CN111793186A - 聚氨酯抛光垫片层的制备方法 - Google Patents
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Abstract
本发明属于聚氨酯应用技术领域,具体涉及一种聚氨酯抛光垫片层的制备方法,包括以下步骤:(1)多元醇、中空聚合物微球和抗氧剂混合后制得异氰酸根质量含量为7.5‑15%的预聚物;(2)通过薄膜蒸发的方法,得到游离二异氰酸酯单体含量小于0.1%的低游离预聚体;(3)将低游离预聚体组分与扩链剂组分充分混合,浇注于模具中开模、硫化制得聚氨酯抛光垫片层。本发明采用的低游离聚氨酯预聚体,具有流动性好、凝胶时间长且成型速度快的优点,可显著改进聚氨酯抛光垫片层的物理机械性能,同时通过采用低聚物类的胺类或醇类固化剂,进一步提升了产品的成型工艺,具有优良的抛光效果,今儿满足市场对高性能聚氨酯抛光垫的需求。
Description
技术领域
本发明属于聚氨酯应用技术领域,具体涉及一种聚氨酯抛光垫片层的制备方法。
背景技术
化学机械抛光(CMP)技术是目前最好的实现全局平面化的工艺技术,通过机械摩擦完成对抛光件表面形成的化学反应物的去除,主要是用于超精密表面(如硅晶片、微型集成电路、存储器等)的加工以获得光洁表面的技术。
抛光垫的表面片层目前均是由聚氨酯弹性体材料制作而成,考虑到由于在抛光过程中抛光液的存在,目前聚氨酯抛光垫的片层主要是抗水解、耐酸碱的聚四氢呋喃醚型弹性体,但是在耐磨性、力学强度方面却往往表现不佳。CMP的抛光效果借助的是磨粒的作用,很容易在集成电路上留下划痕和缺陷,无法适应现在的微型化工艺及严格平整度要求。
目前,在预聚体生产过程中,总是存在一定游离未反应的二异氰酸酯单体和一些多聚产物。在制备低游离聚氨酯预聚体时,二异氰酸酯单体大量过量(NCO/OH>2),游离的二异氰酸酯单体上-NCO基团相对于低聚物上的-NCO基团活性高,聚合物多元醇更容易与游离的二异氰酸酯单体上的-NCO基团反应,从而使得预聚体体系中生成大量三单元结构低聚物。
发明内容
本发明要解决的技术问题是:克服现有技术的不足,提供一种聚氨酯抛光垫片层的制备方法,采用该方法制备的聚氨酯抛光垫,工艺操作性更好、质量风险更低,具有更高的机械性能和更优良的抛光效果,满足市场对高性能聚氨酯抛光垫的需求。
本发明所述的聚氨酯抛光垫片层的制备方法,包括以下步骤:
(1)将多元醇、中空聚合物微球和抗氧剂混合后脱水至含水率≤0.03%,然后与二异氰酸酯在70-85℃下反应,得到异氰酸根质量含量为7.5-15%的预聚物;
(2)通过薄膜蒸发的方法将步骤(1)反应制得的预聚物中未反应的游离二异氰酸酯单体分离出去,得到游离二异氰酸酯单体含量小于0.1%的低游离预聚体;
(3)将低游离预聚体组分与扩链剂组分充分混合,浇注于模具中开模、硫化制得聚氨酯抛光垫片层。
步骤(1)中所述的多元醇、中空聚合物微球和抗氧剂以及二异氰酸酯的质量比为30-74:0.1-0.5:0.1-0.5:25-70。
所述的多元醇为数均分子量为250-2000,官能度为2的聚四氢呋喃醚多元醇或数均分子量为1000-2000的聚己内酯多元醇中的一种或一种以上,优选聚四氢呋喃醚多元醇。在合成聚氨酯预聚体时在聚四氢呋喃醚二醇中添加部分聚酯多元醇,借助于其更强的结晶性,通过控制多元醇的加入量可以在不影响聚氨酯弹性体抗水解、耐酸碱特性的前提下有效地提高抛光垫片层的机械强度,使抛光垫具有更高的除去率及平坦化能力。
所述的中空聚合物微球粒径为10-150μm,优选中钢集团马鞍山矿院新材料科技有限公司生产的中空聚合物微球。所述的抗氧剂优选为抗氧剂1076。
在制备预聚体的异氰酸酯原料中加入中空聚合物微球和抗氧剂可以有效降低划痕的产生,与此同时,可有效提高聚氨酯抛光片层的光稳定性和抗黄变能力,因而使其具有优良的耐候性和色泽稳定性,延缓了产品的老化,延长了产品的使用寿命和存储期限。
所述的二异氰酸酯为2,4-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、50%2,4’-二苯基甲烷二异氰酸酯与50%4,4'-二苯基甲烷二异氰酸酯混合物、液化MDI、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或二环己基甲烷-4,4'-二异氰酸酯中的一种或一种以上。
所述的扩链剂为4-氯-3,5-二氨基苯甲酸异丁酯、3,3'-二氯-4,4'-二氨基二苯基甲烷、1,4-丁二醇、对苯二酚二羟乙基醚、聚四亚甲基醚二醇双(对氨基苯甲酸)酯、4-氯-3,5-二氨基苯甲酸异丁酯或1,3-丙二醇-双(4—氨基苯甲酸)酯中的一种或一种以上。
所述的低游离预聚体与扩链剂的质量比为10:20-35。
所述的聚氨酯抛光垫片层的密度为0.75-0.95g/cm3,邵氏硬度为40-70D。
