CN1030391C - 一种改性沥青及其制备方法 - Google Patents
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Abstract
本发明涉及一种用于机械挤出包覆金属管道的改性沥青及其制备方法,其主要成份为氧化沥青、无规聚丙烯、短切玻璃纤维、再生橡胶、滑石粉及交联剂等组成,通过物理、化学方法使上述物质混熔、交联,其生成物可用于金属管道直接包覆,也可在管道的保温层上包覆。由于采用沥青、再生橡胶为主要原料,使之具有价格低廉的特点,并具有良好的防腐性能、低温柔韧性、较高的抗拉强度、抗应力开裂等特性。
Description
本发明涉及一种可用于机械挤出包覆金属管道的改性沥青材料及其制备方法。
目前,国内外用于埋地输油、气、水管的金属管道防腐涂层,主要是采用以下材料,如氧化沥青、煤焦油瓷漆、焦油环氧、聚烯烃树脂、环氧粉末及胶粘带。对于具有保温要求的输送管道,能作为管道保温层的外护层材料的一般只有聚烯烃树脂。由于上述防腐材料涂层薄抗冲击性、耐候性差,或有不密闭的气孔、针孔存在,至使防腐性能不能满足技术要求。近年来发展起来的金属管道“黄夹克”、“黑夹克”虽具有较好的防腐保温的综合性能,但由于其消耗大量价格昂贵的化工材料使其工业应用受到影响。国外开发的新型防腐材料如EP125852、US4404316、DE3203226、SU1174662、SU1062229、SU1116260等公开的技术内容仍是占有相当多成份的高级化工材料或其制成品并属于涂敷物或缠绕式密封胶带材料,做为防腐保温材料,仍具有价格昂贵或工艺性差的缺陷。
本发明的目的在于提供一种改性沥青及其制备方法。其产物可用作机械挤出包覆金属管道的防腐材料。可用于金属管道直接包覆或在管道保温层上包覆。由于采用氧化沥青和再生橡胶为主要原料,使之具有价格低廉的特点,具有良好的防腐性能、低温柔韧性,较高的抗拉强度、抗应力开裂等特性。同时具有很好的机械剂出包覆性能和较高的软化点。从而克服黄(黑)夹克的造价昂贵及沥青基片材包覆材料工艺复杂、可靠性差等现有技术带来的缺陷。使管道防腐保温材料用于机械挤出包覆输
送管道的技术具有更加广阔的前景。本发明所涉及的改性沥青是在氧化沥青中添加无规聚丙烯、再生橡胶、短切玻璃纤维、滑石粉、交联助剂等改性物质,不含有挥发性有机溶剂(可避免因挥发性溶剂的挥发造成的针孔等密封的缺陷)。在不改变氧化沥青原有防腐特性的前题下,通过物理、化学改性。
一种改性沥青,其特征在于:由氧化沥青、无规聚丙烯、再生橡胶、短切玻璃纤维、交联助剂、抗氧剂、硬脂酸(或油酸)、有机过氧化物、滑石粉、氯化石蜡各组份经混合或化合而成。其中各组份的重量百分比为:
组份 重量(%)
氧化沥青 30~80%
无规聚丙烯 5~22%
再生橡胶 5~40%
短切玻璃纤维 5~20%
交联助剂 0.025~4.4%
抗氧剂 0.001~1%
硬脂酸(或油酸) 0.5~7%
滑石粉 5~20%
氯化石蜡 0.5~25%
有机过氧化物为无规聚丙烯的0.01~5%。一种改性沥青(本发明)的制备方法,其特征在于:将针入度为10~80的氧化沥青粉碎成为重量不超过1000克的碎块,放入沥青加热锅中进行熬制,加热温度控制在230~240℃左右,当沥青完全熔化后保温在180~230℃,并以150~200转/分的速度进行搅拌约60~120分钟,然后将经过偶联剂溶液处理并烘干的短切玻璃纤维分批加入。待其散开后将液态1,2-聚丁二烯成二乙烯苯作为交联助剂加入混匀。再加入无规聚丙烯,在上述填加组分(除玻璃纤维外)完全熔化、混合均匀时,将含有机过氧化物的液体滴加入上述混合物中,然后用滑石粉脱模制成片材,降温至60~80℃时与再生橡胶(切成碎块的)混炼,并加入硬脂酸或油酸处理过的滑石粉、抗氧剂、氯化石蜡。混炼均匀后再加入滑石粉脱模并将滑石粉作为隔离剂制成5~15毫米厚的片材,盘卷后储备。
本发明所述的氧化沥青可以是由常减压得到的重油,经进一步吹气氧化制得的氧化沥青,也可以是低硫石蜡基氧化沥青,其针入度在25℃时为10~80。
本发明所述的无规聚丙烯为制造聚丙烯的副产品。特性粘度(135℃时十氢萘溶剂中)为1.6~1.9左右。
