CN112646376A - 一种碳纤维橡胶复合管及其制备方法 - Google Patents
一种碳纤维橡胶复合管及其制备方法 Download PDFInfo
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- CN112646376A CN112646376A CN202011352000.XA CN202011352000A CN112646376A CN 112646376 A CN112646376 A CN 112646376A CN 202011352000 A CN202011352000 A CN 202011352000A CN 112646376 A CN112646376 A CN 112646376A
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- carbon fiber
- rubber
- parts
- pipe
- tube
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- Rigid Pipes And Flexible Pipes (AREA)
Abstract
本发明涉及一种碳纤维橡胶复合管，包括内管、套设在所述的内管外部的外管、形成在所述的内管与所述的外管之间的碳纤维骨架层，所述的内管的材质包括硅橡胶、聚苯硫醚颗粒；所述外管的材质包括硅橡胶。其制备方法，包括制备硅橡胶、内胶橡胶片，通过内胶橡胶片成形内管，内管外周面上包覆至少一层碳纤维布成形碳纤维骨架层，当包覆多层碳纤维布时，层与层之间涂抹粘合剂后固化，通过硅橡胶成形外管，并附着于碳纤维骨架层的外周面，定型得到复合管，将复合管经硫化得到碳纤维橡胶复合管。本发明的结构特征以及材料配比使得橡胶管具有较强的耐腐蚀性能，可作为化学试剂的载体。
Description
技术领域
本发明属于管材技术领域，具体涉及一种碳纤维橡胶复合管及其制备方法。
背景技术
橡胶管是现代工业中的重要部件，潮湿环境、腐蚀性化学试剂等均会对橡胶管造成腐蚀。现有技术普通的硅胶管用硅胶通过挤出成管状，这种硅胶管并不具有很好的耐腐蚀性，不能应用于特殊环境以及腐蚀性化学试剂的运输。
参见公开号为CN111057381A的中国专利，公开了一种橡胶管及其制备方法，所述橡胶管包括：内管；所述内管的材质包括乙丙橡胶和/或丁腈橡胶；复合在所述内管上的钢丝骨架层；复合在所述钢丝骨架层上的硅橡胶复合材料层；所述硅橡胶复合材料层由包括如下重量份的原料制备得到：甲基乙烯基硅橡胶70～100份；气相法白炭黑20～50份；羟基硅油1～10份；硅烷偶联剂1～5份；低熔点玻璃粉20～50份；高岭土20～50份；三氧化二锑10～50份；硼酸锌10～50份；双二五1～5份。该专利提供的橡胶管具有较优的阻燃耐火性能和耐高温老化性能，但是其耐腐蚀性仍然存在局限。
综上所述，现有技术还缺少一种耐腐蚀性的橡胶管。
发明内容
本发明的一个目的是提供一种碳纤维橡胶复合管，解决了现有的橡胶管耐腐蚀性能差的问题。
为达到上述目的，本发明采用的技术方案是：
一种碳纤维橡胶复合管，包括内管、套设在所述的内管外部的外管、形成在所述的内管与所述的外管之间的碳纤维骨架层，所述的内管的材质包括硅橡胶、聚苯硫醚颗粒；所述外管的材质包括硅橡胶。
其中，内管主要提供柔软性和耐腐蚀性；
外管主要增强橡胶管的强度，起到保护内管以及碳纤维骨架层的作用，以及提供柔软性；
