CN104327240A - 一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料及制备方法 - Google Patents
一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料及制备方法 Download PDFInfo
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Abstract
一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,由A、B两组分组成,所述A、B两组分重量比为1:1,所述A组分原料按照重量份数计为:聚醚多元醇1:45~80份,聚醚多元醇2:0~15份,表面活性剂:1.0~2.0份,催化剂:0.1~2.0份,成核剂:1~5份,阻燃剂:10~20份,发泡剂:10~20份;所述B组分原料按重量份数计为:多异氰酸酯:60~80份,预聚体:15~30份,稀释剂:5~10份;其中,所述的A组分中聚醚多元醇1为3~5官能度、分子量300~800的聚氧化丙烯多元醇;聚醚多元醇2为2~4官能度、分子量为150~600的聚氧化丙烯多元醇。
Description
技术领域
本发明涉及聚氨酯材料技术领域,尤其是涉及一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料及制备方法。
背景技术
已知的,瓦斯是煤炭生成过程中的伴生气体,其主要成分为甲烷。在煤矿生产过程中,因为瓦斯爆炸所造成的损失是所有矿山事故中最为严重的。它不但严重威胁煤矿工人的生命财产安全,还极大地限制了矿井的生产能力,降低了生产效率,限制了我国煤矿行业的可持续发展。因此,有效防范与控制瓦斯事故是解决我国煤矿安全问题的关键。
在治理煤矿瓦斯事故中,瓦斯抽放是最有效的措施之一,我国政府及相关部门对此给予了高度重视。2002年,国家煤矿安全监察局制定了“先抽后采,以风定产,监测监控”的煤矿瓦斯防治方针,强化了瓦斯抽放治理瓦斯灾害的地位。
目前我国煤矿普遍采用的瓦斯钻孔封孔方法主要有两种:水泥砂浆封孔和高分子发泡材料封孔。水泥砂浆封孔工艺采用分段密封,由于水泥极易形成气体通路,导致漏气严重,劳动强度大,抽采效率低,预抽采时间长,从而降低了煤炭开采效率。
高分子发泡材料封孔,以聚氨酯为主,是利用聚氨酯材料的自身发泡压力使材料渗入钻孔煤壁裂隙,形成闭孔材料,从而能大大提高封孔质量。由于聚氨酯材料具有用量小、劳动强度低、封孔效果较好等优点,使其在瓦斯钻孔封孔方面得到了推广和应用。
目前,聚氨酯密封胶价格较高,为了尽可能降低密封胶的使用量,降低使用成本,需要使密封胶的发泡倍率尽可能的最大化。而现有的聚氨酯密封胶发泡倍率仅为5~10倍,若再提高其发泡倍率,则会导致密封胶形成的固结体的闭孔率降低,密封性将显著下降,封孔后的密封质量得不到保证。若发泡倍率提高而闭孔率不变,则又因聚氨酯化学反应生成的热量无法散出,导致固结体“烧芯”,有引发火灾的危险。
发明内容
为了克服背景技术中的不足,本发明公开了一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,本发明是在确保芯部温度不超过110℃的前提下,该材料具有高发泡倍率(约15~20倍),低使用量,高闭孔率(闭孔率大于90%)、高密闭性、低反应放热、高阻燃的特点,粘结强度高、抗剪切性强及韧性好,耐冲击,耐酸碱,完全满足煤矿密封瓦斯用材料的使用。
本发明同时还提供了一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料的制备方法,其方法简单易行,生产周期短,整个生产过程中不产生废液、废渣和废气,不对环境造成污染,不影响工人健康。
为了实现所述发明目的,本发明采用如下技术方案:
一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,由A、B两组分组成,所述A、B两组分重量比为1:1:
所述A组分原料按照重量份数计为:
聚醚多元醇1:50~75份
