CN112708092B - 冰激凌冷藏柜用组合聚醚及其制备方法和应用 - Google Patents

冰激凌冷藏柜用组合聚醚及其制备方法和应用 Download PDF

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CN112708092B
CN112708092B CN202011563136.5A CN202011563136A CN112708092B CN 112708092 B CN112708092 B CN 112708092B CN 202011563136 A CN202011563136 A CN 202011563136A CN 112708092 B CN112708092 B CN 112708092B
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王玉
唐国涛
殷守相
肖健美
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于聚氨酯硬泡技术领域，具体涉及一种冰激凌冷藏柜用组合聚醚及其制备方法和应用。该组合聚醚是由下列重量份数的原料制成：聚醚多元醇Ⅰ20～40份；聚醚多元醇Ⅱ20～30份；聚醚多元醇Ⅲ30～40份；聚醚多元醇Ⅳ5～10和聚醚多元醇Ⅴ5～10份；催化剂Ⅰ0.5～0.8份；催化剂Ⅱ1.0～2.0份；催化剂Ⅲ0.5～1.5份；催化剂Ⅳ0.5～1.0份；泡沫稳定剂4～10份；水1.5～3.5份；发泡剂20～40份。本发明的组合聚醚与聚合MDI反应后生成的聚氨酯泡沫具有较好的高低温尺寸稳定性，较高的闭孔率，较低的吸水率，导热系数低；本发明同时提供其制备方法及应用，科学合理、简单易行。

