CN105175673A - 一种煤矿用高水含量低发热聚氨酯充填材料及其制备方法 - Google Patents

一种煤矿用高水含量低发热聚氨酯充填材料及其制备方法 Download PDF

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CN105175673A
CN105175673A CN201510339613.2A CN201510339613A CN105175673A CN 105175673 A CN105175673 A CN 105175673A CN 201510339613 A CN201510339613 A CN 201510339613A CN 105175673 A CN105175673 A CN 105175673A
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闫宇欣
林鹏
柏广峰
薛纪波
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Shanxi Yubang Science And Technology Co ltd
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Abstract

本发明属于高分子材料合成领域，具体涉及一种煤矿用高水含量低发热聚氨酯充填材料及其制备方法；该充填材料由双液型高分子A组份和B组份注浆发泡而成，其使用时，A组份和B组份按照0.5～1.5：1的质量比混合浇注于待填充的区域；其中A组份是由聚醚或聚酯多元醇及助剂组成的组合料，B组份是由有机多异氰酸酯化合物为主体的组合料。本发明充填材料粘度低、流动性好、绿色环保具有较高的抗压强度和发泡倍率，同时发泡后，材料的高含水量这些都赋予了材料优良的承载和变形能力，有效避免在掘进过程中出现顶煤破碎及塌落等问题，而注浆过程中较低的发泡温度也明显地提高了矿下作业的安全系数。

