CN112194890A - 一种聚氨酯材料及其制备方法 - Google Patents

一种聚氨酯材料及其制备方法 Download PDF

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CN112194890A
CN112194890A CN202011113253.1A CN202011113253A CN112194890A CN 112194890 A CN112194890 A CN 112194890A CN 202011113253 A CN202011113253 A CN 202011113253A CN 112194890 A CN112194890 A CN 112194890A
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姜盼
李成章
张德伟
李娟�
杜建周
王玉霞
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Nantong Haotai Products & Chemicals Co ltd
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Abstract

本发明公开了一种聚氨酯材料,包括:32—40质量份多异氰酸酯、43—50质量份聚醚多元醇、4—6质量份扩链剂、3—7质量份有机硅泡沫稳定剂、2.5—5质量份硅微粉、0.06质量份催化剂,其中多异氰酸酯为聚(1,4‑环己烷二甲醇己二酸酯),所述聚醚多元醇为聚碳酸酯二醇,所述扩链剂为1,4‑丁二醇,所述催化剂为二丁基锡二月桂酸酯。制备方法,其具体步骤包括S1.在反应釜中搅拌聚碳酸酯二醇,真空脱水,放入聚(1,4‑环己烷二甲醇己二酸酯),添加二丁基锡二月桂酸酯和有机硅泡沫稳定剂;再加入1,4‑丁二醇、硅微粉,进行快速搅拌1小时;然后熟化和冷却。本发明制得的聚氨酯保温材料性能完全可满足应用工艺中各项要求,压缩强度大,耐水解稳定性,抗老化,不易燃烧。

