CN110698715A - 一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法 - Google Patents
一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法 Download PDFInfo
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- CN110698715A CN110698715A CN201910982490.2A CN201910982490A CN110698715A CN 110698715 A CN110698715 A CN 110698715A CN 201910982490 A CN201910982490 A CN 201910982490A CN 110698715 A CN110698715 A CN 110698715A
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- polymethacrylimide
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- 238000004132 cross linking Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
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- 239000004033 plastic Substances 0.000 claims description 55
- 239000003504 photosensitizing agent Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 24
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- 239000003431 cross linking reagent Substances 0.000 claims description 17
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 16
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- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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Abstract
本发明公开一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,包括如下步骤:(1)将各原料混合均匀,然后注入密闭的平面模具中并在30‑60℃下进行聚合反应;(2)反应至反应液凝固,变成均匀的透明状态后,升温至60‑130℃下进行后聚合处理20‑60h,得到聚(甲基)丙烯酰亚胺预聚板;(3)将聚(甲基)丙烯酰亚胺预聚板在180‑260℃下加热发泡,得到所述聚(甲基)丙烯酰亚胺泡沫;(4)将聚(甲基)丙烯酰亚胺泡沫在电子加速器下进行双面辐照处理,得到交联聚(甲基)丙烯酰亚胺泡沫。本发明制备得到的聚(甲基)丙烯酰亚胺泡沫力学性能和耐热性能,相对于常规泡沫明显提高。
Description
技术领域
本发明涉及材料制备领域,尤其是一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法。
背景技术
聚(甲基)丙烯酰亚胺(PMI)泡沫材料是由(甲基)丙烯酸、(甲基)丙烯腈及共聚单体通过自由基共聚制备得到,其分子侧链上含有大量羧基、腈基等强极性基团,使PMI泡沫具有极高的比强度,高温下羧基和腈基发生酰亚胺化反应,使材料的耐热性能提高。PMI泡沫拥有高比强度、高耐热性能、耐腐蚀等优点,被广泛应用于航空航天、风力发电、新能源汽车、运动器材、高铁船舶以及医疗器械等领域。PMI泡沫的聚合原理及反应过程如下式所示:
然而,制备由碳纤维/双马来酰亚胺预浸料制成的覆盖层的夹层构件时,需要在热压罐中(在最高到200℃下几个小时)固化后另外还要在直到约240℃下再后处理几个小时,常规的PMI泡沫无法达到该使用工艺的要求。