Description

一种煤矿用高水含量低发热聚氨酯充填材料及其制备方法
技术领域
本发明涉及一种用于煤矿及相关行业中对煤（岩）体进行充填的材料，尤其
涉及一种煤矿用高水含量低发热聚氨酯充填材料及其制备方法。
背景技术
煤矿行业中经常出现废弃老洞、溜眼（煤仓），工作面巷道的顶板需要填充密闭，并有比较高的抗压强度；以避免巷道顶部的岩煤层松散，冒顶等问题。而现有的煤矿用聚氨酯充填材料气味大对人员造成伤害，对环境造成污染且反应温度一般超过100℃，容易引起有机聚氨酯泡沫材料的自燃，甚至瓦斯气体和煤体的爆炸，进而产生安全事故。因此，煤矿开采过程中抗压强度不够和发泡温度过高是限制聚氨酯类发泡充填材料发展的关键问题，今后需要对这些问题进行改进以提高生产的安全系数。
发明内容
本发明所要解决的技术问题是：现有煤矿用聚氨酯充填材料普遍存在气味大，污染环境，抗压强度不够和发泡温度过高等问题，存在很大的安全隐患。
针对以上技术问题，本发明所采取的技术方案是：提供一种煤矿用高水含量低发热聚氨酯充填材料，由双液型高分子A组份和B组份发泡而成，使用时，A组份和B组份按照0.5～1.5：1的质量比混合浇注于待填充的区域即可。
A组份是由聚醚或聚酯多元醇及助剂组成的组合料，以重量份数计，原料组成为：
聚醚或聚酯多元醇10～70份
醇胺0.1～30份
阻燃剂0～40份
催化剂0.2～4份
发泡剂2～30份
乳化剂0.5～25份
水10～60份
B组份是由有机多异氰酸酯化合物为主体的组合料，以重量份数计，原料组成为：
多异氰酸酯化合物70～90份
添加剂10～30份
所述A组分中的聚醚多元醇选用官能度不小于2，羟值为30～300mgKOH/g的聚醚多元醇中的一种或多种。聚酯多元醇为羟值50～300mgKOH/g的芳香族聚酯多元醇及改性芳香族聚酯多元醇中的一种或多种。
所述A组分中的醇胺选用甘油、三乙醇胺、1,4丁二醇，二乙醇胺，二甘醇及三甘醇中的一种或多种。
所述A组分中的阻燃剂选用TCPP、TCEP、TEP、TDCPP、三（二溴丙基）磷酸酯、四（2-氯乙基）亚乙基二磷酸酯、DMMP及DEEP中的一种或一种以上。
所述A组分中的催化剂体系由胺类催化剂与有机金属类催化剂复合而成，复配比例为1：1或1：2.其中胺类催化剂是脂肪胺类、脂环胺类、芳香胺类和醇胺类中的一种或多种；有机金属催化剂是羧酸盐和锡、钾、铅、汞、锌、钛、铋等一种或多种。
所述A组分中的发泡剂包括化学发泡剂和物理发泡剂一种或多种。化学发泡剂是水，物理发泡剂为二氯一氟乙烷、戊烷、五氟丙烷及二氯甲烷中的一种或多种。
所述A组分中的水的用量范围在10～60wt%。最高可以达到60wt%。
所述B组分中的多异氰酸酯化合物多苯基多异氰酸酯、异氰酸酯预聚体或碳化二亚胺改性二异氰酸酯的一种或多种。
所述的B组分中添加剂为醋酸酯、碳酸酯、磷酸三氯丙酯的一种或多种。
本发明所述的一种煤矿用高水含量低发热聚氨酯充填材料的制备方法，具体步骤如下：
A组分的制备：将聚醚或聚酯多元醇、醇胺、催化剂、发泡剂、乳化剂和水加入反应釜，在温度5～35℃搅拌速度50-400r/min的条件混合2～4h，抽样检验合格后出料密闭包装。
B组分的制备：将多异氰酸酯及添加剂加入反应釜，在室温条件下,搅拌速度50～400r/min的条件下混合1～3h，整个操作过程为无水环境，经抽样检验合格后出料，氮气置换包装即可。
本发明中所使用的双液型高分子A组份和B组份，其粘度范围为100-200mPa·s/25℃，易于运输和泵的输送，施工方便；发泡固化过程中，内部最高温度在85℃以下。
本发明的有益效果是：所提供的高水含量低发热聚氨酯充填材料在常温下可以发泡固化，使用温度宽，固化速度可调，发泡倍率可调；最高反应温度不高于85℃，诠释了聚氨酯材料反映温度低发热的范畴；材料浆液的气味小、粘度低、渗透性强，具有一定的柔韧性，同时也对填充区域起到了一定的加固作用；发明生产及使用过程中产品各组份及聚合产品不属于有毒品，对人体无害，无污染，符合环保法规的要求；材料可用于煤矿的安全生产，可提高煤矿井下的安全系数，为矿井的高效生产提供给了保障；此外，本发明提供的材料除了用于煤矿行业，还可以用于建筑、采矿、浇注等行业的加固填充。
具体实施方案
实施例1
A组份选取聚醚多元醇220A:350kg和330N：500kg；聚酯多元醇3152:200kg；三乙醇胺：100kg；胺类催化剂三乙烯二胺：1.5kg；有机金属类催化剂T-12：0.6kg；增塑剂邻苯二甲酸二丁酯5kg；阻燃剂TCEP：150kg和DMMP：50kg；乳化剂苯乙基酚聚氧乙烯醚：5kg；物理发泡剂141B：200kg；化学发泡剂水：20kg；水：300kg。将各单体料依次加入反应釜中，在温度25℃、搅拌速度100r/min的条件下混合2.5h，得到的组合料。
B组份是选用烟台万华聚氨酯股份有限公司的多亚甲基多苯基异氰酸酯PM200：700kg、PM400：300kg和二氯甲烷：50kg；醋酸酯；50kg。将单体料依次加入反应釜中，在温度25℃搅拌速度100r/min的条件混合2.5h，得到的组合料。
