CN116872592A - 一种高强度耐磨聚氨酯复合板及其加工工艺 - Google Patents
一种高强度耐磨聚氨酯复合板及其加工工艺 Download PDFInfo
- Publication number
- CN116872592A CN116872592A CN202310031847.5A CN202310031847A CN116872592A CN 116872592 A CN116872592 A CN 116872592A CN 202310031847 A CN202310031847 A CN 202310031847A CN 116872592 A CN116872592 A CN 116872592A
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- Prior art keywords
- polyurethane
- wear
- resistant
- boron nitride
- hexagonal boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Abstract
本发明提供一种高强度耐磨聚氨酯复合板及其加工工艺,引入等量的羟基封端的聚甲基三氟丙基硅氧烷、八苯胺丙基笼状聚倍半硅氧烷来合成氨基化、有机硅改性的聚氨酯;通过羟基化玻璃纤维对改性聚氨酯进行改性,通入超临界氮气,微孔发泡、注塑成型得到聚氨酯基材;用多巴胺对六方氮化硼改性并经煅烧制得含碳六方氮化硼,结合水热法得到含碳六方氮化硼负载二硫化钼的纳米复合材料,再用多巴胺、氨基硅烷进行改性,得到耐磨填料,来制备耐磨聚氨酯;然后用十六烷基三甲基溴化铵、甲基三甲氧基硅烷、硅酸铝纤维、二氧化钛在耐磨聚氨酯表面制备一层具有二氧化硅、硅酸铝纤维、二氧化钛的气凝胶层,得到耐磨层。
Description
技术领域
本发明涉及复合板领域,具体是一种高强度耐磨聚氨酯复合板及其加工工艺。
背景技术
聚氨酯材料具有优异的耐磨性、自润滑性、良好的附着力,被广泛应用在轮胎、胶辊、传送带、防腐涂层、密封环等各领域。然而随着加工技术的高速发展和使用环境的严苛要求,在越来越多的环境中,需要聚氨酯材料具备更加出色耐磨性、耐酸碱、高抗冲等性能。
目前市场上提高聚氨酯材料的性能通常采取以下几种措施:(1)在聚氨酯材料中加入无机填料,但是无机填料分子量较小,会使整体材料变脆,弹性变差;(2)提高聚氨酯本质材料的结晶度,从而提高材料强度,但是会使材料流动性变差,加工难度大;(3)在聚氨酯材料中加入表面能较低的有机大分子填料,存在有机大分子填料与聚氨酯材料质检具有较差相容性,容易从聚氨酯材料中脱落的问题。
发明内容
本发明的目的在于提供一种高强度耐磨聚氨酯复合板及其加工工艺,以解决现有技术中的问题。
为了解决上述技术问题,本发明提供如下技术方案:
一种高强度耐磨聚氨酯复合板,包括聚氨酯基材和热压贴合在聚氨酯基材两侧的耐磨层,所述聚氨酯基材由超临界氮气微孔注塑制备得到;
以质量份数计,耐磨层中各组分含量为:改性聚氨酯30-45份、耐磨填料5-15份、N,N-二甲基乙酰胺6-14份。
进一步的,耐磨填料的制备包括以下步骤:
(1)六方氮化硼、三(羟甲基)氨基甲烷混合,超声搅拌20-25min,加入盐酸多巴胺振荡5-6h,离心、干燥,转移到管式炉中,氩气保护下加热至850-890℃保温1-2h,冷却后即得含碳六方氮化硼;
(2)二水钼酸钠、硫脲、含碳六方氮化硼、去离子水混合,超声搅拌,转移至高压反应釜中,在195-200℃反应20-22h,冷却至18-25℃,用无水乙醇、去离子水洗涤3-5次,加入多巴胺、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷,超声反应1h,离心、干燥后得到耐磨填料。