Description

冰激凌冷藏柜用组合聚醚及其制备方法和应用
技术领域
本发明属于聚氨酯硬泡技术领域，具体涉及一种冰激凌冷藏柜用组合聚醚及其制备方法和应用。
背景技术
聚氨酯泡沫塑料是组合聚醚和异氰酸酯发生反应制得的，具有优良的保温隔热性能、力学性能、耐化学品性能，特别是具有优异的绝热性能，而广泛应用于冰箱、冰柜、热水器、冷库板、夹芯板、管道保温、冷藏集装箱等绝热保温领域。组合聚醚是由聚醚多元醇、聚酯多元醇、硅油、催化剂等助剂混合而成。
冰激凌冷藏柜是保温冷链领域中很特殊的一种，它是近年来新兴的用于售卖冰激凌时起到展示和冷藏的作用，该类产品用于大型商店、冷饮店等相关机构。用来制作和保存、出售冰激凌。和传统的冰箱冰柜不同，冰箱冰柜是连续使用的，长时间保持低温状态，对聚氨酯泡沫的要求主要是低温的尺寸稳定性。而冰激凌冷藏柜则不同，首先冷藏箱不是全封闭的，上半部是玻璃的，下半部是有聚氨酯泡沫用于保温的冷藏箱，因此对保温性能要求更高。其次，冰激凌冷藏柜是间歇使用的，使用时保持温度在零下15℃至零下25℃，不使用时是常温状态，因此冷藏箱是在低温和常温反复切换进行，聚氨酯泡沫具有热胀冷缩的特点，因此对保温材料的热胀冷缩的比例要小，即高低温尺寸稳定性的要求更高；第三、因为保温箱不是封闭的，使用时冷热交换会产生凝露，会被保温材料吸收，一般情况下保温材料有一定的吸水率，吸水后再低温，泡沫的尺寸稳定性能会变差。因此在冰激凌冷藏柜中使用的聚氨酯泡沫材料对泡沫的闭孔率和吸水率比普通的聚氨酯泡沫要求高。
基于以上原因，使用普通的冰箱冰柜用组合聚醚产品生产的聚氨酯泡沫，无法满足在冰激凌冷藏柜中使用的要求。
发明内容
本发明要解决的技术问题是提供一种冰激凌冷藏柜用组合聚醚，与聚合MDI反应后生成的聚氨酯泡沫具有较好的高低温尺寸稳定性，较高的闭孔率，较低的吸水率，导热系数低；本发明同时提供其制备方法及应用，科学合理、简单易行。
本发明所述的冰激凌冷藏柜用组合聚醚，由以下重量份数的原料制成：
Figure RE-GDA0002963237820000011
Figure RE-GDA0002963237820000021
其中，聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚醚多元醇Ⅲ、聚醚多元醇Ⅳ和聚醚多元醇Ⅴ共计100份。
聚醚多元醇Ⅰ以蔗糖和二元醇为起始剂，与环氧丙烷开环聚合而成，官能度为4.0-4.3，羟值为400-430mgKOH/g；优选为山东一诺威新材料有限公司的INOVOL R8110。
聚醚多元醇Ⅱ以山梨醇和三元醇为起始剂，与环氧丙烷开环聚合而成，官能度为5.5-5.8，羟值为475-520mgKOH/g；优选为山东一诺威新材料有限公司的INOVOL R6350。
聚醚多元醇Ⅲ以山梨醇为主起始剂，与环氧丙烷开环聚合而成，羟值为 455-505mgKOH/g；优选为山东一诺威新材料有限公司的INOVOL R6048
聚醚多元醇Ⅳ以山梨醇和水为起始剂，与环氧丙烷开环聚合而成，官能度为4，羟值为 740-780mgKOH/g；优选为山东一诺威新材料有限公司的INOVOL R403。
聚醚多元醇Ⅴ是以丙三醇为起始剂的高活性聚醚多元醇，官能度为3，羟值为540-570mgKOH/g；优选为山东一诺威新材料有限公司的INOVOL S303A。
催化剂Ⅰ为迈图高新材料集团的催化剂C-10。
催化剂Ⅱ为迈图高新材料集团的催化剂C-15。
催化剂Ⅲ为迈图高新材料集团的催化剂C-31。
催化剂Ⅳ为2,4,6-三(二甲胺基甲基)苯酚。
复合发泡剂为20-50wt％的异戊烷与50-80wt％的1,1,1,4,4,4-六氟丁烯(1336mzzm)混合。
泡沫稳定剂为L-16186，生产厂家为迈图高新材料集团。
本发明所述的冰激凌冷藏柜用组合聚醚的制备方法，包括以下步骤：
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、聚醚多元醇Ⅴ、泡沫稳定剂、水和催化剂搅拌混合均匀，制成干白料；将干白料降温至20-30℃，将干白料、复合发泡剂通过三组分静态预混器混合后，即得冰激凌冷藏柜用环保型组合聚醚。
本发明所述的冰激凌冷藏柜用组合聚醚的应用，按重量比组合聚醚：聚合MDI＝1：1.1-1.4 混合均匀进行反应，制备聚氨酯硬质泡沫。
与现有技术相比，本发明的有益效果如下：
(1)本发明采用五种聚醚多元醇复配，生产的组合聚醚与聚合MDI反应后生成的聚氨酯泡沫具有较高的压缩强度和较好的高温和低温的尺寸稳定性，从而满足冰激凌冷藏柜对泡沫的要求；
(2)本发明采用官能度为3，羟值为540-570mgKOH/g的聚醚多元醇Ⅴ，该聚醚多元醇一般作为聚氨酯软质泡沫塑料或弹性体的交联剂使用，本发明将其用于聚氨酯硬泡中，提高反应的交联度，既提高了聚氨酯泡沫的闭孔率，使闭孔率达到97％以上，又降低了泡沫的吸水率，吸水率低于2％，减少了冷凝水对泡沫性能的影响；
(3)本发明采用高粘性泡沫稳定剂L-16186，生成的泡沫泡孔更加均匀细腻，具有较低的导热系数，并且提高了聚氨酯泡沫的闭孔率；
(4)本发明采用异戊烷与1,1,1,4,4,4-六氟丁烯的混合物作为发泡剂，零DOP，低GWP，环保性能良好，使聚合MDI与组合聚醚反应时形成细密均匀密闭的泡孔，也有效的降低导热系数，提高尺寸稳定性好，提高保温性能；
(5)本发明的组合聚醚制备过程在常温下进行，生产能耗低，操作简单，该组合聚醚与聚合MDI反应也是在常温、常压下进行，工艺简单，挥发低，无三废产生。
具体实施方式
下面结合实施例对本发明做进一步说明，但不限定本发明。
实施例中用到的所有原料除特殊说明外，均为市购。原料的用量均以重量份数计。
实施例1-8
各实施例的组合聚醚采用如下方法制备：
将配方量的聚醚多元醇、泡沫稳定剂、水和催化剂搅拌混合均匀，制成干白料；将干白料降温至27℃，然后将干白料、异戊烷和1,1,1,4,4,4-六氟丁烯通过三组份静态预混器，混合后形成均一稳定的液体，即得冰激凌冷藏柜用环保型组合聚醚。
组合聚醚的应用方法如下：
用制备的组合聚醚与聚合MDI按配方量混合均匀进行化学反应，即得聚氨酯硬质泡沫塑料。
将实施例1-8制备的聚氨酯硬质泡沫塑料参考测试标准GB/T 26689-2011进行性能检测。实施例1-8的组合聚醚的原料组成与制备的聚氨酯硬质泡沫塑料的性能测试结果见表1。
表1实施例1-8的原料组成与聚氨酯硬质泡沫塑料性能测试结果
Figure RE-GDA0002963237820000041
对比例1-4
各对比例的组合聚醚采用如下方法制备：
将配方量的聚醚多元醇、泡沫稳定剂、水和催化剂搅拌混合均匀，制成干白料；将干白料降温至27℃，然后将干白料、异戊烷和1,1,1,4,4,4-六氟丁烯通过三组份静态预混器，混合后形成均一稳定的液体，即得组合聚醚。
组合聚醚的应用方法如下：
用制备的组合聚醚与聚合MDI按配方量混合均匀进行化学反应，即得聚氨酯硬质泡沫塑料。
将对比例1-4制备的聚氨酯硬质泡沫塑料参考测试标准(GB/T 26689-2011)进行性能检测。对比例1-4的组合聚醚的原料组成与制备的聚氨酯硬质泡沫塑料的性能测试结果见表2。
表2对比例1-4的原料组成与聚氨酯硬质泡沫塑料性能测试结果
Figure RE-GDA0002963237820000051

