CN106832212A - 储水式电热水器用聚氨酯组合聚醚及其制备方法和应用 - Google Patents
储水式电热水器用聚氨酯组合聚醚及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于聚氨酯技术领域,具体涉及一种储水式电热水器用聚氨酯组合聚醚及其制备方法和应用。所述组合聚醚由质量比为1:1‑1.3的A组分和B组分组成,A组分由如下质量百分比的原料制成:聚醚多元醇Ⅰ 21‑27%、聚醚多元醇Ⅱ11‑22%、聚醚多元醇III 10‑15%、聚醚多元醇IV 7‑15%、聚酯多元醇15‑20%、泡沫稳定剂1‑1.5%、发泡剂13‑15%、催化剂2‑3%、水0.5‑2.0%;B组分为多亚甲基多苯基多异氰酸酯。本发明的组合聚醚产品对臭氧层无破坏,环保性能优,制备方法简单,制得的聚氨酯泡沫导热系数低,密闭性好,强度高,吸水率以及使用稳定性良好。
Description
技术领域
本发明属于聚氨酯技术领域,具体涉及一种储水式电热水器用聚氨酯组合聚醚及其制备方法和应用。
背景技术
电热水器按加热功率大小可分为:储水式(又称容积式或储热式)、即热式、速热式(又称半储水式)三种,储水式电热水器比较常用。从电热水器产品来看,产品结构持续调整,呈现出升级的趋势:一是高端化,3000元以上热水器的市场零售量份额提高到18%;二是容积大,储水60L产品占比增长迅速;三是美观,储水式热水器方形机在市场占比突破10%。随着人们生活水平的进步,消费者对电热水器的能耗、外观提出了更苛刻的要求,更美观、更高效、更节能成为电热水器行业的研发方向。
在储水式电热水器中,以前一般采用聚苯作为保温材料,随着社会发展,聚氨酯以其超优的保温效果和生产时良好的宽容性已经逐步淘汰掉聚苯,成为水箱保温的唯一选择。然而传统聚氨酯泡沫一般采用CFCs系列发泡剂,其对大气臭氧层具有极强的破坏作用,是导致全球气温回暖、皮肤癌患者增多的元凶之一。为了维护生态环境,国际公约已经对其生产和使用做出了严格的限制和规定。因此,各个厂家先后推出141b、全水、环戊烷等组合聚醚,然而,141b仍然不能满足ODP要求。截至目前,国内外大型品牌热水器一般采用环戊烷或者水作为发泡材料,虽然满足了ODP要求,但是环戊烷和水导热率都相对较高。为了达到良好的保温效果,许多厂家不得不增加保温层的厚度,然而这直接导致水箱储水量降低,用户只能使用笨重的热水器,且进行多次加热,才能满足热水用量的需求。
目前亟需开发一种储水式电热水器用聚氨酯组合聚醚,能够制备出低导热率的聚氨酯泡沫。
发明内容
本发明的目的是提供一种储水式电热水器用聚氨酯组合聚醚,其制得的聚氨酯泡沫导热率低,绝热性好,闭孔率高,强度高,稳定性好;本发明同时提供其科学合理、简单易行的制备方法和应用。
本发明所述的储水式电热水器用聚氨酯组合聚醚,其特征在于:由A组分和B组分组成,A组分和B组分的质量比为1:1-1.3,其中:
A组分由如下质量百分比的原料制成:
B组分为多亚甲基多苯基多异氰酸酯;优选烟台万华的PM200或德国拜耳的44V20。
所述的聚醚多元醇Ⅰ为3-8官能度,数均分子量为300-1200的聚醚多元醇;并且以山梨醇为起始剂;优选一诺威新材料有限公司生产的YNW-6207;
所述的聚醚多元醇Ⅱ为4-6官能度,数均分子量为500-700的聚醚多元醇;并且以蔗糖和甘油为起始剂;优选山东一诺威新材料有限公司生产的YNW-8345;
所述的聚醚多元醇III为4-5官能度,数均分子量为500-700的聚醚多元醇,并且以山梨醇和甘油为起始剂;优选山东一诺威新材料有限公司生产的YNW-6001B;
所述的聚醚多元醇IV为4官能度,数均分子量为500-700的聚醚多元醇,并且以甲基邻苯二胺为起始剂;优选济宁华凯树脂有限公司的K-410HN;
