CN114853974A - 一种金属雕花板用聚氨酯组合聚醚及其制备方法和应用 - Google Patents
一种金属雕花板用聚氨酯组合聚醚及其制备方法和应用 Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 35
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Abstract
本发明涉及一种金属雕花板用聚氨酯组合聚醚及其制备方法和应用,聚氨酯组合聚醚按重量份数计包括:40‑60份聚醚多元醇Ⅰ,20‑40份聚醚多元醇Ⅱ,5‑35份聚酯多元醇,3‑10份蓖麻油,20‑50份阻燃剂,2‑6份催化剂,0.5‑3.5份泡沫稳定剂,1‑3份化学发泡剂,8‑15份物理发泡剂,其中,聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇和蓖麻油的四者之和为100份;其中,聚醚多元醇Ⅰ为蔗糖聚醚多元醇;聚醚多元醇Ⅱ为高官能度蔗糖聚醚多元醇;聚酯多元醇为芳香族聚酯多元醇。由其制得的中间泡沫层保证了金属雕花板成品不易弯曲、以及与上下层的粘结性能;且,其还具备优异阻燃性能,采用异戊烷作为发泡剂成本较低。
Description
技术领域
本发明涉及聚氨酯泡沫塑料技术领域,尤其涉及一种金属雕花板用聚氨酯组合聚醚及其制备方法和应用。
背景技术
随着我国建筑行业不断发展,对外墙保温装饰板用的金属雕花板脱颖而出,金属雕花板表面是经特殊图层处理过的优质彩色浮雕饰面金属板,中间层是经阻燃处理的硬质高密度聚氨酯发泡保温断热层,底面是起到隔热保温防潮作用的铝箔保护层。
中间层的材料通常选用聚氨酯硬质泡沫塑料,其是一种保温隔热、耐水耐潮、优良的防火性、耐化学、黏结性好以及使用寿命长等优良性能的材料。对于国内目前的金属雕花板生产线,多采用发泡机注料至传送带上,之后进入层压机,在熟化一定时间后进行切割,存放、打包等方式进行连续生产。所得到的金属雕花板成品厚度一般为10-30mm,长度一般为1500-2500mm,宽度约400-600mm。
由于金属雕花板成品的板型较薄,因此中间的聚氨酯发泡层需要足够的支撑强度才能保证金属雕花板不会出现弯曲现象,同时聚氨酯需要和外层金属雕花板与铝箔之间有一个良好的粘接性能,而且聚氨酯的难燃程度也越发重要。
因此,亟需提供一种如何设计金属雕花板用聚氨酯组合聚醚及其制备方法,以基于该聚氨酯组合聚醚制得中间层材料,使得最终的金属雕花板满足上述要求。
发明内容
本发明所要解决的技术问题是提供一种金属雕花板用聚氨酯组合聚醚及其制备方法和应用。
为解决上述问题,本发明所采取的技术方案是:
一方面,提供了一种金属雕花板用聚氨酯组合聚醚,按重量份数计,其包括:
40-60份聚醚多元醇Ⅰ,20-40份聚醚多元醇Ⅱ,5-35份聚酯多元醇,3-10份蓖麻油,20-50份阻燃剂,2-6份催化剂,0.5-3.5份泡沫稳定剂,1-3份化学发泡剂,8-15份物理发泡剂,其中,聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇和蓖麻油的四者之和为100份;
其中,所述聚醚多元醇Ⅰ为4-5官能度,羟值为370-410mgKOH/g,25℃下的粘度为10000-13000mPa.s的蔗糖聚醚多元醇;
所述聚醚多元醇Ⅱ为5-6官能度,羟值为365-395mgKOH/g, 25℃下的粘度为5500-7500mPa.s的高官能度蔗糖聚醚多元醇;
所述聚酯多元醇为2官能度,羟值为360-410mgKOH/g,25℃下的粘度为3500-4500mPa.s的芳香族聚酯多元醇,具有较高的伯羟基含量、较高的苯环含量。
作为发明的一种实施方式,所述蓖麻油为羟值为163mgKOH/g的脂肪酸的三甘油酯。
作为发明的一种实施方式,所述阻燃剂由磷酸三(1-氯-2-丙基)酯与磷酸三乙酯按照质量分数5-30:5-30的比例复配而成,由两种阻燃剂复配进行使用,降低成本的同时保证氧指数更高。
作为发明的一种实施方式,所述催化剂为叔胺类催化剂和金属盐类三聚催化剂,叔胺类催化剂优选PC-8(N,N二甲基环己胺)、BDMA(N,N二甲基苄胺),金属盐类三聚催化剂优选TMR-2。
作为发明的一种实施方式,所述泡沫稳定剂为非水解硅碳类表面活性剂,优选生产厂家为赢创徳固赛特种化学有限公司的B8525。
作为发明的一种实施方式,所述化学发泡剂为水,优选为去离子水;物理发泡剂为异戊烷,成本价格低。
作为发明的一种实施方式,金属雕花板用聚氨酯组合聚醚,按重量份数计,其包括:
55-60份聚醚多元醇Ⅰ,25-30份聚醚多元醇Ⅱ,10份聚酯多元醇,5份蓖麻油,40-45份阻燃剂,4.2-4.4份催化剂,2份泡沫稳定剂,2.6-2.8份化学发泡剂,10份物理发泡剂,其中,聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇和蓖麻油的四者之和为100份。
第二方面,提供了一种金属雕花板用聚氨酯组合聚醚的制备方法,所述方法包括:
按照质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中后,通过搅拌器搅拌一段时间制得组合聚醚。
作为发明的一种实施方式,所述搅拌器的搅拌温度为15-25℃,搅拌速率为800-1000r/min,搅拌时间为20-30min。
第三方面,提供了一种如第一方面所述的聚氨酯组合聚醚的应用,其作为金属雕花板中中间层聚氨酯硬质泡沫的A组分,B组分为多苯基多亚甲基多异氰酸酯;
在使用时,将组分质量比为1:1.1-1.5的A组分和B组分在发泡机设备的作用下混合均匀后,注料至传送带上的金属板上,再与铝箔保护层同时输送至层压机,经熟化、切割后制得金属雕花板。
具体地,将A组分、B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备得作用下通过发泡枪头将A组分和B组分混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板;
所述B组分中的多苯基多亚甲基多异氰酸酯,优选万华化学集团股份有限公司的PM-200。
采用上述技术方案所产生的有益效果在于:
(1)采用本发明制得的组合聚醚与异氰酸酯反应生成的泡沫(中间泡沫层)具有足够的支撑强度,使金属雕花板成品不易弯曲;
(2)聚醚多元醇、聚酯多元醇以及蓖麻油搭配使用能够提高金属雕花板中金属板、铝箔保护层与聚氨酯泡沫之间的粘接性能;
(3)制备的金属雕花板用聚氨酯材料成品具有优异阻燃性能;
(4)相对于市面上普遍采用的HCFC-141B、HFC-245fa发泡剂而言,本发明采用异戊烷作为发泡剂,其成本较低,市场竞争力强;
(5)本发明的组合聚醚是在常温下进行制备,既节约能源,又能减少供能设备和繁琐的操作。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面结合具体实施例对发明进行清楚、完整的描述。
下述实施例中,所用的聚醚多元醇Ⅰ为聚醚多元醇8840,由河北亚东化工集团有限公司生产;
所用的聚醚多元醇Ⅱ为聚醚多元醇380A,由河北亚东化工集团有限公司生产;
所用的聚酯多元醇为聚酯多元醇PS3152,由青岛瑞诺化工有限公司生产;
所用的蓖麻油,由江苏豪龙化工有限公司生产;
所用的阻燃剂由磷酸三(1-氯-2-丙基)酯(TCPP)和磷酸三乙酯(TEP)按照质量分数5-30:5-30的比例复配而成,三(1-氯-2-丙基)酯与磷酸三乙酯张家港瑞化工有限公司生产;
所用的催化剂为N,N二甲基环己胺 (PC-8)、N,N二甲基苄胺 (BDMA)和TMR-2,均由新典化学材料(上海)有限公司生产;
所用的泡沫稳定剂为非水解硅碳类表面活性剂B8525,由赢创徳固赛特种化学有限公司生产;
所用的化学发泡剂为去离子水,由实验室制得;
所用的物理发泡剂为异戊烷,由宁夏宝丰能源集团有限公司烯烃厂生产。
所用的B组分为多苯基多亚甲基多异氰酸酯为PM200,由万华化学集团股份有限公司生产。
实施例1
一种聚氨酯组合聚醚,其原料成分如表1所示:
利用聚氨酯组合聚醚在金属雕花板连续线中制备金属雕花板成品的方法如下:
(1)制备聚氨酯组合聚醚:
按照表1中的质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中,通过搅拌器搅拌一段时间制得组合聚醚。
(2)制备金属雕花板成品
将A组分与B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备的作用下通过发泡枪头将A组分和B组分按照质量比1:1.3混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板。
实施例2:
一种聚氨酯组合聚醚,其原料成分如表2所示:
利用聚氨酯组合聚醚在金属雕花板连续线中制备金属雕花板成品的方法如下:
(1)制备聚氨酯组合聚醚:
按照表1中的质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中,通过搅拌器搅拌一段时间制得组合聚醚。