进一步的,六方氮化硼、盐酸多巴胺的质量比为5:2。
进一步的,二水钼酸钠、硫脲、含碳六方氮化硼、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷的质量比为0.3:0.4:0.1:0.1。
进一步的,改性聚氨酯的制备包括以下步骤:将聚四氢呋喃醚二醇、甲苯-2,4-二异氰酸酯、羟基封端的聚甲基三氟丙基硅氧烷、八苯胺丙基笼状聚倍半硅氧烷混合,升温至80-85℃反应2h,抽真空除气泡,得到聚氨酯预聚体;将聚氨酯预聚体与1,4-丁二醇共混挤出、造粒,得到改性聚氨酯。
进一步的,甲苯-2,4-二异氰酸酯、羟基封端的聚甲基三氟丙基硅氧烷、八苯胺丙基笼状聚倍半硅氧烷的质量比为22:3:3;甲苯-2,4-二异氰酸酯与1,4-丁二醇的摩尔比为1:1.25。
进一步的,一种高强度耐磨聚氨酯复合板的加工工艺,包括以下步骤:
S1:用改性聚氨酯制备聚氨酯基材;
S2:将改性聚氨酯、N,N-二甲基乙酰胺混合搅拌,加入耐磨填料转移到螺杆挤出机中挤出,得到耐磨聚氨酯;
S3:将十六烷基三甲基溴化铵、蒸馏水混合,加入甲基三甲氧基硅烷、硅酸铝纤维、二氧化钛、耐磨聚氨酯后超声搅拌0.5-1h,调节pH为8.7-9.2,形成凝胶,转移到无水乙醇中,18-25℃下老化24h,在体积比为1:1的二氯甲烷和蒸馏水的混合溶液中进行溶剂置换,干燥后在80-85℃保温1-2h,升温至115-120℃保温4-5h,得到耐磨层;
S4:将耐磨层热压贴合在聚氨酯基材两侧,得到一种高强度耐磨聚氨酯复合板。
进一步的,十六烷基三甲基溴化铵、甲基三甲氧基硅烷、硅酸铝纤维、二氧化钛的质量比为2:3:3:4。
进一步的,聚氨酯基材的制备包括以下步骤:
1)将玻璃纤维置于浓度为1moL/L的氢氧化钠溶液中超声搅拌,取出后水洗至pH为6.5-7.2,减压、抽滤、干燥后得到羟基化玻璃纤维;
2)将羟基化玻璃纤维、改性聚氨酯经双螺杆挤出机造粒得到聚氨酯复合材料;
3)将聚氨酯复合材料置于微孔发泡注塑机中,通过超临界流体设备注入压力为10-11MPa的超临界氮气,得到预聚体,注射到模具中发泡,冷却后成型,得到聚氨酯基材。
进一步的,羟基化玻璃纤维、改性聚氨酯的质量比为2-4%;超临界氮气体占预聚体的质量分数为0.8-1.2%,注入超临界氮气的速度为230-235mm/s;模具的温度为75-85℃。
本发明的有益效果:
本发明提供一种高强度耐磨聚氨酯复合板及其加工工艺,聚氨酯复合板包括聚氨酯基材和热压复合在聚氨酯基材两侧的耐磨层,制备的聚氨酯复合板具备更加出色的耐磨性、防水性、高强度性能;
针对现有市场聚氨酯材料耐磨性不佳等问题,本发明中聚氨酯基材与耐磨层的制备中使用了改性聚氨酯;用聚四氢呋喃醚二醇、甲苯-2,4-二异氰酸酯制备聚氨酯预聚体,用1,4-丁二醇作为扩链剂,在制备中引入等量的羟基封端的聚甲基三氟丙基硅氧烷、八苯胺丙基笼状聚倍半硅氧烷来合成氨基化、有机硅改性的聚氨酯;引入有机硅、胺基与笼状聚倍半硅氧烷对聚氨酯进行改性,得到一种疏水性好、反应活性位点多、相容性高、耐磨性高的聚氨酯,为后期与其他原料混合时,易于改善相容性;且硅的引入和Si-O-Si交联结构的复杂度会降低可燃有机组分的数量,并产生硅渣屏障层,抑制传热和传质,有助于提高聚氨酯复合板的热稳定性;
在聚氨酯基材的制备中,通过羟基化玻璃纤维对改性聚氨酯进行改性,通入超临界氮气,微孔发泡、注塑成型得到聚氨酯基材;羟基化玻璃纤维的引入使聚氨酯基材轻量化,提高聚氨酯基材的拉伸强度和耐磨性,且通过控制羟基化玻璃纤维与通入超临界氮气的添加量,使羟基化玻璃纤维可以在螺杆挤出和注塑过程中被改性聚氨酯更好包裹保护,避免羟基化玻璃纤维的脱落,从而影响聚氨酯基材的强度;
