CN109435374A - 一种建筑用苯并噁嗪树脂基金属箔复合板及其制备方法 - Google Patents

一种建筑用苯并噁嗪树脂基金属箔复合板及其制备方法 Download PDF

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CN109435374A
CN109435374A CN201811082415.2A CN201811082415A CN109435374A CN 109435374 A CN109435374 A CN 109435374A CN 201811082415 A CN201811082415 A CN 201811082415A CN 109435374 A CN109435374 A CN 109435374A
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benzoxazine resin
metal foil
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prepreg
base metal
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CN109435374B (zh
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陈中浩
蔡徐伟
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Hangzhou Kai Heng New Material Co Ltd
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Abstract

本发明涉及一种建筑用苯并噁嗪树脂基金属复合箔的制备方法，其包括如下步骤：S1，用预热后的苯并噁嗪树脂对单层或多层增强材料纤维布进行浸润，制得预浸料；S2，通过控温轧辊处理控制预浸料的浸润树脂量后，将预浸料单面或双面与金属箔进行复合，之后通过辊压预成型以及模压成型工艺，制得建筑用苯并噁嗪树脂基金属箔复合板。本发明方法简单、工序简便、连续、成本低、实用性强，制备的建筑用苯并噁嗪树脂基金属箔复合材料具有良好的抗压强度、隔热性能和阻燃性能，适用于制备各种建筑用屋面瓦、墙面板和/或隔板中。

Description

一种建筑用苯并噁嗪树脂基金属箔复合板及其制备方法
技术领域
本发明属于建筑用金属箔复合板技术领域，具体涉及一种建筑用苯并噁嗪树脂基金属箔复合板及其制备方法。
背景技术
在建筑行业中通常需要使用各种屋面瓦、墙面板和隔板等，传统此类建材基本都是采用水泥、金属、陶瓷和石棉等材料通过烧制或冶炼等加工流程生产制造，存在质重、安装复杂以及不环保等一系列问题。除此之外，现有的传统屋面瓦类建材结构设计较为单一，在防水隔热、环保等方面还不能完全满足建筑行业的要求。目前，随着人类生活水平的不断提升，一些轻质、美观的多层板应运而生。苯并噁嗪树脂由于其独特的分子结构，使其具有固化收缩率低、耐热耐候性能优异、阻燃性好等特点，使其成为各种无卤阻燃多层板基材优异的胶粘剂。
现有技术中尚未报道树脂基金属箔复合材料在建材领域的规模应用。采用一些热塑性树脂与金属复合作为保温材料的应用见诸于一些研究，但热塑性树脂复合材料在阻燃性和结构强度上难以满足应用要求。因此，采用热固性苯并噁嗪树脂制备建筑用苯并噁嗪树脂基复合金属箔板的研究是一种创造性的新技术，对于提高建筑材料综合性能具有重大意义。
发明内容
本发明所要解决的技术问题是针对上述现有技术的不足，提供一种建筑用苯并噁嗪树脂基金属复合箔的制备方法。该方法中选用双胺型苯并噁嗪树脂作为胶粘剂；通过选择预成型工艺，使得苯并噁嗪树脂基预浸料复合金属箔后，通过高温辊压预成型，然后经连续交替模具的模压成型，解决了纤维、金属箔与树脂基体延展性不一致造成大曲度成型时纤维、金属箔断裂的问题。本发明方法制备的建筑用苯并噁嗪树脂基金属箔复合板具有良好的抗压强度和阻燃性能，适用于制成各种建筑用屋面瓦、墙面板和隔板等。