(2)制备金属雕花板成品
将A组分、B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备的作用下通过发泡枪头将A组分和B组分按照质量比1:1.3混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板。
实施例3
一种聚氨酯组合聚醚,其原料成分如表3所示:
利用聚氨酯组合聚醚在金属雕花板连续线中制备金属雕花板成品的方法如下:
(1)制备聚氨酯组合聚醚:
按照表1中的质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中,通过搅拌器搅拌一段时间制得组合聚醚。
(2)制备金属雕花板成品
将A组分、B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备的作用下通过发泡枪头将A组分和B组分按照质量比1:1.3混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板。
对比例1
一种聚氨酯组合聚醚,其原料成分如表4所示:
利用聚氨酯组合聚醚在金属雕花板连续线中制备金属雕花板成品的方法如下:
(1)制备聚氨酯组合聚醚:
按照表1中的质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中,通过搅拌器搅拌一段时间制得组合聚醚。
(2)制备金属雕花板成品
将A组分、B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备的作用下通过发泡枪头将将A组分和B组分按照质量比1:1.3混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板。
对比例2
一种聚氨酯组合聚醚,其原料成分如表5所示:
利用聚氨酯组合聚醚在金属雕花板连续线中制备金属雕花板成品的方法如下:
(1)制备聚氨酯组合聚醚:
按照表1中的质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中,通过搅拌器搅拌一段时间制得组合聚醚。
(2)制备金属雕花板成品
将A组分、B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备的作用下通过发泡枪头将A组分和B组分按照质量比1:1.3混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板。
对比例3
一种聚氨酯组合聚醚,其原料成分如表6所示:
聚氨酯组合聚醚在金属雕花板连续线中制备金属雕花板成品的方法如下:
(1)制备聚氨酯组合聚醚:
按照表1中的质量份数称取聚醚多元醇Ⅰ、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中,通过搅拌器搅拌一段时间制得组合聚醚。
(2)制备金属雕花板成品
将A组分、B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备的作用下通过发泡枪头将A组分和B组分按照质量比1:1.3混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板。
对比例4
一种聚氨酯组合聚醚,其原料成分如表7所示:
利用聚氨酯组合聚醚在金属雕花板连续线中制备金属雕花板成品的方法如下:
(1)制备聚氨酯组合聚醚:
按照表1中的质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中,通过搅拌器搅拌一段时间制得组合聚醚。
(2)制备金属雕花板成品
将A组分、B组分分别加入至白料料罐与黑料料罐中,控制原料温度为19-23℃,设定发泡机流量并进行校准,校准完毕后,在发泡机设备的作用下通过发泡枪头将A组分和B组分按照质量比1:1.3混合均匀;
将枪头压力调试在110-130Bar后,通过枪头将A组分和B组分混合合后的物料注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,设置层压机线速度为4-15m/min,经熟化、切割后制得金属雕花板。
效果例:
采用行业标准(GB/T 2406.2-2009塑料 用氧指数法测定燃烧行为 第2部分:室温试验)中的方法测试由实施例1-实施例3、对比例1-对比例3制得的成品中中间泡沫层的氧指数,结果如表8所示。
