CN107417918B - 可交联pbo共聚物及其制备方法和用途 - Google Patents
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Abstract
Description
技术领域
本发明涉及可交联PBO共聚物及其制备方法和用途,属高分子材料领域。
背景技术
含苯并二噁唑结构的高分子具有显著的发色团效应,能产生强的荧光现象,用于光致变色、光伏电池、有机发光二极管和DNA荧光检测。全芳香性苯并二噁唑类聚合物具有高强度、高模量和耐高温等优异性能。但芳香性苯并二噁唑类聚合物熔点太高(高于分解温度)和不溶于有机溶剂,带来了成型加工的困难。
在苯并二噁唑类聚合物的分子主链中引入柔性链段或引入侧基可降低熔点和改善其溶解性。Macromolecules 2004,37,第3815页记载了4,6-二氨基间苯二酚二盐酸盐、对苯二甲酸和癸二酸在聚磷酸介质中共聚合反应,合成了主链含8个亚甲基的PBO共聚物,作为蓝光材料使用,但该共聚物不溶于普通的有机溶剂,限制了其应用。CN2017100353026记载了2-甲基-4,6-二氨基间苯二酚二盐酸盐和不同的脂肪族二元羧酸在聚磷酸介质中反应,合成了一系列的可交联聚亚烃基苯并二噁唑均聚物,作为模塑树脂使用。目前低熔点的可交联PBO共聚物没见相关报道。
发明内容
本发明的目的是提供一种低熔点可交联PBO共聚物。
本发明的另一个目的是提供该可交联PBO共聚物的制备方法。
本发明可交联PBO共聚物,其结构如下:
式中m=1,2,3,4,5,6,7,8,9,10;x/y=1/99~7/3
本发明可交联PBO共聚物的合成方法通过式(3)所示的2-甲基-4,6-二氨基间苯二酚二盐酸盐、式(4)所示的脂肪族二元羧酸和对苯二甲酸于聚磷酸中共聚合反应制备。
2-甲基-4,6-二氨基间苯二酚二盐酸盐和脂肪族二元羧酸的摩尔比为0.8-1.2:1,优选0.95-1.05:1。
HOOC(CH2)mCOOH (4)
式中m=1,2,3,4,5,6,7,8,9,10。反应温度采用逐步升温法,室温至200℃。
具体方法:氮气保护下,在30℃~130℃温度下,2-甲基-4,6-二氨基间苯二酚二盐酸盐先在聚磷酸中脱除氯化氢,优选60℃~90℃。然后加入对苯二甲酸和脂肪族二元羧酸,反应温度逐步升温至200℃进行共聚合反应。优选先在120℃反应,接着在150℃反应,最后在195℃反应。
聚合反应溶液浓度为3wt%~30wt%,优选8wt%~15wt%。
对苯二甲酸和脂肪族二元羧酸摩尔比为1:99至7:3。
上述方法制备的可交联PBO共聚物经热处理,形成式(2)所示的交联聚合物,热处理温度为200℃~400℃。
本发明优点:所述可交联PBO共聚物溶于一些常见的有机溶剂(如N-甲基吡咯烷酮、二甲基亚砜和甲酸等),可用溶液法成膜,而且熔点(140℃~250℃)低于热分解温度(400℃~500℃),易于热塑成型。该PBO共聚物热处理后可形成交联结构,进一步提高了制品的耐热性、耐溶剂性和力学性能。
附图说明
图1是本发明可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)的FTIR谱图。
图2是本发明可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)的FTIR谱图。
图3是本发明可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)的1HNMR谱图。
图4是本发明可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)的1HNMR谱图
图5是本发明可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)的DSC谱图。
图6是本发明可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)的DSC谱图。
图7是本发明可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)的TG谱图。
图8是本发明可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)的TG谱图。
具体实施方式
下面给出几个实施例对本发明可交联PBO共聚物的制备方法做进一步详细说明。
实施例1:可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)的合成