本发明所述的交联助剂是含有二个及二个以上双键的烯烃的单体或齐聚体。如1,2-聚丁二烯(数均分子量一般在2000~7000),或二乙烯苯。
本发明所述的再生橡胶为废旧橡胶制品,如废旧轮胎除去帘线后经机械粉碎制得。
本发明所述的短切玻璃纤维,其长度为5~15毫米,单纤维直径为8~13微米,玻璃纤维表面经硅烷偶联剂处理,该偶联剂可以是A-174(r-甲基丙烯酰氧(基)丙基三甲氧基硅烷),也可以是A-1100(r-胺丙基三乙氧基硅烷)。当硅烷偶联剂水溶液涂布在玻璃纤维表面后,在水溶液中OR基水解成OH基。也即烷氧基水解成硅烷醇。其与玻璃纤维表面亲水基团反应或缩合,产生化学反应,生成化学键合。而硅烷分子另一端的R′宫能性有机基团能与改性沥青中的有机基团反应,产生物理或化学键合。因此使亲水的玻璃纤维同氧化沥青,无规聚丙烯、橡胶等憎水物之间由硅烷偶联剂作用产生物理或化学键合,从而变得相容,提高改性沥青的强度及抗应力开裂能力。
本发明所述的抗氧剂可以是N-异丙基-N′-苯基-对苯二胺,也可以是2,2,4-三甲基-6-乙氧基-1,2-二氧化喹啉。
本发明所述的滑石粉,主要成分为含水硅酸镁,比重2.7~2.8克/厘米,粒径2~10微米,经硬脂酸或油酸处理。
本发明所述的有机过氧化物为叔丁基过氧化氢或异丙苯基过氧化氢或过氧化异丙苯或过氧化二叔丁烷、或过氧化二异丙苯、溶解在甲苯或***等有机溶剂中。有机过氧化物作为一种交联引发剂混炼在上述沥青混熔物中,受热后分解生成游离基,开始引发交联反应,使得无规聚丙烯、1,2-聚丁二烯(或二乙烯苯)、及沥青中的有机活性基团以及通过化学及物理的键合而连接上的硅烷偶联剂上的官能性活性基团,通过连锁加成及连锁转移产生共交联,从而在该混合物中由分子链相互交联生成三维的空间网状结构。使得该混合物表现出类似橡胶的质感,改善整个物质的抗拉强度、低温柔韧性,提高软化点。
实施例:将针入度为20的低硫石蜡基氧化沥青500份(重量)粉碎后放入加热锅中熬制。加热温度控制在230~240℃之间。当沥青完全熔化后以200转/分左右的速度搅拌约60分钟,促其充分熔化。然后将经硅烷偶联剂处理过的短切玻璃纤维50份(重量)烘干后少量多次加入。待玻璃纤维被搅拌分散开后,在200℃左右的温度下将液态1,2-聚丁二烯18份(重量)、特性粘度1.8(135℃时+氢萘溶剂中)的无规聚丙烯180份(重量)依次加入沥青加热锅中,搅拌至完全混合均匀(无规聚丙烯为燕山石化总公司向阳化工厂产或辽阳化纤厂产,液态1,2-聚丁二烯为化工部晨光化工研究院-分院产)。再将1.4份(重量)的叔丁基过氧化氢或异丙基苯过氧化氢溶解在适量的甲苯或***中,搅拌均匀后对加热锅进行滴加,控制在5至10分钟左右滴加完毕。然后持续搅拌20至35分钟,比时反应已基本结束(其过程中加入的有机溶剂也在加热反应中挥发出去)。将此混熔物用滑石粉脱模压制成厚度10毫米左右的片材,待其降温至60~80℃时即可与再生橡胶混炼。首先将开放式双辊炼胶机的辊距调节8毫米左右,速比1∶1.25,前辊筒温度保持55~60,后辊筒温度保持在45~50℃左右,将200份(重量)的再生橡胶块投入,同时加入90份(重量)经硬脂酸或油酸处理过的滑石粉(其中滑石粉85份、硬脂酸5份),再加入作抗氧剂0.1份(重量)的N-异丙基-N′-苯基-对苯二胺以及8份(重量)氯化石蜡。待基本混炼均匀后,再加入前述的经滑石粉脱模的沥青混熔物片材,直至完全混合均匀。前后共需约35~40分钟,然后调整辊距压制成10毫米左右的片材,并分割、盘卷。
本发明的改性沥青在用于机械挤出包覆管道时,只需将盘卷储备的片材放入挤出机的加温装置中,经加热后将其挤出包覆在管道上。
Claims (6)
1、一种改性沥青,其特征在于:用氧化沥青、无规聚丙烯、再生橡胶、经硅烷偶联处理过的短切玻璃纤维、交联助剂、抗氧剂、硬脂酸或油酸、有机过氧化物、滑石粉、氯化石蜡各组份经混合或化合而成;其中各原料的重量(份)为:
组份 重量(份)
氧化沥青 500
无规聚丙烯 180
再生橡胶 200
经硅烷偶联剂处理过的
短切玻璃纤维 50