专利CN200710167607.9中通过往体系中增加交联剂的用量,尤其是离子交联剂的用量,使泡沫产生交联结构使泡沫的热变形温度提高到>250℃,使泡沫材料能够满足严苛的制件制备工艺。但是,该专利中的交联剂在(甲基)丙烯酸和(甲基)丙烯腈混合液中溶解度较低,且添加量过多,容易导致聚合反应异常,无法得到均匀的PMI塑料板,影响最终的PMI泡沫塑料。
专利CN200810088893.4中通过加入马来酰亚胺第三单体进行共聚,使得到的PMI材料侧链的酰亚胺结构含量提高,从而提高材料的耐热性能。但是,通过该方法得到的PMI泡沫材料热变形温度提高不多,只有200℃左右,仍然无法满足碳纤维/双马来酰亚胺预浸料的固化工艺。
专利CN201510472532.X中通过往体系中加入氧化钙或氧化镁成核剂,制备得到了高热变形温度小孔聚甲基丙烯酰亚胺泡沫,然而,该泡沫热变形温度也只有200℃左右,无法满足碳纤维/双马来酰亚胺预浸料的固化工艺。
专利CN201510472393.0通过往体系中加入三溴苯基马来酰亚胺、甲基膦酸二甲酯DMMP或无机氧化物等耐热添加剂,提高PMI泡沫的耐热温度到220℃左右,也无法满足碳纤维/双马来酰亚胺预浸料的固化工艺。
光引发剂又名光敏剂在光固化体系中至关重要,在实际配方中,大多数是小分子光引发剂,分子量小,迁移性大,在成膜过程中容易挥发或发生迁移而导致涂层变黄,降低了光引发效率。
综上所述,要满足碳纤维/双马来酰亚胺预浸料的固化工艺,需要使PMI泡沫的耐热温度提高到250℃左右,而常规PMI泡沫都无法达到这么高的热变形温度,要进一步提高热变形温度,需要提高体系的交联密度,但是,如果PMI塑料板的交联密度提高了,那么PMI塑料板在发泡过程中容易发生开裂现象,这导致了目前大部分PMI泡沫的热变形温度低。提高PMI泡沫的热变形温度,可以使PMI泡沫满足碳纤维/双马来酰亚胺预浸料的固化工艺,这进一步拓宽了PMI泡沫的应用领域,尤其在航空航天工业领域的应用。
发明内容
为了解决上述问题,本发明提供了一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法。
一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于,包括如下步骤:
(1)将(甲基)丙烯腈30-70重量份、(甲基) 丙烯酸30-70重量份、第三共聚单体0-10重量份、引发剂0.1-2重量份、发泡剂5-15重量份、光敏剂0.5-5重量份、交联剂1-3重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于30-60℃下反应60-100h,得到透明的塑料板,然后将塑料板在60-130℃下热处理20-60h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在180-230℃下发泡2-6h,得到聚甲基丙烯酰亚胺泡沫塑料;
(4)将聚甲基丙烯酰亚胺泡沫塑料进行辐照,辐照能量为1-4Mev,辐照剂量为200-1000KGy,得到辐射交联聚甲基丙烯酰亚胺泡沫塑料。
所述的光敏剂为所述的光敏剂为一种聚离子液型光敏剂,按照以下方法制备:
在反应釜中,按重量份计加入(甲基)丙烯腈100份,3-10份4-丙烯酰氧基二苯甲酮,0.01-0.5份1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,0.01-0.5份(Z)-9-十八烯酸铜(II)盐,0.01-0.5份3-(2-甲氧基吡啶-3-基)丙烯酸,1000-3000份水,1-4份分散剂,0.5-2份过氧化苯甲酰,在80℃-95℃反应5-12h,过滤,烘干后得到聚离子液型光敏剂。
所述第三共聚单体,指为了调节竞聚率,改善聚合物性能的烯属不饱和单体,所述第三共聚单体为马来酰亚胺及其衍生物、苯乙烯、马来酸或其酸酐、衣康酸或其酸酐、乙烯基吡咯烷酮、氯乙烯、偏二氯乙烯中的一种或几种的组合物。
所述第三共聚单体优选马来酰亚胺、苯乙烯、马来酸酐、衣康酸、乙烯基吡咯烷酮。
所述引发剂为偶氮二异丁腈、偶氮二异戊睛或偶氮二异庚腈、过氧化二苯甲酰、过氧化月桂酰、过氧化辛酸叔丁酯或过氧化二缩酮、十六烷基过二碳酸酯、丁基过二碳酸酯、戊基过二碳酸酯、过新戊酸叔丁基酯、过苯甲酸叔丁基酯、过2-乙基己酸叔丁基酯、偶氮-双(4-氰基戊酸)或者偶氮-双(4-氰基戊酸)中的一种或几种的组合物。