本发明采用独特的分子蒸馏技术组合分离工艺,进料温度控制在90℃,蒸馏时控制温度为130-150℃,真空度控制在0.1mbar,进料速率为600g/h,经两级薄膜蒸发器分离之后得高性能聚氨酯预聚体。然后将体系中游离的二异氰酸酯单体通过独特的分子蒸馏技术进行分离,即可得到游离二异氰酸酯含量较低、相对分子质量分布较窄、分子结构更为规整的高性能聚氨酯预聚体。低游离的预聚体由于流动性好、凝胶时间长且成型速度快,从而缩短脱模时间,提高生产效率,并且低游离预聚体显著改进了材料的成型性能和物理机械性能,使其更适用于高速、高承载等动态性能要求高的工作环境中,将低游离预聚体引入到聚氨酯抛光垫片层的制备当中可以借助其更长的凝胶时间来控制填料的分布,并使抛光垫具有更稳定的性能、更长的寿命和更优良的抛光效果。
与现有技术相比,本发明的有益效果如下:
1、本发明合成预聚体时游离的TDI较少,赋予聚氨酯抛光垫更好的动态性能。
2、本发明合成的预聚体为游离二异氰酸酯单体含量小于0.1%的低游离预聚体,流动性好、凝胶时间长且成型速度快,使预聚体分子的结构更规整排列。
3、本发明固化剂扩链剂组分中创新性的采用了低聚二胺类扩链剂1,3-丙二醇-双(4-氨基苯甲酸)酯和4-氯-3,5-二氨基苯甲酸异丁酯,可赋予聚氨酯抛光垫良好的机械性能。
(4)本发明制备的聚氨酯抛光垫片层具有更长的产品的使用寿命和存储期限,机械性能更好,抛光效更高,且抛光效果更佳优良会在被抛光件表面产生更少的划痕。
具体实施方式
下面结合实施例对本发明做进一步的说明。
实施例中用到的所有原料若无特殊说明,均为市购。
实施例1
(1)预聚体组分的制备
将69.4g的PTMG1000,0.3g的1076和0.3g中空聚合物微球在温度100℃、真空度0.095MPa条件下脱水至含水率为0.03%,与30g的TDI-100在75℃条件下反应2.5h,得到含量为8.8%的预聚体,通过薄膜蒸发的方法,蒸馏时控制温度为135℃最终得到异氰酸根质量含量为6.2%,游离二异氰酸酯单体含量小于0.1%的低游离预聚体。
(2)聚氨酯抛光垫片层的制备
将预聚体加热到80℃,然后110℃熔化XYlink 1604 ,按照预聚体/XYlink 1604=100/16.3的比例充分混合,浇注于模具中开模、硫化制得邵氏硬度为50D聚氨酯抛光垫片层。
实施例2
(1)预聚体组分的制备
将52.7g的PTMG1000,8.4g的PTMG250,0.3g的1076和0.3g中空聚合物微球在温度100℃、真空度0.095MPa条件下脱水至含水率为0.03%,与38.3g的TDI-100在75℃条件下反应2.5h,得到含量为11.2%的预聚体,通过薄膜蒸发的方法,蒸馏时控制温度为135℃最终得到异氰酸根质量含量为8.0%,游离二异氰酸酯单体含量小于0.1%的低游离预聚体。
(2)聚氨酯抛光垫片层的制备
将预聚体加热到80℃,然后135℃熔化XYlink 740M,按照预聚体/XYlink 740M=100/26.9的比例充分混合,浇注于模具中开模、硫化制得邵氏硬度为60D聚氨酯抛光垫片层。
实施例3
(1)预聚体组分的制备
将34.5g的PTMG650,8.9g的PTMG250,0.3g的1076和0.3g中空聚合物微球在温度100℃、真空度0.095MPa条件下脱水至含水率为0.03%,与56g的MDI-100在75℃条件下反应2.5h,得到含量为11.4%的预聚体,通过薄膜蒸发的方法,蒸馏时控制温度为150℃最终得到异氰酸根质量含量为8.5%,游离二异氰酸酯单体含量小于0.1%的低游离预聚体。
(2)聚氨酯抛光垫片层的制备
将预聚体加热到80℃,然后135℃熔化XYlink 740M,按照预聚体/XYlink 740M=100/28.6的比例充分混合,浇注于模具中开模、硫化制得邵氏硬度为65D聚氨酯抛光垫片层。
实施例4
将17.4g的PCL-1000,20.2g的PTMG250,0.3g的1076和0.3g中空聚合物微球在温度100℃、真空度0.095MPa条件下脱水至含水率为0.03%,与61.8g的MDI-50在75℃条件下反应2.5h,得到含量为12.5%的预聚体,通过薄膜蒸发的方法,蒸馏时控制温度为150℃最终得到异氰酸根质量含量为9.5%,游离二异氰酸酯单体含量小于0.1%的低游离预聚体。
(2)聚氨酯抛光垫片层的制备
将预聚体加热到80℃,然后135℃熔化XYlink 740M,按照预聚体/XYlink 740M=100/31.9的比例充分混合,浇注于模具中开模、硫化制得邵氏硬度为70D聚氨酯抛光垫片层。
实施例5
将15.3g的PCL-1000,28.2g的PTMG250,0.3g的1076和0.3g中空聚合物微球在温度100℃、真空度0.095MPa条件下脱水至含水率为0.03%,与55.9g的TDI-100在75℃条件下反应2.5h,得到含量为16.2%的预聚体,通过薄膜蒸发的方法,蒸馏时控制温度为135℃最终得到异氰酸根质量含量为10%,游离二异氰酸酯单体含量小于0.1%的低游离预聚体。
