CN114133525A - 一种自修复耐高温聚氨酯弹性体的制备方法及其应用 - Google Patents
一种自修复耐高温聚氨酯弹性体的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开一种自修复耐高温聚氨酯弹性体、制备方法及其应用,所述自修复耐高温聚氨酯弹性体利用双硫键、氢键、配位键、离子键的多重可逆交联作用进行自修复;该聚氨酯弹性体由以下质量份原料制出:聚四亚甲基醚二醇55~65份、4,4二苯基甲烷二异氰酸酯20~30份、六亚甲基二异氰酸酯20~25份、3,3'‑二硫代双(丙酰肼)2~4份、1‑(2‑氨基乙基)咪唑啉‑2‑酮1~2份、氯化铁0.2~0.4份、氯化铜0.2~0.4份、丙酮20~30份、扩链剂9~18份、催化剂0.2~0.3份、改性高分子粉料1~15份。本发明制出的自修复耐高温聚氨酯弹性体无需外界刺激,即使在常压常温条件下,也能实现自修复功能,有效克服聚氨酯类活塞在工作时由于内能转换造成的损伤、形变和磨损问题,且具有硬度高、耐磨、耐高温、耐高压等优点。
Description
技术领域
本发明属于自修复高分子材料合成领域,还属于聚氨酯弹性体技术领域,具体涉及一种自修复耐高温聚氨酯弹性体的制备方法及其应用。
背景技术
活塞和胶皮是泥浆泵在钻井过程中最重要部件之一,其工作环境十分恶劣。在钻井过程中,泥浆泵活塞损坏而频繁更换,大大降低了钻井工作效率,影响生产进度,并且在更换泥浆泵活塞的费用上也浪费巨大。
活塞一般是用橡胶或者普通聚氨酯制作,但橡胶活塞存在硬度低、耐高温差、承压能力差、耐磨性低等缺点,相比于橡胶活塞,现有聚氨酯活塞虽然表现出更良好的耐磨性,但随着泵送时间的增加、内能的不断转换,造成磨损增大、泵内温度不断升高,导致聚氨酯活塞严重的损伤及不可逆的形变。因此,如何研制出一种可自修复、耐高温、耐高压聚氨酯弹性体具有重要意义,以克服聚氨酯类活塞在工作时造成的不可逆损伤问题。
发明内容
针对现有技术的不足之处,本发明的目的在于提供一种自修复耐高温聚氨酯弹性体的制备方法及其应用。
本发明的技术方案概述如下:
一种自修复耐高温聚氨酯弹性体,其特征在于,所述自修复耐高温聚氨酯弹性体利用双硫键、氢键、配位键、离子键的多重可逆交联作用进行自修复;该聚氨酯弹性体由以下质量份原料制出:聚四亚甲基醚二醇55~65份、4,4二苯基甲烷二异氰酸酯20~30份、六亚甲基二异氰酸酯20~25份、3,3'-二硫代双(丙酰肼)2~4份、1-(2-氨基乙基)咪唑啉-2-酮1~2份、氯化铁0.2~0.4份、氯化铜
0.2~0.4份、丙酮20~30份、扩链剂9~18份、催化剂0.2~0.3份、改性高分子粉料1~15份。
优选的是,所述扩链剂为3,3’-二氯-4,4’-二氨基二苯基甲烷、1,4-丁二醇、氢醌-双(β-羟乙基)醚中的一种或几种。
优选的是,所述催化剂为二丁基锡二月桂酸酯、二醋酸二丁基锡、三乙胺、三乙烯二胺、五甲基二乙烯三胺中的一种或多种。
优选的是,所述改性高分子粉料为改性芳纶、改性超高分子量聚乙烯中的一种或两种。
优选的是,所述改性芳纶的制备方法为:将芳纶研磨成粒径为10~100μm的微粒,再按1g/(1~1.5)mL的比例将其加入到质量浓度为50%的磷酸溶液中,搅拌分散后,升温至100~120℃反应15~60min,过滤后,再用蒸馏水洗涤至中性,即得改性芳纶。
优选的是,所述改性超高分子量聚乙烯的制备方法为:将改性超高分子量聚乙烯研磨成粒径为10~100μm的微粒,再按1g/(1~1.5)mL的比例将其加入到由重铬酸钾、质量分数为98%的浓硫酸、水按1:2:10质量比配制的混合溶液中,25℃室温搅拌处理15~60min,过滤后,再用蒸馏水洗涤至中性,即得改性超高分子量聚乙烯。
优选的是,所述重铬酸钾、质量分数为98%的浓硫酸、水的质量比为1:2:10。
本发明还进一步提供一种自修复耐高温聚氨酯弹性体的制备方法,包括以下步骤:
S1:在温度为110~120℃、真空度≤0.1MPa条件下,将聚四亚甲基醚二醇脱水处理3h后,再加入4,4二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、催化剂,于氮气保护下,50~60℃搅拌反应20~30min,再升温至75~85℃,继续搅拌反应2~3h,得聚氨酯预聚体;
