CN115073695A - 一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫 - Google Patents

一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫 Download PDF

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CN115073695A
CN115073695A CN202210824619.9A CN202210824619A CN115073695A CN 115073695 A CN115073695 A CN 115073695A CN 202210824619 A CN202210824619 A CN 202210824619A CN 115073695 A CN115073695 A CN 115073695A
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CN115073695B (zh
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信延垒
任丽
任洁洁
吴菲
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Shanghai Yumo Energy Saving Technology Co ltd
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Abstract

本发明涉及一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，由组分A和组分B经喷涂设备喷涂制得，其中组分A包括按照重量份数计的如下成分：多元醇100份、表面活性剂1‑5份、催化剂2‑10份、水0.5‑1.0份、物理发泡剂20‑30份、阻燃剂10‑20份；所述的多元醇为密胺树脂多元醇和聚酯多元醇，两者重量比例为30‑50：50‑70；组分B为多苯基多亚甲基多异氰酸酯。本发明通过加入密胺树脂多元醇、复合阻燃剂、三类复合催化剂、环保物理发泡剂及改变原料组分比例，在保证聚氨酯泡沫材料满足良好的机械性能、低导热系数性能的基础上，大大提高了材料的防火性、安全性和舒适性。

Description

一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫
技术领域
本发明涉及一种喷涂型环保聚氨酯泡沫，特别涉及一种用于集装箱模块化建筑保温的聚氨酯泡沫，属于有机材料合成技术领域。
背景技术
随着经济的发展，集装箱行业也迎来了前所未有的发展机遇，但是发展过程中也难免出现亟待解决的难题，如空置的集装箱占用大面积的土地、维护费用高、废旧集装箱的回收利用等问题。为了能够安全、低碳、环保、节约、高效地解决这些问题，人们通常将废旧的集装箱改造成供人们居住和生活的模块化建筑房屋。
集装箱经过建筑师和设计师重新改造，充分发挥其灵活性和适应性强的特质，展示出一系列富有创造力的集装箱模块化建筑。如集装箱酒店、集装箱博物馆、集装箱学生公寓、军营等。而集装箱的外围护构件为金属结构，其导热系数很大，且集装箱模块建筑通常是暴露在室外环境中，对室内的居住环境非常不利。因此，较之传统的建筑结构类型，必须对集装箱模块建筑进行保温隔热改造，以保证良好的室内热环境。常用的保温材料有岩棉、聚苯乙烯、玻璃棉、聚氨酯等，其中聚氨酯是保温性能最优的材料。经喷涂施工可制得连续、无缝隙的整体保温体系，有效防止冷热桥和冷凝现象，且保温层与基材100％粘接。现有的喷涂型聚氨酯泡沫材料有不少，但它是易燃有机材料，一般通过添加阻燃剂来提高聚氨酯泡沫的阻燃性，但对于集装箱维护的聚氨酯材料不仅机械性能要求高，难燃级别要求也高需满足建筑防火规范要求，还要使用环保、无毒的原料，确保室内居住环境的安全性和舒适性，通常能满足利用的力学等方面性能要求的聚氨酯材料直接加阻燃剂很难实现。
发明内容
本发明的目的是克服上述不足而提供一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，大大提高了集装箱模块建筑的安全性和舒适性。
本发明采取的技术方案为：
一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，由组分A和组分B经喷涂设备喷涂制得，其中组分A包括按照重量份数计的如下成分：多元醇100份、表面活性剂1-5份、催化剂2-10份、水0.5-1.0份、物理发泡剂20-30份、阻燃剂10-20份；所述的多元醇为密胺树脂多元醇和聚酯多元醇，两者重量比例为30-50：50-70；
组分B为多苯基多亚甲基多异氰酸酯；
