CN111892695B - 耐γ辐照的改性树脂及其制备方法、层压板及其制备工艺与应用 - Google Patents

耐γ辐照的改性树脂及其制备方法、层压板及其制备工艺与应用 Download PDF

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CN111892695B
CN111892695B CN202010670531.7A CN202010670531A CN111892695B CN 111892695 B CN111892695 B CN 111892695B CN 202010670531 A CN202010670531 A CN 202010670531A CN 111892695 B CN111892695 B CN 111892695B
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modified resin
gamma irradiation
boric acid
glue solution
resin
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CN111892695A (zh
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唐昌万
李磊
魏世明
李军
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SICHUAN FIBERGLASS GROUP CO Ltd
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Abstract

本发明第一方面提供了一种耐γ辐照的改性树脂，为硼酸对环氧树脂接枝改性制得，包括：环氧树脂、固化剂、促进剂、硼酸、偶联剂和有机溶剂；第二方面提供了耐γ辐照的改性树脂的制备方法，包括如下步骤：S1、将环氧树脂进行硼酸接枝改性得到改性树脂胶液，S2、调节步骤S1所得改性树脂胶液的凝胶时间；第三方面提供了含有耐γ辐照的改性树脂的层压板的制备工艺；第四方面提供了含有耐γ辐照的改性树脂的层压板的应用；本发明所提供的耐γ辐照的改性树脂，在经过硼酸接枝改性后，其抗辐照强度明显增强，改性后的改性树脂与玄武岩纤维布结合制成的层压板，在累计辐照剂量达5Х106Gy时能够保证足够的抗拉伸强度和抗弯曲强度，适用于各种强γ强度环境。

Description

耐γ辐照的改性树脂及其制备方法、层压板及其制备工艺与 应用
技术领域
本发明属于纤维增强复合材料领域，涉及一种耐γ辐照的改性树脂及其制备方法、层压板及其制备工艺与应用。
背景技术
玄武岩矿因其火山喷发熔浆冷却形成的原因，其矿物原料经高温熔融后拉制出的纤维成分中相比于玻璃纤维的主要区别，是含有7～10％的Fe2O3,这为玄武岩纤维开发特定用途的复合材料提供了可能性。
随着传统化石燃料的逐渐枯竭，发展高效清洁的新型能源一直是科研工作者关注的热点问题，其中核能因为巨大的能源发展潜力，被科学家们视为未来最具有希望的清洁能源而成为研究的焦点。核工业生产过程中利用中长寿命核素进行加工利用如同位素富集分离及利用，医疗用品γ射线辐照消毒，或者受控核反应中产生中长寿命的放射性核素的实践如核能发电及核能供热，但是其发展过程中伴随而来的核安全问题同时也引起了人们的极大关注。核能射线辐照到控制设备或者承载构件后，会使设备或承载构件的材料发生辐照失效，产生巨大的安全隐患；核工业生产过程中将产生大量放射性固体废物，废物的包装储存和处置要求包装材料长期耐受核能射线而保持强度足够使用要求。
