CN113912807A - 一种含五氟丙烷的聚醚多元醇混合物及其应用 - Google Patents
一种含五氟丙烷的聚醚多元醇混合物及其应用 Download PDFInfo
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Abstract
本发明公开了一种含五氟丙烷的聚醚多元醇混合物及其应用,将聚醚多元醇混合物由聚醚多元醇和发泡剂1,1,3,3‑五氟丙烷在催化剂的作用下,混合而成;其中,催化剂为甲基苯乙烯;聚醚多元醇为KY‑835、KY‑400、KY‑635、KY‑4110中的一种:本发明的混合聚醚多元醇在配制组合时,无须另外添加发泡剂,由于本产品不含有卤素元素,因此本产品在合成聚氨酯硬泡沫使用过程中,不产生有害气体,不会对环境造成污染,健康环保,大大提高了本聚氨酯硬泡沫的应用范围。
Description
技术领域
本发明涉及燃聚氨酯保温板材的生产技术领域,尤其涉及一种含五氟丙烷的聚醚多元醇混合物及其应用。
背景技术
目前随着过渡性发泡剂一氟二氯乙烷(以下简称:HCFC-141b)被替代,第三代发泡剂的研究日趋深入,以1,1,3,3-五氟丙烷(以下简称:HFC-245fa)及1,1,1,3,3-五氟丁烷HFC365mfc(以下简称:HFC-365mfc)代表的HFC类发泡剂被许多业内人士认为是当前HCFC-141b最理想的替代品。在2021年6月17日,中国常驻联合国代表团向联合国秘书长交存了中国政府接受《<关于消耗臭氧层物质的蒙特利尔议定书>基加利修正案》的接受书,该修正案将于2021年9月15日结我国生效,在2024年之后控制使用HFCs之时,可能没有使用HFCs的权限。
目前HFC-245fa与其它发泡剂相比,具有较低的沸点(15.3度),较高的蒸汽压,其相对分子质量与CFC-11相近,在泡沫中用量大致与CFC-11相同,用它所发的泡沫老化后的导热系数均比HCFC-141b有所改进,且与许多聚醚多元醇都有较好的相容性。虽然HFC-245fa是一种HFC物质,也就是说它有直接的全球变暖效应潜能,但是,TEWl(总的全球温室效应当量)的分析告诉我们,在绝大部分情况下,HFC-245fa比那些CWP值很低或者是零的发泡剂对气候的影响要小。通过几种ODP为零的发泡剂制成的泡沫的K值(绝热系数),在所有的测试温度下面的结果表明:用HFC-245fa发泡的泡沫的K值与环戊烷或者是水/异丁烷反应产生的二氧化碳的K值相当或者有很大程度的改善。当平均温度低于10℃时,HFC-245fa的性能要远远超过所有其它的发泡剂,包括HCFC-14lb。这是因为HFC-245fa提供了包括沸点、低蒸汽态的热传导率、低发散率、以及在聚氨酯中的低的溶解率等最佳的组合。结果是产生细小的泡沫孔,在泡沫孔中的大部分发泡剂处于蒸汽状态,只有当发泡剂处于泡沫孔中,并且发泡剂处于蒸汽状态的情况下,它才能作为一种绝缘气体。在许多情况下,HFC-245fa可以作为一种非常有效地降低费用的发泡解决方案。
虽然HFC-245fa有着最佳的物理特性的组合,目前能够使用的或者正在开发的ODP值为零的发泡剂中为最好,但是我们也知道人们对HFC-245fa相对较低的沸点有着这样那样的担心,这是因为较低的沸点会使其在原先使用HCFC-141b的发泡组合料系统中的应用变得困难,无法将它与发泡组合料系统装入包装桶中运输。但HFC-245fa的运输、包装与储存由HFC-245fa的沸点比室温较低,为15.3℃,在高温下有气压升高的可能。在室温25℃时,气体的压力为150kPa左右,而在50℃时的压力为345kPa,所以对HFC-245fa的包装都要求是用碳钢制造的高压容器,耐压等级应达到400kPa以上(50℃时的饱和蒸汽压345kPa+10%的保险系数),并要求有泄压装置。
发明内容
为了达到上述目的,本发明采用的技术方案如下:一种含五氟丙烷的聚醚多元醇混合物,所述的聚醚多元醇混合物由聚醚多元醇和发泡剂1,1,3,3-五氟丙烷在催化剂的作用下,混合而成;其中,催化剂为甲基苯乙烯;聚醚多元醇为KY-835、KY-400、KY-635、KY-4110中的一种:聚醚多元醇的通式为:
在KY-835中,n为5~8,R’为丙三醇和蔗糖,丙三醇与蔗糖的摩尔比为3:7;
在KY-400中,n为5~8,R’甲苯二胺;
在KY-635中,n为5~8,R’为甘油和山梨醇,甘油与山梨醇的摩尔比为4:6;
在KY-4110中,n为5~8,R’为二甘醇和蔗糖,二甘醇和蔗糖的摩尔比为4:6。
本发明所述的聚醚多元醇混合物中聚醚多元醇、发泡剂和催化剂的质量配比为:320~350:75~90:0.2~0.5;经过发明人的测试,当在这个比例下限使用时,该混合物在应用时存在用量大,应用配比不易调整,而超过这个比例上限时,该混合料在运输时存在不安全现象。
本发明的制备方法如下:在压力反应釜中加入一定量的聚醚多元醇,然后再加入一定量的发泡剂1,1,3,3-五氟丙烷和催化剂甲基苯乙烯,在14~18℃的条件下混合搅拌反应30min;得到产品:含五氟丙烷的聚醚多元醇混合物。
一种含五氟丙烷的聚醚多元醇混合物在制备聚氨酯保温材料中的应用,步骤如下:
1)在混合反应釜中,加入含发泡剂1,1,3,3-五氟丙烷的聚醚多元醇混合物40~80份,聚醚多元醇20~50份,催化剂0.5~6份,泡沫稳定剂1~4份,水0.5~4份和阻燃剂8~30份,控制反应温度在15℃以下,搅拌反应30min;
2)取出混合料100份与100份异氰酸酯在下进行混合反应,制得泡沫制品即为聚氨酯保温材料。
本发明所述的聚醚多元醇20~50份中,聚醚多元醇为KY-835或KY-4110中的一种。
本发明所述的催化剂为胺类催化剂,所述的胺类催化剂为三乙烯二胺、二甲基环己胺、双(二甲胺基乙基)醚溶液中的一种或者上述多种混合物。
本发明的泡沫稳定剂为M-8805、M-8808或M-8860中的其中一种;上述三种泡沫稳定剂的通式为:
其中,P=C3H6O(C2H4O)x(C3H6O)y R,R=1~4个C的烷基或羟基;;x=10~50;y=10~50;n=2~20;本泡沫稳定剂为由江苏美思德化学股份有限公司购得。
本发明所述的阻燃剂为磷酸三(2-氯丙基)酯。
胺类催化剂工艺特点是反应初期速度快,随着聚醚相对分子质量增大,反应速度逐渐减慢。该工艺具有无须脱除催化剂,物耗能耗较低,在PU发泡配方中可以少加或不加胺催化剂等优点。
本发明的优点在于:本发明的混合聚醚多元醇在配制组合时,无须另外添加发泡剂,由于本产品不含有卤素元素,因此本产品在合成聚氨酯硬泡沫使用过程中,不产生有害气体,不会产生腐蚀性、毒性的烟雾,不会对环境造成污染,健康环保,大大提高了本聚氨酯硬泡沫的应用范围。
附图说明
图1含HFC-245和HCFC-141b的聚醚混合物与饱和蒸气压关系图;
图2含HFC-245的聚醚混合物随温度与时间失重关系图。
其中,图1中线条自上而下分别为:HFC-245、HCFC-141b;图2中线条自上而下分别为:40℃、35℃、30℃、25℃。
具体实施方式
下面结合附图说明和具体实施方式对本发明作进一步详细的描述。
制备实施例:1)在压力反应釜中加入一定量的聚醚多元醇KY-835、KY-4110、KY-635及KY-400中的其中一种,然后再加入一定量的发泡剂1,1,3,3-五氟丙烷和催化剂甲基苯乙烯,在14~18℃的条件下混合搅拌反应30min;得到产品:含五氟丙烷的聚醚多元醇混合物;
应用实施例:1)在混合反应釜中,加入含发泡剂1,1,3,3-五氟丙烷的聚醚多元醇混合物(就是上述制备实施例1的产品)40~80份,聚醚多元醇20~50份,催化剂0.5~6份,泡沫稳定剂1~4份,水0.5~4份和阻燃剂8~30份,控制反应温度在15℃以下,搅拌反应30min;
2)取出混合料100份与100份异氰酸酯在下进行混合反应,制得泡沫制品即为聚氨酯保温材料。
制备实施例1:在一只1L压力反应釜中,聚醚多元醇KY-835 350g,然后再加入HFC-245fa90g、催化剂0.5g,控制温度14-18℃条件下,混合搅拌反应30分钟。得到产品的的性能参数如下:
产品外观:无色至棕色透明液体;粘度(cSt):500-600,25℃。
制备实施例2:在一只1L压力反应釜中,聚醚多元醇KY-4110 350g,然后再加入HFC-245fa 90g、催化剂0.5g,控制温度14-18℃条件下,混合搅拌反应30分钟。得到产品的的性能参数如下:
产品外观:无色至棕色透明液体;粘度(cSt):450-550,25℃。
制备实施例3:在一只1L压力反应釜中,聚醚多元醇KY-835 325g,然后再加入HFC-245fa165g、催化剂0.5g,控制温度14-18℃条件下,混合搅拌反应30分钟。得到产品的的性能参数如下:
产品外观:无色至棕色透明液体;粘度(cSt):400-500,25℃。
应用实施例:
将上述制备实施例产品进行如下的应用试验:
将实施例1、2和3中指的的阻燃聚醚多元醇与聚醚KY-4110进行合成聚氨酯硬质泡沫,最终得到的产品性能参数如下表所示:
表1为各批次聚氨酯硬质泡沫的合成配方(各组分含量为质量份)
注:混合料贮存稳定性是指除异氰酸酯以外的所有反应原料混合均匀后,在40度时放置一周后,该混合料再与异氰酸酯反应特性是否与放置前与异氰酸酯反应特性一至;异氰酸酯指数是指聚氨酯配方中异氰酸酯过量的程度。
表2为各批次聚氨酯硬质泡沫的性能参数
注:料温是指原料混合的物料温度;
乳白时间是指在液相聚氨酯混合物料中即出现乳白现象,该时间在聚氨酯泡沫体生成中称为乳白时间;
纤维时间是指在一定条件下,聚氨酯反应物从液态物质形成凝胶所需的时间;
不粘时间是指聚氨酯泡沫成型时表面不粘手的时间;
自由发泡密度是指聚氨酯发泡时,不受外压而成型后泡沫的密度;
需要说明的是,上述仅仅是本发明的较佳实施例,并非用来限定本发明的保护范围,在上述实施例的基础上所做出的任意组合或等同变换均属于本发明的保护范围。
Claims (9)
2.如权利要求1所述的聚醚多元醇混合物,其特征在于,所述的聚醚多元醇混合物中聚醚多元醇、发泡剂和催化剂的质量配比为:320~350:75~90:0.2~0.5。
3.一种如权利要求1或2所述的聚醚多元醇混合物的制备方法,其特征在于,所述的制备方法如下:
在压力反应釜中加入一定量的聚醚多元醇,然后再加入一定量的发泡剂1,1,3,3-五氟丙烷和催化剂甲基苯乙烯,在14~18℃的条件下混合搅拌反应30min;得到产品:含五氟丙烷的聚醚多元醇混合物。
4.一种如权利要求1所述的含五氟丙烷的聚醚多元醇混合物在制备聚氨酯保温材料中的应用。
5.如权利要求4所述的应用,其特征在于,所述应用的详细步骤如下:
1)在混合反应釜中,加入含发泡剂1,1,3,3-五氟丙烷的聚醚多元醇混合物40~80份,聚醚多元醇20~50份,催化剂0.5~6份,泡沫稳定剂1~4份,水0.5~4份和阻燃剂8~30份,控制反应温度在15℃以下,搅拌反应30min;
2)取出混合料100份与100份异氰酸酯在下进行混合反应,制得泡沫制品即为聚氨酯保温材料。
6.如权利要求5所述的应用,其特征在于,所述的聚醚多元醇20~50份中,聚醚多元醇为KY-835或KY-4110中的一种。
7.如权利要求5或6所述的应用,其特征在于,所述的催化剂为胺类催化剂,所述的胺类催化剂为三乙烯二胺、二甲基环己胺、双(二甲胺基乙基)醚溶液中的一种或者上述多种混合物。
9.如权利要求5或6所述的应用,其特征在于,所述的阻燃剂为磷酸三(2-氯丙基)酯。
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JP2004083847A (ja) * | 2002-06-28 | 2004-03-18 | Central Glass Co Ltd | 発泡剤組成物、硬質ポリウレタンフォームまたはポリイソシアヌレートの調製用のプレミックスおよび該フォームの製造方法 |
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