组分A与组分B的重量比例为100～102：100。
所述的组分A中密胺树脂多元醇，粘度为5000-15000mPa.s(25℃)，羟值为120-220mgKOH/g；聚酯多元醇，粘度为10000-15000mPa.s(25℃)，羟值为150-200mgKOH/g。
所述的密胺树脂多元醇选江苏长能节能新材料科技有限公司的EDS-5083H、EDS-5083L中的一种或者两种的任意比例混合物。
所述的聚酯多元醇选自淄博瑞诺化工科技有限公司的PS-3175。
所述的催化剂为发泡型、凝胶型和三聚型催化剂三者复合，发泡型催化剂选反应型胺类催化剂，如二甲氨基乙氧基乙醇(DMAEE)、二甲基乙醇胺(DMEA)、三甲基羟乙基丙二胺、三甲基羟乙基乙二胺(Dabco T)等；凝胶型催化剂选环保型有机铋催化剂，如异辛酸铋、新癸酸铋、月桂酸铋等；三聚型催化剂选碱金属催化剂，如醋酸钾、油酸钾、异辛酸钾(K-15)等；进一步优选三甲基羟乙基乙二胺、异辛酸铋和异辛酸钾三者复配，较佳的比例为3：1：2。
所述的水优选为去离子水。
所述的物理发泡剂为环保型第四代HFO发泡剂，如一氯三氟丙烯(LBA)、六氟丁烯(FEA-1100)中的一种或两种的混合物。
所述的表面活性剂为非硅表面活性剂，可选上海麦豪新材料科技有限公司的LS系列产品、赢创集团的LK系列产品，进一步优选上海麦豪新材料科技有限公司的LS-6650。
所述的阻燃剂为TCPP(三(2-氯丙基)磷酸酯)、TCEP(三(2-氯乙基)磷酸酯)、TEP(磷酸三乙酯)、DMMP(甲基膦酸二甲酯)中的一种或几种，较佳的为TCPP与TEP混合物，优选质量比为1：1。
所述的多苯基多亚甲基多异氰酸酯，粘度150-700mPa.s(25℃)，NCO质量分数30-32％，可选万华集团的PM200、PM400、PM700，巴斯夫的M20S、M70L，亨斯迈5005、5888，科思创的44V20、44V40、44V70，韩国锦湖的M200，SR500等。
上述的聚氨酯泡沫的制备方法采用常规方法，组分A在制备时只需将其各成分在具有安全装置的搅拌速度为500rpm的混合釜中均匀混合，混合时最好在不锈钢混合釜内进行，混合时间0.5-1小时，静置0.5-1小时消泡后，放出即得组分A；将组分A和组分B经聚氨酯喷涂机器喷涂在集装箱波纹围护板上制备而成。喷涂设备优选美国固瑞克A系、E系或H系，进一步优选H系喷涂机；按照喷涂施工工艺员熟知的操作，管路加热温度设定35-45℃，管路压力设定1200-1800psi。
本发明的优势在于：
1)采用密胺树脂多元醇，其为三聚氰胺起始的多元醇，结构中的三嗪环体和氮元素赋予聚氨酯泡沫良好的机械性能、阻燃性和低生烟量；
2)磷、氯复合的阻燃剂体系，提高泡沫的阻燃性，降低泡沫燃烧时的生烟量；
3)采用反应型胺催化剂，在泡沫成型过程中结合到聚氨酯树脂中，从而无挥发性；同时采用无毒的钾和铋金属催化剂，保证了建筑内环境的安全性；
4)采用低羟值多元醇和低水量，提高泡沫的NCO指数，形成异氰脲酸酯六元环状结构，提高泡沫的耐火焰贯穿能力和降低泡沫燃烧时的生烟量；
5)采用了零臭氧消耗(ODP)、低温室气体效应(GWP)的第四代环保发泡为物理发泡剂。
本发明通过加入密胺树脂多元醇、复合阻燃剂、三类复合催化剂、环保物理发泡剂及改变原料组分比例，在保证聚氨酯泡沫材料满足良好的机械性能、低导热系数性能的基础上，大大提高了材料的防火性、安全性和舒适性。制得的聚氨酯泡沫的阻燃性能依据GB8624-2012建筑材料及制品燃烧性能分级判定可燃性为B1级；依据ISO5660-1对火反应试验—热释放、产烟量及质量损失率，第1部分：热释放速率(锥形量热仪法)，测试时间900秒，总热释放量小于20MJ/m2，总生烟量小于100m2/m2；聚氨酯泡沫的导热系数(K值)小于0.0205W/m·k，热阻值(R值)大于7.0ft2·h·℉/BTU。
具体实施方式
为了能够详细地阐述本发明的技术方案，下面结合典型实施例对本发明做进一步说明。
以下实施例中所用到的原料来源如下：
密胺树脂多元醇a：EDS-5083L，羟值200-220mgKOH/g，粘度5000-7000mPa.s，购于江苏长能节能新材料科技有限公司；
聚酯多元醇b：PS-3175，羟值175-195mgKOH/g，粘度10000-12000mPa.s，购于淄博瑞诺新材料股份有限公司；
聚醚多元醇A：SD-8345，羟值430-470mgKOH/g，粘度6000-8000mPa.s，购于上海东大化学有限公司
聚酯多元醇：PS-2412，羟值240mgKOH/g，粘度4500mPa.s，购于斯泰潘南京化学有限公司；
表面活性剂LS-6650，购于上海麦豪化工科技有限公司；
聚氨酯复合催化剂Dabco T、异辛酸铋和K-15购于EVONIK；
阻燃剂TCPP购于江苏法力克化工有限公司；
阻燃剂TEP购于张家港雅瑞化工有限公司；
物理发泡剂LBA购于中化蓝天霍尼韦尔新材料有限公司；
