CN113150218A - 一种镜片制造用的互穿网络聚合物的制备方法 - Google Patents
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Abstract
一种镜片制造用的互穿网络聚合物的制备方法,包括:步骤1、将聚醚二元醇、扩链剂、异氰酸盐和甲基丙烯酸羟乙酯置入第一反应容器进行搅拌,温度为60~80℃,时间为1~2h,形成聚氨酯;步骤2、将丙烯酸、甲基丙烯酸甲酯、丙烯酸‑2‑乙基己酯、甲基丙烯酸羟乙酯和过氧化苯甲酰置入第二反应容器进行搅拌,温度为50~80℃,时间为1~2h,形成丙烯酸酯;步骤3、将聚氨酯置入具有丙烯酸酯的第二反应容器中进行搅拌,温度为60~80℃,聚氨酯与丙烯酸酯聚合反应形成互穿网络聚合物。本发明的制备方法所形成的互穿网络聚合物(TPUAc),具备了TPU的热塑性和耐磨耗性,同时具备了丙烯酸酯的刚性和透明性。
Description
技术领域
本发明涉及互穿网络聚合物的制备方,尤其是涉及一种镜片制造用的互穿网络聚合物的制备方法。
背景技术
近代以来,市场对眼镜镜片的需求越来越多,包括太阳眼镜、近/远视眼镜、隐形眼镜和美瞳等等。
而目前眼镜采用较多的是塑料镜片,塑料镜片材质主要分为以下两类:1、浇注型,如:亚克力、聚氨酯等等;2、注塑型,如:聚碳酸酯类、丙烯酸酯类、聚苯乙烯类等等。其中浇注型的镜片工艺复杂、时间漫长、产量少,而对于注塑型的镜片,聚碳酸酯类镜片虽然具备极佳的耐冲击性及透光率,但是几乎不耐所有有机溶剂,而丙烯酸酯类和聚苯乙烯类虽然耐溶剂性虽然尚可,但是耐冲击性能却没有良好的性能。此外,上述的材料所做的镜片耐刮性也不佳,且容易破碎伤害使用者。
发明内容
本发明技术方案是针对上述情况的,为了解决上述问题而提供一种镜片制造用的互穿网络聚合物的制备方法,所述制备方法包括:
步骤1、将聚醚二元醇、扩链剂、异氰酸盐和甲基丙烯酸羟乙酯置入第一反应容器进行搅拌,温度为60~80℃,时间为1~2h,形成聚氨酯;
步骤2、将丙烯酸、甲基丙烯酸甲酯、丙烯酸-2-乙基己酯、甲基丙烯酸羟乙酯和过氧化苯甲酰置入第二反应容器进行搅拌,温度为50~80℃,时间为1~2h,形成丙烯酸酯;
步骤3、将聚氨酯置入具有丙烯酸酯的第二反应容器中进行搅拌,温度为60~80℃,聚氨酯与丙烯酸酯聚合反应形成互穿网络聚合物。
进一步,在互穿网络聚合物中,聚氨酯的占比为65~75%,丙烯酸酯的占比为25~35%。
进一步,在步骤1中,聚氨酯的NCO值为33.2。
进一步,在步骤1中,聚醚二元醇为PTMEG1000、PTMEG2000和PTMEG3000中的一种或多种混合。
进一步,在步骤1中,扩链剂为1,4丁二醇和乙二醇中的一种或两种混合。
进一步,在步骤1中,异氰酸盐为异佛尔酮二异氰酸酯和氢化苯基甲烷二异氰酸酯中的一种或两种混合。
进一步,在步骤2中,具体包括:
步骤2.1、将丙烯酸、甲基丙烯酸甲酯、丙烯酸-2-乙基己酯和甲基丙烯酸羟乙酯置入第二反应容器进行搅拌,温度为50~60℃,时间为0.4~0.6h;
步骤2.2、升温至60~80℃,加入过氧化苯甲酰进行搅拌,时间为1~1.2h,形成丙烯酸酯。
进一步,在步骤2中,丙烯酸酯的酸值百分比为25~35%。
采用上述技术方案后,本发明的效果是:本发明的制备方法所形成的互穿网络聚合物(TPUAc),具备了TPU的热塑性和耐磨耗性,同时具备了丙烯酸酯的刚性和透明性,利用该互穿网络聚合物制作的镜片具备极佳的耐磨、耐刮、耐溶剂的性能,以及极佳的光学性能。
具体实施方式
下面通过实施例对本发明技术方案作进一步的描述:
本发明提供一种镜片制造用的互穿网络聚合物的制备方法,该制备方法包括:
步骤1、将聚醚二元醇、扩链剂、异氰酸盐和甲基丙烯酸羟乙酯置入第一反应容器进行搅拌,温度为60~80℃,时间为1~2h,形成聚氨酯(TPU);
步骤2、将丙烯酸(AA)、甲基丙烯酸甲酯(MMA)、丙烯酸-2-乙基己酯(2EHA)、甲基丙烯酸羟乙酯(HEMA)和过氧化苯甲酰置入第二反应容器进行搅拌,温度为50~80℃,时间为1~2h,形成丙烯酸酯;
步骤3、将聚氨酯置入具有丙烯酸酯的第二反应容器中进行搅拌,温度为60~80℃,聚氨酯与丙烯酸酯聚合反应形成互穿网络聚合物(简称为TPUAc)。