用六方氮化硼、二硫化钼作为改性聚氨酯的填料,来制备耐磨聚氨酯;然后用十六烷基三甲基溴化铵、甲基三甲氧基硅烷、硅酸铝纤维、二氧化钛在耐磨聚氨酯表面制备一层具有二氧化硅、硅酸铝纤维、二氧化钛的气凝胶层,得到耐磨层,使气凝胶层分散均匀且紧密的附着在耐磨聚氨酯表面,使耐磨层拥有大量的凹凸结构,且表面有大量疏水的甲基,外加气凝胶本身所具有的三维网状空间结构,使耐磨层具有优异的疏水性能,提高了聚氨酯复合板在潮湿环境中的稳定性;
六方氮化硼、二硫化钼虽然耐磨性较强,但是具有化学惰性,本发明以六方氮化硼为载体,采用多巴胺对六方氮化硼改性并经煅烧制得含碳六方氮化硼,结合水热法得到含碳六方氮化硼负载二硫化钼的纳米复合材料,然后再用多巴胺、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷进行改性,得到耐磨填料,有效改善六方氮化硼、二硫化钼在改性聚氨酯中分散的均匀性,进一步提高三者的相容性,协同提升聚氨酯复合板的耐磨性及拉伸强度。
附图说明
附图用来提供对本发明的进一步理解,并且构成说明书的一部分,与本发明的实施例一起用于解释本发明,并不构成对本发明的限制。在附图中:
图1是本发明实施例、对比例的强度测试,即测试样品的拉伸强度图;
图2是本发明实施例、对比例测试样品的摩擦系数图;
图3是本发明实施例、对比例测试样品的接触角图。
具体实施方式
下面将结合本发明的实施例,对本发明中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,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。
需要说明,若本发明实施例中有涉及方向性指示诸如上、下、左、右、前、后……,则该方向性指示仅用于解释在某一特定姿态如各部件之间的相对位置关系、运动情况等,如果该特定姿态发生改变时,则该方向性指示也相应地随之改变。另外,各个实施例之间的技术方案可以相互结合,但是必须是以本领域普通技术人员能够实现为基础,当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在,也不在本发明要求的保护范围之内。
以下结合具体实施例对本发明的技术方案做进一步详细说明,应当理解,以下实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:一种高强度耐磨聚氨酯复合板的加工工艺,包括以下步骤:
S1:用改性聚氨酯制备聚氨酯基材:
1)将玻璃纤维置于浓度为1moL/L的氢氧化钠溶液中超声搅拌,取出后水洗至pH为6.5,减压、抽滤、干燥后得到羟基化玻璃纤维;
2)将羟基化玻璃纤维2g、改性聚氨酯100g经双螺杆挤出机造粒得到聚氨酯基材;
3)将聚氨酯复合材料置于微孔发泡注塑机中,通过超临界流体设备注入压力为10MPa的超临界氮气,得到预聚体,注射到模具中发泡,冷却后成型,得到聚氨酯板;羟基化玻璃纤维、改性聚氨酯的质量比为2%;超临界氮气体占预聚体的质量分数为0.8%,注入超临界氮气的速度为230mm/s;模具的温度为75℃;
所述改性聚氨酯的制备包括以下步骤:将78g聚四氢呋喃醚二醇、22g甲苯-2,4-二异氰酸酯、3g羟基封端的聚甲基三氟丙基硅氧烷、3g八苯胺丙基笼状聚倍半硅氧烷混合,升温至80℃反应2h,抽真空除气泡,得到聚氨酯预聚体;将摩尔比为1:1.25的聚氨酯预聚体与1,4-丁二醇共混挤出、造粒,得到改性聚氨酯;