对实施例1-实施例3、对比例1-对比例3制得的成品的进行了弯曲测试和粘结性能测试,得到的结果如表9所示。
弯曲测试:将切割后的成品放置于晾板间,将其温度控制在于25-28℃,第二天观察是否出现弯曲现象,若弯曲,说明其支撑强度不足。
中间泡沫层与上下层的粘结性能测试:在出板后其成型12小时后对上下钢板进行剥离试验,考察泡沫与上层金属板以及铝箔板粘接情况,粘接多则不易脱壳,说明粘结性良好。
由表8和表9可知,本发明制备的金属雕花板用聚氨酯材料成品(即,中间泡沫层)具有优异阻燃性能;另外,采用本发明制得的组合聚醚与异氰酸酯反应生成的泡沫具有足够的支撑强度,使金属雕花板成品不易弯曲,且金属雕花板中中间泡沫层与上下层的粘结性能良好。
但是,如果组合聚醚配方缺少蓖麻油会影响金属雕花板成品中中间泡沫层与上下层的粘结性能;配方缺少聚醚多元醇和聚酯多元醇时,不仅会影响金属雕花板成品中中间泡沫层与上下层的粘结性能,还会影响成品金属雕花板成品中中间泡沫层的支撑强度;配方中的阻燃剂只使用TCPP时,保证成品其他性能时,会影响金属雕花板中中间泡沫层的阻燃性能,若保证同等水平的阻燃情况时,需要更多的TCPP添加量,由于TCPP在配方中是不参与反应的,因此会导致聚氨酯泡沫支撑强度下降,成品易出现泡沫支撑强度不足,导致成品金属雕花板弯曲;配方中的阻燃剂只采用TEP时,价格较高,不具有市场竞争力,而两者协同使用不仅价格具有竞争力,且具有更优异的性能。
Claims (9)
1.一种金属雕花板用聚氨酯组合聚醚,其特征在于,按重量份数计,其包括:
40-60份聚醚多元醇Ⅰ,20-40份聚醚多元醇Ⅱ,5-35份聚酯多元醇,3-10份蓖麻油,20-50份阻燃剂,2-6份催化剂,0.5-3.5份泡沫稳定剂,1-3份化学发泡剂,8-15份物理发泡剂,其中,聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇和蓖麻油的四者之和为100份;
其中,所述聚醚多元醇Ⅰ为4-5官能度,羟值为370-410mgKOH/g,25℃下的粘度为10000-13000mPa.s的蔗糖聚醚多元醇;
所述聚醚多元醇Ⅱ为5-6官能度,羟值为365-395mgKOH/g, 25℃下的粘度为5500-7500mPa.s的高官能度蔗糖聚醚多元醇;
所述聚酯多元醇为2官能度,羟值为360-410mgKOH/g,25℃下的粘度为3500-4500mPa.s的芳香族聚酯多元醇。
2.根据权利要求1所述的一种金属雕花板用聚氨酯组合聚醚,其特征在于,所述蓖麻油其官能度为2.7,羟值为163mgKOH/g。
3.根据权利要求1所述的一种金属雕花板用聚氨酯组合聚醚,其特征在于,所述阻燃剂由磷酸三(1-氯-2-丙基)酯与磷酸三乙酯按照质量分数5-30:5-30的比例复配而成。
4.根据权利要求1所述的一种金属雕花板用聚氨酯组合聚醚,其特征在于,所述催化剂为叔胺类催化剂和/或金属盐类三聚催化剂。
5.根据权利要求1所述的一种金属雕花板用聚氨酯组合聚醚,其特征在于,所述泡沫稳定剂为非水解硅碳类表面活性剂。
6.根据权利要求1所述的一种金属雕花板用聚氨酯组合聚醚,其特征在于,所述化学发泡剂为水,物理发泡剂为异戊烷。
7.一种金属雕花板用聚氨酯组合聚醚的制备方法,其特征在于,所述方法包括:
按照质量份数称取聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂;
依次将所述聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇、蓖麻油、阻燃剂、催化剂、泡沫稳定剂、化学发泡剂和物理发泡剂加入反应釜中后,通过搅拌器搅拌一段时间制得组合聚醚。
8.根据权利要求7所述的一种金属雕花板用聚氨酯组合聚醚的制备方法,其特征在于,所述搅拌器的搅拌温度为15-25℃,搅拌速率为800-1000r/min,搅拌时间为20-30min。
9.一种如权利要求1-6任一项所述的聚氨酯组合聚醚的应用,其特征在于,作为金属雕花板中中间层聚氨酯硬质泡沫的A组分,B组分为多苯基多亚甲基多异氰酸酯;
在使用时,将组分质量比为1:1.1-1.5的A组分和B组分在发泡机设备的作用下混合均匀后,注料至传送带传送的金属板上,再与铝箔保护层同时输送至层压机,经熟化、切割后制得金属雕花板。
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