碳纤维骨架层起到支撑以及连接内管和外管的作用，提供主要的力学性能，也提供一定耐腐蚀性。
优选地，所述的硅橡胶按重量份计，包括以下原料组分：
甲基乙烯基硅橡胶 100份；
白炭黑 30-50份；
硅油 1-15份；
硅烷偶联剂 1-3份；
阻燃剂 20-100份；
硫化剂 1-3份。
进一步优选地，所述的甲基乙烯基硅橡胶由二甲基硅氧烷与少量乙烯基硅氧烷共聚而成，对硅橡胶起到耐老化、防潮、电绝缘性的作用。
进一步优选地，所述的白炭黑即二氧化硅，对硅橡胶起到补强作用，按制备方法分，包括气相二氧化硅、液相二氧化硅等。
更进一步优选地，所述的白炭黑包括气相二氧化硅，提高对内管的增强效果。
进一步优选地，所述的硅油选自环氧基硅油、异氰酸酯基硅油、羟基硅油、羧基硅油中的一种或多种，提高内管的力学强度和耐腐蚀性。硅油是不同聚合度链状结构的聚有机硅氧烷，对硅橡胶起到抗氧化、耐腐蚀、抗压缩的作用。硅油可以列举出环氧基硅油、异氰酸酯基硅油、羟基硅油、羧基硅油、甲基硅油、苯基硅油。
更进一步优选地，所述硅油选自环氧基硅油、异氰酸酯基硅油。
进一步优选地，所述的硅烷偶联剂选自氨乙基氨丙基三甲氧基硅烷、缩水甘油基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷中的一种或多种，提高强度、抗气候性。硅烷偶联剂的分子结构式一般为:Y-R-Si(OR)3，式中Y为有机官能基,Si（OR）为硅烷氧基，硅烷氧基对无机物具有反应性，有机官能基对有机物具有反应性或相容性，硅烷偶联剂起增加硅橡胶粘连性、强度、抗水、抗气候等性能的作用。硅烷偶联剂可以列举出自氨乙基氨丙基三甲氧基硅烷、缩水甘油基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷。
更进一步优选的，所述硅烷偶联剂为缩水甘油基丙基三甲氧基硅烷。
进一步优选地，所述的阻燃剂选自氢氧化铝、氢氧化镁、三氧化二锑、硼酸锌中的一种或多种，提高各组分的阻燃作用。阻燃剂是赋予易燃聚合物难燃性的功能性助剂，起阻燃的作用。阻燃剂可以列举出氢氧化铝、氢氧化镁、三氧化二锑、硼酸锌、聚磷酸铵、八溴醚、磷酸三苯酯、六溴环十二烷、聚磷酸铵、十溴二苯醚、磷酸三苯酯、十溴二苯乙烷，从硅橡胶组分主要为甲基乙烯基硅橡胶、白炭黑、硅油。
进一步优选地，所述的硫化剂选自2，5-二甲基-2，5-双(叔丁基过氧化）已烷、过氧化二叔丁烷、过氧化环己酮、过氧化月桂酸、过氧化叔丁基叔戊酸酯中的一种或多种，提高耐老化、耐热性。硫化剂是N，N'-间苯撑双马来酰亚胺，起防止硫化返原，改善耐热性，降低生热，耐老化的作用。硫化剂可以列举出2，5-二甲基-2，5-双(叔丁基过氧化）已烷、过氧化二叔丁烷、过氧化环己酮、过氧化月桂酸、过氧化叔丁基叔戊酸酯、硫黄、一氯化硫、硒、碲。
优选地，所述的聚苯硫醚颗粒占内管重量的20%-60%。进一步优选地，所述的聚苯硫醚颗粒占内管重量的30%-50%，过多的聚苯硫醚颗粒会导致橡胶管硬度过高、脆性增强，过少的聚苯硫醚颗粒会降低橡胶管的耐腐蚀性能。
优选地，所述的聚苯硫醚颗粒的平均粒径为50-80μm。进一步优选的，所述聚苯硫醚颗粒的平均粒径为60-75微米，平均粒径过大，橡胶管柔软度降低；平均粒径过小，橡胶管力学性能差。
聚苯硫醚（PPS）是分子主链中含有如下结构单元的特种工程塑料，熔点约280℃，有优异的理化性能，具有力学强度高、耐高温、高阻燃、抗辐射、硬度高、热稳定性好、电性能优良等特点，尤其是聚苯硫醚的耐化学药品性极好，内管中含有聚苯硫醚颗粒可以有效的提高橡胶管的耐腐蚀性。