S2:将氯化铁、氯化铜溶解于丙酮中,再加入1-(2-氨基乙基)咪唑啉-2-酮,40~50℃搅拌反应1~2h后,加入3,3'-二硫代双(丙酰肼),搅拌溶解后,得自修复单体溶液;
S3:将S2所得自修复单体溶液加入S1所得聚氨酯预聚体中,50~55℃搅拌反应3~4h,再加入改性高分子粉料,搅拌均匀、脱泡处理后,得聚氨酯混合物;
S4:110~130℃熔化扩链剂后,加入S3所得聚氨酯混合物中,搅拌均匀后,并倒入90℃金属模具中,脱模35~45min,再于90~120℃硫化16~24h,得所述自修复耐高温聚氨酯弹性体。
本发明还进一步提供一种自修复耐高温聚氨酯弹性体在活塞或活塞胶皮中的应用。
本发明的有益效果:
(1)本发明以聚四亚甲基醚二醇为软段,以4,4二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯为硬段,由于软段和硬段间存在排斥作用,导致软段和硬段在不同区域高度集中,形成具有微相分离的形状记忆聚氨酯分子链,并进一步利用聚氨酯预聚体中游离-NCO与3,3'-二硫代双(丙酰肼)、Fe3+/Cu2+/1-(2-氨基乙基)咪唑啉-2-酮配合物中的-NH2的亲核加成反应,在聚氨酯分子链中引入双硫键、氢键、配位键、离子键及咪唑啉酮六元杂环结构,将双硫键、氢键、配位键、离子键、形状记忆效应相结合,通过多重动态可逆交联作用实现自修复。
(2)本发明制出的自修复耐高温聚氨酯弹性体无需外界刺激,即使在常压常温条件下,也能实现自修复功能,有效克服聚氨酯类活塞在工作时由于内能转换造成的损伤、形变和磨损问题。
(3)本发明制备出的聚氨酯弹性体具有硬度高、耐磨、耐高温、耐高压等优点,能显著延长聚氨酯活塞或聚氨酯胶皮的使用寿命。
附图说明
图1为本发明一种自修复耐高温聚氨酯弹性体的制备方法流程图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
实施例1
一种自修复耐高温聚氨酯弹性体的制备方法,包括以下步骤:
S1:将芳纶研磨成粒径为10μm的微粒,再按1g/1mL的比例将其加入到质量浓度为50%的磷酸溶液中,搅拌分散后,升温至100℃反应15min,过滤后,再用蒸馏水洗涤至中性,即得改性芳纶;
S2:按质量份原料依次称取聚四亚甲基醚二醇55份、4,4二苯基甲烷二异氰酸酯20份、六亚甲基二异氰酸酯20份、3,3'-二硫代双(丙酰肼)2份、1-(2-氨基乙基)咪唑啉-2-酮1份、氯化铁0.2份、氯化铜0.2份、丙酮20份、3,3’-二氯-4,4’-二氨基二苯基甲烷9份、二丁基锡二月桂酸酯0.2份、改性芳纶2份;
S3:在温度为110℃、真空度≤0.1MPa条件下,将聚四亚甲基醚二醇脱水处理3h后,再加入4,4二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二丁基锡二月桂酸酯,于氮气保护下,50℃搅拌反应20min,再升温至75℃,继续搅拌反应2h,得聚氨酯预聚体;
S4:将氯化铁、氯化铜溶解于丙酮中,再加入1-(2-氨基乙基)咪唑啉-2-酮,40℃搅拌反应1h后,加入3,3'-二硫代双(丙酰肼),搅拌溶解后,得自修复单体溶液;
S5:将S4所得自修复单体溶液加入S3所得聚氨酯预聚体中,50℃搅拌反应3h,再加入改性高分子粉料,搅拌均匀、脱泡处理后,得聚氨酯混合物;
S6:110℃熔化3,3’-二氯-4,4’-二氨基二苯基甲烷后,加入S5所得聚氨酯混合物中,搅拌均匀后,并倒入90℃金属模具中,脱模35min,再于90℃硫化16h,得所述自修复耐高温聚氨酯弹性体。
实施例2
一种自修复耐高温聚氨酯弹性体的制备方法,包括以下步骤:
S1:将改性超高分子量聚乙烯研磨成粒径为50μm的微粒,再按1g/1.25mL的比例将其加入到由重铬酸钾、质量分数为98%的浓硫酸、水按1:2:10质量比配制的混合溶液中,25℃室温搅拌处理40min,过滤后,再用蒸馏水洗涤至中性,即得改性超高分子量聚乙烯;
S2:按质量份原料依次称取聚四亚甲基醚二醇60份、4,4二苯基甲烷二异氰酸酯25份、六亚甲基二异氰酸酯20份、3,3'-二硫代双(丙酰肼)3份、1-(2-氨基乙基)咪唑啉-2-酮1.5份、氯化铁0.3份、氯化铜0.3份、丙酮25份、氢醌-双(β-羟乙基)醚14份、二醋酸二丁基锡0.25份、改性高分子粉料8份;