Claims (3)

1.一种冰激凌冷藏柜用组合聚醚，其特征在于：由以下重量份数的原料制成：
聚醚多元醇Ⅰ 20～40份
聚醚多元醇Ⅱ 20～30份
聚醚多元醇Ⅲ 20～40份
聚醚多元醇Ⅳ 5～10份
聚醚多元醇Ⅴ 5～10份
催化剂Ⅰ 0.5～0.8份
催化剂Ⅱ 1.0～2.0份
催化剂Ⅲ 1.0～1.5份
催化剂Ⅳ 0.5～1.0份
泡沫稳定剂 4～10份
水 1.5～3.5份
复合发泡剂 20～40份；
其中，聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚醚多元醇Ⅲ、聚醚多元醇Ⅳ和聚醚多元醇Ⅴ共计100份；
聚醚多元醇Ⅰ以蔗糖和二元醇为起始剂，与环氧丙烷开环聚合而成，官能度为4.0-4.3，羟值为400-430mgKOH/g；
聚醚多元醇Ⅱ以山梨醇和三元醇为起始剂，与环氧丙烷开环聚合而成，官能度为5.5-5.8，羟值为475-520mgKOH/g；
聚醚多元醇Ⅲ以山梨醇为主起始剂，与环氧丙烷开环聚合而成，羟值为455-505mgKOH/g；
聚醚多元醇Ⅳ以山梨醇和水为起始剂，与环氧丙烷开环聚合而成，官能度为4，羟值为740-780mgKOH/g；
聚醚多元醇Ⅴ是以丙三醇为起始剂的高活性聚醚多元醇，官能度为3，羟值为540-570mgKOH/g；
泡沫稳定剂为L-16186；
催化剂Ⅰ为C-10；催化剂Ⅱ为C-15；催化剂Ⅲ为C-31；催化剂Ⅳ为2,4,6-三（二甲胺基甲基）苯酚；
复合发泡剂为20-50wt%的异戊烷与50-80wt%的1,1,1,4,4,4-六氟丁烯混合。
2.一种权利要求1所述的冰激凌冷藏柜用组合聚醚的制备方法，其特征在于：包括以下步骤：
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、聚醚多元醇Ⅴ、泡沫稳定剂、水和催化剂搅拌混合均匀，制成干白料；将干白料降温至20-30℃，将干白料、复合发泡剂通过三组分静态预混器混合后，即得冰激凌冷藏柜用环保型组合聚醚。
3.一种权利要求1所述的冰激凌冷藏柜用组合聚醚的应用，其特征在于：按重量比组合聚醚：聚合MDI=1:1.1-1.4混合均匀进行反应，制备聚氨酯硬质泡沫。
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