其中,加入聚醚二元醇可避免成品出现龟裂、老化、不耐磨耗的问题;扩链剂能与线型聚合物链上的官能团反应而使分子链扩展、分子量增大;异氰酸盐用于形成TPU的主结构及氢键;丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸羟乙酯作为形成丙烯酸酯的原料;由于丙烯酸-2-乙基己酯含有羟基,可以在开始时先接入TPU的尾端,即先有部分丙烯酸酯已经接入TPU,其他丙烯酸类化合物的丙烯酸酯基即沿着丙烯酸-2-乙基己酯所建构的链开始反应并且穿透了正在聚合中的主链。
本发明的制备方法所形成的互穿网络聚合物(TPUAc),具备了TPU的热塑性和耐磨耗性,同时具备了丙烯酸酯的刚性和透明性,利用该互穿网络聚合物制作的镜片具备极佳的耐磨、耐刮、耐溶剂的性能,以及极佳的光学性能。
此外,在本发明中,聚氨酯在温度为70℃左右的环境中形成,能够形成线性聚合,不产生侧链反应,可以维持聚氨酯的热塑性,易于加工。
此外,在本发明中,利用甲基丙烯酸羟乙酯的羟基与聚氨酯反应作为桥接物,使得聚氨酯和丙烯酸类相容性问题得以解决。
此外,在丙烯酸酯形成过程中,若在温度为70℃左右或更低的环境下反应超过1小时的话,容易发生爆聚现象。其中,爆聚的产生是由于丙烯酸系列的反应过于剧烈,使得整体产生交联而终止了反应。在本发明中,过氧化苯甲酰作为过氧化物,过氧化苯甲酰在70℃左右的环境下的半衰期为10小时,当在半衰期未达到前,其反应还处于可控阶段,有利于控制丙烯酸酯系列在整体中的反应率,因此可以避免超过1小时的反应过程中发生爆聚现象。
具体地,在互穿网络聚合物中,聚氨酯的占比为65~75%,丙烯酸酯的占比为25~35%。聚丙烯酸酯之聚合只在主链尾端,且不超过主链35%,因此仍然保留了TPU良好的热塑性。
更具体地,在步骤1中,聚氨酯的NCO值为33.2。在步骤1中,NCO值达到最终NCO值的65~75%,为丙烯酸酯保留了反应空间。
具体地,在步骤1中,聚醚二元醇为PTMEG1000、PTMEG2000和PTMEG3000中的一种或多种混合。
具体地,在步骤1中,扩链剂为1,4丁二醇和乙二醇中的一种或两种混合。
具体地,在步骤1中,异氰酸盐为异佛尔酮二异氰酸酯和氢化苯基甲烷二异氰酸酯中的一种或两种混合。
具体地,在步骤2中,具体包括:
步骤2.1、将丙烯酸、甲基丙烯酸甲酯、丙烯酸-2-乙基己酯和甲基丙烯酸羟乙酯置入第二反应容器进行搅拌,温度为50~60℃,时间为0.4~0.6h;
步骤2.2、升温至60~80℃,加入过氧化苯甲酰进行搅拌,时间为1~1.2h,形成丙烯酸酯。
更具体地,在步骤2中,丙烯酸酯的酸值百分比为25~35%。加入过氧化苯甲酰后每间隔10min检测依次丙烯酸酯的酸值百分比,直到酸值百分比达到上述范围,通过测试酸值百分比可以计算丙烯酸酯类的反应率,从而确定步骤2中终止反应的时间。其中,酸值百分比=(AA的酸值+MMA的酸值+2EHA的酸值+HEMA的酸值)×丙烯酸酯的占比×反应率,AA的酸值为65mg·KOH/g,MMA的酸值为47mg·KOH/g,2EHA的酸值为25mg·KOH/g,HEMA的酸值为36mg·KOH/g,丙烯酸酯的占比为25~35%。
【实施例1】
在本实施例中,镜片制造用的互穿网络聚合物的制备方法包括:
步骤1、将7.5kgPTMEG2000、0.5kg1,4丁二醇、2.06kg异佛尔酮二异氰酸酯置入第一反应容器进行搅拌,温度为70℃,时间为1h,形成TPU;
步骤2.1、将0.3kg丙烯酸、1.25kg甲基丙烯酸甲酯、0.35kg丙烯酸-2-乙基己酯和2.10kg甲基丙烯酸羟乙酯置入第二反应容器进行搅拌,温度为50℃,时间为0.5h;
步骤2.2、升温至60~80℃,加入0.01kg过氧化苯甲酰进行搅拌,时间为1h,形成丙烯酸酯,丙烯酸酯的酸值百分比为25%;
步骤3、将TPU置入具有丙烯酸酯的第二反应容器中进行搅拌,温度为70℃,聚氨酯与丙烯酸酯聚合反应形成TPUAc。
取出1kg上述TPUAc材料,通过卧式注塑机,以145℃的温度注塑镜片。
【实施例2】
在本实施例中,制备方法与实施例1类似,所不同的是:
在步骤1中,将3.0kgPTMEG1000、1.85kg1,4丁二醇、4.0kg异佛尔酮二异氰酸酯和1.2kg氢化苯基甲烷二异氰酸酯置入第一反应容器进行搅拌;
在步骤2.1中,将0.5kg丙烯酸、0.3kg甲基丙烯酸甲酯、0.85kg丙烯酸-2-乙基己酯和1.35kg甲基丙烯酸羟乙酯置入第二反应容器进行搅拌。
取出3kg上述TPUAc材料,通过卧式注塑机,以155℃的温度注塑镜片。
将实施例1、实施例2所制造的镜片与市面上通过亚克力、浇注型聚氨酯(CPU)、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)和聚苯乙烯(PS)材料制造的镜片共同进行测试,测试结果如下表所示:
测试项目 | 实施例1 | 实施例2 | 亚克力 | CPU | PC | PMMA | PS |
可加工性 | 优 | 优 | 普通 | 普通 | 优 | 优 | 优 |
透光率 | 93% | 93% | 95% | 93% | 93% | 94% | 90% |
耐刮性 | 优 | 优 | 普通 | 普通 | 普通 | 差 | 差 |
耐磨性 | 优 | 优 | 普通 | 普通 | 普通 | 差 | 差 |
耐溶剂性 | 优 | 优 | 差 | 优 | 差 | 差 | 普通 |
缩水率 | 优 | 优 | 优 | 差 | 优 | 优 | 优 |
尺寸精度 | 优 | 优 | 优 | 差 | 优 | 优 | 优 |
耐冲击性 | 优 | 优 | 优 | 普通 | 优 | 差 | 差 |
表1
由此可知,本发明制备的TPUAc材料所制作的镜片在加工性、透光率、耐刮性、耐磨性、耐溶剂性、缩水率、尺寸精度和耐冲击性都可以达到优良水平。通过TPU与丙烯酸酯形成互穿网络结构,克服了传统TPU收缩率以及刚性不足的缺点,同时利用了TPU耐刮、耐磨及耐溶剂等优点,使得材料满足镜片各方面的要求。
以上所述实施例,只是本发明的较佳实例,并非来限制本发明的实施范围,故凡依本发明申请专利范围所述的构造、特征及原理所做的等效变化或修饰,均应包括于本发明专利申请范围内。
Claims (8)
1.一种镜片制造用的互穿网络聚合物的制备方法,其特征在于:所述制备方法包括:
步骤1、将聚醚二元醇、扩链剂、异氰酸盐和甲基丙烯酸羟乙酯置入第一反应容器进行搅拌,温度为60~80℃,时间为1~2h,形成聚氨酯;
步骤2、将丙烯酸、甲基丙烯酸甲酯、丙烯酸-2-乙基己酯、甲基丙烯酸羟乙酯和过氧化苯甲酰置入第二反应容器进行搅拌,温度为50~80℃,时间为1~2h,形成丙烯酸酯;
步骤3、将聚氨酯置入具有丙烯酸酯的第二反应容器中进行搅拌,温度为60~80℃,聚氨酯与丙烯酸酯聚合反应形成互穿网络聚合物。
2.根据权利要求1所述的镜片制造用的互穿网络聚合物的制备方法,其特征在于:在互穿网络聚合物中,聚氨酯的占比为65~75%,丙烯酸酯的占比为25~35%。
3.根据权利要求2所述的镜片制造用的互穿网络聚合物的制备方法,其特征在于:在步骤1中,聚氨酯的NCO值为33.2。
4.根据权利要求1所述的镜片制造用的互穿网络聚合物的制备方法,其特征在于:在步骤1中,聚醚二元醇为PTMEG1000、PTMEG2000和PTMEG3000中的一种或多种混合。
5.根据权利要求1所述的镜片制造用的互穿网络聚合物的制备方法,其特征在于:在步骤1中,扩链剂为1,4丁二醇和乙二醇中的一种或两种混合。
6.根据权利要求1所述的镜片制造用的互穿网络聚合物的制备方法,其特征在于:在步骤1中,异氰酸盐为异佛尔酮二异氰酸酯和氢化苯基甲烷二异氰酸酯中的一种或两种混合。
7.根据权利要求1所述的镜片制造用的互穿网络聚合物的制备方法,其特征在于:在步骤2中,具体包括:
步骤2.1、将丙烯酸、甲基丙烯酸甲酯、丙烯酸-2-乙基己酯和甲基丙烯酸羟乙酯置入第二反应容器进行搅拌,温度为50~60℃,时间为0.4~0.6h;
步骤2.2、升温至60~80℃,加入过氧化苯甲酰进行搅拌,时间为1~1.2h,形成丙烯酸酯。
8.根据权利要求1所述的镜片制造用的互穿网络聚合物的制备方法,其特征在于:在步骤2中,丙烯酸酯的酸值百分比为25~35%。
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