S3:在温度为115℃、真空度≤0.1MPa条件下,将聚四亚甲基醚二醇脱水处理3h后,再加入4,4二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二醋酸二丁基锡,于氮气保护下,55℃搅拌反应25min,再升温至80℃,继续搅拌反应2.5h,得聚氨酯预聚体;
S4:将氯化铁、氯化铜溶解于丙酮中,再加入1-(2-氨基乙基)咪唑啉-2-酮,45℃搅拌反应1.5h后,加入3,3'-二硫代双(丙酰肼),搅拌溶解后,得自修复单体溶液;
S5:将S4所得自修复单体溶液加入S3所得聚氨酯预聚体中,55℃搅拌反应3.5h,再加入改性高分子粉料,搅拌均匀、脱泡处理后,得聚氨酯混合物;
S6:120℃熔化氢醌-双(β-羟乙基)醚后,加入S5所得聚氨酯混合物中,搅拌均匀后,并倒入90℃金属模具中,脱模40min,再于105℃硫化20h,得所述自修复耐高温聚氨酯弹性体。
实施例3
一种自修复耐高温聚氨酯弹性体的制备方法,包括以下步骤:
S1:将芳纶研磨成粒径为10~100μm的微粒,再按1g/1.5mL的比例将其加入到质量浓度为50%的磷酸溶液中,搅拌分散后,升温至120℃反应60min,过滤后,再用蒸馏水洗涤至中性,即得改性芳纶;
S2:按质量份原料依次称取聚四亚甲基醚二醇65份、4,4二苯基甲烷二异氰酸酯30份、六亚甲基二异氰酸酯25份、3,3'-二硫代双(丙酰肼)4份、1-(2-氨基乙基)咪唑啉-2-酮2份、氯化铁0.4份、氯化铜0.4份、丙酮30份、3,3’-二氯-4,4’-二氨基二苯基甲烷18份、三乙胺0.3份、改性芳纶4份;
S3:在温度为110-120℃、真空度≤0.1MPa条件下,将聚四亚甲基醚二醇脱水处理3h后,再加入4,4二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、三乙胺,于氮气保护下,60℃搅拌反应30min,再升温至85℃,继续搅拌反应3h,得聚氨酯预聚体;
S4:将氯化铁、氯化铜溶解于丙酮中,再加入1-(2-氨基乙基)咪唑啉-2-酮,50℃搅拌反应2h后,加入3,3'-二硫代双(丙酰肼),搅拌溶解后,得自修复单体溶液;
S5:将S4所得自修复单体溶液加入S3所得聚氨酯预聚体中,55℃搅拌反应4h,再加入改性芳纶,搅拌均匀、脱泡处理后,得聚氨酯混合物;
S6:130℃熔化3,3’-二氯-4,4’-二氨基二苯基甲烷后,加入S5所得聚氨酯混合物中,搅拌均匀后,并倒入90℃金属模具中,脱模45min,再于120℃硫化24h,得所述自修复耐高温聚氨酯弹性体。
对比例与实施例1相同,区别在于:
S2中:称取3,3'-二硫代双(丙酰肼)3.4份,且制备原料中不包含1-(2-氨基乙基)咪唑啉-2-酮、氯化铁、氯化铜;
S4中自修复单体溶液不包含1-(2-氨基乙基)咪唑啉-2-酮与Fe3+、Cu2+的配合物,该自修复单体溶液制备方法为:将3.4份3,3'-二硫代双(丙酰肼)加入20份丙酮中,搅拌溶解后,即得。
对实施例1~3及对比例制备的聚氨酯弹性体进行硬度、拉伸强度、扯断伸长率、撕裂强度、滚筒磨耗量、回弹值、热变形温度进行检测,试验结果如表1所示。
表1实施例1~3及对比例制备的聚氨酯弹性体性能检测结果
由表1可知,相比于未添加Fe3+/Cu2+/1-(2-氨基乙基)咪唑啉-2-酮配合物的对比例,实施例1制备的自修复聚氨酯弹性体在滚筒磨耗量、回弹值、拉伸强度、扯断伸长率、直角撕裂强度等方面均得到显著提升,证明了Fe3+/Cu2+/1-(2-氨基乙基)咪唑啉-2-酮配合物能大幅度提升聚氨酯自修复性能。
实施例1~3以聚四亚甲基醚二醇为软段,以4,4二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯为硬段,由于软段和硬段间存在排斥作用,导致软段和硬段在不同区域高度集中,形成具有微相分离的形状记忆聚氨酯分子链,并进一步利用聚氨酯预聚体中游离-NCO与3,3'-二硫代双(丙酰肼)、Fe3+/Cu2+/1-(2-氨基乙基)咪唑啉-2-酮配合物中的-NH2的亲核加成反应,在聚氨酯分子链中引入双硫键、氢键、配位键、离子键及咪唑啉酮六元杂环结构,将双硫键、氢键、配位键、离子键、形状记忆效应相结合,通过多重动态可逆交联作用实现自修复。
实施例1~3制出的自修复耐高温聚氨酯弹性体无需外界刺激,即使在常压常温条件下,也能实现自修复功能,有效克服聚氨酯类活塞在工作时由于内能转换造成的损伤、形变和磨损问题。
