CN111087652A - 一种硅橡胶耐热添加剂及其制备方法 - Google Patents
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- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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Abstract
Description
技术领域
本公开涉及硅橡胶领域,具体涉及一种硅橡胶耐热添加剂及其制备方法。
背景技术
硅橡胶是一种以Si原子和O原子交替键合构成分子主链骨架、各种有机基团作为侧基的特种橡胶。因其不同于普通橡胶的碳链结构,硅橡胶具有优异的耐高低温性、耐候性、电绝缘性、抗霉菌和生理惰性等。普通硅橡胶一般可以在-50~260℃温度范围内长期使用并保持弹性,而苯基硅橡胶耐热温度更是达到300~350℃。但随着科技的发展,尤其是航空航天领域的发展,当前硅橡胶的耐热性已经不能满足一些特殊领域的使用要求。因此,硅橡胶的耐热性有待进一步提高。
目前主要通过加入无机耐热添加剂或硅树脂等方式来提高硅橡胶的耐热性。常用的无机耐热添加剂有氧化铁、氧化铈、氧化镍、氧化钴、白炭黑等,或通过对这些金属氧化物进行改性、以不同比例混合制得耐热添加剂;宋远周等采用纳米CeO2、纳米Fe2O3和经硅烷偶联剂处理过的Al2O3作为耐热填料制备耐热硅橡胶,显著提高了硅橡胶的耐热性;由于硅树脂能与硅橡胶交联,提高了硅橡胶的交联度,起到了补强作用,还一定程度上破坏了硅橡胶的螺旋结构,使主链更难发生解扣式降解,从而提高硅橡胶的耐高温性能;Kang Min-Joo等通过对纳米二氧化硅进行臭氧处理,增加其在硅树脂中的扩散度,并用熔融共混法将混有纳米二氧化硅的硅树脂加入硅橡胶中制备一种新型硅橡胶/硅树脂复合材料,随着复合材料中的硅树脂含量增加,复合材料的热稳定性有显著的提高。
综上所述,当前对于耐热添加剂的研究有一定的进展,但现有的耐热添加剂还存在不足:金属氧化物极性较大,与硅橡胶的相容性较差,难以分散,添加过多会导致硅橡胶弹性及力学性能严重下降;硅树脂与硅橡胶的相容性较好,但对硅橡胶的耐高温性能提高有限,对硅橡胶的硬度等力学性能也有一定影响。因此,研究一种高效的硅橡胶耐热添加剂,制备具有良好耐高温和力学性能的硅橡胶具有重要意义。
发明内容
本公开的目的在于提供一种硅橡胶耐热添加剂及其制备方法,使所述硅橡胶耐热添加剂用于硅橡胶的制备时不仅可提高硅橡胶的耐热性能,还能提高硅橡胶的力学性能。
为实现上述目的,技术方案如下:
一种硅橡胶耐热添加剂,所述硅橡胶耐热添加剂的化学结构为:
一种硅橡胶耐热添加剂的制备方法,所述制备方法的具体步骤为:
(1)在受阻酚溶液中滴加硅烷偶联剂和催化剂,在氮气保护下进行反应,反应结束后再进行蒸馏、分液和干燥,得到受阻酚硅烷偶联剂反应物;
(2)配制白炭黑溶液,然后加入受阻酚硅烷偶联剂反应物,在氮气保护下搅拌反应,反应结束后冷却,然后再进行抽滤、洗涤和真空干燥,最后得到硅橡胶耐热添加剂。
所述受阻酚溶液的配制方法为将受阻酚溶于甲苯或氯苯中,所述受阻酚溶液的浓度为10-50wt%。
所述受阻酚为2,6-二叔丁基-4-羟甲基苯酚或2,2'-亚甲基双-(4-甲基-6-叔丁基苯酚)。
所述硅烷偶联剂的结构式为:(OR)3SiCH2CH2CH2NCO,其中R为-CH3或-CH2CH3。
所述催化剂的添加量为0.5-3g;所述催化剂为三乙胺。
所述白炭黑为气相法或沉淀法白炭黑。
所述白炭黑溶液的配制方法为将白炭黑溶于甲苯、水或乙醇中,所述白炭黑溶液的固含量为2%-85%。
所述受阻酚的质量为硅烷偶联剂质量的0.4-1.1倍,所述硅烷偶联剂的质量为白炭黑质量的0.2-1倍。
所述步骤(1)中反应的温度为20-110℃,所述反应的时间为0.5-24h。
所述步骤(2)中反应的温度为30-120℃,反应的时间为2-12h。
所述真空干燥的温度为60℃。