为此，本发明第一方面提供了一种建筑用苯并噁嗪树脂基金属箔复合板的制备方法，其包括如下步骤：
S1，用预热后的苯并噁嗪树脂对单层或多层增强材料纤维布进行浸润，制得预浸料；
S2，通过控温轧辊处理控制预浸料的浸润树脂量后，将预浸料单面或双面与金属箔进行复合，之后通过辊压预成型以及模压成型工艺，制得建筑用苯并噁嗪树脂基金属箔复合板。
根据本发明方法，所述苯并噁嗪树脂选自通式(I)所示的双胺型苯并噁嗪树脂中的至少一种；
其中，在通式(I)中，R1选自C1-C10的亚烷基、 中的一种或多种；R2选自氢、饱和或不饱和的烃基中的一种或多种。
根据本发明方法，所述苯并噁嗪树脂的分子量为450-530。
在本发明的一些实施例中，所述苯并噁嗪选自苯酚-苯双胺型苯并噁嗪和/或苯酚-二氨基二苯甲烷型苯并噁嗪。
根据本发明方法，在步骤S1中，将苯并噁嗪树脂预热至90-130℃，优选为120-130℃。
根据本发明方法，所述浸润的时间为0.5-10min；优选为1-5min。
本发明可采用本领域常规的浸润设备(例如，如图1所示)进行苯并恶嗪树脂的浸润。如无特殊说明，该设备的操作方法均为本领域常规方法。
根据本发明方法，所述预浸料中苯并噁嗪树脂的含量为10wt％-40wt％。
根据本发明方法，在步骤S2中，所述轧辊处理的温度为130-180℃；和/或所述浸润树脂量为所述预浸料重量的10wt％-40wt％，优选为25wt％。
根据本发明方法，在步骤S2中，所述辊压预成型工艺的温度为180-230℃；和/或所述模压成型的温度为200-230℃，所述模压成型的压力为0.01-0.05MPa，所述模压成型的时间为1-10min。
本发明可采用常规的模压设备(例如，如图2所示)将控制预浸树脂量后的预浸料与金属箔复合。如无特殊说明，该设备的操作方法均为本领域常规方法。
根据本发明方法，所述增强材料纤维布选自玻璃纤维布、碳纤维布和玄武岩纤维布中的一种或多种。优选所述纤维布的规格为200g-2000g玻璃纤维编织布或400g-4000g玻璃纤维毛毡布；更优选所述纤维布的规格为600g玻璃纤维编织布或800g玻璃纤维毛毡布。
根据本发明方法，所述金属箔选自铝箔或覆不锈钢膜的铝合金箔；优选所述金属箔的厚度为0.01-0.05mm，更优选为0.02mm。
在本发明的一些具体实施例中，所述建筑用苯并噁嗪树脂基金属箔复合板的制备方法如下：
将苯并噁嗪树脂预热至90-130℃后浸润单层或多层增强材料纤维布，浸润0.5-10min后，制得预浸料；
在130-180℃下经控温轧辊将预浸料碾压平整，控制浸润树脂量为预浸料重量的10wt％-40wt％，单面或双面与金属箔进行复合后，通过180-230℃下的高温辊压预成型后，再拖入连续交替模具进行模压成型(温度为200-230℃，压力为0.01-0.05MPa，时间为1-10min)，制得各种花纹或曲面要求的建筑用苯并噁嗪树脂基金属箔复合板。
本发明第二方面提供了一种根据本发明第一方面所述方法制备的建筑用苯并噁嗪树脂基金属箔复合板，所述复合板的面密度为0.17-0.22g/cm2，弯曲强度为400-1200MPa，阻燃性能为ULV0，隔热系数为0.07-0.09W/(m·K)。
本发明第三方面提供了一种根据本发明第一方面所述方法制备的建筑用苯并噁嗪树脂基金属箔复合板或根据本发明第二方面所述的建筑用苯并噁嗪树脂基金属箔复合板在建筑用屋面瓦、墙面板和/或隔板中的应用。
本发明的有益效果：
本发明提供的建筑用苯并噁嗪树脂基金属箔复合材料的制备方法简单、工序简便、连续、成本低、实用性强，制备的建筑用苯并噁嗪树脂基金属箔复合材料具有良好的抗压强度和阻燃性能，同时导热系数可以达到0.09W/(m·K)，隔热性能佳，适用于制备各种建筑用屋面瓦、墙面板和隔板中。