所述的引发剂优选偶氮二异丁腈、过氧化二苯甲酰、过新戊酸叔丁基酯、十六烷基过二碳酸酯、过2-乙基己酸叔丁基酯。
所述发泡剂为多元醇类或脲类,所述发泡剂为异丙醇、叔丁醇、叔戊醇、尿素、甲基脲、二甲基脲、异丁醇、正丁醇或己醇中一种或几种的组合物。
所述的发泡剂优选异丙醇、叔丁醇、甲基脲、尿素、正丁醇。
所述交联剂为金属氧化物、金属氢氧化物、金属盐类、多元醇类或多元烯烃类,所述交联剂为氧化钙、氧化镁、丙烯酰胺(AM)、甲基丙烯酰胺(MAM)、三聚氰酸三烯丙酯、甲基丙烯酸烯丙酯、甲基丙烯酸金属盐、丙烯酸金属盐、金属氧化物、丙烯酸烯丙基酯、甲基丙烯酸烯丙基酯、烯丙基丙烯酰胺、烯丙基甲基丙烯酰胺、亚甲基-二-丙烯酰胺或-甲基丙烯酰胺、二亚乙基双(碳酸烯丙基酯)、乙二醇二丙烯酸酯或-二甲基丙烯酸酯、二甘醇二丙烯酰胺或-二甲基丙烯酰胺、三甘醇二丙烯酰胺或-二甲基丙烯酰胺、四甘醇二丙烯酰胺或-二甲基丙烯酰胺、三丙二醇二丙烯酰胺或-二甲基丙烯酰胺、1,3-丁二醇二丙烯酸酯或-二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯或-二甲基丙烯酸酯、新戊二醇二丙烯酸酯或-二甲基丙烯酸酯、己二醇-1,6-二丙烯酸酯或-二甲基丙烯酸酯、三羟甲基丙烷二丙烯酸酯或-二甲基丙烯酸酯,三羟甲基丙烷三丙烯酸酯或-三甲基丙烯酸酯、季戊四醇三丙烯酸酯或-三甲基丙烯酸酯、季戊四醇四丙烯酸酯或-四甲基丙烯酸酯、季戊四醇衍生物、三烯丙基异氰尿酸酯或三烯丙基氰尿酸酯中一种或几种的组合物。
所述的交联剂优选氧化钙、甲基丙烯酰胺、三聚氰酸三烯丙酯、甲基丙烯酸钙、三丙二醇二丙烯酰胺。
所述辐照方式为电子束、γ射线、中子束或粒子束辐照中的至少一种。
本发明的主要原理是通过本体浇注,制备得到透明PMI塑料板材,然后将PMI塑料板材在高温下发泡得到PMI泡沫,将PMI泡沫进一步辐照交联,提高PMI泡沫塑料的交联密度,从而得到高耐热的PMI泡沫塑料。
跟现有技术相比,本发明的有益效果:与常规的往配方中加入交联剂的方式相比,本发明采用先发泡后交联的方式,交联密度的提高不会导致发泡开裂等缺陷,从而促进材料力学性能和热学性能大幅度提高;与常规的往配方中加入交联剂的方式相比,本发明采用先发泡后交联的方式,不会影响原配方工艺所得泡沫的密度,不需要为了控制产品密度而提高发泡温度;与常规的往配方中加入交联剂的方式相比,本发明采用先发泡后交联的方式,不会产生增加交联剂从而导致聚合不正常的现象发生。
本发明光敏剂为五元共聚物,基体单体为(甲基)丙烯腈,有利于提高和聚甲基丙烯酰亚胺塑料相容性,离子液的胺基结构可以使分子内产生氢键反应, 吡啶结构的加入有利于大分子光敏剂的光引发性能的提高, 十八烯酸铜的金属络配合物分布在大分子光敏剂的表面,有利于提高光敏剂的稳定性。
附图说明
图1为实施例2辐射交联聚甲基丙烯酰亚胺泡沫塑料样品的傅立叶红外光谱图。
具体实施方式
下面通过具体实施例对该发明作进一步说明:
各性能测试方法如下:
1、密度按ASTM D1622进行测试;
2、压缩强度按ASTM D1621进行测试;
3、热变形温度按DIN53424进行测试;
实施例1
(1)将(甲基)丙烯腈30重量份、(甲基)丙烯酸70重量份、苯乙烯1重量份、偶氮二异丁腈0.1重量份、异丙醇5重量份、光敏剂0.5重量份、氧化钙1-3重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于30℃下反应100h,得到透明的塑料板,然后将塑料板在60℃下热处理60h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在180℃下发泡2h,得到聚甲基丙烯酰亚胺泡沫塑料;
(4)将聚甲基丙烯酰亚胺泡沫塑料进行辐照,辐照能量为4Mev,辐照剂量为200KGy,得到辐射交联聚甲基丙烯酰亚胺泡沫塑料。
所述的光敏剂为所述的光敏剂为一种聚离子液型光敏剂,按照以下方法制备:
在反应釜中,按重量份计加入(甲基)丙烯腈100份,7份4-丙烯酰氧基二苯甲酮,0.2份1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,0.3份(Z)-9-十八烯酸铜(II)盐,0.02份3-(2-甲氧基吡啶-3-基)丙烯酸,2000份水,2份分散剂,1份过氧化苯甲酰,在86℃反应7h,过滤,烘干后得到聚离子液型光敏剂。