优选地，所述的碳纤维骨架层包括至少一层碳纤维布。考虑到内管和外管更好的粘附以及整个橡胶管的力学强度，所述的碳纤维骨架层包括多层碳纤维布，多层所述的碳纤维布从内至外包覆在所述的内管上，且内层所述的碳纤维布的厚度大于外层所述的碳纤维布的厚度，可增加橡胶管的柔软性。
进一步优选的，所述纤维骨架层为两层，通过胶粘剂粘合。胶粘剂可以列举出丁钠橡胶、异戊橡胶、聚硫橡胶、聚氨酯橡胶、氯磺化聚乙烯弹性体。考虑到碳纤维骨架层的特定材质，更进一步优选的，所述胶粘剂为有机硅胶粘剂。
优选的，所述内管的厚度为3-4mm，所述外管的厚度为2-3mm，所述碳纤维骨架层厚度为0.08-0.80mm；进一步优选的，所述碳纤维骨架层厚度为0.32mm。
本发明的另一个目的是提供一种碳纤维橡胶复合管的制备方法。
为达到上述目的，本发明采用的技术方案是：
一种碳纤维橡胶复合管的制备方法，包括：
S1：制备硅橡胶：按重量份计，包括以下原料：
甲基乙烯基硅橡胶 100份；
白炭黑 30-50份；
硅油 1-15份；
硅烷偶联剂 1-3份；
阻燃剂 20-100份；
硫化剂 1-3份，
S2：制备内胶橡胶片：按重量份计，包括以下原料：
硅橡胶 100份；
聚苯硫醚颗粒 50-100份，
S3：通过内胶橡胶片成形内管，具体可以采用如挤出成形的方式，
S4：在内管外周面上包覆至少一层厚度为0.08-0.80m的碳纤维布成形碳纤维骨架层，当包覆多层碳纤维布时，层与层之间涂抹粘合剂后固化，
S5：通过硅橡胶成形外管，具体可以采用如挤出成形的方式，并附着于碳纤维骨架层的外周面，在300～400℃下定型，得到复合管，
S6：将复合管经硫化得到碳纤维橡胶复合管。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
本发明的结构特征以及材料配比使得橡胶管具有较强的耐腐蚀性能，可作为化学试剂的载体。
附图说明
附图1为本实施例的示意图。
以上附图中：
1、外管，2、碳纤维骨架层，3、内管。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
如图1所示的一种碳纤维橡胶复合管，包括外管1、碳纤维骨架层2和内管3，外管1、碳纤维骨架层2和内管3从外到内依次分布，外管1同轴套设在内管3外，碳纤维骨架层2包覆在内管3的外周面。内管3的厚度为4mm，外管1的厚度为2mm，碳纤维骨架层2为碳纤维布，厚度为0.40mm，碳纤维骨架层2厚度为0.40mm可为多层，本实施例中，碳纤维骨架层厚度为两层，两层碳纤维骨架层间用有机硅胶粘剂粘连。
实施例一：
S1、按以下材料及组分制备硅橡胶：
甲基乙烯基硅橡胶100份；
气相二氧化硅50份；
环氧基硅油10份；
缩水甘油基丙基三甲氧基硅烷2份；
氢氧化铝25份；
过氧化环己酮1份，
S2、将S1制备的硅橡胶100重量份与平均粒径为70μm的聚苯硫醚颗粒50重量份制成内胶橡胶片，
S3、将S2制备的内胶橡胶片经挤出，得到内管，
S4、将S3制备的内管外部附上2层厚度为0.32mm的碳纤维布，其中靠内层的碳纤维布厚度为0.2mm，靠外层的碳纤维布为0.12mm，碳纤维骨架层间涂抹有机硅胶粘剂后固化，
S5、将S1制备的硅胶像制成外管，经挤出工艺，附着于碳纤维骨架层的外表面，并在300～400℃下定型，得到复合胶管；
S6、将S5制备的复合胶管经硫化，得到碳纤维橡胶复合管。
实施例二：
S1、按以下材料及组分制备硅橡胶：
甲基乙烯基硅橡胶100份；