S2:将改性聚氨酯、N,N-二甲基乙酰胺混合搅拌,加入耐磨填料转移到螺杆挤出机中挤出,得到耐磨聚氨酯;
以质量份数计,耐磨层中各组分含量为:改性聚氨酯30份、耐磨填料5份、N,N-二甲基乙酰胺6份;
所述耐磨填料的制备包括以下步骤:
(1)0.5g六方氮化硼、0.01mol/L三(羟甲基)氨基甲烷混合,超声搅拌20min,加入0.2g盐酸多巴胺振荡5h,离心、干燥,转移到管式炉中,氩气保护下加热至850℃保温2h,冷却后即得含碳六方氮化硼;
(2)0.3g二水钼酸钠、0.4g硫脲、0.1g含碳六方氮化硼、40mL去离子水混合,超声搅拌,转移至高压反应釜中,在195℃反应22h,冷却至18℃,用无水乙醇、去离子水洗涤3次,加入多巴胺0.12g、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷0.1g,超声反应1h,离心、干燥后得到耐磨填料;
S3:将2g十六烷基三甲基溴化铵、40mL蒸馏水混合,加入3g甲基三甲氧基硅烷、3g硅酸铝纤维、3g二氧化钛、耐磨聚氨酯后超声搅拌0.5h,调节pH为8.7,形成凝胶,转移到无水乙醇中,18℃下老化24h,在体积比为1:1的二氯甲烷和蒸馏水的混合溶液中进行溶剂置换,干燥后在80℃保温1h,升温至115℃保温5h,得到耐磨层;
S4:将耐磨层热压贴合在聚氨酯基材两侧,得到一种高强度耐磨聚氨酯复合板。
实施例2:一种高强度耐磨聚氨酯复合板的加工工艺,包括以下步骤:
S1:用改性聚氨酯制备聚氨酯基材:
1)将玻璃纤维置于浓度为1moL/L的氢氧化钠溶液中超声搅拌,取出后水洗至pH为7,减压、抽滤、干燥后得到羟基化玻璃纤维;
2)将羟基化玻璃纤维3g、改性聚氨酯100g经双螺杆挤出机造粒得到聚氨酯基材;
3)将聚氨酯复合材料置于微孔发泡注塑机中,通过超临界流体设备注入压力为11MPa的超临界氮气,得到预聚体,注射到模具中发泡,冷却后成型,得到聚氨酯板;羟基化玻璃纤维、改性聚氨酯的质量比为3%;超临界氮气体占预聚体的质量分数为1%,注入超临界氮气的速度为233mm/s;模具的温度为80℃;
所述改性聚氨酯的制备包括以下步骤:将78g聚四氢呋喃醚二醇、22g甲苯-2,4-二异氰酸酯、3g羟基封端的聚甲基三氟丙基硅氧烷、3g八苯胺丙基笼状聚倍半硅氧烷混合,升温至82℃反应2h,抽真空除气泡,得到聚氨酯预聚体;将摩尔比为1:1.25的聚氨酯预聚体与1,4-丁二醇共混挤出、造粒,得到改性聚氨酯。
S2:将改性聚氨酯、N,N-二甲基乙酰胺混合搅拌,加入耐磨填料转移到螺杆挤出机中挤出,得到耐磨聚氨酯;
以质量份数计,耐磨层中各组分含量为:改性聚氨酯40份、耐磨填料10份、N,N-二甲基乙酰胺7份;
所述耐磨填料的制备包括以下步骤:
(1)0.5g六方氮化硼、0.01mol/L三(羟甲基)氨基甲烷混合,超声搅拌22min,加入0.2g盐酸多巴胺振荡5.5h,离心、干燥,转移到管式炉中,氩气保护下加热至870℃保温1.5h,冷却后即得含碳六方氮化硼;
(2)0.3g二水钼酸钠、0.4g硫脲、0.1g含碳六方氮化硼、40mL去离子水混合,超声搅拌,转移至高压反应釜中,在198℃反应21h,冷却至22℃,用无水乙醇、去离子水洗涤4次,加入多巴胺0.12g、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷0.1g,超声反应1h,离心、干燥后得到耐磨填料;
S3:将2g十六烷基三甲基溴化铵、40mL蒸馏水混合,加入3g甲基三甲氧基硅烷、3g硅酸铝纤维、3g二氧化钛、耐磨聚氨酯后超声搅拌0.8h,调节pH为9,形成凝胶,转移到无水乙醇中,22℃下老化24h,在体积比为1:1的二氯甲烷和蒸馏水的混合溶液中进行溶剂置换,干燥后在83℃保温1.5h,升温至118℃保温4.5h,得到耐磨层;