目前，核能射线科研生产场所大量的辐照到的控制设备或者承载构件或者辅助结构一般采用高含铅等重金属的合金材料、水泥制品来作为结构件，废物包装也采用水泥箱或石墨铸铁箱，这些材料密度大、结构笨重，使用很不方便。申请号为CN201510731460.6的发明专利公开了一种耐γ射线辐照的聚丙烯复合材料及其制备方法，该发明生产的聚丙烯复合材料经过50KGy累积剂量γ射线辐照，没有出现明显的黄变，仍然具有优良的透明性，同时力学性能几乎没有下降。该产品可以用于低放射场合如医疗用品γ射线辐照消毒环境构件，但是不能用于更强剂量辐照的环境。
发明内容
针对现有技术中上述的不足，本发明第一方面提供了一种耐γ辐照的改性树脂，为硼酸对环氧树脂接枝改性制得，包括：环氧树脂、固化剂、促进剂、硼酸、偶联剂和有机溶剂。
进一步地，按质量百分比计，以100份的有机溶剂为基准，所述环氧树脂的含量为80-120份，所述固化剂的含量为50-100份，所述促进剂的含量为0.5-2份，所述硼酸的含量为1.5-15份，所述偶联剂的含量为1-2份。
进一步地，所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂或双酚S型环氧树脂中的一种，优选为双酚A型环氧树脂，更优选为E44双酚A缩水甘油醚型环氧树脂。
进一步地，所述固化剂为酚醛树脂。
进一步地，所述促进剂为二甲基苄胺或二甲基咪唑。
进一步地，所述有机溶剂包括工业酒精和/或甲苯，优选地，所述有机溶剂为工业酒精和甲苯按质量百分比1:1复配的混合物。
本发明第二方面提供了前述耐γ辐照的改性树脂的制备方法，包括如下步骤：
S1、将环氧树脂进行硼酸接枝改性得到改性树脂胶液；
S2、调节步骤S1所得改性树脂胶液的凝胶时间。
进一步地，所述步骤S1具体包括：
S11、将环氧树脂加入到带冷凝水回流装置的三口瓶中，搅拌升温至80℃-90℃；
S12、向步骤S11中的三口瓶中缓慢加入硼酸，保持反应温度为80℃-90℃，持续40分钟-60分钟；
S13、向步骤S12中的三口瓶中加入有机溶剂，反应温度降低至40℃以下；
S14、向步骤S13中的三口瓶中加入固化剂和偶联剂，持续搅拌30分钟-50分钟既得改性树脂胶液。
进一步地，所述步骤S2具体包括：使用促进剂调节步骤S1所制得的改性树脂胶液的凝胶时间至300秒-400秒。
本发明第三方面提供了一种含有耐γ辐照的改性树脂的层压板的制备工艺，包括如下步骤：
T1、将前述的耐γ辐照的改性树脂的胶液浸渍到玄武岩纤维布上，烘制得到半固化片；
T2、将若干步骤T1所得半固化片叠合热压即得。
本发明第四方面提供了一种含有耐γ辐照的改性树脂的层压板。
本发明第五方面提供了一种含有耐γ辐照的改性树脂的层压板的应用，如前述所制得的含有耐γ辐照的改性树脂的层压板，应用于强γ辐照环境下的结构件中，包括植物育种γ辐照的操作控制台、核电站核岛内部检修平台和扶手和核工业低中放射性固体废物储存运输处置包装箱。
本发明的有益效果是：
本发明所提供的耐γ辐照的改性树脂，在经过硼酸接枝改性后，其抗辐照强度明显增强，改性后的改性树脂与玄武岩纤维布结合制成的层压板，在累计辐照剂量达5Х106Gy时能够保证足够的抗拉伸强度和抗弯曲强度，适用于各种强γ强度环境。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本实施例提供了一种耐γ辐照的改性树脂、制备方法及含有其的层压板的制备工艺与应用，具体包括：(1)耐γ辐照的改性树脂的制备，(2)含有耐γ辐照的改性树脂的层压板的制备，(3)树脂的凝胶时间测试方法，(4)半固化片流动度测试方法，(5)树脂含量测试方法，(6)挥发物含量测试方法，(7)材料抗拉伸强度测试方法，(8)材料抗弯曲强度测试方法。
具体如下：
测试例1
本测试例为树脂的凝胶时间测试方法，具体为小刀法。
