CN116120512B - 低温感慢回弹聚氨酯材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种低温感慢回弹聚氨酯材料及其制备方法,所述低温感慢回弹聚氨酯材料由A组份与B组份组成,所述A组份包括聚醚多元醇A、聚醚多元醇B、特殊多元醇C、稳泡剂、扩链剂、催化剂、发泡剂;按质量份数比计,所述聚醚多元醇A用量为30‑60份,所述聚醚多元醇B用量为15‑30份,所述特殊多元醇C用量为20‑50份;所述B组份为聚醚型预聚异氰酸酯,具体为MDI和多元醇改性MDI的混合物。本发明通过采用聚醚二醇、接枝聚醚多元醇、慢回弹聚醚这三种聚醚的搭配制备聚氨酯发泡材料,在降低聚氨酯温度敏感性的同时达到舒适的应用手感;本发明在0℃及0℃以下的环境下,聚氨酯材料硬度变化小,使用时不受温度的限制。
Description
技术领域
本发明涉及聚氨酯技术领域,具体涉及一种低温感慢回弹聚氨酯材料及其制备方法。
背景技术
聚氨酯慢回弹泡沫也被称为记忆泡沫、粘弹性泡沫、低回弹泡沫,受力后可以顺应不同部位的形状,与施力物体接触面积最大化,应力梯度最小化,受力集中点得到缓解,移除外力时缓慢复原,恢复时间可从几秒到数十秒。因此,慢回弹泡沫被广泛应用于各类垫材,如枕头、床垫、腰枕、护颈、耳塞等,与传统垫材相比,可减轻对人体的挤压感,有利于血液循环,具有更高的舒适性。
由于聚氨酯慢回弹泡沫材料具有特殊的黏弹特性,体现很柔软的材料特性,并有很强的冲击能吸收能力。慢回弹应用到鞋材上,能适应人体脚型,使人的重力得以在整个脚接触面上分散给人以很好的舒适感。
由于慢回弹聚氨酯海绵具有很好的形状记忆特性,较强的能量吸收及减震抗震等性能,因而在缓冲材料领域得到了广泛的应用,如医疗、医药、箭靶、头盔内垫、赛车坐垫乃至功能鞋垫、床上用品、家具等。特别是近十多年来大量用于高级轿车中作为座垫与头枕,用于家居中作为高档慢回弹枕头及床垫和用于体育鞋材中的慢回弹缓冲鞋垫时,普通慢回弹聚氨酯海绵硬度及物理性能会随环境温度的变化,产生明显的变化:低温变硬,反弹变慢;高温变软,反弹变快。尤其是在冬天作为座椅、床垫和枕头等产品时,就会使人感受不到舒适感,甚至是不舒服的硬物感。
聚氨酯泡沫是常用的缓冲材料,透气性高,具有优良的抗疲劳性能,聚氨酯作为一种高分子材料,温度对聚氨酯的物性如回弹性、压陷硬度、舒适因子等有较大的影响,温度降低会使聚氨酯网络中的一些链段冻结,明显影响链段的迁移性。近年来,为降低生产成本,低密度产品已成为发展趋势,为了降低密度,需要增加发泡剂水的用量,随着水用量的增加,泡沫中硬段含量增加,温敏性升高,随着环境温度的变化变得过硬或过软,舒适性变差。
而在北方的冬天,温度经常为零下10℃以下,甚至更低,聚氨酯材料聚氨酯材料的使用会受到限制,要求在北方零度以下有良好保持慢回弹综合效果。
目前大部分聚氨酯发泡材料对使用温度比较敏感,在低温下(<0℃),尤其是北方的冬天,室外温度经常零下10度以下甚至更低,聚氨酯材料会变硬,严重影响其舒适度。聚氨酯发泡材料应用于鞋垫、鞋脚床的制备受到限制,在达到施工性,密度,硬度等各项基础上,温度低时,各项性能会降低,导致在低温环境下使用舒适度严重受影响。因此急需开发一种能满足在北方零度以下环境下能良好保持慢回弹综合效果的聚氨酯材料。
发明内容
本发明目的在于解决现有技术存在的问题,提供一种低温感慢回弹聚氨酯材料及其制备方法。
为了实现上述目的,本发明提出以下技术方案:一种低温感慢回弹聚氨酯材料,由A组份和B组份组成,所述A组份包括聚醚多元醇A、聚醚多元醇B、特殊多元醇C、稳泡剂、扩链剂、催化剂、发泡剂;按质量份数比计,所述聚醚多元醇A用量为30-60份,所述聚醚多元醇B用量为15-30份,所述特殊多元醇用量为20-50份;
进一步地,所述聚醚多元醇A为聚醚二醇,官能度为2,粘度1200-2000mpa.s,羟值26-30mgKOH/g,分子量3500-4500,具有优异的链段柔顺性,其制品对低温敏感度低;优选上海高桥GED-28或山东蓝星东大EP-3600。
所述聚醚多元醇B为接枝聚醚多元醇,羟值18-30 mgKOH/g,官能度为2.5-3,粘度≤8000mpa.s,分子量5000-9000,固含量为35-45%的苯乙烯-丙烯腈接枝聚合物多元醇,优选上海高桥GPOP-H45,壳牌MD22-40,可改善硬度,提高承载性能;