向250ml三口瓶内,氮气保护下,先加入67.40g聚磷酸,室温搅拌下加入3.66g 2-甲基-4,6-二氨基间苯二酚二盐酸盐,升温至60℃,搅拌脱除氯化氢12个小时,然后加入1.88g己二酸和0.54g对苯二甲酸,先在120℃反应6个小时,接着在150℃反应3个小时,最后在195℃反应3个小时,反应溶液冷却至60℃后,搅拌下倒入300ml水中,过滤,用水洗至中性,60℃真空干燥得到3.69g淡黄色固体,收率94.2%。所得聚合物可溶于N-甲基吡咯烷酮、二甲基亚砜、间甲苯酚、甲酸、乙酸、浓硫酸和甲磺酸。
上述合成的可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)经IR和1HNMR检测,为目标产物,IR和1HNMR分析结果如下:
IR(KBr,cm-1):2929,2853,1726,1627,1586,1403,1367,1152,1080;1H NMR(CF3COOD,400MHz,δ(ppm)):8.79-8.47(m,0.8H),8.46-8.26(m,1H),3.61(m,3.2H),2.94(m,3H),2.40(m,3.2H)。
上述合成的可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)在DSC谱图上,熔融峰峰值温度为186.6℃,交联反应吸热峰峰值温度为256.6℃。
上述合成的可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)在TG谱图上,起始热分解温度为439.8℃。
上述合成的可交联PBO共聚物(对苯二甲酸:己二酸摩尔比=2:8)于空气氛下,在250℃处理30分钟后,不再溶于间N-甲基吡咯烷酮、二甲基亚砜、甲苯酚、甲酸、乙酸、浓硫酸和甲磺酸中。
实施例2:可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)的合成
向250ml三口瓶内,氮气保护下,先加入67.40g聚磷酸,室温搅拌下加入3.66g 2-甲基-4,6-二氨基间苯二酚二盐酸盐,升温至90℃,搅拌脱除氯化氢12个小时,然后加入2.28g癸二酸和0.80g对苯二甲酸,先在120℃反应6个小时,接着在150℃反应3个小时,最后在195℃反应3个小时,反应溶液冷却至60℃后,搅拌下倒入300ml水中,过滤,用水洗至中性,60℃真空干燥得到4.29g淡黄色固体,收率97.5%。所得聚合物可溶于N-甲基吡咯烷酮、二甲基亚砜、间甲苯酚、甲酸、乙酸、浓硫酸和甲磺酸。
上述合成的可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)经IR和1HNMR检测,为目标产物,IR和1HNMR分析结果如下:
IR(KBr,cm-1):2929,2853,1726,1627,1586,1403,1367,1152,1080;1H NMR(CF3COOD,400MHz,δ(ppm)):8.79-8.47(m,1.2H),8.47-8.31(m,1H),3.51(m,2.8H),2.97(m,3H),2.17(m,2.8H),1.65-1.54(m,5.6H)。
上述合成的可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)在DSC谱图上,熔融峰峰值温度为177.7℃,交联反应吸热峰峰值温度为303.0℃。
上述合成的可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)在TG谱图上,起始热分解温度为454.3℃。
上述合成的可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7)于空气氛下,在250℃处理30分钟后,不再溶于N-甲基吡咯烷酮、二甲基亚砜、间甲苯酚、甲酸、乙酸、浓硫酸和甲磺酸中。
可交联PBO共聚物可作为模塑树脂使用,下面举例说明其用途
在双斜边马来酰亚胺-环氧酚醛树脂基金刚石砂轮中,添加马来酰亚胺-环氧酚醛树脂质量10%的本发明可交联PBO共聚物(对苯二甲酸:癸二酸摩尔比=3:7),在相同模压工艺条件下,得到的金刚石砂轮的性能列于表1
表1
从表中数据可看出,添加可交联PBO共聚物后,抗折强度提高了40%多,韧性提高,对金刚石的把持力增强,砂轮的尖角保持性提高,砂轮每修整一次,开槽锰钢锯条齿数较未添加砂轮提高了2倍多。
Claims (5)
2.一种如权利要求1所述的可交联PBO共聚物,其特征在于,步骤(1)所述反应温度选60℃~90℃;步骤(2)逐步升温先在120℃反应,接着在150℃反应,最后在195℃反应。
4.如权利要求1所述的可交联PBO共聚物,其特征在于,对苯二甲酸和脂肪族二元羧酸摩尔比为1:99至7:3;2-甲基-4,6-二氨基间苯二酚二盐酸盐和脂肪族二元羧酸的摩尔比为0.8-1.2:1。
5.如权利要求3所述的交联PBO共聚物,其特征在于,热处理温度为200℃~400℃。
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