(2)聚氨酯抛光垫片层的制备
将预聚体加热到80℃,然后110℃熔化XYlink 1604,按照预聚体/XYlink 1604=100/26的比例充分混合,浇注于模具中开模、硫化制得邵氏硬度为75D聚氨酯抛光垫片层。
对比例1
(1)预聚体组分的制备
将74.2g的PTMG1000在温度100℃、真空度0.095MPa条件下脱水至含水率为0.03%,与25.8的TDI-100在75℃条件下反应2.5h,最终得到异氰酸根质量含量为6.2%,游离二异氰酸酯单体含量小于0.1%的低游离预聚体。
(2)聚氨酯抛光垫片层的制备
将预聚体加热到80℃,然后110℃熔化MOCA,按照预聚体/MOCA=100/17.7的比例充分混合,浇注于模具中开模、硫化制得邵氏硬度为49D聚氨酯抛光垫片层。
将实施例1-5以及对比例1制备的聚氨酯抛光垫片层进行性能测试,测试结果见表1。硬度按照《GB/T531-1999橡胶袖珍硬度计压入硬度实验方法》进行测试;拉伸强度和断裂伸长率按照(GB/T 1040-92塑料拉伸性能测试方法》进行测试;压缩疲劳测试,通过一个惰性杠杆系统对试样施加一定的压缩负荷﹐并通过一个传动系统对试样施加具有规定振幅的周期性高频压缩﹐在一定条件下测定试样在一定时间内的压缩疲劳温升。
表1实施例1-5以及对比例1制备的聚氨酯抛光垫片层测试结果
当然,上述内容仅为本发明的较佳实施例,不能被认为用于限定对本发明的实施例范围。本发明也并不仅限于上述举例,本技术领域的普通技术人员在本发明的实质范围内所做出的均等变化与改进等,均应归属于本发明的专利涵盖范围内。
Claims (10)
1.一种聚氨酯抛光垫片层的制备方法,其特征在于:包括以下步骤:
(1)将多元醇、中空聚合物微球和抗氧剂混合后脱水至含水率≤0.03%,然后与二异氰酸酯在70-85℃下反应,得到异氰酸根质量含量为7.5-15%的预聚物;
(2)通过薄膜蒸发的方法将步骤(1)反应制得的预聚物中未反应的游离二异氰酸酯单体分离出去,得到游离二异氰酸酯单体含量小于0.1%的低游离预聚体;
(3)将低游离预聚体组分与扩链剂组分充分混合,浇注于模具中开模、硫化制得聚氨酯抛光垫片层。
2.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:步骤(1)中所述的多元醇、中空聚合物微球和抗氧剂以及二异氰酸酯的质量比为30-74:0.1-0.5:0.1-0.5:25-70。
3.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的多元醇为数均分子量为250-2000,官能度为2的聚四氢呋喃醚多元醇或数均分子量为1000-2000的聚己内酯多元醇中的一种或一种以上。
4.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的中空聚合物微球粒径为10-150μm。
5.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的抗氧剂为抗氧剂1076。
6.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的二异氰酸酯为2,4-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、50%2,4’-二苯基甲烷二异氰酸酯与50%4,4'-二苯基甲烷二异氰酸酯混合物、液化MDI、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或二环己基甲烷-4,4'-二异氰酸酯中的一种或一种以上。
7.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的薄膜蒸发蒸馏时温度为130-150℃。
8.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的扩链剂为4-氯-3,5-二氨基苯甲酸异丁酯、3,3'-二氯-4,4'-二氨基二苯基甲烷、1,4-丁二醇、对苯二酚二羟乙基醚、聚四亚甲基醚二醇双(对氨基苯甲酸)酯、4-氯-3,5-二氨基苯甲酸异丁酯或1,3-丙二醇-双(4—氨基苯甲酸)酯中的一种或一种以上。
9.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的低游离预聚体与扩链剂的质量比为10:20-35。
10.根据权利要求1所述的聚氨酯抛光垫片层的制备方法,其特征在于:所述的聚氨酯抛光垫片层的密度为0.75-0.95g/cm3,邵氏硬度为40-70D。
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