附图说明
下面结合附图来对本发明作进一步详细说明。
图1示出了本发明所采用的浸润设备示意图。图中附图标记的含义如下：1-放卷装置；2-储长器；3-前牵引装置；4-挤胶装置；5-升降车；6-预浸槽；7-纠偏装置；8-后牵引装置；9-放保护膜装置；10-双收卷装置。
图2示出了本发明所采用的控制浸润树脂量后的预浸料与金属箔复合模压设备示意图。图中附图标记的含义如下：1-底座；2-压机主体；3-座台；4-中空板；5-推杆电机；6-运动杆；7-连接杆；8-光滑座台；9-稳定装置。
具体实施方式
下面将结合附图和实施例对本发明作进一步说明，这些实施例仅起说明性作用，并不局限于本发明的应用范围。
本发明所得建筑用苯并噁嗪树脂基金属箔复合板的性能测试方法如下：
(1)面密度：常规测试方法测量单位面积材料的质量；
(2)弯曲强度：使用上海精密仪器仪表有限公司生产的WDW-S100液晶显示电子拉力试验机，依照GB/T 3356-2014进行测试；
(3)阻燃性能：使用上海能共实业有限公司生产的水平垂直燃烧试验仪NG-HVR，依照GB/T 2408-2008进行测试；
(4)导热系数：使用西安夏溪电子科技有限公司生产的TC3000E便携式导热系数仪，依照GB/T 22588-2008进行测试。
实施例
实施例1
采用如图1所示的浸润设备，进行苯并噁嗪树脂的浸润。加热预浸槽110℃融化分子量为490的DDM苯并噁嗪树脂(即式(I)中，R1 R2为H的苯酚-二氨基二苯甲烷型苯并噁嗪树脂)，至树脂完全融化，铺设单层玻璃纤维布(600g玻璃纤维编织布)通过预热苯并噁嗪树脂，预浸2分钟，至纤维布完全浸润。通过130℃轧辊碾压平整得预浸料，控制浸润树脂量为预浸料重量的30wt％。然后采用如图2所示的模压设备将预浸料双面与铝箔进行复合，通过一组高温200℃辊压预成型，再拖入连续交替模具模压成型，波纹型模具，模压温度为220℃，模压时间为8分钟，压力为0.02MPa，最后制得苯并噁嗪树脂基金属箔复合板。该复合板的厚度为0.6mm。其性能测试结果见表1。
实施例2
采用如图1所示的浸润设备，进行苯并噁嗪树脂的浸润。加热预浸槽120℃融化分子量为490的DDM型苯并噁嗪树脂，至树脂完全融化，铺设两层玻璃纤维布(400g玻璃纤维毛毡布)通过预热苯并噁嗪树脂，预浸4分钟，至纤维布完全浸润，通过150℃轧辊碾压平整得预浸料，控制浸润树脂量为预浸料重量的25wt％。然后采用如图2所示的模压设备将预浸料双面与铝箔进行复合，通过一组高温200℃辊压预成型，再拖入连续交替模具模压成型，波纹型模具，模压温度为220℃，模压时间为6分钟，压力为0.02MPa，最后制得苯并噁嗪树脂基金属箔复合板。该复合板的厚度为0.8mm。其性能测试结果见表1。
实施例3
采用如图1所示的浸润设备，进行苯并噁嗪树脂的浸润。加热预浸槽130℃融化分子量为490的DDM型苯并噁嗪树脂，至树脂完全融化，铺设两层玻璃纤维布(600g玻璃纤维毛毡布)通过预热苯并噁嗪树脂，预浸4分钟，至纤维布完全浸润，通过160℃轧辊碾压平整得预浸料，控制浸润树脂量为预浸料重量的22wt％。然后采用如图2所示的模压设备将预浸料双面与铝箔进行复合，通过一个高温200℃辊压预成型，再拖入连续交替模具模压成型，波纹型模具，模压温度为230℃，模压时间为4分钟，压力为0.02MPa，最后制得苯并噁嗪树脂基金属箔复合板。该复合板的厚度为1.1mm。其性能测试结果见表1。
实施例4
采用如图1所示的浸润设备，进行苯并噁嗪树脂的浸润。加热预浸槽130℃融化分子量为490的DDM型苯并噁嗪树脂，至树脂完全融化，铺设两层玄武岩纤维布(200g玄武岩纤维布)通过预热苯并噁嗪树脂，预浸8分钟，至纤维布完全浸润，通过150℃轧辊碾压平整得预浸料，控制浸润树脂量为预浸料重量的20wt％。然后采用如图2所示的模压设备将预浸料双面与铝箔进行复合，通过一个高温200℃辊压预成型，再拖入连续交替模具模压成型，波纹型模具，模压温度为230℃，模压时间为4分钟，压力为0.02MPa，最后制得苯并噁嗪树脂基金属箔复合板。该复合板的厚度为0.8mm。其性能测试结果见表1。