气相二氧化硅50份；
羟基硅油5份；
环氧基硅油5份
乙烯基三乙氧基硅烷3份；
氢氧化铝25份；
过氧化环己酮3份，
S2、将S1制备的硅橡胶100重量份与平均粒径为50μm的聚苯硫醚颗粒100重量份制成内胶橡胶片,
S3、将S2制备的内胶橡胶片经挤出，得到内管，
S4、将S3制备的内管外部附上2层厚度为0.11mm的碳纤维布，其中靠内层的碳纤维布厚度为0.8mm，靠外层的碳纤维布为0.3mm，碳纤维骨架层与层之间涂抹有机硅胶粘剂后固化，
S5、将S1制备的硅胶像制成外管，经挤出工艺，附着于碳纤维骨架层的外表面，并在300～400℃下定型，得到复合胶管；
S6、将S5得到的复合胶管经硫化，得到碳纤维橡胶复合管。
实施例三：
S1、按以下材料及组分制备硅橡胶：
甲基乙烯基硅橡胶100份；
气相二氧化硅30份；
羟基硅油15份；
缩水甘油基丙基三甲氧基硅烷1份；
乙烯基三乙氧基硅烷1份；
氢氧化镁20份；
过氧化环己酮3份，
S2、将S1制备的硅橡胶100重量份与平均粒径为80μm的聚苯硫醚颗粒80重量份制成内胶橡胶片，
S3、将S2制备的内胶橡胶片经挤出，得到内管，
S4、将S3制备的内管外部附上2层厚度为0.61mm的碳纤维布，其中靠内层的碳纤维布厚度为0.4mm，靠外层的碳纤维布为0.21mm，碳纤维骨架层与层之间涂抹有机硅胶粘剂后固化，
S5、将S1制备的硅胶像制成外管，经挤出工艺，附着于碳纤维骨架层的外表面，并在300～400℃下定型，得到复合胶管，
S6、将S5得到的复合胶管经硫化，得到碳纤维橡胶复合管。
实施例四：
S1、按以下材料及组分制备硅橡胶：
甲基乙烯基硅橡胶100份；
气相二氧化硅50份；
环氧基硅油10份；
缩水甘油基丙基三甲氧基硅烷2份；
氢氧化铝25份；
过氧化环己酮1份，
S2、将S1制备的硅橡胶100重量份与平均粒径为70μm的聚苯硫醚颗粒50重量份制成内胶橡胶片，
S3、将S2制备的内胶橡胶片经挤出，得到内管，
S4、将S3制备的内管外部附上2层厚度为0.32的碳纤维布，其中靠内层的碳纤维布厚度为0.1mm，靠外层的碳纤维布为0.22mm，碳纤维骨架层间涂抹有机硅胶粘剂后固化，
S5、将S1制备的硅胶像制成外管，经挤出工艺，附着于碳纤维骨架层的外表面，并在300～400℃下定型，得到复合胶管，
S6、将S5得到的复合胶管经硫化，得到碳纤维橡胶复合管。
实施例五：
将实施例一的S2中的平均粒径为70μm的聚苯硫醚颗粒更换为聚对苯二甲酸丁二醇酯颗粒，其余步骤与实施例一相同。
实施例六：
在实施例一的S2中不添加平均粒径为70μm的聚苯硫醚颗粒，其余步骤与实施例一相同。
按照实施例一至四的方法分别制备内直径为25mm、外直径为38mm的碳纤维橡胶复合管，并分别检测各橡胶管的最小弯曲半径，结果如下表所示：
| 实施例一 | 实施例二 | 实施例三 | 实施例四 | |
| 最小弯曲半径 | 65mm | 63mm | 66mm | 85mm |
上述结果可以看出，实施例一至三碳纤维橡胶复合管的最小弯曲半径明显小于实施例四制备的碳纤维橡胶复合管的最小弯曲半径，也就是说，实施例一至三的碳纤维橡胶复合管的柔性优于实施例四的碳纤维橡胶复合管，可能与实施例一至三的碳纤维布从内到外各层厚度递减有关。
将实施例一至六制备的碳纤维橡胶复合管和网上购买的普通的市售硅胶橡胶管中装满72%的硫酸，分别于72小时、120小时后观察橡胶管的腐蚀情况，结果如下表：
| 时间 | 实施例一 | 实施例二 | 实施例三 | 实施例四 | 实施例五 | 实施例六 | 市售硅胶管 |