Description

一种聚氨酯材料及其制备方法
技术领域
本发明属于聚氨酯型高分子材料生产领域,具体涉及一种聚氨酯材料及其制备方法。
背景技术
目前常用的建筑保温材料主要分为有机材料和无机材料两大类,有机材料包括膨胀聚苯板、挤塑聚苯板、酚醛、发泡聚苯乙烯等,无机材料包括发泡陶瓷、发泡水泥、岩棉和玻璃棉等。结合现阶段建筑节能技术应用现状和发展瓶颈,亟需研发制备一种高效节能复合保温板材,以取代传统匀质保温材料如EPS板、XPS板、PU板和岩棉板等。
目前聚氨酯具有导热系数低、保温性能好、防潮、防水、耐老化、不熔化等特性,同时,具有容重轻、可减少制成品的自重量等优点,是一种新兴的有机高分子材料被誉为“第五大塑料”。而作为建筑保温材料,传统聚氨酯材料生产制备存在缺陷,在保温、阻燃、力学性能等方面还有欠缺,导热系数、吸水率、氧指数等关键指标还有提升空间。
发明内容
为了解决上述不足,本发明要解决的问题采用聚氨酯做为建筑保温材料时,现有的聚氨酯材料生产制备存在缺陷,保温、阻燃、力学性能等方面无法满足更高的使用要求。
本发明采用以下技术方案,一种聚氨酯材料,制备原料包括:32—40质量份多异氰酸酯、43—50质量份聚醚多元醇、4—6质量份扩链剂、3—7质量份有机硅泡沫稳定剂、2.5—5质量份硅微粉、0.06质量份催化剂,其中多异氰酸酯为聚(1,4-环己烷二甲醇己二酸酯),所述聚醚多元醇为聚碳酸酯二醇,所述扩链剂为1,4-丁二醇,所述催化剂为二丁基锡二月桂酸酯。
进一步地,所述聚(1,4-环己烷二甲醇己二酸酯)分子量为1190。
进一步地,所述有机硅泡沫稳定剂为低粘度二甲基硅油和甲基苯基硅油的混合物。
相应地,提供所述聚氨酯材料的制备方法,其具体步骤如下:
S1.在反应釜中加入聚碳酸酯二醇,进行搅拌,加热温度850-1250℃;
S2.将聚碳酸酯二醇抽真空脱水,直到水分含量低于1%;
S3.放入聚(1,4-环己烷二甲醇己二酸酯),加热至65-105℃,添加二丁基锡二月桂酸酯和有机硅泡沫稳定剂,反应2-5小时,并进行真空脱气泡;
S4.加入1,4-丁二醇、硅微粉,进行快速搅拌0.5-2小时;
S5.将混合物倒入已预热好的模具中,放入110-135℃的真空烘箱中,熟化8-15小时以上;
进一步地,S2步骤中采用卡尔·费休法测定原材料及体系中的水分。
进一步地,S5步骤中的模具,内表面涂覆有硅油。
进一步地,S5步骤中的模具所述模具为一模多腔结构。
进一步地,还包括S7.按照要求尺寸切裁。
进一步地,S7.热稳定性测试条件:加热速率为8-15℃/min,加热范围为25~600℃,氛围为氮气。
本发明的有益效果是:
本发明以4,4’-二环己基甲烷二异氰酸酯、聚碳酸酯二醇、1,4-丁二醇、有机硅泡沫稳定剂、硅微粉为原理制备聚氨酯保温材料,成本较低,选用了特定的较大官能度的聚氨酯原料,及科学选用筛选助剂材料和物料配比,有效地提高了制品抗压强度,而且制得的聚氨酯保温材料性能完全可满足应用工艺中各项要求,各项指标达到或超过国外同类产品技术水平,其制品具有如下优点:密度高,可根据不同应用场合,密度在200~500千克/立方进行调节,压缩强度大,可达4~20MPa,导热系数0.052.具有低导热系数,低透湿系数,低吸水率,满足保冷要求。具有耐水解稳定性,抗老化,耐酸碱等化学药品性能优良,不易燃烧,阻燃性满足国家安全要求密度要求;-165度-180度管托密度在300-500之间。
附图说明
图1为本发明所述的聚氨酯材料制备方法的工艺流程简图。
具体实施方式
下面结合附图和具体实施例详细描述一下本发明的具体内容。
实施例一:
聚氨酯制备原料按质量份数配比:
序号 名称 份数
1 聚(1,4-环己烷二甲醇己二酸酯) 32
2 聚碳酸酯二醇 43
3 1,4-丁二醇 4
4 二丁基锡二月桂酸酯 0.06
5 低粘度二甲基硅油、甲基苯基硅油 3
6 硅微粉 2.5
制备方法如下:
S1.在反应釜中加入聚碳酸酯二醇,进行搅拌,加热温度100℃;
S2.将聚碳酸酯二醇抽真空脱水,采用卡尔·费休法测定原材料及体系中的水分,直到水分含量低于1%,;
S3.放入聚(1,4-环己烷二甲醇己二酸酯),加热至75℃,添加二丁基锡二月桂酸酯和低粘度二甲基硅油、甲基苯基硅油,反应3小时以上,并进行真空脱气泡;
S4.加入1,4-丁二醇、硅微粉,进行快速搅拌1小时;
S5.将混合物倒入已预热好的模具中,模具内表面涂覆有硅油,放入120℃的真空烘箱中,熟化10小时以上;
S6.冷却,对成品的力学性能、热稳定性检测;热稳定性测试条件:加热速率为10℃/min,加热范围为25~600℃,氛围为氮气。
实施例二:
制备方法同实施例一,聚氨酯制备原料按质量份数配比:
序号 名称 份数
1 聚(1,4-环己烷二甲醇己二酸酯) 37
2 聚碳酸酯二醇 46
3 1,4-丁二醇 5
4 二丁基锡二月桂酸酯 0.06
5 低粘度二甲基硅油、甲基苯基硅油 5
6 硅微粉 4
实施例三:
制备方法同实施例一,聚氨酯制备原料按质量份数配比:
序号 名称 份数
1 聚(1,4-环己烷二甲醇己二酸酯) 40
2 聚碳酸酯二醇 20
3 1,4-丁二醇 3
4 二丁基锡二月桂酸酯 0.06
5 低粘度二甲基硅油、甲基苯基硅油 7
6 硅微粉 5
实施例四:
其他部分与实施例一相同,除了S5步骤中的模具所述模具为一模多腔结构,成本后按照要求尺寸切裁。
本发明的工作原理:
聚氨酯保温材料是一种性能优良的合成材料,它具有比强度高、导热系数小等优点,主要用做保温隔热材料,其次为结构材料。强度硬质聚氨酯泡沫保冷管托,是以多官能度有机异氰酸酯及混合聚醚多元醇为主要原料。本发明通过原料调控设计、助剂添加开发满足市场需求的阻燃保温型聚氨酯材料,通过系统研究不同配方对材料导热、阻燃的影响。确定以多异氰酸酯、聚醚多元醇、有机硅泡沫稳定剂、硅微粉等为原料,合成一种低成本高阻燃性能的聚氨酯保温材料;通过掌握添加剂、配方、工艺、性能之间规律,实现导热系数、吸水率、氧指数性能改善,系统研究等对聚氨酯保温建材构件微结构和性能影响。与传统方法制得的聚氨酯保温材料力学性能测试对比结果如下:
合成方法 本发明 传统方法一 传统方法二
拉伸强度/Mpa 45.7 30.4 24.7
断裂伸长率/% 453.7 453.7 452.1
100%模量 4.88 4.53 3.81
300%模量 19.50 17.76 11.04
综上所述,本发明所述的聚氨酯及其制备方法,制得的聚氨酯保温材料性能完全可满足应用工艺中各项要求,压缩强度大,耐水解稳定性,抗老化,不易燃烧。
以上显示和描述了本发明的基本原理、主要特征及优点。前、后、左、右、末端、前端等方位指示词仅为说明结构,非限定。本行业的技术人员应该了解,上述实施方式只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围内。

