的质量比为1:0.3。再将粉末状产物与双-[γ-(三乙氧基硅)丙基]四硫化物、气相二氧化硅按照质量比为1:0.3:0.3混合,在90℃下,以200r/min的速度搅拌3h,即可得到改性蒙脱土。将改性蒙脱土分散到质量分数为70%的乙醇水溶液中,在3000rpm的转速下均质剪切分散30min,再置于冰浴中超声(40kHz)处理2h,制得改性蒙脱土分散液,蒙脱土浓度为2g/L。
实施例2
(1)将50g玻璃纤维在480℃下煅烧1h,得到预处理后的玻璃纤维,然后将预处理后的玻璃纤维与0.5g硅烷偶联剂KH550浸渍于实施例1得到的改性蒙脱土分散液中,超声1h,然后在110℃下加热,使得改性蒙脱土沉积至玻璃纤维表面。
(2)然后将经步骤(1)处理后的玻璃纤维浸于2.5L含有亚铁离子的多巴胺水溶液中(多巴胺浓度为2g/L),震荡36h后干燥,将处理后的玻璃纤维在过硫酸钠的水溶液中,于50℃下处理50min。
(3)将经步骤(2)处理后的玻璃纤维与聚乳酸混合后,玻璃纤维与聚乳酸的质量比为50:200,通过双螺杆密炼机挤出制成改性玻璃纤维,然后编织成型,得,真空绝热板复合膜用改性玻纤布。
实施例3
(1)将40g玻璃纤维在480℃下煅烧1h,得到预处理后的玻璃纤维,然后将预处理后的玻璃纤维与0.5g硅烷偶联剂KH550浸渍于实施例1得到的改性蒙脱土分散液中,超声1h,然后在110℃下加热,使得改性蒙脱土沉积至玻璃纤维表面。
(2)然后将经步骤(1)处理后的玻璃纤维浸于2L含有亚铁离子的多巴胺水溶液中(多巴胺浓度为2g/L),震荡36h后干燥,将处理后的玻璃纤维在过硫酸钠的水溶液中,于50℃下处理50min。
(3)将经步骤(2)处理后的玻璃纤维与聚乳酸混合后,玻璃纤维与聚乳酸的质量比为40:200,通过双螺杆密炼机挤出制成改性玻璃纤维,然后编织成型,得,真空绝热板复合膜用改性玻纤布。
实施例4
(1)将60g玻璃纤维在480℃下煅烧1h,得到预处理后的玻璃纤维,然后将预处理后的玻璃纤维与0.5g硅烷偶联剂KH550浸渍于实施例1得到的改性蒙脱土分散液中,超声1h,然后在110℃下加热,使得改性蒙脱土沉积至玻璃纤维表面。
(2)然后将经步骤(1)处理后的玻璃纤维浸于3L含有亚铁离子的多巴胺水溶液中(多巴胺浓度为2g/L),震荡36h后干燥,将处理后的玻璃纤维在过硫酸钠的水溶液中,于50℃下处理50min。
(3)将经步骤(2)处理后的玻璃纤维与聚乳酸混合后,玻璃纤维与聚乳酸的质量比为60:200,通过双螺杆密炼机挤出制成改性玻璃纤维,然后编织成型,得,真空绝热板复合膜用改性玻纤布。
测试以上实施例制备的改性玻纤布的力学性能,结果如表1所示。
表1改性玻纤布的力学性能
Figure BDA0002857817140000041
实施例5
一种真空绝热板复合膜,包括依次设置的聚乙烯层、尼龙层、铝箔层、聚酯层、热固性树脂层和改性玻纤布。改性玻纤布可选择实施例2-4中的任一种。聚酯层为PET层或PU层;热固性树脂层为环氧树脂层。在聚酯层和玻纤布之间设置热固性树脂层,热固性树脂层其在加热固化后形成三维网状结构,由于其分子链交联后已经被固定,无法自由运动,因此再次加热也不能改变其形状,因此提高了复合膜的耐热性。
以上所述仅是本发明的优选实施方式,并不用于限制本发明,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。

Claims (10)

1.一种真空绝热板复合膜用改性玻纤布的制备方法,其特征在于,包括以下步骤:
(1)将玻璃纤维在450-500℃下煅烧1-1.5h,得到预处理后的玻璃纤维,然后将所述预处理后的玻璃纤维与硅烷偶联剂浸渍于改性蒙脱土分散液中,然后在110-120℃下加热,使得改性蒙脱土沉积至玻璃纤维表面;
(2)然后将经步骤(1)处理后的玻璃纤维浸于含有金属离子的多巴胺水溶液中,震荡30-36h后干燥,将处理后的玻璃纤维在氧化剂的水溶液中,于40℃-60℃下处理20min-50min;
(3)将经步骤(2)处理后的玻璃纤维与聚乳酸混合后,通过双螺杆密炼机挤出制成改性玻璃纤维,然后编织成型,得到所述真空绝热板复合膜用改性玻纤布。
2.根据权利要求1所述的制备方法,其特征在于,在步骤(1)中,改性蒙脱土的制备方法包括以下步骤:
将钠基蒙脱土与3-磺丙基十六烷基二甲基铵在70-80℃下反应,反应完全后再与双-[γ-(三乙氧基硅)丙基]四硫化物和气相二氧化硅混合,在90-95℃下反应,反应完全后得到所述改性蒙脱土。
3.根据权利要求1所述的制备方法,其特征在于:在步骤(1)中,所述玻璃纤维与硅烷偶联剂的质量比为40-60:0.5-0.6。
4.根据权利要求1所述的制备方法,其特征在于:在步骤(1)中,所述金属离子为铁离子、亚铁离子、铜离子和锰离子中的一种或几种。
5.根据权利要求1所述的制备方法,其特征在于:在步骤(1)中,所述氧化剂为过硼酸钠、过硼酸钾、过氧化氢、过硫酸钾、过硫酸钠、过醋酸钠和过醋酸钾中的一种或几种。
6.根据权利要求1所述的制备方法,其特征在于:步骤(1)中的玻璃纤维与步骤(2)中的含有金属离子的多巴胺水溶液中的多巴胺的质量比为100-200:10-50。
7.根据权利要求1所述的制备方法,其特征在于:在步骤(3)中,玻璃纤维与聚乳酸的质量比为40-60:200-250。
8.一种权利要求1-7中任一项所述的制备方法所制备的真空绝热板复合膜用改性玻纤布。
9.一种真空绝热板复合膜,其特征在于:包括依次设置的聚乙烯层、尼龙层、铝箔层、聚酯层、热固性树脂层和权利要求8所述的真空绝热板复合膜用改性玻纤布。
10.根据权利要求9所述的真空绝热板复合膜,其特征在于:所述聚酯层为PET层或PU层;所述热固性树脂层为环氧树脂层。
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