实施例1~3制备出的聚氨酯弹性体具有硬度高、耐磨、耐高温、耐高压等优点,应用于活塞或活塞胶皮时,能显著延长活塞或胶皮的使用寿命。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。
Claims (9)
1.一种自修复耐高温聚氨酯弹性体,其特征在于,所述自修复耐高温聚氨酯弹性体利用双硫键、氢键、配位键、离子键的多重可逆交联作用进行自修复;该聚氨酯弹性体由以下质量份原料制出:聚四亚甲基醚二醇55~65份、4,4二苯基甲烷二异氰酸酯20~30份、六亚甲基二异氰酸酯20~25份、3,3'-二硫代双(丙酰肼)2~4份、1-(2-氨基乙基)咪唑啉-2-酮1~2份、氯化铁0.2~0.4份、氯化铜0.2~0.4份、丙酮20~30份、扩链剂9~18份、催化剂0.2~0.3份、改性高分子粉料1~15份。
2.根据权利要求1所述的一种自修复耐高温聚氨酯弹性体,其特征在于,所述扩链剂为3,3’-二氯-4,4’-二氨基二苯基甲烷、1,4-丁二醇、氢醌-双(β-羟乙基)醚中的一种或几种。
3.根据权利要求1所述的一种自修复耐高温聚氨酯弹性体,其特征在于,所述催化剂为二丁基锡二月桂酸酯、二醋酸二丁基锡、三乙胺、三乙烯二胺、五甲基二乙烯三胺中的一种或多种。
4.根据权利要求1所述的一种自修复耐高温聚氨酯弹性体,其特征在于,所述改性高分子粉料为改性芳纶、改性超高分子量聚乙烯中的一种或两种。
5.根据权利要求4所述的一种自修复耐高温聚氨酯弹性体,其特征在于,所述改性芳纶的制备方法为:将芳纶研磨成粒径为10~100μm的微粒,再按1g/(1~1.5)mL的比例将其加入到质量浓度为50%的磷酸溶液中,搅拌分散后,升温至100~120℃反应15~60min,过滤后,再用蒸馏水洗涤至中性,即得改性芳纶。
6.根据权利要求4所述的一种自修复耐高温聚氨酯弹性体,其特征在于,所述改性超高分子量聚乙烯的制备方法为:将改性超高分子量聚乙烯研磨成粒径为10~100μm的微粒,再按1g/(1~1.5)mL的比例将其加入到由重铬酸钾、质量分数为98%的浓硫酸、水配制的混合溶液中,25℃室温搅拌处理15~60min,过滤后,再用蒸馏水洗涤至中性,即得改性超高分子量聚乙烯。
7.根据权利要求6所述的一种自修复耐高温聚氨酯弹性体的制备方法,其特征在于,所述重铬酸钾、质量分数为98%的浓硫酸、水的质量比为1:2:10。
8.根据权利要求1~7任一项所述的一种自修复耐高温聚氨酯弹性体的制备方法,其特征在于,包括以下步骤:
S1:在温度为110~120℃、真空度≤0.1MPa条件下,将聚四亚甲基醚二醇脱水处理3h后,再加入4,4二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、催化剂,于氮气保护下,50~60℃搅拌反应20~30min,再升温至75~85℃,继续搅拌反应2~3h,得聚氨酯预聚体;
S2:将氯化铁、氯化铜溶解于丙酮中,再加入1-(2-氨基乙基)咪唑啉-2-酮,40~50℃搅拌反应1~2h后,加入3,3'-二硫代双(丙酰肼),搅拌溶解后,得自修复单体溶液;
S3:将S2所得自修复单体溶液加入S1所得聚氨酯预聚体中,50~55℃搅拌反应3~4h,再加入改性高分子粉料,搅拌均匀、脱泡处理后,得聚氨酯混合物;
S4:110~130℃熔化扩链剂后,加入S3所得聚氨酯混合物中,搅拌均匀后,并倒入90℃金属模具中,脱模35~45min,再于90~120℃硫化16~24h,得所述自修复耐高温聚氨酯弹性体。
9.根据权利要求1~7任一项所述的一种自修复耐高温聚氨酯弹性体在活塞或活塞胶皮中的应用。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103242645A (zh) * | 2013-05-31 | 2013-08-14 | 四川大学 | 高耐磨共混聚合物材料或制品及其制备方法 |
CN106117486A (zh) * | 2016-06-27 | 2016-11-16 | 青岛科技大学 | 含酰腙键的二元醇、含酰腙键和双硫键的二元醇、自修复聚氨酯弹性体及其制备方法 |
CN107383332A (zh) * | 2017-08-22 | 2017-11-24 | 广东电网有限责任公司电力科学研究院 | 一种聚氨酯聚合物及其制备方法和应用 |