一个能加热并稳定控制温度在(160±2)℃的钢质平台，一把大约150mmХ10mm的长条形刀片，一个精度0.01秒的秒表。配制好的树脂胶液取样2ml，快速倒入已经恒温的平台中部，倒完开始计时；不断用刀尖搅拌并挑起树脂，随时间推移，树脂粘度逐步变大，至树脂被挑起后能够成丝；当树脂拉丝一拉即断不能继续拉丝时，停止计时，以秒为单位记录测得的时间。每次平行测试三次，取平均值作为该树脂的凝胶时间。
测试例2
本测试例为半固化片流动度测试方法。
玄武岩纤维布预浸树脂半固化片上，取六张50mmХ50mm样品，对齐叠好；两张100mmХ100mm的表面光洁的不锈钢板和两张100mmХ100mm的离型薄膜(如聚四氟乙烯薄膜)；按照中心对齐方式依次放置一张不锈钢板、一张离型薄膜、叠好的样品、另一张离型薄膜、另一张不锈钢板。一个能加热并稳定控制温度在(160±2)℃的压机，预热到温度稳定后，将叠合好的前述材料小心地放置在压机中部，加压到3MPa,保温保压15分钟，撤去压力，取出样品。用精度0.5mm的直尺测量玄武岩纤维布边缘到树脂流出最远边缘的距离，用mm表示。每次平行测试两组，取平均值作为该玄武岩纤维布预浸料的流动度。
测试例3
本测试例为树脂含量的测试方法，具体为灼烧法。
玄武岩纤维布预浸树脂半固化片上，裁切100mmХ100mm样品，在天平上称重m1，精确至0.0001g；马弗炉升温至(625±20)℃，恒温，将样品放置进马弗炉灼烧30min，取出，玄武岩纤维布上的树脂已经完全灼烧干净，称重得m2，精确至0.0001g；玄武岩纤维布预浸料树脂含量为(m1-m2)/m1Х100％。每次测试三个样品，取平均值作为该玄武岩纤维布预浸料的树脂含量。
测试例4
本测试例为挥发物含量的测试方法，具体为干燥法。
玄武岩纤维布预浸树脂半固化片上，裁切100mmХ100mm样品，在天平上称重m1，精确至0.0001g；干燥箱升温至压制成型相同的温度(160±5)℃，恒温，将样品放置进干燥箱干燥30min，取出，称重得m2，精确至0.0001g；玄武岩纤维布预浸料挥发物含量为(m1-m2)/m1Х100％。每次测试三个样品，取平均值作为该玄武岩纤维布预浸料的挥发物含量。
制备例1
本制备例的目的在于制备耐γ辐照的改性树脂，具体地，包括如下步骤：
S1、将E44双酚A缩水甘油醚型环氧树脂进行硼酸接枝改性得到改性树脂胶液；
S11、用电子天平称取E44双酚A缩水甘油醚型环氧树脂后加入到带有搅拌器和冷凝器的三口瓶中，搅拌升温至85℃；
S12、向步骤S11中的三口瓶中缓慢加入硼酸，保持反应温度为85℃，持续50分钟；
S13、向步骤S12中的三口瓶中加入有机溶剂(工业酒精和甲苯的混合物)，反应温度降低至40℃以下；
S14、向步骤S13中的三口瓶中加入酚醛树脂和硅烷偶联剂KH560，持续搅拌40分钟既得改性树脂胶液；
S2、调节步骤S1所得改性树脂胶液的凝胶时间，具体为，使用二甲基咪唑调节步骤S1所制得的改性树脂胶液的凝胶时间至300秒-400秒，改性树脂胶液的凝胶时间测试方法参见前述测试例1。
其中，E44双酚A缩水甘油醚型环氧树脂购自巴陵石化环氧树脂厂；硼酸购自成都科隆化学品公司；工业酒精购自德阳市川西化工公司；甲苯购自德阳市川西化工公司；酚醛树脂购自山东圣泉新材料有限公司；硅烷偶联剂KH560购自江苏晨光化工股份公司；二甲基咪唑购自德阳市川西化工公司。
制备例2
本制备例的目的在于制备含有耐γ辐照的改性树脂的层压板，具体地，包括如下步骤：
T1、将制备例1中所制得的耐γ辐照的改性树脂的胶液浸渍到玄武岩纤维布上，浸渍了树脂胶液的玄武岩纤维布放进烘箱进行烘制，制成半固化片，半固化片流动度控制在20毫米，树脂质量百分比控制在38％，挥发物质量百分比0.3％(其中，半固化片流动度测试方法参见测试例2，树脂质量百分比测试方法参见测试例3，挥发物质量百分比测试方法参见测试例4)；
T2、将若干步骤T1所得半固化片叠合热压即得。
