CN111410815A - 一种改性酚醛树脂泡沫材料 - Google Patents
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Abstract
本发明公开了一种改性酚醛树脂泡沫材料,其发泡原料的主要组成为热固性酚醛树脂、表面活性剂、发泡剂、酸固化剂和改性剂,改性剂为醚类化合物和/或热塑性酚醛树脂粉末,醚类化合物为乙二醇单乙醚和/或二乙二醇单丁醚。该改性酚醛树脂泡沫材料中的发泡原料中包含乙二醇单乙醚和/或二乙二醇单丁醚,发泡固化所得的泡沫体闭孔率高,导热系数低,并且闭孔结构稳定持久,有助于延长泡沫体的使用寿命,降低包含酚醛泡沫材料的产品维护成本,尤其适用于保温建筑材料以及空调管道材料等绝热要求高的产品。
Description
技术领域
本发明涉及酚醛泡沫材料技术领域,具体涉及一种改性酚醛树脂泡沫材料。
背景技术
酚醛泡沫由于具有低导热系数、轻质、阻燃、发烟量低、抗腐蚀、易成型加工等许多优异的性能,作为绝热保温材料具有很大实用价值,已在建筑外墙保温、中央空调通风管道等得到广泛应用。
酚醛泡沫的发泡原料组分如CN103694626A中所述的,包括酚醛树脂、发泡剂、表面活性剂、固化剂或其它添加剂。目前,国内酚醛泡沫板存在两个问题:一、导热系数高,导热系数大于0.030W/m·K;二、酚醛泡沫中闭合的孔结构使其具有热绝缘性,但孔结构随着泡沫体使用时间的延长而破裂,导致导热系数增加,因此现有的酚醛泡沫保温性能的长期稳定较差。降低导热系数并且改善保温效果的长期稳定性是酚醛泡沫行业中技术人员亟待解决的主要技术问题。
发明内容
本发明的目的在于克服现有技术中存在的缺陷,提供一种改性酚醛树脂泡沫材料,所得酚醛泡沫具有结构稳定持久的闭孔结构。
为了实现上述技术效果,本发明的技术方案为:一种改性酚醛树脂泡沫材料,其发泡原料的主要组成为热固性酚醛树脂、表面活性剂、发泡剂、酸固化剂和改性剂,所述改性剂为醚类化合物和/或热塑性酚醛树脂粉末,所述醚类化合物为乙二醇单乙醚和/或二乙二醇单丁醚。
优选的技术方案为,所述热固性酚醛树脂与醚类化合物的重量之比为100:(1~30)。醚类化合物加入量过少对酚醛泡沫导热系数没有明显改善,加入量过多影响泡沫性能。
优选的技术方案为,所述热固性酚醛树脂与热塑性酚醛树脂粉末的重量之比为100:(0.5~8)。热塑性酚醛树脂加入量过少对酚醛泡沫导热系数没有明显改善,加入量过多影响泡沫固化时间。
优选的技术方案为,所述改性剂由醚类化合物和热塑性树脂粉末组合而成。两种改性剂同时使用对于改善酚醛树脂发泡体闭孔结构的持久稳定性具有协同作用。
优选的技术方案为,按重量份数计,发泡原料的主要组成为热固性酚醛树脂100份、表面活性剂2~6份、发泡剂3~20份、醚类化合物3~15份、热塑性酚醛树脂粉末1~5份、酸固化剂10~30份。
优选的技术方案为,所述热固性酚醛树脂由苯酚、甲醛在碱性条件下反应制得;所述苯酚与甲醛的摩尔比为1:(1.5~3.0);所述热固性酚醛树脂的固含量75~85%,含水量为3~10%,粘度为2000~8000mPa·s。
优选的技术方案为,所述热塑性酚醛树脂粉末的粒径为300~1000目。粒径过大或过小,粉末与热固性酚醛的相容性差。
优选的技术方案为,所述发泡原料的组成还包括尿素,所述热固性酚醛树脂与尿素的重量之比为100:(2~10)。