实施例2
(1)将(甲基)丙烯腈38重量份、(甲基)丙烯酸62重量份、马来酰亚胺2.8重量份、过氧化二苯甲酰0.48重量份、叔丁醇7重量份、光敏剂2.5重量份、甲基丙烯酰胺2.6重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于36℃下反应92h,得到透明的塑料板,然后将塑料板在74℃下热处理52h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在190℃下发泡2.8h,得到聚甲基丙烯酰亚胺泡沫塑料;
(4)将聚甲基丙烯酰亚胺泡沫塑料进行辐照,辐照能量为3.4Mev,辐照剂量为360KGy,得到辐射交联聚甲基丙烯酰亚胺泡沫塑料。
所述的光敏剂为所述的光敏剂为一种聚离子液型光敏剂,按照以下方法制备:
所述的光敏剂为在反应釜中,按重量份计加入(甲基)丙烯腈100份,3份4-丙烯酰氧基二苯甲酮,0.01份1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,0.01份(Z)-9-十八烯酸铜(II)盐,0.01份3-(2-甲氧基吡啶-3-基)丙烯酸,1000份水,1份分散剂,0.5份过氧化苯甲酰,在80℃℃反应5h,过滤,烘干后得到聚离子液型光敏剂。
实施例3
(1)将(甲基)丙烯腈46重量份、(甲基)丙烯酸54重量份、马来酸酐4.6重量份、过新戊酸叔丁基酯0.86重量份、甲基脲9重量份、光敏剂3.5重量份、三聚氰酸三烯丙酯2.2重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于42℃下反应82h,得到透明的塑料板,然后将塑料板在88℃下热处理44h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在200℃下发泡3.6h,得到聚甲基丙烯酰亚胺泡沫塑料;
(4)将聚甲基丙烯酰亚胺泡沫塑料进行辐照,辐照能量为2.8Mev,辐照剂量为520KGy,得到辐射交联聚甲基丙烯酰亚胺泡沫塑料。
所述的光敏剂为所述的光敏剂为一种聚离子液型光敏剂,按照以下方法制备:
所述的光敏剂为在反应釜中,按重量份计加入(甲基)丙烯腈100份,10份4-丙烯酰氧基二苯甲酮,0.5份1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,0.5份(Z)-9-十八烯酸铜(II)盐,0.5份3-(2-甲氧基吡啶-3-基)丙烯酸,3000份水,4份分散剂,2份过氧化苯甲酰,在95℃反应12h,过滤,烘干后得到聚离子液型光敏剂。
实施例4
(1)将(甲基)丙烯腈54重量份、(甲基)丙烯酸46重量份、衣康酸6.4重量份、十六烷基过二碳酸酯1.24重量份、尿素11重量份、光敏剂4.5重量份、甲基丙烯酸钙1.8重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于48℃下反应76h,得到透明的塑料板,然后将塑料板在102℃下热处理36h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在210℃下发泡4.4h,得到聚甲基丙烯酰亚胺泡沫塑料;
(4)将聚甲基丙烯酰亚胺泡沫塑料进行辐照,辐照能量为2.2Mev,辐照剂量为680KGy,得到辐射交联聚甲基丙烯酰亚胺泡沫塑料。
所述的光敏剂为所述的光敏剂为一种聚离子液型光敏剂,按照以下方法制备:在反应釜中,按重量份计加入(甲基)丙烯腈100份,3份4-丙烯酰氧基二苯甲酮,0.5份1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,0.01份(Z)-9-十八烯酸铜(II)盐,0.5份3-(2-甲氧基吡啶-3-基)丙烯酸,1000份水,4份分散剂,0.5份过氧化苯甲酰,在95℃反应12h,过滤,烘干后得到聚离子液型光敏剂。
实施例5
