CN114044878A - 一种耐热高硬度聚氨酯筛网弹性体的制备工艺 - Google Patents
一种耐热高硬度聚氨酯筛网弹性体的制备工艺 Download PDFInfo
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Abstract
本发明属于聚氨酯筛网技术领域,尤其是一种耐热高硬度聚氨酯筛网弹性体的制备工艺,聚氨酯筛网弹性体强度大、硬度高、耐热性能好,生产的筛网具有很高的强度、刚度和承载冲击大,结构坚固,抗震抗拉能力强,能较好的发挥筛网的筛分效率,耐磨性能好,耐热性好,钢丝绳筛网具有重量轻、筛分效率高、不堵孔、抗磨擦、抗冲击、抗撕裂、寿命长,噪声低、安装方便、综合效益高等优点,可广泛应用于、矿山、煤炭等行业的筛分机上,适合中粒度的各类物质筛分需求,适用于孔径在5mm~40mm的中等尺寸物料的筛分分离。
Description
技术领域
本发明属于聚氨酯筛网技术领域,尤其是一种耐热高硬度聚氨酯筛网弹性体的制备工艺。
背景技术
筛网的发展经历了多个发展阶段。起初,筛网的材质是金属材料,加工工艺是采用机械的方式来加工,如钢板冲孔、钢丝编织、钢丝焊接等方式。随着新材料的发展,不锈钢材质的筛网开始在洗选行业逐步应用。替代了耐磨性较差的普通钢材。由于金属筛网在使用过程中均存在着耐磨性差、噪音大、维修工作繁重等缺点,后来又用耐磨性极佳的聚氨酯弹性体来制作各种用途和结构的筛网,克服了金属筛网的缺点。又由于聚氨酯弹性体属于高聚物材料,其模量与金属相差较大,所以由聚氨酯弹性体制作的筛网存在着开孔率低,之后又开发了兼具金属筛网开孔率高、减震效果好的金属和聚氨酯弹性体的复合筛网。目前该种筛网和聚氨酯筛网一样已成为筛网中的重要品种,在洗选行业得到了较为广泛的应用。以往聚氨酯弹性体筛板的加工制造主要以浇注型为主,采用热塑性聚氨酯弹性体并不普遍。主要是以前我国的热塑性聚氨酯品种少,质量稳定性不能完全满足筛板对材质的要求,再则也没有专用于热塑性聚氨酯的专用设备。随着我国热塑性聚氨酯的高速发展和其加工设备的进步,热塑性聚氨酯筛板在筛板中的比例在逐年增加。例如,中国专利CN105646839A公开了一种精细耐磨筛网用聚氨酯弹性体及其制备方法,弹性体在反应过程中添加了纳米硅微粉助剂,实际应用效果不好,中国专利CN109570017A公开了复合型筛网骨架、热塑性弹性体筛网及制备方法,以工程塑料和纤维为原料采用注塑成型工艺制备复合型筛网骨架,采用注塑成型工艺,筛网一般面积和体积较大,而注塑此种体积较大长度较大的筛网,需要有筛孔,注射设备造价极高、模具成本较高,也脱离客观实际,应用效果并不好,本领域技术人员,亟待开发出一种耐热高硬度聚氨酯筛网弹性体的制备工艺。
发明内容
针对上述问题,本发明旨在提供一种耐热高硬度聚氨酯筛网弹性体的制备工艺。
本发明通过以下技术方案实现:
一种耐热高硬度聚氨酯筛网弹性体的制备工艺,包括如下步骤:
第一、将聚己二酸二乙二醇酯二醇、聚氧化丙烯三醇、丙三醇,分别在110℃减水2h,聚己二酸二乙二醇酯二醇和聚氧化丙烯三醇、丙三醇加入反应釜,60~65℃加热并搅拌均匀后,加入4,4’-二苯基甲烷二异氰酸酯,70~75℃搅拌反应1.5~2h得到预聚物;
第二、将预聚物加热至75~80℃,加入扩链剂1,4-丁二醇,匀速搅拌0.5~1h,得到黏稠聚合物;
端羟基硅橡胶的硫化交联反应简式如下:
第三、密炼共混:将黏稠聚合物、端羟基硅橡胶以及交联剂加入到密炼机中,依次加入端羟基硅橡胶、交联剂、硫化剂,混炼6~8min后出料,将混炼胶料加入挤出机中动态挤出胶条放入110~120℃预热的模具,采用硫化机在160~170℃,12~14MPa下硫化4min,即得。
交联型聚氨酯中的化学交联通过增强分子链间相互作用提高聚氨酯的硬度和强度,然而,交联结构促进软硬段的混合,降低硬段微相的增强作用,交联网络结构的形成阻碍了链段的运动,交联结构和硅橡胶的引入可显著提高聚氨酯弹性体耐热性。
进一步的,所述步骤一挤出机机筒温度一区50~55℃、二区55~60℃、三区55~60℃,螺杆直径40~50mm、螺杆长径比16~20、机头温度55~60℃。
进一步的,所述步骤一的聚己二酸二乙二醇酯二醇∶聚氧化丙烯三醇∶4,4’-二苯基甲烷二异氰酸酯∶1,4-丁二醇的质量比为0.93~0.95∶0.02~0.03∶2.5~3∶1.8~2。
二丁基二月桂酸锡在本申请中可以起到聚氨酯的催化作用、而且还作为硅橡胶的硫化剂起到硫化作用,使线型聚合物交联成网状结构的弹性硅橡胶。
进一步的,所述步骤三的硫化剂为正硅酸乙酯、二丁基二月桂酸锡、甲基三乙氧基硅烷中的其中一种或多种,所述交联剂为β-(3,4-环氧环己基)乙基三乙氧基硅烷。
β-(3,4-环氧环己基)乙基三乙氧基硅烷用既作聚氨酯交联剂又可以作为黏附促进剂,分子中的环氧基与基才发生反应,分子中的烷氧基在水解后通过缩合形成硅氧烷键而促进硅橡胶交联,交联剂促进聚氨酯弹性体的黏附力、耐溶剂、耐冲击、耐磨、耐候及耐久性能,特别用于需耐久性的高性能筛网场合,提高交联密度进一步提高硬度。
进一步的,所述步骤三混炼工艺为170~180℃、50~60r/min,填充系数0.60~0.80,单位压力0.4~0.6MPa、转子转速40~60rpm。
进一步的,所述步骤三为长径比为25~30,压缩比为2.5~3.0之间的单螺纹螺杆挤出机的下料口110℃,机身1区120~125℃、2区130~140℃、3区140~150℃、机颈区155~160℃、机头155~160℃,转速65~80rpm。
进一步的,所述步骤三的混炼胶料为质量份数计,黏稠聚合物90~100phr、端羟基硅橡胶65~75phr、交联剂5~7phr、硫化剂0.5~1phr。
本发明的有益效果:
本发明采用相物理共混改性,实现有机硅和聚氨酯材料的性能互补,吸收水分产生水解交联,利用硅橡胶耐高温、耐低温的优势与聚氨酯进行改性,将热塑性基弹性体采用动态挤出共混工艺加工,具有更好耐磨性和耐热性能,且其表面摩擦性能也得到改善,其中交联型聚氨酯中的化学交联通过增强分子链间相互作用提高聚氨酯的硬度和强度,然而,交联结构促进软硬段的混合,降低硬段微相的增强作用,交联网络结构的形成阻碍了链段的运动,交联结构和硅橡胶的引入可显著提高聚氨酯弹性体耐热性。硅橡胶发挥物理交联点作用,有效提高聚氨弹性体力学性能,化学交联结构的形成赋予其优异的力学性能,PPG-3和丙三醇作为增容剂,β-(3,4-环氧环己基)乙基三乙氧基硅烷用既作聚氨酯交联剂又可以作为黏附促进剂,分子中的环氧基与基才发生反应,分子中的烷氧基在水解后通过缩合形成硅氧烷键而促进硅橡胶交联。
相比先有技术本发明具有如下优点:
本发明公开的耐热高硬度聚氨酯筛网弹性体弹性好, 能较好的发挥筛网的筛分效率,耐磨性能好,硬度高、强度大、耐热性好,钢丝绳筛网具有重量轻、筛分效率高、不堵孔、抗磨擦、抗冲击、抗撕裂、寿命长,噪声低、安装方便、综合效益高等优点,可广泛应用于、矿山、煤炭等行业的筛分机上,适合中粒度的各类物质筛分需求,耐酸耐碱耐高温,防水防火防静电,适用于孔径在5mm~40mm的中等物料的筛分分离。
具体实施方式
下面用具体实施例说明本发明,但并不是对本发明的限制。
实施例1
第一、将工业品CMA-24聚己二酸二乙二醇酯二醇、聚氧化丙烯三醇、丙三醇,分别在110℃减水2h,聚己二酸二乙二醇酯二醇和聚氧化丙烯三醇N3010、丙三醇加入反应釜,65℃加热并搅拌均匀后,加入工业品MDI-100Wannate 4,4’-二苯基甲烷二异氰酸酯,75℃搅拌反应2h得到预聚物;其中,聚己二酸二乙二醇酯二醇∶聚氧化丙烯三醇∶4,4’-二苯基甲烷二异氰酸酯∶1,4-丁二醇的质量比为0.95∶0.03∶3∶2,第二、将预聚物加热至80℃,加入扩链剂1,4-丁二醇,匀速搅拌1h,得到黏稠聚合物;第三、质量份数计,黏稠聚合物100phr、端羟基硅橡胶75phr、交联剂7phr、硫化剂1phr,密炼共混:将黏稠聚合物、端羟基硅橡胶以及交联剂加入到密炼机中,依次加入端羟基硅橡胶、交联剂、硫化剂,硫化剂为二丁基二月桂酸锡、甲基三乙氧基硅烷中的质量比1比1的混合物,交联剂为β-(3,4-环氧环己基)乙基三乙氧基硅烷,混炼工艺为180℃、60r/min,填充系数0.80,单位压力0.6MPa、转子转速60rpm,混炼8min后出料,将混炼物加入长径比为30,压缩比为3.0之间的单螺纹螺杆挤出机的下料口110℃,机身1区120℃、2区140℃、3区150℃、机颈区160℃、机头160℃,转速80rpm,挤出机中动态挤出胶条放入120℃预热的模具,采用平板硫化机在170℃,14MPa下硫化4min,即得,端羟基硅橡胶:SDB-41、β-(3,4-环氧环己基)乙基三乙氧基硅烷迈图CoatOsi 1770Silane。
其中产品性能,硬度邵氏92.5A、断裂伸长率405.5%、回弹性36.6%、磨耗24.8mm3、拉伸强度31.2MPa,维卡软化点151.8℃,能够满足聚氨酯筛网的强度要求。
实施例2
第一、将工业品CMA-1024聚己二酸二乙二醇酯二醇、聚氧化丙烯三醇、丙三醇,分别在110℃减水2h,聚己二酸二乙二醇酯二醇和聚氧化丙烯三醇N3010、丙三醇加入反应釜,60℃加热并搅拌均匀后,加入工业品Wannate MDI-1004,4’-二苯基甲烷二异氰酸酯,70℃搅拌反应1.5得到预聚物;其中,聚己二酸二乙二醇酯二醇∶聚氧化丙烯三醇∶4,4’-二苯基甲烷二异氰酸酯∶1,4-丁二醇的质量比为0.93∶0.02∶2.5∶1.8,第二、将预聚物加热至75℃,加入扩链剂1,4-丁二醇,匀速搅拌0.5h,得到黏稠聚合物;第三、质量份数计,黏稠聚合物90phr、端羟基硅橡胶65phr、交联剂5phr、硫化剂0.5phr,密炼共混:将黏稠聚合物、端羟基硅橡胶以及交联剂加入到密炼机中,依次加入端羟基硅橡胶、交联剂、硫化剂,硫化剂为二丁基二月桂酸锡、正硅酸乙酯中的质量比1比1的混合物,交联剂为β-(3,4-环氧环己基)乙基三乙氧基硅烷,混炼工艺为170℃、50r/min,填充系数0.60,单位压力0.4MPa、转子转速40rpm,混炼6min后出料,将混炼物加入长径比为25,压缩比为2.5之间的单螺纹螺杆挤出机的下料口110℃,机身1区120℃、2区130℃、3区140℃、机颈区155℃、机头155℃,转速65rpm,挤出机中动态挤出胶条放入110℃预热的模具,采用硫化机在160℃,12MPa下硫化4min,即得,其中端羟基硅橡胶SDL-1-43、β-(3,4-环氧环己基)乙基三乙氧基硅烷信越KBE 303。