| 72小时 | 无腐蚀 | 无腐蚀 | 无腐蚀 | 无腐蚀 | 无腐蚀 | 无腐蚀 | 轻微腐蚀 |
| 120小时 | 无腐蚀 | 无腐蚀 | 无腐蚀 | 无腐蚀 | 轻微腐蚀 | 轻微腐蚀 | 严重腐蚀 |
上述结果可以看出，采用本实施例制备的硅胶橡胶管（实施例一-实施例四）相对于市售的硅胶橡胶管具有较强的耐腐蚀性能，将本实施例制备硅胶橡胶管使用的聚苯硫醚颗粒换成实施例五的聚对苯二甲酸丁二醇酯颗粒，或实施例六中不添加颗粒，制备的橡胶管耐腐蚀性能降低，但也高于市售的普通的硅胶橡胶管。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种碳纤维橡胶复合管，其特征在于：包括内管、套设在所述的内管外部的外管、形成在所述的内管与所述的外管之间的碳纤维骨架层，所述的内管的材质包括硅橡胶、聚苯硫醚颗粒；所述外管的材质包括硅橡胶。
2.根据权利要求1所述的碳纤维橡胶复合管，其特征在于：所述的硅橡胶按重量份计，包括以下原料组分：
甲基乙烯基硅橡胶 100份；
白炭黑 30-50份；
硅油 1-15份；
硅烷偶联剂 1-3份；
阻燃剂 20-100份；
硫化剂 1-3份。
3.根据权利要求2所述的碳纤维橡胶复合管，其特征在于：所述的硅油选自环氧基硅油、异氰酸酯基硅油、羟基硅油、羧基硅油中的一种或多种。
4.根据权利要求2所述的碳纤维橡胶复合管，其特征在于：所述的硅烷偶联剂选自氨乙基氨丙基三甲氧基硅烷、缩水甘油基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷中的一种或多种。
5.根据权利要求2所述的碳纤维橡胶复合管，其特征在于：所述的阻燃剂选自氢氧化铝、氢氧化镁、三氧化二锑、硼酸锌中的一种或多种。
6.根据权利要求2所述的碳纤维橡胶复合管，其特征在于：所述的硫化剂选自2，5-二甲基-2，5-双(叔丁基过氧化）已烷、过氧化二叔丁烷、过氧化环己酮、过氧化月桂酸、过氧化叔丁基叔戊酸酯中的一种或多种。
7.根据权利要求1所述的碳纤维橡胶复合管，其特征在于：所述的聚苯硫醚颗粒占内管重量的20%-60%。
8.根据权利要求1所述的碳纤维橡胶复合管，其特征在于：所述的聚苯硫醚颗粒的平均粒径为50-80μm。
9.根据权利要求1所述的碳纤维橡胶复合管，其特征在于：所述的碳纤维骨架层包括至少一层碳纤维布，当所述的碳纤维骨架层包括多层碳纤维布时，多层所述的碳纤维布从内至外包覆在所述的内管上，且内层所述的碳纤维布的厚度大于外层所述的碳纤维布的厚度。
10.一种制备上述任意一项权利要求所述的碳纤维橡胶复合管的方法，其特征在于：包括：
S1：制备硅橡胶：按重量份计，包括以下原料：
甲基乙烯基硅橡胶 100份；
白炭黑 30-50份；
硅油 1-15份；
硅烷偶联剂 1-3份；
阻燃剂 20-100份；
硫化剂 1-3份，
S2：制备内胶橡胶片：按重量份计，包括以下原料：
硅橡胶 100份；
聚苯硫醚颗粒 50-100份，
S3：通过内胶橡胶片成形内管，
S4：在内管外周面上包覆至少一层厚度为0.08-0.80m的碳纤维布成形碳纤维骨架层，当包覆多层碳纤维布时，层与层之间涂抹粘合剂后固化，
S5：通过硅橡胶成形外管，并附着于碳纤维骨架层的外周面，在300～400℃下定型，得到复合管，
S6：将复合管经硫化得到碳纤维橡胶复合管。
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