所述的聚酯多元醇为粘度2500-3500mpa.s/25℃,官能度为2-3苯酐的低酸值聚酯多元醇,优选山东一诺威股份有限公司生产的B503。
其中:
所述的泡沫稳定剂为非水解硅碳类表面活性剂,优选沧州维达的R-660。
所述的发泡剂为环戊烷、异戊烷、HFC-245fa三者质量比50:15:35的混合物。故用其所生产的组合聚醚属于无氟型组合聚醚,具有绿色环保的特点。比强度高、粘结性强、高温尺寸稳定性、闭孔率低。
所述的催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、三亚乙基二胺、N,N,N,N-四甲基亚乙基二胺、三乙胺、N-乙基吗啡啉、N-甲基吗啡啉、N,N-二甲基苄胺、五甲基二乙烯三胺、N,N'-二羟乙基哌嗪、N,N'-二乙基-2-甲基哌嗪、1,3,5-三(二甲基胺丙基)-1,3,5-六氢化三嗪或二月桂酸二丁基锡中的一种或多种。优选的催化剂为N,N-二甲基环己胺、五甲基二乙烯三胺、1,3,5-三(二甲基胺丙基)-1,3,5-六氢化三嗪,三者质量比为0.4-0.6:0.5-0.7:1-3。
所述的储水式电热水器用聚氨酯组合聚醚的制备方法,包括以下步骤:
(1)A组分的制备:将聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚醚多元醇III、聚醚多元醇IV、聚酯多元醇、水、泡沫稳定剂、催化剂,常温下搅拌均匀,加入发泡剂,混合均匀;
(2)B组分的制备:将多亚甲基多苯基多异氰酸酯称量备用。
使用时,将A组分和B组分按照质量比1:1-1.3混合使用。
本发明的有益效果如下:
(1)本发明的组合聚醚采用环戊烷、异戊烷、HFC-245fa三者质量比40:40:20的混合物作为发泡剂,ODP基本为0,对臭氧层基本无伤害。
(2)本发明的组合聚醚采用甲基邻苯二胺聚醚,可以增加泡沫强度以及泡沫细腻程度,其本身自催化效果可以提高泡沫熟化速率。
(3)本发明的组合聚醚可长时间储存不分层变质,对设备要求相对较低,传统环戊烷型发泡机即可使用。
(4)生成的泡沫导热系数低,导热系数小于0.02W/m.k,与传统的环戊烷聚氨酯泡沫相比,导热系数降低10.5%以上,远低于目前的环戊烷体系。在电热储水箱中,相同体积条件下,存水量可以提高10%以上,且密闭性好,强度高,吸水率以及使用稳定性良好。
(5)组合聚醚制备方法以及聚氨酯泡沫的施工过程均在常温常压下操作,气味小,室内施工发泡时不会对操作人员造成损害。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
(1)A组分的制备:
A组分原料组成见表1。
表1实施例1中A组分原料组成
将称量好的上述原料(除发泡剂外)加入反应釜中,在常温下搅拌0.5h,充分混合,然后加入发泡剂,再充分混合1h,混合完毕后称量100kg。发泡剂为环戊烷、异戊烷、HFC-245fa以50:15:35的混合发泡剂。
(2)B组分的制备:称量120kg烟台万华PM200。
(3)将A组分与B组分按照质量比1:1.2通过高压机均匀混合化发泡,打入300mm×300mm×100mm模具中,其模压泡密度38.6kg/m3,制得聚氨酯硬泡材料,制得的产品质量指标见表4。
实施例2
(1)A组分的制备:
A组分原料组成见表2。
表2实施例2中A组分原料组成
将称量好的上述原料(除发泡剂外)加入反应釜中,在常温下搅拌0.5小时,充分混合,然后加入发泡剂,再充分混合1h。混合完毕后称量100kg。发泡剂为环戊烷、异戊烷、HFC-245fa以50:15:35的混合发泡剂。
(2)B组分的制备:称量120kg德国拜耳的44V20。
(3)将A组分与B组分按照质量比1:1.2通过高压机均匀混合化发泡,打入300mm×300mm×100mm模具中,其模压泡密度控制在36.6kg/m3,制得聚氨酯硬泡材料,制得的产品质量指标见表4。