其中产品性能,硬度邵氏92.2A、断裂伸长率409.2%、回弹性36.3%、磨耗25.6mm3、拉伸强度31.8MPa,维卡软化点150.6℃,能够满足聚氨酯筛网的强度要求。
注:以上性能检测参考GB/T 9867 -2008化橡胶或热塑性橡胶耐磨性能的测定(旋转辊筒式磨耗机法);GB/T528-2009硫化橡胶或热塑性橡胶拉伸应力应变性能的测定;GB/T531.2-2009硫化橡胶或热塑性橡胶压入硬度试验方法第二部分:便携式橡胶国际硬度计法;GB/T1681-2009硫化橡胶回弹性的测定;GB/T529-2008硫化橡胶或热塑性橡胶撕裂强度的测定;GB/T7759-1996硫化橡胶、热塑性橡胶常温、高温和低温下压缩永久变形测定;GB/T33091-2016聚氨酯筛网。
Claims (6)
1.一种耐热高硬度聚氨酯筛网弹性体的制备工艺,其特征在于,制备工艺包括如下步骤:
第一、将聚己二酸二乙二醇酯二醇和聚氧化丙烯三醇、丙三醇加入反应釜,60~65℃加热并搅拌均匀后,加入4,4’-二苯基甲烷二异氰酸酯,70~75℃搅拌反应1.5~2h得到预聚物;第二、将预聚物加热至75~80℃,加入扩链剂1,4-丁二醇,匀速搅拌0.5~1h,得到黏稠聚合物;第三、密炼共混:将黏稠聚合物、端羟基硅橡胶以及交联剂加入到密炼机中,依次加入端羟基硅橡胶、交联剂、硫化剂,混炼6~8min后出料,将混炼胶料加入挤出机中动态挤出胶条放入110~120℃预热的模具,采用硫化机在160~170℃,12~14MPa下硫化4min,即得。
2.根据权利要求1所述的耐热高硬度聚氨酯浇注筛网的生产工艺方法,其特征在于,所述步骤一的聚己二酸二乙二醇酯二醇∶聚氧化丙烯三醇∶4,4’-二苯基甲烷二异氰酸酯∶1,4-丁二醇的质量比为0.93~0.95∶0.02~0.03∶2.5~3∶1.8~2。
3.根据权利要求1所述的耐热高硬度聚氨酯浇注筛网的生产工艺方法,其特征在于,所述步骤三的硫化剂为正硅酸乙酯、二丁基二月桂酸锡、甲基三乙氧基硅烷中的其中一种或多种,所述交联剂为β-(3,4-环氧环己基)乙基三乙氧基硅烷。
4.根据权利要求1所述的耐热高硬度聚氨酯浇注筛网的生产工艺方法,其特征在于,所述步骤三混炼工艺为170~180℃、50~60r/min,填充系数0.60~0.80,单位压力0.4~0.6MPa、转子转速40~60rpm。
5.根据权利要求1所述的耐热高硬度聚氨酯浇注筛网的生产工艺方法,其特征在于,所述步骤三为长径比为25~30,压缩比为2.5~3.0之间的单螺纹螺杆挤出机的下料口110℃,机身1区120~125℃、2区130~140℃、3区140~150℃、机颈区155~160℃、机头155~160℃,转速65~80rpm。
6.根据权利要求1所述的耐热高硬度聚氨酯浇注筛网的生产工艺方法,其特征在于,所述步骤三的混炼胶料为质量份数计,黏稠聚合物90~100phr、端羟基硅橡胶65~75phr、交联剂5~7phr、硫化剂0.5~1phr。
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