多苯基多亚甲基多异氰酸酯PM200、PM700购于万华化学。
实施例1
一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，由组分A和组分B反应制得；其中组分A组成如下：密胺树脂多元醇、聚酯多元醇、表面活性剂、催化剂、水、物理发泡剂、阻燃剂；组分B为多苯基多亚甲基多异氰酸酯；具体重量份比组成见表1。
制备方法：将组分A各原料在具有安全装置的搅拌速度为500rpm的混合釜中均匀混合，混合时最好在不锈钢混合釜内进行，混合时间1小时，静置1小时消泡后，放出即得组分A。将组分A和组分B经聚氨酯高压喷涂机器喷涂在干燥的木板或者水泥板上制备聚氨酯泡沫。泡沫熟化48小时后测试各项性能。
实施例2-6
一种用于集装箱模块建筑保温的喷涂型环保聚氨酯泡沫，由组分A和组分B反应制得，具体组成如下表1，制备方法同实施例1。
制备用于集装箱模块建筑保温的喷涂型环保聚氨酯泡沫实施例1-6的配方如下表1。
表1
Figure BDA0003745944650000041
对比例1
一种喷涂型聚氨酯泡沫，由组分A和组分B反应制得；其中组分A组成如下：聚醚多元醇、聚酯多元醇、表面活性剂、催化剂、水、物理发泡剂、阻燃剂；组分B为多苯基多亚甲基多异氰酸酯；具体重量份比组成见表2。
制备方法：将组分A各原料在具有安全装置的搅拌速度为500rpm的混合釜中均匀混合，混合时最好在不锈钢混合釜内进行，混合时间1小时，静置1小时消泡后，放出即得组分A。将组分A和组分B经聚氨酯高压喷涂机器喷涂在干燥的木板或者水泥板上制备聚氨酯泡沫。泡沫熟化48小时后测试各项性能。
对比例2-3
一种喷涂型聚氨酯泡沫，由组分A和组分B反应制得，具体组成如下表2，制备方法同对比例1。
制备喷涂型聚氨酯泡沫对比例1-3的配方如下表2。
表2
Figure BDA0003745944650000051
制得的聚氨酯泡沫的性能测试采用以下标准：
泡沫密度采用ASTM D1622，抗压强度采用ASTM D1621，拉伸强度采用ASTM D1623，闭孔率采用ASTM D6226，导热系数采用ASTM C518，燃烧性能分级采用GB/T 8624-2012，总热释放量采用ISO 5660-1，总生烟量采用ISO 5660-1。
实施例1-6制得的聚氨酯泡沫的性能如下表3。
表3
项目 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
泡沫密度，kg/m<sup>3</sup> 43.5 42.2 42.7 43.8 42.5 41.5
抗压强度，kPa 241 295 279 252 223 344
拉伸强度，kPa 286 335 308 297 273 386
闭孔率，％ 95.7 96.2 95.6 95.1 95.5 96.1
导热系数，mW/m.k(20℃) 19.82 20.21 20.17 20.34 20.45 20.03
热阻值，ft2·h·℉/BTU 7.26 7.13 7.14 7.08 7.04 7.19
燃烧性能分级 B1 B1 B1 B1 B1 B1
总热释放量，MJ/m<sup>2</sup> 12.3 17.6 15.8 16.9 17.5 8.7
总生烟量，m<sup>2</sup>/m<sup>2</sup> 47.6 56.9 50.2 76.3 85.6 35.1
对比例1-3制得的聚氨酯泡沫的性能如下表4。
表4
项目 对比例1 对比例2 对比例3
泡沫密度，kg/m<sup>3</sup> 44.3 43.7 43.5
抗压强度，kPa 175 158 218
拉伸强度，kPa 236 192 241
闭孔率，％ 96.2 95.7 95.9
导热系数，mW/m.k(20℃) 20.13 20.05 20.20
热阻值，ft2·h·℉/BTU 7.15 7.18 7.13
燃烧性能分级 B2 B2 B3
总热释放量，MJ/m<sup>2</sup> 31.6 25.8 35.3
总生烟量，m<sup>2</sup>/m<sup>2</sup> 375.1 307.4 483.7
经测试，实施例1-6所制备的聚氨酯泡沫材料能具有良好的机械性能、低导热系数，且泡沫的燃烧性能达到了GB 8624 B1级；泡沫燃烧过程中的总热释放量小于20MJ/m2，总生烟量小于100m2/m2。本发明制备的聚氨酯泡沫防火性能满足国内法规《建筑设计防火规范》GB 50016要求，同时满足澳新市场法规要求，并出口至新西兰用于集装箱模块化建筑保温。而对比例1-3所制备的聚氨酯泡沫燃烧性能值达到B2或者B3，且燃烧过程的热释放量高，并生成大量的烟，不能满足要求，且聚氨酯泡沫的强度较低。
上述虽然对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。