Claims (9)

1.一种聚氨酯材料,其特征在于:制备原料包括:32—40质量份多异氰酸酯、43—50质量份聚醚多元醇、4—6质量份扩链剂、3—7质量份有机硅泡沫稳定剂、2.5—5质量份硅微粉、0.06质量份催化剂,其中多异氰酸酯为聚(1,4-环己烷二甲醇己二酸酯),所述聚醚多元醇为聚碳酸酯二醇,所述扩链剂为1,4-丁二醇,所述催化剂为二丁基锡二月桂酸酯。
2.根据权利要求1所述的一种聚氨酯材料,其特征在于:所述聚(1,4-环己烷二甲醇己二酸酯)分子量为1000-1250。
3.根据权利要求1或2所述的一种聚氨酯材料,其特征在于:所述有机硅泡沫稳定剂为低粘度二甲基硅油和甲基苯基硅油的混合物。
4.一种聚氨酯材料的制备方法,其特征在于:具体步骤如下:
S1.在反应釜中加入聚碳酸酯二醇,进行搅拌,加热温度850-1250℃;
S2.将聚碳酸酯二醇抽真空脱水,直到水分含量低于1%;
S3.放入聚(1,4-环己烷二甲醇己二酸酯),加热至65-105℃,添加二丁基锡二月桂酸酯和有机硅泡沫稳定剂,反应2-5小时,并进行真空脱气泡;
S4.加入1,4-丁二醇、硅微粉,进行快速搅拌0.5-2小时;
S5.将混合物倒入已预热好的模具中,放入110-135℃的真空烘箱中,熟化8-15小时以上;
S6.冷却,对成品的力学性能、热稳定性检测。
5.根据权利要求4所述的一种聚氨酯材料的制备方法,其特征在于:所述S2步骤中采用卡尔·费休法测定原材料及体系中的水分。
6.根据权利要求4所述的一种聚氨酯材料的制备方法,其特征在于:所述S5步骤中的模具,内表面涂覆有硅油。
7.根据权利要求4或6所述的一种聚氨酯材料的制备方法,其特征在于:所述S5步骤中的模具所述模具为一模多腔结构。
8.根据权利要求4所述的一种聚氨酯材料的制备方法,其特征在于:还包括S7.按照要求尺寸切裁。
9.根据权利要求4所述的一种聚氨酯材料的制备方法,其特征在于:所述S7.热稳定性测试条件:加热速率为8-15℃/min,加热范围为25~600℃,氛围为氮气。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199269A (zh) * 2011-03-21 2011-09-28 黎明化工研究院 一种耐热型热塑性聚氨酯弹性体及其制备方法
CN105461877A (zh) * 2015-12-21 2016-04-06 中国科学院山西煤炭化学研究所 一种用于密封材料的热固化聚氨酯弹性体组合料的合成方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199269A (zh) * 2011-03-21 2011-09-28 黎明化工研究院 一种耐热型热塑性聚氨酯弹性体及其制备方法
CN105461877A (zh) * 2015-12-21 2016-04-06 中国科学院山西煤炭化学研究所 一种用于密封材料的热固化聚氨酯弹性体组合料的合成方法

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