DE102017125179A1 (de) * | 2017-10-26 | 2019-05-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Modifizierte Härterkomponente für ein Polymer und insbesondere für 2K-Formulierungen mit selbstheilenden Eigenschaften |
DE102017125178A1 (de) * | 2017-10-26 | 2019-05-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Elektronische und elektrotechnische Baugruppe bzw. Bauteil mit selbstheilender Beschichtung mit elektrischer Isolationswirkung |
CN110790888A (zh) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | 基于多重动态可逆作用的高强度室温自修复聚氨酯弹性体及其制备与应用 |
CN111826075A (zh) * | 2020-07-03 | 2020-10-27 | 安徽朗凯奇防水科技股份有限公司 | 自修复有机氟硅改性聚氨酯防水涂料及其制备方法 |
CN112122437A (zh) * | 2020-08-05 | 2020-12-25 | 浙江安胜科技股份有限公司 | 一种保温容器智能化拉伸处理方法 |
-
2021
- 2021-12-16 CN CN202111547969.7A patent/CN114133525A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103242645A (zh) * | 2013-05-31 | 2013-08-14 | 四川大学 | 高耐磨共混聚合物材料或制品及其制备方法 |
CN106117486A (zh) * | 2016-06-27 | 2016-11-16 | 青岛科技大学 | 含酰腙键的二元醇、含酰腙键和双硫键的二元醇、自修复聚氨酯弹性体及其制备方法 |
CN107383332A (zh) * | 2017-08-22 | 2017-11-24 | 广东电网有限责任公司电力科学研究院 | 一种聚氨酯聚合物及其制备方法和应用 |
DE102017125179A1 (de) * | 2017-10-26 | 2019-05-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Modifizierte Härterkomponente für ein Polymer und insbesondere für 2K-Formulierungen mit selbstheilenden Eigenschaften |
DE102017125178A1 (de) * | 2017-10-26 | 2019-05-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Elektronische und elektrotechnische Baugruppe bzw. Bauteil mit selbstheilender Beschichtung mit elektrischer Isolationswirkung |
CN110790888A (zh) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | 基于多重动态可逆作用的高强度室温自修复聚氨酯弹性体及其制备与应用 |
CN111826075A (zh) * | 2020-07-03 | 2020-10-27 | 安徽朗凯奇防水科技股份有限公司 | 自修复有机氟硅改性聚氨酯防水涂料及其制备方法 |
CN112122437A (zh) * | 2020-08-05 | 2020-12-25 | 浙江安胜科技股份有限公司 | 一种保温容器智能化拉伸处理方法 |
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