Claims (10)

1.一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，由组分A和组分B经喷涂设备喷涂制得，其特征是，其中组分A包括按照重量份数计的如下成分：多元醇100份、表面活性剂1-5份、催化剂2-10份、水0.5-1.0份、物理发泡剂20-30份、阻燃剂10-20份；所述的多元醇为密胺树脂多元醇和聚酯多元醇，两者重量比例为30-50：50-70；
组分B为多苯基多亚甲基多异氰酸酯；
组分A与组分B的重量比例为100～102：100。
2.根据权利要求1所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的组分A中密胺树脂多元醇，粘度为5000-15000mPa.s(25℃)，羟值为120-220mgKOH/g；聚酯多元醇，粘度为10000-15000mPa.s(25℃)，羟值为150-200mgKOH/g。
3.根据权利要求1所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的催化剂为发泡型、凝胶型和三聚型催化剂三者复合，发泡型催化剂选反应型胺类催化剂，凝胶型催化剂选环保型有机铋催化剂，三聚型催化剂选碱金属催化剂。
4.根据权利要求3所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的催化剂为三甲基羟乙基乙二胺、异辛酸铋和异辛酸钾三者复配。
5.根据权利要求1所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的物理发泡剂为环保型第四代HFO发泡剂一氯三氟丙烯、六氟丁烯中的一种或两种混合。
6.根据权利要求1所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的阻燃剂为TCPP、TCEP、TEP、DMMP中的一种或几种。
7.根据权利要求6所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的阻燃剂为TCPP与TEP的混合物。
8.根据权利要求1所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的多苯基多亚甲基多异氰酸酯，粘度为150-700mPa.s(25℃)，NCO质量分数30-32％。
9.根据权利要求1所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，所述的表面活性剂为非硅表面活性剂。
10.根据权利要求1所述的一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫，其特征是，组分A在制备时只需将其各成分在具有安全装置的搅拌下的混合釜中均匀混合，混合时间0.5-1小时，静置0.5-1小时消泡后，放出即得组分A；将组分A和组分B经聚氨酯喷涂机器喷涂在集装箱波纹围护板上制备而成。
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