本公开的有益效果是:提供了一种硅橡胶耐热添加剂及其制备方法,所述硅橡胶耐热添加剂克服了常用硅橡胶耐热添加剂相容性差、效率低的缺点,可保证硅橡胶在长期使用过程中性能的稳定,在制备本公开所述硅橡胶耐热添加剂的过程中受阻酚与硅烷偶联剂进行反应得到氨基甲酸酯,所述氨基甲酸酯可负载于白炭黑上,能够提高硅橡胶耐热添加剂捕捉自由基的能力,用于硅橡胶中可有效抑制硅橡胶热氧降解,同时硅橡胶耐热添加剂还起到硅橡胶补强的作用,使得所述硅橡胶耐热添加剂不仅能够提高硅橡胶的耐热性能,还能够提高硅橡胶的力学性能。
具体实施方式
以下各步骤仅用以说明本公开的技术方案,而非对其限制;尽管参照前述各步骤对本公开进行了详细的说明,但本领域的普通技术人员应当理解:其依然可以对前述各步骤所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本公开各步骤技术方案的范围。
实施例1
一种硅橡胶耐热添加剂的制备方法,所述制备方法的具体步骤为:
(1)在配有磁搅拌、冷凝管、滴定管和氮气保护的三口瓶中加入2,2'-亚甲基双-(4-甲基-6-叔丁基苯酚)溶液(3g的2,2'-亚甲基双-(4-甲基-6-叔丁基苯酚)溶于12g甲苯中),将5g异氰酸丙基三乙氧基硅烷和1g三乙胺滴加至反应体系,在氮气保护下80℃反应8h,反应结束后再进行蒸馏、分液和干燥,得到受阻酚硅烷偶联剂反应物;
(2)将10g气相法白炭黑(比表面积200m3/g)分散于20g甲苯中,然后加入受阻酚硅烷偶联剂反应物,在氮气保护下70℃搅拌反应8h,反应结束后冷却,然后再进行抽滤、洗涤和60℃真空干燥8h,最后得到硅橡胶耐热添加剂。
实施例2
一种硅橡胶耐热添加剂的制备方法,所述制备方法的具体步骤为:
(1)在配有磁搅拌、冷凝管、滴定管和氮气保护的三口瓶中加入2,6-二叔丁基-4-羟甲基苯酚溶液(1.6g的2,6-二叔丁基-4-羟甲基苯酚溶于16g氯苯中),将4g异氰酸丙基三乙氧基硅烷和0.5g三乙胺滴加至反应体系,在氮气保护下20℃反应24h,反应结束后再进行蒸馏、分液和干燥,得到受阻酚硅烷偶联剂反应物;
(2)将8g气相法白炭黑(比表面积200m3/g)分散于400g甲苯中,然后加入受阻酚硅烷偶联剂反应物,在氮气保护下30℃搅拌反应12h,反应结束后冷却,然后再进行抽滤、洗涤和60℃真空干燥8h,最后得到硅橡胶耐热添加剂。
实施例3
一种硅橡胶耐热添加剂的制备方法,所述制备方法的具体步骤为:
(1)在配有磁搅拌、冷凝管、滴定管和氮气保护的三口瓶中加入2,6-二叔丁基-4-羟甲基苯酚溶液(6.6g的2,6-二叔丁基-4-羟甲基苯酚溶于13.2g甲苯中),将6g异氰酸丙基三乙氧基硅烷和3g三乙胺滴加至反应体系,在氮气保护下110℃反应0.5h,反应结束后再进行蒸馏、分液和干燥,得到受阻酚硅烷偶联剂反应物;
(2)将6g气相法白炭黑(比表面积200m3/g)分散于7.06g甲苯中,然后加入受阻酚硅烷偶联剂反应物,在氮气保护下120℃搅拌反应2h,反应结束后冷却,然后再进行抽滤、洗涤和60℃真空干燥8h,最后得到硅橡胶耐热添加剂。
实施例4
分别将实施例1-3中所制备的硅橡胶耐热添加剂用于硅橡胶的制备,其中硅橡胶的制备方法为:90质量份0.06mol%乙烯基含量的甲基乙烯基硅橡胶(分子量56万)、10质量份1mol%乙烯基含量的甲基乙烯基硅橡胶(分子量60万)、30质量份气相法白炭黑(比表面积300m3/g)、8质量份羟基硅油(羟基含量6wt%)在捏合机中混合,室温下混炼4h;再加热至150℃继续混炼2h,然后抽真空混炼1h,冷却至室温,得到硅橡胶基础胶;
将上述基础胶在开炼机上加入10质量份硅橡胶耐热添加剂(实施例1、实施例2和实施例3所制备的硅橡胶耐热添加剂)和1.5质量份2,5-二甲基-2,5-二叔丁基过氧化已烷,混炼均匀后出片;在165℃下分别硫化15min和10min,得到耐热硅橡胶试样,再于180℃下二段硫化4h,得到用于热性能和力学性能测试的样品。
对比例1:
90质量份0.06mol%乙烯基含量的甲基乙烯硅橡胶(分子量56万)、10质量份1mol%乙烯基含量的甲基乙烯基硅橡胶(分子量60万)、30质量份气相法白炭黑(比表面积300m3/g)、8质量份羟基硅油(羟基含量6wt%)在捏合机中混合,室温下混炼4h;再加热至150℃继续混炼2h,然后抽真空混炼1h,冷却至室温,得到硅橡胶基础胶;
