CN106832209B - 超高密度高强度聚氨酯喷涂材料及其制备方法和应用 - Google Patents

超高密度高强度聚氨酯喷涂材料及其制备方法和应用 Download PDF

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CN106832209B
CN106832209B CN201710051345.3A CN201710051345A CN106832209B CN 106832209 B CN106832209 B CN 106832209B CN 201710051345 A CN201710051345 A CN 201710051345A CN 106832209 B CN106832209 B CN 106832209B
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殷晓峰
徐业峰
李欣
周生鹏
杜孝林
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于聚氨酯技术领域，具体涉及一种超高密度高强度聚氨酯喷涂材料及其制备方法和应用。所述材料由A组分和B组分组成，A组份为，以质量百分数计：聚醚多元醇A 22～34％；聚醚多元醇B 10～22％；聚醚多元醇C 0～18％；聚酯多元醇D 5～15％；交联剂5～12％；抗氧剂2～2.5％；泡沫稳定剂1～1.5％；化学发泡剂0.02～0.2％；催化剂2～4％；物理发泡剂1.5～2.5％；降粘剂19～25％。B组份为多亚甲基多苯基多异氰酸酯。本发明材料具有施工宽容度高，制得的泡沫塑料的密度高、压缩强度高、与基材粘结好，表面硬度高等特点，可广泛应用于需要耐受外界压力的保温防护工程。