所述特殊多元醇C为慢回弹聚醚聚氧化丙烯多元醇,羟值为350-480mgKOH/g,官能度为2.5-3,不饱和度为0.005-0.05mmol/g,优选的有上海高桥GE303,蓝星东大DL400;用于生产慢回弹泡沫的低分子量聚醚,对温度敏感性低。
进一步地,所述B组份为聚醚型预聚异氰酸酯,具体为MDI和多元醇改性MDI的混合物,其中MDI为30-60%的二苯基甲烷二异氰酸酯,多元醇改性MDI为40-70%的二苯基甲烷二异氰酸酯与聚醚多元醇的预聚体。由于所述B组份以苯为原料合成,其分子结构中含有两个苯环,具有对称的分子结构,制得的聚氨酯制品具有良好的力学性能。
进一步地,所述聚醚型预聚异氰酸酯的规格为粘度:600-1200mpa.s,NCO含量为19%,采用上述B组份的异氰酸酯能很好地在保证力学性能的前提下提高其拉伸性能和柔软性。
进一步地,所述扩链剂为乙二醇,通过扩链反应生成线性高分子,用量1-3份。
进一步地,所述发泡剂为水,用量0.6-1.5份。
进一步地,所述催化剂由60%三亚乙基二胺和40%的三甲基羟乙基乙二胺复配而成,低雾化性,相比传统催化剂有更好的开孔效果;催化剂使用量1-3份。
进一步地,所述稳泡剂为聚醚改性有机硅类表面活性剂,具有良好的乳化性、稳定性和适应性,改善发泡性能,拓宽施工宽容度,稳泡剂使用量0.5-1.5份。
本发明还公布了一种低温感慢回弹聚氨酯材料的制备方法,所述方法步骤包括:
S1.将聚醚多元醇A、聚醚多元醇B、特殊多元醇C、扩链剂、发泡剂、催化剂,稳泡剂按比例搅拌均匀,形成A组份,另外准备好异氰酸酯B组份;
S2.A组份加入浇注机A料缸内,B组份加入浇注机B料缸内;
S3.A组份和B组份经浇注机枪头搅拌混合后出料,注射在模具中,两组分在模具中反应成型,制得聚氨酯低温感慢回弹材料;
进一步地,所述的工艺条件:料温25-35℃,模具温度50-65℃,熟化时间4-8min,比例A组分/B组分:100/70-80。
进一步地,所述的低温感慢回弹聚氨酯材料应用于鞋材,特别是鞋脚床上的应用,在达到施工性,密度,硬度等各项基础上,温度低时,硬度变化小,在低温环境下使用舒适度不受影响。
与现有技术相比,本发明的有益效果是:
1、本发明通过采用聚醚二醇、接枝聚醚多元醇、慢回弹聚醚这三种聚醚的搭配,可降低聚氨酯温度敏感性的同时达到舒适的应用手感。
2、本发明在0℃及0℃以下的环境下,硬度变化小,在低温环境下使用舒适度不受影响,特别适用于北方零度以下环境下使用。
3、将本发明聚氨酯发泡材料应用于鞋脚床的制备,在达到施工性,密度,硬度等各项基础上,降低了低温敏感性,提高了舒适度等性能。
具体实施方式
下面通过实施例对本发明作进一步的说明,但并不作为对本发明限制的依据。
实施例1:一种低温感慢回弹聚氨酯材料,由A组份和B组份混合发泡而成,其中:A组份为,成份组成(以重量份计):聚醚多元醇A为60份(官能度2,羟值28);聚醚多元醇B为20份(官能度3,羟值30);特殊多元醇C为20份(官能度3,羟值420);泡沫稳定剂为0.5份;催化剂为2.5份;发泡剂水为0.8份;扩链剂2份;B组份异氰酸酯74份。
实施例2:一种低温感慢回弹聚氨酯材料,由A组份和B组份混合发泡而成,其中:A组份为,成份组成(以重量份计):聚醚多元醇A为30份(官能度2,羟值30);聚醚多元醇B为30份(官能度2.5,羟值20);特殊多元醇C为40份(官能度2.8,羟值350);泡沫稳定剂为1.5份;催化剂为1份;发泡剂水为0.6份;扩链剂1份;B组份异氰酸酯76份。
实施例3:一种低温感慢回弹聚氨酯材料,由A组份和B组份混合发泡而成,其中:A组份为,成份组成(以重量份计):聚醚多元醇A为45份(官能度2,羟值28);聚醚多元醇B为25份(官能度2.8,羟值24);特殊多元醇C为30份(官能度3,羟值380);泡沫稳定剂为1份;催化剂为1.5份;发泡剂水为0.8份;扩链剂1.5份;B组份异氰酸酯78份。