(1)将(甲基)丙烯腈70重量份、(甲基)丙烯酸30重量份、乙烯基吡咯烷酮10重量份、过2-乙基己酸叔丁基酯2重量份、正丁醇15重量份、光敏剂5重量份、三丙二醇二丙烯酰胺1重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于60℃下反应60h,得到透明的塑料板,然后将塑料板在130℃下热处理20h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在230℃下发泡6h,得到聚甲基丙烯酰亚胺泡沫塑料;
(4)将聚甲基丙烯酰亚胺泡沫塑料进行辐照,辐照能量为1Mev,辐照剂量为1000KGy,得到辐射交联聚甲基丙烯酰亚胺泡沫塑料。
所述的光敏剂为所述的光敏剂为一种聚离子液型光敏剂,按照以下方法制备:在反应釜中,按重量份计加入(甲基)丙烯腈100份,10份4-丙烯酰氧基二苯甲酮,0.5份1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,0.01份(Z)-9-十八烯酸铜(II)盐,0.01份3-(2-甲氧基吡啶-3-基)丙烯酸,3000份水,1份分散剂,2份过氧化苯甲酰,在80℃反应12h,过滤,烘干后得到聚离子液型光敏剂。
对比例1
(1)将(甲基)丙烯腈30重量份、(甲基)丙烯酸70重量份、苯乙烯1重量份、AIBN 0.1重量份、异丙醇5重量份、氧化钙1-3重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于30℃下反应100h,得到透明的塑料板,然后将塑料板在60℃下热处理60h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在180℃下发泡2h,得到聚甲基丙烯酰亚胺泡沫塑料;
对比例2
(1)将(甲基)丙烯腈54重量份、(甲基)丙烯酸46重量份、衣康酸6.4重量份、十六烷基过二碳酸酯1.24重量份、尿素11重量份、甲基丙烯酸钙1.8重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于48℃下反应76h,得到透明的塑料板,然后将塑料板在102℃下热处理36h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在210℃下发泡4.4h,得到聚甲基丙烯酰亚胺泡沫塑料;
对比例3
(1)将(甲基)丙烯腈70重量份、(甲基)丙烯酸30重量份、乙烯基吡咯烷酮10重量份、过2-乙基己酸叔丁基酯2重量份、正丁醇15重量份、三丙二醇二丙烯酰胺1重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于60℃下反应60h,得到透明的塑料板,然后将塑料板在130℃下热处理20h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在230℃下发泡6h,得到聚甲基丙烯酰亚胺泡沫塑料;
对比例4
(1)将(甲基)丙烯腈70重量份、(甲基)丙烯酸30重量份、乙烯基吡咯烷酮10重量份、过2-乙基己酸叔丁基酯2重量份、正丁醇15重量份、三丙二醇二丙烯酰胺8重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于60℃下反应60h,得到透明的塑料板,然后将塑料板在130℃下热处理20h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在230℃下发泡6h,得到聚甲基丙烯酰亚胺泡沫塑料;
所得PMI塑料板在发泡过程中开裂。
对比例5
(1)将(甲基)丙烯腈54重量份、(甲基)丙烯酸46重量份、衣康酸6.4重量份、十六烷基过二碳酸酯1.24重量份、尿素11重量份、甲基丙烯酸钙8重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于48℃下反应76h,得到透明的塑料板,然后将塑料板在102℃下热处理36h,得到聚甲基丙烯酰亚胺塑料;
聚合过程异常,所得PMI塑料板不均匀。
下表列出了实施例和对比实施例中制备的材料的各项性能参数。
表观 | 密度kg/m<sup>3</sup> | 压缩强度MPa | 热变形温度℃ | |
实施例1 | 正常 | 110 | 4.7 | 260 |
实施例2 | 正常 | 98 | 4.0 | 258 |
实施例3 | 正常 | 86 | 3.3 | 256 |
实施例4 | 正常 | 74 | 2.5 | 254 |
实施例5 | 正常 | 50 | 1.1 | 250 |