聚醚多元醇2:0~15份
表面活性剂:1.0~2.0份
催化剂:0.1~2.0份
成核剂:1~5份
阻燃剂:10~20份
发泡剂:10~20份
所述B组分原料按重量份数计为:
多异氰酸酯:60~80份
预聚体:15~30份
稀释剂:5~10份;
其中,所述的A组分中聚醚多元醇1为3~5官能度、分子量300~800的聚氧化丙烯多元醇;聚醚多元醇2为2~4官能度、分子量为150~600的聚氧化丙烯多元醇。
本发明所述的A组分中催化剂为胺类和/或金属类催化剂;所述胺类和/或金属类催化剂优选为N,N-二甲基环己胺、五甲基二乙烯三胺、N,N-二甲基苄胺、双(2-二甲氨基乙基)醚、三乙烯二胺、有机锡、有机铋和有机锌化合物的一种或几种组合。
本发明所述A组分中的阻燃剂为磷酸酯类阻燃剂,优选磷酸三氯丙酯或甲基磷酸二甲酯中的一种或两种组合。
本发明所述A组分中的成核剂为白炭黑、滑石粉、碳酸钙、氢氧化铝、氢氧化镁、硅酸钠、硅酸钾中的一种或几种组合。
本发明所述A组分中的表面活性剂包括硅氧烷/环氧乙烷/环氧丙烷共聚物,优选为空气产品公司(Air Products)、高施密特公司(Goldschmidt AG)、南京美思德制造商生产的表面活性剂。
本发明所述A组分中的发泡剂为1,1-二氯-1-氟乙烷(HCFC-141b)、1,1,1,3,3-五氟丙烷、1,1,1,3,3-五氟丁烷和水中的一种或几种组合。
本发明所述的B组分原料中的多异氰酸酯为多亚甲基多苯基多异氰酸酯、聚合MDI或液化改性MDI,优选为烟台万华的PM-200,8002,Huntsman的5005S,Bayer的44V20,BASF的M20S。
本发明所述的B组分原料中的预聚体为以聚氧化丙烯多元醇PPG和二苯基甲烷二异氰酸酯为原料合成的预聚物,其中多元醇优选2~3官能度,分子量为300~2000的聚氧化丙烯多元醇,所述二苯基甲烷二异氰酸酯优选4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯中的一种或两种;
本发明所述B组分原料中的稀释剂为邻苯二甲酸酯类或磷酸酯类,优选邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二辛酯(DOP)、磷酸三乙酯(TEP)、磷酸三丁酯(TBP)等中的一种或几种组合。
一种如权利要求1所述的煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料的制备方法,包括以下步骤:
(1)A组份的制备:将聚醚多元醇1、聚醚多元醇2、催化剂、表面活性剂、阻燃剂、发泡剂、成核剂按配方比例投入反应釜中,室温下搅拌混合1~2小时后出料,密封包装;
(2)B组份料的制备:
a.预聚体的制备:将真空脱水的聚氧化丙烯多元醇PPG和二苯基甲烷二异氰酸酯按比例投入反应釜中,在80~110℃、真空度为0.05~0.1MPa的环境下搅拌1~3小时后,投入阻聚剂,降温出料;
b.将多异氰酸酯、预聚体、稀释剂按比例投入反应釜中,室温下搅拌混合1~2小时后出料,氮气置换密封包装。
由于采用了上述技术方案,本发明具有如下有益效果:本发明的关键点是:
1、提高了发泡倍数。本发明通过调整聚醚多元醇的骨架结构、催化剂的复配和预聚体的合成,使得发泡在初始阶段,发泡剂开始气化挥发时,聚氨酯黏液既具有足够的强度,可以将发泡剂气体包裹起来。通过这种方式,提高了发泡剂的利用效率,可以在不增加发泡剂用量的情况下,提高了发泡倍数,且最终发泡生成的固结体强度好。
2、维持了高的闭孔率。本发明通过优选催化剂、表面活性剂、成核剂和预聚体的合成,提高了密封胶的乳化成核性能,使得生成的固结体泡孔细腻,闭孔率高。
本发明相对于现有的技术具有以下效果和优点:
1、提高了发泡倍率,减少了密封胶的使用量,降低了使用成本。由于提高了发泡倍率,相同的密封体积即可使用较少的密封胶用量,降低了使用企业的成本。
2、固结体闭孔率高,维持了较高的密封性。由于固结体的闭孔率高,此密封胶用于密封时可以维持很好的密封效果。使用此密封胶封孔抽真空,真空度可以达到0.098MPa。
具体实施方式
通过下面的实施例可以详细的解释本发明,公开本发明的目的旨在保护本发明范围内的一切技术改进。