按照上述实施例1-3配方中的用量,先将A组份中的聚醚多元醇A、聚醚多元醇B、特殊多元醇C、扩链剂、发泡剂、催化剂,稳泡剂混合后搅拌均匀,然后将A组份加入浇注机A料缸内,B组份加入浇注机B料缸内;A组份和B组份经浇注机枪头搅拌混合后出料,注射在模具中,料温25-35℃,模具温度50-65℃,熟化时间4-8min,两组份在模具中反应成型,分别制得聚氨酯低温感慢回弹材料。
对比例:采用国内某客户应用于鞋垫制品的聚氨酯浆料。
将实施例1-3制备的低温感慢回弹聚氨酯材料以及对比例中的聚氨酯浆料制备成同等密度及大小的鞋垫后检测其性能,检测标准按GB/T 24451-2020《慢回弹软质聚氨酯泡沫塑料》的标准在常温下及进行物理性能检测,并依据SRIS 0101标准,采用Asker C 型硬度计,在0℃、-10℃及-40℃下检测硬度变化,检测结果如下表所示。
从上述表格中可知,实施例1-3中制备的低温感慢回弹聚氨酯材料,在常温下各物理性能指标优异,与对比例性能相差不大,但实施例1-3在低温环境(0℃、-10℃及-40℃)下的复原时间变化及硬度变化和常温环境(25℃)相比更小,而对比例在低温环境下(0℃、-10℃及-40℃)的复原时间变化及硬度变化和常温环境(25℃)相比更大。因此本发明的低温感慢回弹聚氨酯材料的使用过程受温度的影响较小,可满足北方零度以下环境下使用。
以上所述,仅为本发明的较佳实例,并非对本发明任何形式上和实质上的限制,凡属本发明思路下的技术方案均属于本发明的保护范围,凡依据本发明实质技术对上述实例所做的任何等效变更和修饰也应视为本发明的保护范围。
Claims (7)
1.一种低温感慢回弹聚氨酯材料,其特征在于,由A组份与B组份组成,所述A组份包括聚醚多元醇A、聚醚多元醇B、特殊多元醇C、稳泡剂、扩链剂、催化剂、发泡剂;按质量份数比计,所述聚醚多元醇A用量为30-60份,所述聚醚多元醇B用量为15-30份,所述特殊多元醇C用量为20-50份;所述B组份为聚醚型预聚异氰酸酯;
所述聚醚多元醇A为聚醚二醇,粘度1200~2000mpa.s,羟值26~30mgKOH/g,分子量3500~4500;
所述聚醚多元醇B为接枝聚醚多元醇,羟值18-30 mgKOH/g,官能度为2.5-3,粘度≤8000mpa.s,分子量5000-9000,固含量为35-45%的苯乙烯-丙烯腈接枝聚合物多元醇;
所述特殊多元醇C为慢回弹聚醚聚氧化丙烯多元醇,羟值为350-480mgKOH/g,官能度为2.5-3,不饱和度为0.005-0.05mmol/g;
所述B组份为MDI和多元醇改性MDI的混合物,其中MDI为 30-60%的二苯基甲烷二异氰酸酯,多元醇改性MDI为40-70%的二苯基甲烷二异氰酸酯与聚醚多元醇的预聚体;
所述B组份的规格为粘度:600-1200mpa.s,NCO含量为19%。
2.根据权利要求1所述的一种低温感慢回弹聚氨酯材料,其特征在于,扩链剂为乙二醇,通过扩链反应生成线性高分子,用量1-3份,发泡剂为水,用量0.6-1.5份。
3.根据权利要求2所述的一种低温感慢回弹聚氨酯材料,其特征在于,所述催化剂由60%三亚乙基二胺和40%的三甲基羟乙基乙二胺复配而成,催化剂使用量1-3份;所述稳泡剂为聚醚改性有机硅类表面活性剂,稳泡剂使用量0.5-1.5份。
4.根据权利要求3所述的低温感慢回弹聚氨酯材料的制备方法,其特征在于,所述方法步骤包括:
S1.将聚醚多元醇A、聚醚多元醇B、特殊多元醇C、稳泡剂、扩链剂、催化剂、发泡剂按比例搅均匀,形成A组份,另外准备好B组份;
S2.A组份加入浇注机A料缸内,B组份加入浇注机B料缸内;
S3.A组份和B组份经浇注机枪头搅拌混合后出料,注射在模具中,两组分在模具中反应成型,制得聚氨酯低温感慢回弹材料。
5.根据权利要求4所述的低温感慢回弹聚氨酯材料的制备方法,其特征在于,所述步骤S3中反应成型的工艺条件如下:料温25-35℃,模温50-65℃,熟化时间4-8min,比例A组份/B组份:100/70-80。
6.一种权利要求3所述的低温感慢回弹聚氨酯材料在鞋材上的应用。
7.根据权利要求6所述的低温感慢回弹聚氨酯材料在鞋材上的应用,其特征在于,所述的低温感慢回弹聚氨酯材料在鞋脚床上的应用。
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