对比例1 | 正常 | 110 | 3.6 | 195 |
对比例2 | 正常 | 74 | 1.7 | 190 |
对比例3 | 正常 | 50 | 0.8 | 185 |
对比例4 | 发泡开裂 | 150 | - | - |
对比例5 | 聚合不正常 | - | - | - |
如上表所示,基于实施例1/4/5和对比例1/2/3的比较,相同配方工艺得到的泡沫板,经过辐照处理后,压缩强度和热变形温度明显提高,说明辐照工艺促进了PMI泡沫交联密度的提高;基于实施例5和对比例4的比较,通过增加配方中交联剂的含量来提高交联密度,会导致泡沫密度大幅度提高,且发生发泡开裂的现象,而发泡后辐照交联保持密度不变,且不会出现开裂现象;基于实施例4、对比例2和对比例5的比较,通过增加配方中的交联剂来提高交联密度,会出现聚合异常,从而导致所得PMI泡沫板出现产品缺陷,需要对聚合工艺进行调整,工艺复杂,而辐照后交联则不存在以上缺点。
对比例6
不加入1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,其它同实施例1,热变形温度227℃。
对比例7
不加入(Z)-9-十八烯酸铜(II)盐,其它同实施例1,热变形温度238℃。
对比例8
不加入3-(2-甲氧基吡啶-3-基)丙烯酸,其它同实施例1,热变形温度242℃。
Claims (11)
1.一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于,包括如下步骤:
(1)将(甲基)丙烯腈30-70重量份、(甲基)丙烯酸30-70重量份、第三共聚单体0-10重量份、引发剂0.1-2重量份、发泡剂5-15重量份、光敏剂0.5-5重量份、交联剂1-3重量份混合均匀,充分溶解后注入密闭的平面模具中;
(2)将模具置于30-60℃下反应60-100h,得到透明的塑料板,然后将塑料板在60-130℃下热处理20-60h,得到聚甲基丙烯酰亚胺塑料;
(3)将板材在180-230℃下发泡2-6h,得到聚甲基丙烯酰亚胺泡沫塑料;
(4)将聚甲基丙烯酰亚胺泡沫塑料进行辐照,辐照能量为1-4Mev,辐照剂量为200-1000KGy,得到辐射交联聚甲基丙烯酰亚胺泡沫塑料。
2.根据权利要求1所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述的光敏剂为一种聚离子液型光敏剂,按照以下方法制备:
在反应釜中,按重量份计加入(甲基)丙烯腈100份,3-10份4-丙烯酰氧基二苯甲酮,0.01-0.5份1-烯丙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐,0.01-0.5份(Z)-9-十八烯酸铜(II)盐,0.01-0.5份3-(2-甲氧基吡啶-3-基)丙烯酸,1000-3000份水,1-4份分散剂,0.5-2份过氧化苯甲酰,在80℃-95℃反应5-12h,过滤,烘干后得到聚离子液型光敏剂。
3.根据权利要求1所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述第三共聚单体,指为了调节竞聚率,改善聚合物性能的烯属不饱和单体,所述第三共聚单体为马来酰亚胺及其衍生物、苯乙烯、马来酸或其酸酐、衣康酸或其酸酐、乙烯基吡咯烷酮、氯乙烯、偏二氯乙烯中的一种或几种的组合物。
4.根据权利要求3所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述第三共聚单体选自马来酰亚胺、苯乙烯、马来酸酐、衣康酸、乙烯基吡咯烷酮。
5.根据权利要求1所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述引发剂为偶氮二异丁腈、偶氮二异戊腈或偶氮二异庚腈、过氧化二苯甲酰、过氧化月桂酰、过氧化辛酸叔丁酯或过氧化二缩酮、十六烷基过二碳酸酯、丁基过二碳酸酯、戊基过二碳酸酯、过新戊酸叔丁基酯、过苯甲酸叔丁基酯、过2-乙基己酸叔丁基酯、偶氮-双(4-氰基戊酸)或者偶氮-双(4-氰基戊酸)中的一种或几种的组合物。
6.根据权利要求5所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述的引发剂选自偶氮二异丁腈、过氧化二苯甲酰、过新戊酸叔丁基酯、十六烷基过二碳酸酯、过2-乙基己酸叔丁基酯。