步骤T2中热压的具体方法为：在两张表面光滑洁净的不锈钢模板上分别涂上二甲基硅油脱模剂后，根据将要压制层压板的厚度，将不同数量张数的半固化胶片叠放于两张模板之间，然后连同模板一起置于层压机中，于160℃温度条件下，缓慢加压至5MPa,根据板材厚度保温保压时间200min。保温保压至设定时间后，降温至50℃以下得到板状层压制品。
实施例1
按制备例1的方法制备耐γ辐照的改性树脂，具体地，按100克的有机溶剂(其中，工业酒精和甲苯各50克)为基准，E44双酚A缩水甘油醚型环氧树脂的含量为100克，酚醛树脂的含量为70克，二甲基咪唑的含量为1克，硼酸的含量为15克，硅烷偶联剂的含量为1.5克。
将所制得的改性树脂按制备例2的方法浸渍在玄武岩纤维布上，压制成层压板A1。
实施例2
其余条件与实施例1相同，所不同之处在于，硼酸的含量为11克。
将所制得的改性树脂按制备例2的方法浸渍在玄武岩纤维布上，压制成层压板A2。
实施例3
其余条件与实施例1相同，所不同之处在于，硼酸的含量为8克。
将所制得的改性树脂按制备例2的方法浸渍在玄武岩纤维布上，压制成层压板A3。
实施例4
其余条件与实施例1相同，所不同之处在于，硼酸的含量为5克。
将所制得的改性树脂按制备例2的方法浸渍在玄武岩纤维布上，压制成层压板A4。
实施例5
其余条件与实施例1相同，所不同之处在于，硼酸的含量为1.5克。
将所制得的改性树脂按制备例2的方法浸渍在玄武岩纤维布上，压制成层压板A5。
对比例1
其余条件与实施例1相同，所不同之处在于，硼酸的含量为20克。
将所制得的改性树脂按制备例2的方法浸渍在玄武岩纤维布上，压制成层压板D1。
对比例2
其余条件与实施例1相同，所不同之处在于，硼酸的含量为0.5克。
将所制得的改性树脂按制备例2的方法浸渍在玄武岩纤维布上，压制成层压板D2。
对比例3
其余条件与实施例1相同，所不同之处在于，将制备例2中的玄武岩纤维布替换为普通玻璃纤维布，制得层压板D3。
对比例4
玄武岩纤维布，与常规酚醛树脂+环氧树脂体系预浸后压制的复合材料层压板D4。
对比例5
普通玻璃纤维布，与常规酚醛树脂+环氧树脂体系预浸后压制的复合材料层压板D5(即市售3240层压板)。
实验例
将上述实施例1-5和对比例1-5中的各层压板(A1、A2、A3、A4、A5、D1、D2、D3、D4、D5)，分别在未做γ射线辐照，辐照累计剂量为1Х105Gy，5Х105Gy，1Х106Gy，5Х106Gy，五种情况下按国标《GB/T 1040.4-2006塑料拉伸性能的测试》和国标《GB/T 9341-2008塑料弯曲性能的测定》分别对层压板的抗拉伸强度和抗弯曲强度进行测试，所得实验数据参见表1和表2。
表1材料的抗拉伸强度(单位MPa)
Figure BDA0002582114000000101
表2材料的抗弯曲强度(单位MPa)
Figure BDA0002582114000000102
Figure BDA0002582114000000111
由表1及表2实验数据可以看出，当环氧树脂、酚醛树脂、促进剂、硼酸、偶联剂和有机溶剂的加量在本技术方案要求保护的范围内时，即对应的实施例为A1-A5，当累计辐射剂量最大(5Х106Gy)时，材料的抗拉伸强度均大于450MPa，材料的抗弯曲强度均大于400MPa，但是，随着硼酸加量的减少，材料的抗拉伸强度和抗弯曲强度相应的降低。
对于对比例D1，其硼酸的含量为20克，超过所要求的硼酸的保护范围，但是，所制得的层压板的抗拉伸强度和抗弯曲强度与实施例A1相比，并没有明显的改善，增加了材料的成本。
对于对比例D2，其硼酸的含量为0.5克，远远低于所要求的硼酸的保护范围，所制得的层压板的抗拉伸强度和抗弯曲强度，明显弱于实施例A1，尤其是在增大辐射剂量后，其抗拉伸强度和抗弯曲强度急剧降低，表明其抗辐照的性能较差。
对于对比例D3，是将玄武岩纤维布替换为普通玻璃纤维布，在增强辐照计量后，其抗拉伸强度和抗弯曲强度均有一定程度的降低，由此表明经过硼酸接枝改性后的树脂与玄武岩纤维布搭配使用，其抗辐照效果才最优。