实施例5
采用如图1所示的浸润设备，进行苯并噁嗪树脂的浸润。加热预浸槽130℃融化分子量为490的DDM型苯并噁嗪树脂，至树脂完全融化，铺设三层碳纤维布(100g碳纤维布)通过预热苯并噁嗪树脂，预浸8分钟，至纤维布完全浸润，通过150℃轧辊碾压平整得预浸料，控制浸润树脂量为预浸料重量的30wt％。然后采用如图2所示的模压设备将预浸料双面与铝箔进行复合，通过一个高温200℃辊压预成型，再拖入连续交替模压成型，波纹型模具，模压温度为230℃，模压时间为8分钟，压力为0.02MPa，最后制得苯并噁嗪树脂金属箔复合板。该复合板的厚度为0.6mm。其性能测试结果见表1。
对比例1
采用市售ASA/PVC树脂复合板，该复合板的厚度为3mm，其中，增强材料为传统树脂瓦，树脂为ASA树脂。其性能测试结果见表1。
表1苯并噁嗪树脂基金属箔复合板与市售复合板的性能测试结果对比
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (12)

1.一种建筑用苯并噁嗪树脂基金属箔复合板的制备方法，其包括如下步骤：
S1，用预热后的苯并噁嗪树脂对单层或多层增强材料纤维布进行浸润，制得预浸料；
S2，通过控温轧辊处理控制预浸料的浸润树脂量后，将预浸料单面或双面与金属箔进行复合，之后通过辊压预成型以及模压成型工艺，制得建筑用苯并噁嗪树脂基金属箔复合板。
2.根据权利要求1所述的方法，其特征在于，所述苯并噁嗪树脂选自通式(I)所示的双胺型苯并噁嗪树脂中的至少一种；
其中，在通式(I)中，R1选自C1-C10的亚烷基、 中的一种或多种；R2选自氢、饱和或不饱和的烃基中的一种或多种。
3.根据权利要求1或2所述的方法，其特征在于，所述苯并噁嗪树脂的分子量为450-530。
4.根据权利要求1-3中任意一项所述的方法，其特征在于，在步骤S1中，将苯并噁嗪树脂预热至90-130℃。
5.根据权利要求1-4中任意一项所述的方法，其特征在于，所述浸润的时间为0.5-10min。
6.根据权利要求1-5中任意一项所述的方法，其特征在于，所述预浸料中苯并噁嗪树脂的含量为10wt％-40wt％。
7.根据权利要求1-6中任意一项所述的方法，其特征在于，在步骤S2中，所述轧辊处理的温度为130-180℃；和/或所述浸润树脂量为所述预浸料重量的10wt％-40wt％。
8.根据权利要求1-7中任意一项所述的方法，其特征在于，在步骤S2中，所述辊压预成型工艺的温度为180-230℃；和/或所述模压成型的温度为200-230℃，所述模压成型的压力为0.01-0.05MPa，所述模压成型的时间为1-10min。
9.根据权利要求1-8中任意一项所述的方法，其特征在于，所述增强材料纤维布选自玻璃纤维布、碳纤维布和玄武岩纤维布中的一种或多种；优选所述纤维布的规格为200g-2000g玻璃纤维编织布或400g-4000g玻璃纤维毛毡布。
10.根据权利要求1-9中任意一项所述的方法，其特征在于，所述金属箔选自铝箔或覆不锈钢膜的铝合金箔；优选所述金属箔的厚度为0.01-0.05mm。
11.一种根据权利要求1-10中任意一项所述方法制备的建筑用苯并噁嗪树脂基金属箔复合板，所述复合板的面密度为0.18-0.26g/cm2，弯曲强度为400-1200MPa，阻燃性能为ULV0，隔热系数为0.07-0.09W/(m·K)。
12.一种根据权利要求1-10中任意一项所述方法制备的建筑用苯并噁嗪树脂基金属箔复合板或根据权利要求11所述的建筑用苯并噁嗪树脂基金属箔复合板在建筑用屋面瓦、墙面板和/或隔板中的应用。
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