将上述基础胶在开炼机上加入1.5质量份2,5-二甲基-2,5-二叔丁基过氧化已烷,混炼均匀后出片。在165℃下分别硫化15min和10min,得到耐热硅橡胶试样,再于180℃下二段硫化4h,得到用于耐漏电起痕和力学性能测试的硅橡胶样品。
对比例2:
90质量份0.06mol%乙烯基含量的甲基乙烯硅橡胶(分子量56万)、10质量份1mol%乙烯基含量的甲基乙烯基硅橡胶(分子量60万)、30质量份气相法白炭黑(比表面积300m3/g)、8质量份羟基硅油(羟基含量6wt%)在捏合机中混合,室温下混炼4h;再加热至150℃继续混炼2h,然后抽真空混炼1h,冷却至室温,得到硅橡胶基础胶;
将上述基础胶在开炼机上加入1.5质量份2,5-二甲基-2,5-二叔丁基过氧化已烷和10质量份的氧化铈,混炼均匀后出片;在165℃下分别硫化15min和10min,得到耐热硅橡胶试样,再于180℃下二段硫化4h,得到用于耐漏电起痕和力学性能测试的硅橡胶样品。
分别将实施例1、实施例2和实施例3所制备的硅橡胶耐热添加剂用于硅橡胶后得到的耐热硅橡胶样品和对比例1、对比例2所制备的硅橡胶样品,按照GB/T 528-2009测定硅橡胶的拉伸强度及断裂伸长率,按照GB/T 529-2008测定硅橡胶的撕裂强度,按照GB/T531-2008测定硅橡胶的邵氏A硬度,通过热失重分析测试硅橡胶热稳定性参数。
结果如表1,可以看出分别利用实施例1、实施例2和实施例3制备的硅橡胶耐热添加剂添加到硅橡胶的制备中,不仅可以提高硅橡胶的耐热性,而且还能提高硅橡胶的力学性能。
表1硅橡胶的力学性能和热稳定性能
Claims (10)
2.如权利要求书1所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述制备方法的具体步骤为:
(1)在受阻酚溶液中滴加硅烷偶联剂和催化剂,在氮气保护下进行反应,反应结束后再进行蒸馏、分液和干燥,得到受阻酚硅烷偶联剂反应物;
(2)配制白炭黑溶液,然后加入受阻酚硅烷偶联剂反应物,在氮气保护下搅拌反应,反应结束后冷却,然后再进行抽滤、洗涤和真空干燥,最后得到硅橡胶耐热添加剂。
3.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述受阻酚溶液的配制方法为将受阻酚溶于甲苯或氯苯中,所述受阻酚溶液的浓度为10-50wt%。
4.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述受阻酚为2,6-二叔丁基-4-羟甲基苯酚或2,2'-亚甲基双-(4-甲基-6-叔丁基苯酚)。
5.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述硅烷偶联剂的结构式为:(OR)3SiCH2CH2CH2NCO,其中R为-CH3或-CH2CH3。
6.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述催化剂的添加量为0.5-3g;优选地所述催化剂为三乙胺。
7.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述白炭黑溶液的配制方法为将白炭黑溶于甲苯、水或乙醇中,所述白炭黑溶液的固含量为2%-85%;优选地所述白炭黑为气相法或沉淀法白炭黑。
8.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述受阻酚的质量为硅烷偶联剂质量的0.4-1.1倍,所述硅烷偶联剂的质量为白炭黑质量的0.2-1倍。
9.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述步骤(1)中反应的温度为20-110℃,所述反应的时间为0.5-24h。
10.根据权利要求书2中所述的硅橡胶耐热添加剂的制备方法,其特征在于,所述步骤(2)中反应的温度为30-120℃,反应的时间为2-12h;优选地所述真空干燥的温度为60℃。
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