对于对比例D4，是使用玄武岩纤维布与常规酚醛树脂+环氧树脂体系预浸后压制的复合材料层压板，其抗拉伸强度和抗弯曲强度与实施例A1-A5相比，明显偏弱，可见，使用硼酸对树脂进行改性后能够增强材料的抗辐照能力。
对于对比例D5，是市售3240层压板在相同条件下的实验结果，表明本技术方案所制备的层压板的抗辐照能力明显优于市面上常见的层压板。
综上，按本发明的方法所制备出的改性树脂结合玄武岩纤维布，将其压制成层压板，抗辐照性能极优，在5Х106Gy累计辐照剂量下能够保证较好的抗拉伸强度和抗弯曲强度，适用于各种强γ强度环境，例如：植物育种γ辐照的操作控制台、核电站核岛内部检修平台和扶手和核工业低中放射性固体废物储存运输处置包装箱。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种耐γ辐照的改性树脂，其特征在于，为硼酸对环氧树脂接枝改性制得，包括如下原料：环氧树脂和硼酸；还包括有机溶剂、固化剂、促进剂和偶联剂，以重量份计，所述有机溶剂为100份，所述环氧树脂为80-120份，所述固化剂为50-100份，所述促进剂为0.5-2份，所述硼酸为1.5-15份，所述偶联剂为1-2份；
耐γ辐照的改性树脂的制备方法，包括如下步骤：
S1、将环氧树脂进行硼酸接枝改性得到改性树脂胶液；
所述步骤S1具体包括：
S11、将环氧树脂加入到带冷凝水回流装置的三口瓶中，搅拌升温至80℃-90℃；
S12、向步骤S11中的三口瓶中缓慢加入硼酸，保持反应温度为80℃-90℃，持续40分钟-60分钟；
S13、向步骤S12中的三口瓶中加入有机溶剂，反应温度降低至40℃以下；
S14、向步骤S13中的三口瓶中加入固化剂和偶联剂，持续搅拌30分钟-50分钟既得改性树脂胶液
S2、调节步骤S1所得改性树脂胶液的凝胶时间；
所述步骤S2具体包括：使用促进剂调节步骤S1所制得的改性树脂胶液的凝胶时间至300秒-400秒。
2.根据权利要求1所述的耐γ辐照的改性树脂，其特征在于，所述有机溶剂包括工业酒精和/或甲苯。
3.根据权利要求1所述的耐γ辐照的改性树脂，其特征在于，所述有机溶剂为工业酒精与甲苯的混合物。
4.如权利要求1-3任意一项所述的耐γ辐照的改性树脂的制备方法，其特征在于，包括如下步骤：
S1、将环氧树脂进行硼酸接枝改性得到改性树脂胶液；
S2、调节步骤S1所得改性树脂胶液的凝胶时间。
5.根据权利要求4所述的耐γ辐照的改性树脂的制备方法，其特征在于，所述步骤S1具体包括：
S11、将环氧树脂加入到带冷凝水回流装置的三口瓶中，搅拌升温至80℃-90℃；
S12、向步骤S11中的三口瓶中缓慢加入硼酸，保持反应温度为80℃-90℃，持续40分钟-60分钟；
S13、向步骤S12中的三口瓶中加入有机溶剂，反应温度降低至40℃以下；
S14、向步骤S13中的三口瓶中加入固化剂和偶联剂，持续搅拌30分钟-50分钟既得改性树脂胶液。
6.根据权利要求4所述的耐γ辐照的改性树脂的制备方法，其特征在于，所述步骤S2具体包括：使用促进剂调节步骤S1所制得的改性树脂胶液的凝胶时间至300秒-400秒。
7.一种含有耐γ辐照的改性树脂的层压板的制备工艺，其特征在于，包括如下步骤：
T1、将如权利要求1-3任意一项所述的耐γ辐照的改性树脂的胶液浸渍到玄武岩纤维布上，烘制得到半固化片；
T2、将若干步骤T1所得半固化片叠合热压即得。
8.一种含有耐γ辐照的改性树脂的层压板，其特征在于，如权利要求7所述制备工艺制得。
9.一种含有耐γ辐照的改性树脂的层压板的应用，其特征在于，如权利要求8所述的含有耐γ辐照的改性树脂的层压板，应用于强γ辐照环境下的结构件中。
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