交联助剂 18
抗氧剂 0.1
硬脂酸或油酸 5
滑石粉 85
氯化石蜡 8
有机过氧化物 1.4;
交联助剂是含有2个及2个以上双键的烯烃的单体或齐聚体
2、改性沥青的制备方法,其特征在于:将针入度10~80的氧化沥青粉碎成为重量不超过1000克的碎块,放入沥青加热锅中进行熬制,加热温度控制在230~240℃,当沥青完全熔化后保温在180~230℃,并以150~200转/分的速度进行搅拌约60~120分钟,然后将经过硅烷偶联剂溶液处理并烘干的短切玻璃纤维分批加入,待其散开后,将液状交联助剂加入混均,交联助剂是含有2个及2个以上双键的烯烃的单体或齐聚体,再加入无规聚丙烯;在除短切玻璃纤维外的上述填加组份完全熔化、混合均匀时,将过氧化物溶液体滴加入上述混合物中,滴加控制在5~10分钟完成,继续搅拌20~35分钟;然后用滑石粉脱模制成片材,降温至60~80℃时与再生橡胶混炼,并加入硬脂酸或油酸处理过的滑石粉、抗氧剂、氯化石蜡,混炼均匀;使用滑石粉脱模并将滑石粉作为隔离剂制成5~15毫米厚的片材,盘卷后储备。
3、根据权利要求1所述的一种改性沥青,其特征在于:抗氧剂是N-异丙基-N′-苯基-对苯二胺,也可以是2,2,4-三甲基-6-乙氧基-1,2-二氧化喹啉。
4、根据权利要求1所述的一种改性沥青,其特征在于:有机过氧化物可以是叔丁基过氧化氢或异丙苯基过氧化氢或过氧化二叔丁烷或过氧化二异丙苯。
5、根据权利要求2所述的改性沥青的制备方法,其特征在于:抗氧剂是N-异丙基-N′-苯基-对苯二胺,也可以是2,2,4-三甲基-6-乙氧基-1,2-二氧化喹啉。
6、根据权利要求2所述的改性沥青的制备方法,其特征在于:有机过氧化物可以是叔丁基过氧化氢或异丙苯基过氧化氢或过氧化二叔丁烷或过氧化二异丙苯。
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CN100344702C (zh) * | 2006-03-24 | 2007-10-24 | 张平 | 一种沥青填料组合物 |
CN101671144B (zh) * | 2008-09-09 | 2011-11-16 | 河南现代交通道路科技有限责任公司 | 一种胶粉改性沥青及其制备方法 |
CN101864182B (zh) * | 2009-12-09 | 2012-01-04 | 济南开发区星火科学技术研究院 | 一种改性建筑沥青及其生产方法 |
KR101044997B1 (ko) * | 2010-11-25 | 2011-06-29 | 최동순 | 전자부품 보호용 아스팔트 조성물, 이의 제조방법, 및 이를 포함하는 전자 유닛 |
CN105273235A (zh) * | 2014-07-12 | 2016-01-27 | 卢桂才 | 含巯基桥联剂的反应型沥青防水密封膏及其制备方法 |
CN104592774A (zh) * | 2015-01-15 | 2015-05-06 | 吴江华威特种油有限公司 | 一种道路改性沥青 |
CN104774478B (zh) * | 2015-04-07 | 2018-06-08 | 中国石油天然气股份有限公司 | 一种适用于改性石油沥青防腐层挤出成型的sbs改性沥青 |
CN105885693B (zh) * | 2016-03-14 | 2018-05-11 | 北京东方雨虹防水技术股份有限公司 | 一种非固化橡胶沥青防水涂料及其制备方法、复合防水卷材 |
CN108659554B (zh) * | 2017-03-31 | 2021-10-22 | 中国石油化工股份有限公司 | 阻燃低粘橡胶沥青及其制备方法 |
US20190337851A1 (en) * | 2018-05-02 | 2019-11-07 | Building Materials Investment Corporation | Preparation of inured asphalt blown coating |
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