优选的技术方案为,所述发泡原料的发泡温度为65~75℃,发泡固化时间为8~30min。
优选的技术方案为,所述酚醛泡沫材料的密度为20~100kg/m3。
本发明的优点和有益效果在于:
该改性酚醛树脂泡沫材料中的发泡原料中包含乙二醇单乙醚和/或二乙二醇单丁醚,发泡固化所得的泡沫体闭孔率高,导热系数低,并且闭孔结构稳定持久,有助于延长泡沫体的使用寿命,降低包含酚醛泡沫材料的产品维护成本,尤其适用于保温建筑材料以及空调管道材料等绝热要求高的产品。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
发泡原料的基本组成包含热固性酚醛树脂、表面活性剂、发泡剂、酸固化剂,其中:
表面活性剂的作用是减小酚醛树脂及各原料组分之间的界面张力有利于发泡剂等各组分充分均匀地混合在液相酚醛树脂中,有利于得到均匀的泡沫体。表面活性剂的选择范围多为非离子型表面活性剂,包括但不限于脂肪醇聚氧乙烯醚类表面活性剂、含聚氧乙烯醚的有机硅化合物。
发泡剂包含物理发泡剂和化学发泡剂,其中上述发泡剂中常温下呈液态的发泡剂在酚醛树脂中更容易分散,包括但不限于三氯氟甲烷、三氯三氟乙烷、环戊烷、碳酸铵类、碳酸氢盐类。基于含有乙二醇单乙醚和/或二乙二醇单丁醚的发泡原料,优选的发泡剂为选自环戊烷和氟取代烯烃类发泡剂中的一种或两种以上的组合。
发泡原料中的尿素能使发泡制品的泡孔小且致密均匀,闭孔率高,有助于降低导热值。
酸固化剂的选择范围包括无机酸和有机酸,也可以采用无机酸和有机酸并用的方式。优选的酸固化剂为选自对甲基苯磺酸和苯酚磺酸中的至少一种,进一步的,两种有机酸的混合比例优选为7:3。对甲基苯磺酸和苯酚磺酸的加入方式是首先溶于低级醇例如乙醇、乙二醇中,再与除酸固化剂外的发泡原料其他组分的混合物进行混合。
发泡原料中还可以根据需要添加抗腐蚀剂、增强剂、增塑剂、阻燃剂等用于酚醛泡沫材料发泡原料中的已知组分,以达到相应的已知效果。
实施例1
实施例1的热固性改性酚醛树脂泡沫材料制备工艺如下:
先将100份苯酚、172份37%甲醛溶液、2份50%氢氧化钠水溶液加入到反应器,搅拌,缓慢升温至85℃,保温反应120min,加入尿素10份,停止加热后冷却反应液,加酸液调节体系pH值6~7,将反应液进行脱水处理至树脂粘度5000mPa·s。
苯酚与甲醛的摩尔比为1:2,树脂固含量81.5%,水分含量8.1%。
实施例2-3
实施例2基于实施例1,区别在于,反应温度90℃;酚醛树脂固含量79%,水分含量11%。
实施例3基于实施例1,区别在于,酚醛树脂粘度7000mPa·s;酚醛树脂固含量83%,水分含量7.3%。
将实施例1-3的热固定酚醛树脂配置A组发泡原料,A组发泡原料的组成及制备方法为:
S1:将100份酚醛树脂、4份蓖麻油聚氧乙烯醚(表面活性剂)、4份尿素粉末、8份二乙二醇单丁醚、2份热塑性酚醛树脂粉末(型号浙江杭摩F3620,粒径400目)、10份异戊烷/1-氯-3.3.3-三氟丙烯(重量比60/40,发泡剂)预先混合;
S2:将所述酚醛树脂混合物抽入混合浇注机,同时抽入25份浓度为80%的液态对甲基苯磺酸/苯酚磺酸(重量比70/30,乙二醇为溶剂)作为酸催化剂。通过混合浇注机,喷出至连续的铝箔上,进入层压机发泡、固化,形成泡沫产品。在65~75℃下对泡沫材料进行发泡和固化8~30min,试样产品标计为1A、2A、3A。