Description

超高密度高强度聚氨酯喷涂材料及其制备方法和应用
技术领域
本发明属于聚氨酯技术领域，具体涉及一种超高密度高强度聚氨酯喷涂材料及其制备方法和应用。
背景技术
聚氨酯泡沫塑料是目前所有隔热保温材料中的佼佼者，广泛用于供热管道、石油化工管道、交通运输、冰箱冰柜、建筑保温、航空军用等诸多方面。聚氨酯喷涂施工工艺，由于其现场成型，施工速度快，与基材粘结力较好，泡孔细腻且导热系数低等特点，近年来在建筑保温领域应用越加广泛。常规的保温用喷涂用组合聚醚，一般密度设定在8-40kg/m3以内，产品主要起到保温作用，随着泡沫密度的提高，组合聚醚粘度提升较大，产品使用宽容度随之下降，无法做到较高的自由泡密度，在某些特定的使用领域受到限制。随着国内消费水平的提升，一些高档消费方式逐年发展，高档泳池、高档游艇的消费需求越来越大，但由于其工艺的特殊性，其保温与防护一直是行业内难以解决的问题。目前行业内有厂家在使用聚脲喷涂作为防水与防护措施，但由于聚脲产品不发泡，保温性能较差且成本较高，实际的使用效果也不理想。
因此，亟需研发一种高密度喷涂材料用于保温和对基材的防护，解决喷涂材料高密度情况下由于粘度问题造成的混合困难、施工宽容度低的问题。
发明内容
本发明的目的是提供一种具有超高密度与高强度的聚氨酯喷涂材料，其施工宽容度较高，具有泡沫结皮致密，防水效果较好，密度高，抗压强度高，与基材粘结力好的特点；本发明同时提供其制备方法和应用。
本发明所述的超高密度高强度聚氨酯喷涂材料，由A组分和B组分组成，A组份与B组分质量比为100:100～130，其中：
A组份为，以质量百分数计：
B组份为：
多亚甲基多苯基多异氰酸酯，优选烟台万华化学有限公司PM400。
其中：
所述聚醚多元醇A为官能度3～5.5，分子量500～650，起始剂为山梨醇或者起始剂包括山梨醇的聚醚多元醇；优选山东一诺威新材料有限公司YNW-6207或YNW-6205。
所述聚醚多元醇B为官能度3～4，分子量400～600，起始剂为甲苯二胺或者起始剂包括甲苯二胺的聚醚多元醇。优选句容宁武新材料股份有限公司4110HN；上海东大聚氨酯有限公司SD-7100。
所述聚醚多元醇C为官能度7～8，分子量800～1200的聚醚多元醇。优选山东一诺威新材料有限公司370S。
所述聚酯多元醇官能度为2～3，分子量为400～800的聚酯多元醇。优选斯太潘化学有限公司2412，山东一诺威聚氨酯有限公司E504。
所述交联剂为小分子醇类，优选1,4丁二醇。
所述抗氧剂为酚类抗氧剂，优选台湾双键化工股份有限公司1135。
所述降粘剂为添加型卤代磷酸酯类降粘剂，优选磷酸三乙酯(TEP)。
所述泡沫稳定剂为非水解硅碳类表面活性剂，中山东郡化工有限公司H3315。
所述化学发泡剂为水。
所述的抗氧剂为酚类抗氧剂，优选台湾双键化工股份有限公司1135。
所述催化剂为胺类催化剂与有机金属类催化剂的混合物，为五甲基二乙烯三胺(PC-5)、33％的三乙烯二胺溶液(A33)、二月桂酸二丁基锡(T-12)、1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41)四者的混合物，五甲基二乙烯三胺、33％的三乙烯二胺溶液、二月桂酸二丁基锡、1,3,5-三(二甲氨基丙基)六氢三嗪分别占A组份总质量的0.2～0.7％、1.0～1.5％、0.02～0.3％、0.4～0.7％。
所述物理发泡剂为发泡剂Ecomate。
所述的超高密度高强度聚氨酯喷涂材料的制备方法如下：
制备A组份料：将称量好的聚醚多元醇A、聚醚多元醇B、聚醚多元醇C、聚酯多元醇、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、降粘剂、物理发泡剂依次加入反应釜中，在常温下搅拌0.5～1小时即可。
制备B组分料：将多亚甲基多苯基多异氰酸酯，直接装桶。
所述的超高密度高强度聚氨酯喷涂材料的应用是：将A组份与B组分按照重量比100:100～130，经喷涂机进行混合施工，即可得到超高密度高强度聚氨酯喷涂材料。制得的泡沫具有较高的密度与抗压强度，与基材可良好粘结，可广泛应用于船体填充保温防护，大型水坝混泥土结构保温防护，泳池保温防护等工程。
与现有技术相比，本发明具有如下有益效果：
本发明解决高密度喷涂由于粘度问题造成的施工宽容度问题，一方面通过配方内降粘剂种类的选取与数量的确定，降低主体聚醚粘度，最终配方粘度稳定在500～1000mpas之间，同时由于选用的B组分粘度较常规的异氰酸酯粘度较高，减小了施工中黑白料因为粘度不一致造成的串料风险；另一方面，通过小分子醇种类与份数的搭配，提高泡沫韧性以及与基材的粘结力，使泡沫可牢固的附着在基材表面；同时由于主体聚醚官能度及羟值的搭配，提升Ecomate发泡剂的尺寸稳定性，最终制品具有较高的密度及较高的强度。
本发明A组分料生产方便，使用A、B组分，利用喷涂机向基材喷射发泡施工，最终制得的泡沫整体密度可达到200～500kg/m3，泡沫与基材粘结力好，压缩强度2MPa以上，表面硬度达到邵氏40以上，使该材料可应用于应用于船体填充保温防护，大型水坝混泥土结构保温防护，泳池保温防护等需要耐受外界压力的保温防护工程。
本发明可以根据客户要求调整自由泡密度，满足客户对整体密度的需求，同时通过配方调整，获得较高的压缩强度，使泡沫具有优良的承重能力，可广泛用于泳池，船体等耐压情况下的保温防护工程，对于提高公司产品竞争力，推动聚氨酯喷涂行业的发展具有重要意义。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
在1吨反应容器内制备A组份料，分别称量：聚醚多元醇A(山东一诺威新材料有限公司YNW-6205)：50份；聚醚多元醇B(上海东大化学有限公司SD-7100)：30份；聚酯多元醇(优选斯太潘化学有限公司2412)：20份；交联剂(中国石油化工集团公司1,4BG)：8份，抗氧剂(台湾双键1135)：3份；硅油H3315(中山东郡)：2份；化学发泡剂H2O：0.2份；五甲基二乙烯三胺(PC-5)1份；33％的三乙烯二胺溶液(A33)：2份；二月桂酸二丁基锡(T-12)：0.4份；1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41)：1份；降粘剂(张家港雅瑞化工有限公司TEP)：30份；Ecomate：3份。将称量好的聚醚多元醇、聚酯多元醇、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、降粘剂、物理发泡剂，依次加入反应釜中，在常温下搅拌0.5小时，取出进行检验，满足工艺参数，发出泡沫，即得A组份合格产品，从反应釜中取出装桶入库。B组份为多亚甲基多苯基多异氰酸酯。
将A、B组份料按A:B＝100:100重量配比经喷涂机高压混合喷涂施工，即可制得高密度高强度聚氨酯喷涂材料，测试产品质量指标。
实施例1的高密度高强度聚氨酯泡沫塑料达到以下指标，见表1。
表1实施例1泡沫塑料性能参数表
项目 指标
密度Kg/m<sup>3</sup> 200
粘度mpas 630
导热系数w/(/m·K) 0.050
径向抗压强度kPa 2000
闭孔率％ 95
吸水率％ 0.5
粘结强度kpa 1000
表面硬度邵D 50
实施例2
在1吨反应容器内制备A组份料，分别称量：聚醚多元醇A(山东一诺威新材料有限公司YNW-6207)：40份；聚醚多元醇B(句容宁武新材料股份有限公司4110HN)：20份；聚醚多元醇C(山东一诺威新材料有限公司YNW370S)：30份；聚酯多元醇(优选斯太潘化学有限公司2412)：10份；交联剂(中国石油化工集团公司1,4BG)：20份，抗氧剂(台湾双键1135)：4份；硅油H3315(中山东郡)：2份；化学发泡剂H2O：0.05份；五甲基二乙烯三胺(PC-5)0.5份；33％的三乙烯二胺溶液(A33)：2份；二月桂酸二丁基锡(T-12)：0.05份；1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41)：1份；降粘剂(张家港雅瑞化工有限公司TEP)：40份；Ecomate：3份。将称量好的聚醚多元醇、聚酯多元醇、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、降粘剂、物理发泡剂，依次加入反应釜中，在常温下搅拌0.5小时，取出进行检验，满足工艺参数，发出泡沫，即得A组份合格产品，从反应釜中取出装桶入库。B组份为多亚甲基多苯基多异氰酸酯。
将A、B组份料按A:B＝100:130重量配比经喷涂机高压混合喷涂施工，即可制得高密度高强度聚氨酯喷涂材料，测试产品质量指标。
实施例2的高密度高强度聚氨酯泡沫塑料达到以下指标，见表2。
表2实施例2泡沫塑料性能参数表
项目 指标
密度Kg/m<sup>3</sup> 370
粘度mpas 840
导热系数w/(/m·K) 0.060
径向抗压强度kPa 4500
闭孔率％ 95
吸水率％ 0.3
粘结强度kpa 1500
表面硬度邵D 70
本发明制得的泡沫整体密度可达到200-500kg/m3，泡沫与基材粘结力好，压缩强度2MPa以上，表面硬度达到邵氏40以上，使该材料可应用于应用于船体填充保温防护，大型水坝混泥土结构保温防护，泳池保温防护等需要耐受外界压力的保温防护工程。