S4:将耐磨层热压贴合在聚氨酯基材两侧,得到一种高强度耐磨聚氨酯复合板。
实施例3:一种高强度耐磨聚氨酯复合板的加工工艺,包括以下步骤:
S1:用改性聚氨酯制备聚氨酯基材:
1)将玻璃纤维置于浓度为1moL/L的氢氧化钠溶液中超声搅拌,取出后水洗至pH为7.2,减压、抽滤、干燥后得到羟基化玻璃纤维;
2)将羟基化玻璃纤维4g、改性聚氨酯100g经双螺杆挤出机造粒得到聚氨酯基材;
3)将聚氨酯复合材料置于微孔发泡注塑机中,通过超临界流体设备注入压力为11MPa的超临界氮气,得到预聚体,注射到模具中发泡,冷却后成型,得到聚氨酯板;羟基化玻璃纤维、改性聚氨酯的质量比为4%;超临界氮气体占预聚体的质量分数为1.2%,注入超临界氮气的速度为235mm/s;模具的温度为85℃;
所述改性聚氨酯的制备包括以下步骤:将78g聚四氢呋喃醚二醇、22g甲苯-2,4-二异氰酸酯、3g羟基封端的聚甲基三氟丙基硅氧烷、3g八苯胺丙基笼状聚倍半硅氧烷混合,升温至85℃反应2h,抽真空除气泡,得到聚氨酯预聚体;将摩尔比为1:1.25的聚氨酯预聚体与1,4-丁二醇共混挤出、造粒,得到改性聚氨酯;
S2:将改性聚氨酯、N,N-二甲基乙酰胺混合搅拌,加入耐磨填料转移到螺杆挤出机中挤出,得到耐磨聚氨酯;
以质量份数计,耐磨层中各组分含量为:改性聚氨酯45份、耐磨填料15份、N,N-二甲基乙酰胺14份;
所述耐磨填料的制备包括以下步骤:
(1)0.5g六方氮化硼、0.01mol/L三(羟甲基)氨基甲烷混合,超声搅拌25min,加入0.2g盐酸多巴胺振荡6h,离心、干燥,转移到管式炉中,氩气保护下加热至890℃保温1h,冷却后即得含碳六方氮化硼;
(2)0.3g二水钼酸钠、0.4g硫脲、0.1g含碳六方氮化硼、40mL去离子水混合,超声搅拌,转移至高压反应釜中,在200℃反应20h,冷却至25℃,用无水乙醇、去离子水洗涤5次,加入多巴胺0.12g、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷0.1g,超声反应1h,离心、干燥后得到耐磨填料;
S3:将2g十六烷基三甲基溴化铵、40mL蒸馏水混合,加入3g甲基三甲氧基硅烷、3g硅酸铝纤维、3g二氧化钛、耐磨聚氨酯后超声搅拌1h,调节pH为9.2,形成凝胶,转移到无水乙醇中,25℃下老化24h,在体积比为1:1的二氯甲烷和蒸馏水的混合溶液中进行溶剂置换,干燥后在85℃保温1h,升温至120℃保温4h,得到耐磨层;
S4:将耐磨层热压贴合在聚氨酯基材两侧,得到一种高强度耐磨聚氨酯复合板。
对比例1:以实施例3为对照组,用聚氨酯替换改性聚氨酯,其他工序正常。
对比例2:以实施例3为对照组,用玻璃纤维替换羟基化玻璃纤维,其他工序正常。
对比例3:以实施例3为对照组,用六方氮化硼替换耐磨填料,其他工序正常。
对比例4:以实施例3为对照组,用二硫化钼替换耐磨填料,其他工序正常。
对比例5:以实施例3为对照组,在制备耐磨填料时,没有添加3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷,其他工序正常。
对比例6:以实施例3为对照组,去掉步骤S3,其他工序正常。
对比例7:以实施例3为对照组,在制备改性聚氨酯时没有添加3g羟基封端的聚甲基三氟丙基硅氧烷、3g八苯胺丙基笼状聚倍半硅氧烷,其他工序正常。
对比例8:以实施例3为对照组,超临界氮气占预聚体的质量分数为0.7%,其他工序正常。