实施例1
A组分的制备:
将准确计量的聚醚多元醇1(4.2官能度,分子量520)50份、聚醚多元醇2(3官能度,分子量500)7份、催化剂N,N-二甲基环己胺Polycat 8(美国空气化工)0.1份、催化剂五甲基二乙烯三胺Polycat 5(美国空气化工)0.2份、表面活性剂B8453(德国Goldschmidt AG)1.2份、发泡剂HFC-365(Solvay公司)20份、成核剂白炭黑(上海凯茵化工)1.5份和阻燃剂磷酸三氯丙酯TCPP(江苏雅克)20份投入反应釜中,搅拌混合2小时后出料、密封包装;
B组分的制备
将准确计量真空脱水的聚氧化丙烯多元醇GE-303(3官能度,分子量300)(上海高桥)和二苯基甲烷二异氰酸酯MDI-50投入反应釜中,在80~110℃、真空度为0.05~0.1MPa的环境下搅拌2小时后,投入阻聚剂,降温出料得预聚体。
将准确计量的多亚甲基多苯基多异氰酸酯PM-20065份、预聚体25份、稀释剂DOP(濮阳市诚意增塑剂有限公司)10份,投入反应釜中,搅拌混合1小时,出料、氮气置换密封包装。
按照A:B=1:1的重量比分别取A、B组分各l00g,搅拌混合制成固结体,检测产品指标如表1所示:
表1固结体的性能指标
实施例2
A组分的制备:
将准确计量的聚醚多元醇1(4.3官能度,分子量600)75份、催化剂三乙烯二胺(美国Air Products)0.2份、双(2-二甲氨基乙基)醚(美国Air Products)0.3份、表面活性剂AK-8812(南京美思德)1.5份、成核剂碳酸钙(河南科力)3份、发泡剂HCFC-141b(浙江三环)9份、水1份和阻燃剂甲基磷酸二甲酯DMMP(青岛联美)10份投入反应釜中,搅拌混合1小时后出料、密封包装;
B组分的制备
将准确计量真空脱水的聚氧化丙烯多元醇GE-205(2官能度,分子量500)(上海高桥)和二苯基甲烷二异氰酸酯MDI-100投入反应釜中,在80~110℃、真空度为0.05~0.1MPa的环境下搅拌1.5小时后,投入阻聚剂,降温出料得预聚体。
将准确计量的多亚甲基多苯基多异氰酸酯500570份、预聚体20份、稀释剂DBP(濮阳市诚意增塑剂有限公司)10份,投入反应釜中,搅拌混合1小时,出料、氮气置换密封包装。
按照A:B=1:1的重量比分别取A、B组分各l00g,搅拌混合制成固结体,检测产品指标如表2所示:
表2固结体的性能指标
实施例3
A组分的制备:
将准确计量的聚醚多元醇1(4.3官能度,分子量550)60份、聚醚多元醇2(4官能度,分子量300)3份、催化剂N,N-二甲基苄胺Dabco BDMA(美国空气化工)0.5份、催化剂五甲基二乙烯三胺Polycat 5(美国空气化工)0.2份、N,N-二甲基环己胺Polycat8(美国空气化工)0.3份、表面活性剂L-5421(美国迈图)1.7份、发泡剂HFC-245fa(美国Honeywell)17份、成核剂滑石粉(吉林市山威硅石灰矿业有限公司)2.3份、阻燃剂磷酸三氯丙酯TCPP(江苏雅克)10份、阻燃剂甲基磷酸二甲酯DMMP(青岛联美)5份投入反应釜中,搅拌混合2小时,抽样检测后出料、密封包装;
B组分的制备
将准确计量真空脱水的聚氧化丙烯多元醇GE-220(2官能度,分子量2000)(上海高桥)和二苯基甲烷二异氰酸酯MDI-100投入反应釜中,在80~110℃、真空度为0.05~0.1MPa的环境下搅拌2小时后,投入阻聚剂,降温出料得预聚体。
将准确计量的多亚甲基多苯基多异氰酸酯44V2040份、Wannate 8002(烟台万华)37份、预聚体17份、稀释剂DOP(濮阳市诚意增塑剂有限公司)6份,投入反应釜中,搅拌混合1小时,出料、氮气置换密封包装。
按照A:B=1:1的重量比分别取A、B组分各l00g,搅拌混合制成固结体,检测产品指标如表3所示:
表3固结体的性能指标
本发明未详述部分为现有技术。
Claims (10)
1.一种煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,由A、B两组分组成,所述A、B两组分重量比为1:1,其特征是:
所述A组分原料按照重量份数计为:
聚醚多元醇1:50~75份
聚醚多元醇2:0~15份
表面活性剂:1.0~2.0份
催化剂:0.1~2.0份
成核剂:1~5份
阻燃剂:10~20份
发泡剂:10~20份
所述B组分原料按重量份数计为:
多异氰酸酯:60~80份
预聚体:15~30份
稀释剂:5~10份;
其中,所述的A组分中聚醚多元醇1为3~5官能度、分子量300~800的聚氧化丙烯多元醇;聚醚多元醇2为2~4官能度、分子量为150~600的聚氧化丙烯多元醇。
2.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述的A组分中催化剂为胺类和/或金属类催化剂;所述胺类和/或金属类催化剂优选为N,N-二甲基环己胺、五甲基二乙烯三胺、N,N-二甲基苄胺、双(2-二甲氨基乙基)醚、三乙烯二胺、有机锡、有机铋和有机锌化合物的一种或几种组合。
3.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述A组分中的阻燃剂为磷酸酯类阻燃剂,优选磷酸三氯丙酯或甲基磷酸二甲酯中的一种或两种组合。
4.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述A组分中的成核剂为白炭黑、滑石粉、碳酸钙、氢氧化铝、氢氧化镁、硅酸钠、硅酸钾中的一种或几种组合。
5.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述A组分中的表面活性剂包括硅氧烷/环氧乙烷/环氧丙烷共聚物,优选为空气产品公司(Air Products)、高施密特公司(Goldschmidt AG)、南京美思德制造商生产的表面活性剂。
6.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述A组分中的发泡剂为1,1-二氯-1-氟乙烷(HCFC-141b)、1,1,1,3,3-五氟丙烷、1,1,1,3,3-五氟丁烷和水中的一种或几种组合。
7.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述的B组分原料中的多异氰酸酯为多亚甲基多苯基多异氰酸酯、聚合MDI或液化改性MDI,优选为烟台万华的PM-200,8002,Huntsman的5005S,Bayer的44V20,BASF的M20S。
8.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述的B组分原料中的预聚体为以聚氧化丙烯多元醇PPG 和二苯基甲烷二异氰酸酯为原料合成的预聚物,其中多元醇优选2~3官能度,分子量为300~2000的聚氧化丙烯多元醇,所述二苯基甲烷二异氰酸酯优选4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯中的一种或两种。
9.如权利要求1所述的用于煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料,其特征是:所述B组分原料中的稀释剂为邻苯二甲酸酯类或磷酸酯类,优选邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二辛酯(DOP)、磷酸三乙酯(TEP)、磷酸三丁酯(TBP)中的一种或几种组合。
10.一种如权利要求1所述的煤矿井下密封瓦斯用高发泡倍率高闭孔率的聚氨酯材料的制备方法,其特征是:包括以下步骤:
(1)A组份的制备:将聚醚多元醇1、聚醚多元醇2、催化剂、表面活性剂、阻燃剂、发泡剂、成核剂按配方比例投入反应釜中,室温下搅拌混合1~2小时后出料,密封包装;
(2)B组份料的制备:
a.预聚体的制备:将真空脱水的聚氧化丙烯多元醇PPG和异氰酸酯按比例投入反应釜中,在80~110℃、真空度为0.05~0.1MPa的环境下搅拌1~3小时后,投入阻聚剂,降温出料;
b.将多异氰酸酯、预聚体、稀释剂按比例投入反应釜中,室温下搅拌混合1~2小时后出料,氮气置换密封包装。
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