7.根据权利要求1所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述发泡剂为多元醇类或脲类,所述发泡剂为异丙醇、叔丁醇、叔戊醇、尿素、甲基脲、二甲基脲、异丁醇、正丁醇或己醇中一种或几种的组合物。
8.根据权利要求7所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述的发泡剂选自异丙醇、叔丁醇、甲基脲、尿素、正丁醇。
9.根据权利要求1所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述交联剂为金属氧化物、金属氢氧化物、金属盐类、多元醇类或多元烯烃类,所述交联剂为氧化钙、氧化镁、丙烯酰胺(AM)、甲基丙烯酰胺(MAM)、三聚氰酸三烯丙酯、甲基丙烯酸烯丙酯、甲基丙烯酸金属盐、丙烯酸金属盐、金属氧化物、丙烯酸烯丙基酯、甲基丙烯酸烯丙基酯、烯丙基丙烯酰胺、烯丙基甲基丙烯酰胺、亚甲基-二-丙烯酰胺或-甲基丙烯酰胺、二亚乙基双(碳酸烯丙基酯)、乙二醇二丙烯酸酯或-二甲基丙烯酸酯、二甘醇二丙烯酰胺或-二甲基丙烯酰胺、三甘醇二丙烯酰胺或-二甲基丙烯酰胺、四甘醇二丙烯酰胺或-二甲基丙烯酰胺、三丙二醇二丙烯酰胺或-二甲基丙烯酰胺、1,3-丁二醇二丙烯酸酯或-二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯或-二甲基丙烯酸酯、新戊二醇二丙烯酸酯或-二甲基丙烯酸酯、己二醇-1,6-二丙烯酸酯或-二甲基丙烯酸酯、三羟甲基丙烷二丙烯酸酯或-二甲基丙烯酸酯,三羟甲基丙烷三丙烯酸酯或-三甲基丙烯酸酯、季戊四醇三丙烯酸酯或-三甲基丙烯酸酯、季戊四醇四丙烯酸酯或-四甲基丙烯酸酯、季戊四醇衍生物、三烯丙基异氰尿酸酯或三烯丙基氰尿酸酯、叔丁胺中一种或几种的组合物。
10.根据权利要求9所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述的交联剂选自氧化钙、甲基丙烯酰胺、三聚氰酸三烯丙酯、甲基丙烯酸钙、三丙二醇二丙烯酰胺。
11.根据权利要求1所述的一种辐射交联聚甲基丙烯酰亚胺泡沫及其制备方法,其特征在于:所述辐照方式为电子束、γ射线、中子束或粒子束辐照中的至少一种。
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JPH04170408A (ja) * | 1990-11-01 | 1992-06-18 | Mitsubishi Rayon Co Ltd | 発泡性プラスチックス及び発泡プラスチックスの製法 |
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CN102850486A (zh) * | 2012-09-06 | 2013-01-02 | 江苏兆鋆新材料科技有限公司 | 一种大孔径聚甲基丙烯酰亚胺泡沫塑料及其制备方法 |
CN104610562A (zh) * | 2015-02-15 | 2015-05-13 | 浩博(福建)新材料科技有限公司 | 一种聚甲基丙烯酰亚胺泡沫的制备方法 |
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JPH04170408A (ja) * | 1990-11-01 | 1992-06-18 | Mitsubishi Rayon Co Ltd | 発泡性プラスチックス及び発泡プラスチックスの製法 |
GB2458663A (en) * | 2008-03-26 | 2009-09-30 | Thales Holdings Uk Plc | Radome for a radar pressurised horn antenna |
CN102850486A (zh) * | 2012-09-06 | 2013-01-02 | 江苏兆鋆新材料科技有限公司 | 一种大孔径聚甲基丙烯酰亚胺泡沫塑料及其制备方法 |
CN104610562A (zh) * | 2015-02-15 | 2015-05-13 | 浩博(福建)新材料科技有限公司 | 一种聚甲基丙烯酰亚胺泡沫的制备方法 |
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