对比例9:以实施例3为对照组,超临界氮气占预聚体的质量分数为1.3%,其他工序正常。
对比例10:以实施例3为对照组,没有采用超临界氮气注塑成型,其他工序正常。
性能测试:对实施例1-3、对比例1-10所制得的聚氨酯复合板进行性能测试;
拉伸强度测试:参考GB/T528-2009测试;
摩擦系数测试条件:45#钢φ20mm的钢珠,粗糙度1μm,旋转测试方法,半径10mm,旋转速率200r/min,负载80N;
接触角测试:试样置于载物台上,利用微量进样器滴加5μL的蒸馏水于试样表面,测试其接触角;具体数据如表1;
表1
实施例1-3为按照本发明制备的聚氨酯复合板,将实施例3与对比例1-10进行对比可知,根据图1、图2、图3及表1可知,制备的聚氨酯复合板强度高、耐磨性好、防水性优异;
将实施例3与对比例1、对比例7进行对比可知,本发明中聚氨酯基材与耐磨层的制备中皆使用了改性聚氨酯;用聚四氢呋喃醚二醇、甲苯-2,4-二异氰酸酯制备聚氨酯预聚体,在制备中引入等量的羟基封端的聚甲基三氟丙基硅氧烷、八苯胺丙基笼状聚倍半硅氧烷来合成氨基化、有机硅改性的聚氨酯,用1,4-丁二醇作为扩链剂,引入有机硅、胺基与笼状聚倍半硅氧烷对聚氨酯进行改性,得到一种疏水性好、反应活性位点多、相容性高、耐磨性高的聚氨酯,有效提高聚氨酯复合板的耐磨性及拉伸强度;
将实施例3与对比例2、对比例10进行对比可知,在聚氨酯基材的制备中,通过羟基化玻璃纤维对改性聚氨酯进行改性,通入超临界氮气,微孔发泡、注塑成型得到聚氨酯基材;羟基化玻璃纤维的引入有效使聚氨酯基材轻量化,提高聚氨酯基材的拉伸强度和耐磨性;
将实施例3与对比例8、对比例9进行对比可知,通过控制羟基化玻璃纤维与通入超临界氮气的量,使羟基化玻璃纤维可以在螺杆挤出和注塑过程中被改性聚氨酯更好包裹保护,避免羟基化玻璃纤维的脱落,影响聚氨酯基材高强度的保持;
将实施例3与对比例3、对比例4、对比例5进行对比可知,六方氮化硼、二硫化钼虽然耐磨性较强,但是具有化学惰性,本发明以六方氮化硼为载体,采用多巴胺对六方氮化硼改性并经煅烧制得含碳六方氮化硼,结合水热法得到含碳六方氮化硼负载二硫化钼的纳米复合材料,再用多巴胺、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷进行改性,得到耐磨填料;协同提升聚氨酯复合板的耐磨性及拉伸强度;
将实施例3与对比例6进行对比可知,用十六烷基三甲基溴化铵、甲基三甲氧基硅烷、硅酸铝纤维、二氧化钛在耐磨聚氨酯表面制备一层具有二氧化硅、硅酸铝纤维、二氧化钛的气凝胶层,得到耐磨层,使气凝胶层分散均匀且紧密的附着在耐磨聚氨酯表面,使耐磨层拥有大量的凹凸结构,且表面有大量疏水的甲基,外加气凝胶本身所具有的三维网状空间结构使其表面凹凸不平,使聚氨酯复合板具有优异的疏水性能。
综上,本发明制备的聚氨酯复合板不仅具有优异力学性能,同时耐磨防水性好,具有良好的应用前景。
以上所述仅为本发明的为实施例,并非因此限制本发明的专利范围,凡是在本发明的发明构思下,利用本发明说明书所作的等效结构变换,或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。
Claims (10)
1.一种高强度耐磨聚氨酯复合板,其特征在于,所述聚氨酯复合板包括聚氨酯基材和聚氨酯基材两侧的耐磨层;用羟基化玻璃纤维对改性聚氨酯进行改性,再通入超临界氮气,微孔发泡、注塑成型得到聚氨酯基材;
以质量份数计,耐磨层中各组分含量为:改性聚氨酯30-45份、耐磨填料5-15份、N,N-二甲基乙酰胺6-14份;耐磨填料由六方氮化硼和二硫化钼制备得到。