以实施例1所得热固性酚醛树脂为原料,按照下表的发泡原料组成制备1B、1C、1D、1E、1F和对比例1(简称D1),发泡剂和酸固化剂组成、制备过程均同1A:
实施例和对比例所得低导热酚醛泡沫材料的性能检测:
1)泡沫体密度:根据GB/T-6343进行测量,用于建筑领域的热绝缘产品表观密度的测定;
2)导热系数:将长30cm、宽30cm的泡沫试样放置在导热系数测定仪的35℃的热板和15℃的低温板之间进行测量。根据GB/T10294/ISO 8032:1991,酚醛泡沫板的热性能通过防护热板装置测定;
3)加速老化后的导热系数:将泡沫试样在70℃暴露2周后,测量导热系数;
实施例和对比例所得性能检测结果见下表:
D1酚醛树脂发泡体的老化前和老化后导热系数表现均较实施例差,并且,D1老化前后的导热系数差值大于实施例。上表中的数据表明,在酚醛树脂发泡原料中加入乙二醇单乙醚、二乙二醇单丁醚和热塑性酚醛树脂粉末的至少一种,有助于提高酚醛发泡体闭孔结构的数量和持久稳定性。另外,1B、1C和1E对照,1B中仅包含二乙二醇单丁醚,1C中仅包含热塑性酚醛树脂粉末,而1E中同时含有热塑性酚醛树脂粉末和乙二醇单乙醚,1E的导热数据明显优于1B、1C,表明醚类化合物和热塑性酚醛树脂粉末在提高酚醛发泡体闭孔结构的数量和持久稳定性方面具有协同作用。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种改性酚醛树脂泡沫材料,其特征在于,其发泡原料的主要组成为热固性酚醛树脂、表面活性剂、发泡剂、酸固化剂和改性剂,所述改性剂为醚类化合物和/或热塑性酚醛树脂粉末,所述醚类化合物为乙二醇单乙醚和/或二乙二醇单丁醚。
2.根据权利要求1所述的改性酚醛树脂泡沫材料,其特征在于,所述热固性酚醛树脂与醚类化合物的重量之比为100:(1~30)。
3.根据权利要求1所述的改性酚醛树脂泡沫材料,其特征在于,所述热固性酚醛树脂与热塑性酚醛树脂粉末的重量之比为100:(0.5~8)。
4.根据权利要求1或2或3所述的改性酚醛树脂泡沫材料,其特征在于,所述改性剂由醚类化合物和热塑性树脂粉末组合而成。
5.根据权利要求4所述的改性酚醛树脂泡沫材料,其特征在于,按重量份数计,发泡原料的主要组成为热固性酚醛树脂100份、表面活性剂2~6份、发泡剂3~20份、醚类化合物3~15份、热塑性酚醛树脂粉末1~5份、酸固化剂10~30份。
6.根据权利要求1或4所述的改性酚醛树脂泡沫材料,其特征在于,所述热固性酚醛树脂由苯酚、甲醛在碱性条件下反应制得;所述苯酚与甲醛的摩尔比为1:(1.5~3.0);所述热固性酚醛树脂的固含量75~85%,含水量为3~10%,粘度为2000~8000mPa·s。
7.根据权利要求1所述的改性酚醛树脂泡沫材料,其特征在于,所述热塑性酚醛树脂粉末的粒径为300~1000目。
8.根据权利要求1所述的改性酚醛树脂泡沫材料,其特征在于,所述发泡原料的组成还包括尿素,所述热固性酚醛树脂与尿素的重量之比为100:(2~10)。
9.根据权利要求1所述的改性酚醛树脂泡沫材料,其特征在于,所述发泡原料的发泡温度为65~75℃,发泡固化时间为8~30min。
10.根据权利要求1所述的改性酚醛树脂泡沫材料,其特征在于,所述酚醛泡沫材料的密度为20~100kg/m3。
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