Claims (7)

1.一种超高密度高强度聚氨酯喷涂材料，其特征在于：由A组分和B组分组成，A组份与B组分质量比为100:100～130，其中：
A组份为，以质量百分数计：
聚醚多元醇A： 22-34%
聚醚多元醇B： 10-22%
聚醚多元醇C： 0-18%
聚酯多元醇： 5-15%
交联剂： 5-12%
抗氧剂： 2-2.5%
泡沫稳定剂： 1-1.5%
化学发泡剂： 0.02-0.2%
催化剂： 2-4%
物理发泡剂： 1.5-2.5%
降粘剂： 19-25%；
其中：
所述聚醚多元醇A为官能度3～5.5，分子量500～650，起始剂为山梨醇或者起始剂包括山梨醇的聚醚多元醇；
聚醚多元醇B为官能度3～4，分子量400～600，起始剂为甲苯二胺或者起始剂包括甲苯二胺的聚醚多元醇；
聚醚多元醇C为官能度7～8，分子量800～1200的聚醚多元醇；聚酯多元醇为官能度2～3，分子量400～800的聚酯多元醇；
抗氧剂是酚类抗氧剂；
催化剂为胺类催化剂与有机金属类催化剂的混合物，为五甲基二乙烯三胺、33％的三乙烯二胺溶液、二月桂酸二丁基锡、1,3,5-三(二甲氨基丙基)六氢三嗪四者的混合物，五甲基二乙烯三胺、33％的三乙烯二胺溶液、二月桂酸二丁基锡、1,3,5-三(二甲氨基丙基)六氢三嗪分别占A组份总质量的0.2～0.7％、1.0～1.5％、0.02～0.3％、0.4～0.7％；
B组份为：
多亚甲基多苯基多异氰酸酯。
2.根据权利要求1所述的超高密度高强度聚氨酯喷涂材料，其特征在于：所述交联剂为1,4丁二醇。
3.根据权利要求1所述的超高密度高强度聚氨酯喷涂材料，其特征在于：所述泡沫稳定剂为非水解硅碳类表面活性剂。
4.根据权利要求1所述的超高密度高强度聚氨酯喷涂材料，其特征在于：所述化学发泡剂为水。
5.根据权利要求1所述的超高密度高强度聚氨酯喷涂材料，其特征在于：所述物理发泡剂为发泡剂Ecomate；所述降粘剂为磷酸三乙酯。
6.一种权利要求1～5任一所述的超高密度高强度聚氨酯喷涂材料的制备方法，其特征在于：
制备A组份料：将称量好的聚醚多元醇A、聚醚多元醇B、聚醚多元醇C、聚酯多元醇、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、降粘剂、物理发泡剂依次加入反应釜中，在常温下搅拌0.5～1小时即可。
7.一种权利要求1～5任一所述的超高密度高强度聚氨酯喷涂材料的应用，其特征在于：
将A组份与B组分按照重量比100:100～130，经喷涂机进行混合施工，即可得到超高密度高强度聚氨酯喷涂材料。
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