2.根据权利要求1所述的一种高强度耐磨聚氨酯复合板,其特征在于,所述改性聚氨酯的制备包括以下步骤:将聚四氢呋喃醚二醇、甲苯-2,4-二异氰酸酯、羟基封端的聚甲基三氟丙基硅氧烷、八苯胺丙基笼状聚倍半硅氧烷混合,升温至80-85℃反应2h,抽真空后得到聚氨酯预聚体;将聚氨酯预聚体与1,4-丁二醇共混挤出、造粒,得到改性聚氨酯。
3.根据权利要求2所述的一种高强度耐磨聚氨酯复合板,其特征在于,所述甲苯-2,4-二异氰酸酯、羟基封端的聚甲基三氟丙基硅氧烷、八苯胺丙基笼状聚倍半硅氧烷的质量比为22:3:3;甲苯-2,4-二异氰酸酯与1,4-丁二醇的摩尔比为1:1.25。
4.根据权利要求1所述的一种高强度耐磨聚氨酯复合板,其特征在于,所述耐磨填料的制备包括以下步骤:
(1)六方氮化硼、三(羟甲基)氨基甲烷混合,超声搅拌20-25min,加入盐酸多巴胺振荡5-6h,离心、干燥;在氩气保护下,加热至850-890℃保温1-2h,冷却后即得含碳六方氮化硼;
(2)二水钼酸钠、硫脲、含碳六方氮化硼、去离子水混合,超声搅拌,转移至高压反应釜中,在195-200℃反应20-22h,冷却至18-25℃,用无水乙醇、去离子水洗涤3-5次,加入多巴胺、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷,超声反应1h,离心、干燥后得到耐磨填料。
5.根据权利要求4所述的一种高强度耐磨聚氨酯复合板,其特征在于,所述六方氮化硼、盐酸多巴胺的质量比为5:2。
6.根据权利要求4所述的一种高强度耐磨聚氨酯复合板,其特征在于,二水钼酸钠、硫脲、含碳六方氮化硼、3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷的质量比为0.3:0.4:0.1:0.1。
7.根据权利要求1-6任一项所述的一种高强度耐磨聚氨酯复合板的加工工艺,其特征在于,包括以下步骤:
S1:用改性聚氨酯制备聚氨酯基材;
S2:将改性聚氨酯、N,N-二甲基乙酰胺混合搅拌,加入耐磨填料,转移到螺杆挤出机中挤出,得到耐磨聚氨酯;
S3:将十六烷基三甲基溴化铵、蒸馏水混合,加入甲基三甲氧基硅烷、硅酸铝纤维、二氧化钛、耐磨聚氨酯后超声搅拌0.5-1h,调节pH为8.7-9.2,形成凝胶,转移到无水乙醇中,18-25℃下老化24h,在体积比为1:1的二氯甲烷和蒸馏水的混合溶液中进行溶剂置换,干燥后在80-85℃保温1-2h,升温至115-120℃保温4-5h,得到耐磨层;
S4:将耐磨层热压贴合在聚氨酯基材两侧,得到一种高强度耐磨聚氨酯复合板。
8.根据权利要求7所述的一种高强度耐磨聚氨酯复合板的加工工艺,其特征在于,十六烷基三甲基溴化铵、甲基三甲氧基硅烷、硅酸铝纤维、二氧化钛的质量比为2:3:3:4。
9.根据权利要求7所述的一种高强度耐磨聚氨酯复合板的加工工艺,其特征在于,所述聚氨酯基材的制备包括以下步骤:
1)将玻璃纤维置于氢氧化钠溶液中超声搅拌,取出后水洗至pH为6.5-7.2,减压、抽滤、干燥后得到羟基化玻璃纤维;
2)将羟基化玻璃纤维、改性聚氨酯经双螺杆挤出机造粒得到聚氨酯复合材料;
3)将聚氨酯复合材料置于微孔发泡注塑机中,通过超临界流体设备注入压力为10-11MPa的超临界氮气,得到预聚体,注射到模具中发泡,冷却后成型,得到聚氨酯基材。
10.根据权利要求9所述的一种高强度耐磨聚氨酯复合板的加工工艺,其特征在于,羟基化玻璃纤维、改性聚氨酯的质量比为2-4%;超临界氮气体占预聚体的质量分数为0.8-1.2%,注入超临界氮气的速度为230-235mm/s;模具的温度为75-85℃。
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