实施例3
(1)A组分的制备:
A组分原料组成见表3。
表3实施例3中A组分原料组成
将称量好的上述原料(除发泡剂外)加入反应釜中,在常温下搅拌0.5小时,充分混合,然后加入发泡剂,再充分混合1h。混合完毕后称量100kg。发泡剂为环戊烷、异戊烷、HFC-245fa以50:15:35的混合发泡剂。
(2)B组分的制备:称量120kg烟台万华PM200。
(3)将A组分与B组分按照质量比1:1.2通过高压机均匀混合化发泡,打入300mm×300mm×100mm模具中,其模压泡密度控制在35.4kg/m3,制得聚氨酯硬泡材料,制得的产品质量指标见表4。
表4实施例1-3的泡沫产品质量检测数据
由表4可知:组合聚醚产品对臭氧层无破坏,环保性能优;制得的聚氨酯泡沫导热系数低,密闭性好,强度高,吸水率以及使用稳定性良好。与传统的环戊烷聚氨酯泡沫相比,导热系数降低10.5%以上,以此类推,在电热储水箱中,相同体积条件下,存水量可以提高10%以上,符合现在技术发展需求。
Claims (7)
1.一种储水式电热水器用聚氨酯组合聚醚,其特征在于:由A组分和B组分组成,A组分和B组分的质量比为1:1-1.3,其中:
A组分由如下质量百分比的原料制成:
B组分为多亚甲基多苯基多异氰酸酯;
所述的聚醚多元醇Ⅰ为3-8官能度,数均分子量为300-1200的聚醚多元醇;并且以山梨醇为起始剂;
所述的聚醚多元醇Ⅱ为4-6官能度,数均分子量为500-700的聚醚多元醇;并且以蔗糖和甘油为起始剂;
所述的聚醚多元醇III为4-5官能度,数均分子量为500-700的聚醚多元醇;并且以山梨醇和甘油为起始剂;
所述的聚醚多元醇IV为4官能度,数均分子量为500-700的聚醚多元醇;并且以甲基邻苯二胺为起始剂;
所述的聚酯多元醇为粘度2500-3500mpa.s/25℃,官能度为2-3苯酐的低酸值聚酯多元醇。
2.根据权利要求1所述的储水式电热水器用聚氨酯组合聚醚,其特征在于:所述的泡沫稳定剂为非水解硅碳类表面活性剂。
3.根据权利要求1所述的储水式电热水器用聚氨酯组合聚醚,其特征在于:所述的发泡剂为环戊烷、异戊烷、HFC-245fa三者质量比50:15:35的混合物。
4.根据权利要求1所述的储水式电热水器用聚氨酯组合聚醚,其特征在于:所述的催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、三亚乙基二胺、N,N,N,N-四甲基亚乙基二胺、三乙胺、N-乙基吗啡啉、N-甲基吗啡啉、N,N-二甲基苄胺、五甲基二乙烯三胺、N,N'-二羟乙基哌嗪、N,N'-二乙基-2-甲基哌嗪、1,3,5-三(二甲基胺丙基)-1,3,5-六氢化三嗪或二月桂酸二丁基锡中的一种或多种。
5.根据权利要求4所述的储水式电热水器用聚氨酯组合聚醚,其特征在于:所述的催化剂为N,N-二甲基环己胺、五甲基二乙烯三胺、1,3,5-三(二甲基胺丙基)-1,3,5-六氢化三嗪质量比为0.4-0.6:0.5-0.7:1-3的混合物。
6.一种权利要求1-5任一所述的储水式电热水器用聚氨酯组合聚醚的制备方法,其特征在于包括以下步骤:
(1)A组分的制备:将聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚醚多元醇III、聚醚多元醇IV、聚酯多元醇、水、泡沫稳定剂、催化剂,常温下搅拌均匀,加入发泡剂,混合均匀;
(2)B组分的制备:将多亚甲基多苯基多异氰酸酯称量备用。
7.一种权利要求1-5任一所述的储水式电热水器用聚氨酯组合聚醚的应用,其特征在于将A组分和B组分按照质量比1:1-1.3混合使用。
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