将A组份与B组份经气动注浆泵按照体积比1：1的比例高速混合得到固结体。检测其性能：体系最高反应温度84℃，氧指数24，在火焰的直接作用下具有结碳、无滴落物、无熔化现象，多点取样法测得抗压强度平均值15kpa，符合煤矿使用标准。
实施例2
A组份取聚醚多元醇210：300kg和330N：400kg；聚酯多元醇AK-POL-3002：200kg；阻燃聚醚多元醇FR-7190：100kg；三乙醇胺：80kg；胺类催化剂三乙烯二胺：1.0kg；有机金属类催化剂T-12：0.8kg；增塑剂邻苯二甲酸二丁酯：5kg；阻燃剂TCEP：150kg和TEP：80kg；抗静电剂乳化剂苯乙基酚聚氧乙烯醚：10kg；物理发泡剂：150kg；水：150kg。将单体料依次加入反应釜中，在温度15℃搅拌速度200r/min的条件混合2.5h得到的组合料。
B组份是选用烟台万华聚氨酯股份有限公司的多亚甲基多苯基异氰酸酯PM200：800kg、PM400：200kg和醋酸酯：50kg。将单体料依次加入反应釜中，在温度30℃搅拌速度300r/min的条件混合1.5h得到的组合料。
将A组份与B组份经气动注浆泵按照体积比1.1：1的比例高速混合得到固结体。检测其性能：体系最高反应温度83℃，氧指数25，在火焰的直接作用下具有结碳、无滴落物、无熔化现象，多点取样法测得抗压强度平均值15kpa，符合煤矿使用标准。
实施例3
A组份取聚醚多元醇210：150kg、220A：210kg和330N：440kg；聚酯多元醇AK-POL-3002：100kg；阻燃聚醚多元醇FR-7190：100kg；三乙醇胺：85kg；胺类催化剂三乙烯二胺：2.5kg；有机金属类催化剂T-12：0.6kg；阻燃剂TCPP：170kg和DMMP：50kg；乳化剂苯乙基酚聚氧乙烯醚：15kg；物理发泡剂：50kg；化学发泡剂：180kg；水：150kg。将单体料依次加入反应釜中，在温度20℃搅拌速度250r/min的条件混合3h得到的组合料。
B组份是选用烟台万华聚氨酯股份有限公司的多亚甲基多苯基异氰酸酯PM200：750kg、PM400：250kg和醋酸酯：50kg。将单体料依次加入反应釜中，在温度25℃搅拌速度240r/min的条件混合1.5小时得到的组合料。
将A组份与B组份经气动注浆泵按照体积比0.95：1的比例高速混合得到固结体。检测其性能：体系最高反应温度83℃，氧指数25，在火焰的直接作用下具有结碳、无滴落物、无熔化现象，多点取样法测得抗压强度平均值15kpa，符合煤矿使用标准。
实施例4
A组份取聚醚多元醇330N：500kg；聚酯多元醇AK-POL-3002:100kg、3152：300kg；阻燃聚醚多元醇FR-7130：100kg；泡沫胺类催化剂三乙烯二胺：1.0kg；有机金属类催化剂T-12：0.2kg；增塑剂邻苯二甲酸二丁酯：5.0kg；阻燃剂TCPP：170kg和DMMP：50kg；乳化剂苯乙基酚聚氧乙烯醚：20kg；物理发泡剂：50kg；化学发泡剂：180kg；水：200kg。将单体料依次加入反应釜中，在温度18℃搅拌速度220r/min的条件混合3小时得到的组合料。
B组份是选用烟台万华聚氨酯股份有限公司的多亚甲基多苯基异氰酸酯PM200：750kg、PM400：250kg和醋酸酯：50kg。将单体料依次加入反应釜中等单体料在温度30℃搅拌速度320r/min的条件混合1.5h得到的组合料。
将A组份与B组份经气动注浆泵按照体积比1.2：1的比例高速混合得到固结体。检测其性能：体系最高反应温度82.5℃，氧指数25，在火焰的直接作用下具有结碳、无滴落物、无熔化现象，多点取样法测得抗压强度平均值15kpa，符合煤矿使用标准。
以上是本发明的实施方式，应理解本实施例仅用于本发明的创造而用于限制本发明的范围。此外应理解，在参阅本发明讲授的内容之后，本领域的技术人员可以对本发明做各种改动或修改，这些等价形式同样修改于本发明所附于权利要求书所限定的范围。

Claims (10)

1.一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于：由双液型高分子A组份和B组份发泡而成；
所述A组份是由聚醚或聚酯多元醇及助剂组成的组合料，以重量份数计，原料组成为：
聚醚或聚酯多元醇10.0～70份
醇胺0.1～30份
阻燃剂0～40份
催化剂0.2～4份
发泡剂2.0～30份
乳化剂0.5～25份
水10～60份
所述B组份是由有机多异氰酸酯化合物为主体的组合料，以重量份数计，原料组成为：
多异氰酸酯化合物70～90份
添加剂10～30份
其使用时，A组份和B组份按照0.5～1.5：1的质量比混合浇注于待填充的区域即可。
2.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述A组分中的聚醚多元醇选取官能度不小于2，羟值为30～300mgKOH/g的聚醚多元醇中的一种或多种；所选取聚酯多元醇为羟值50～300mgKOH/g的芳香族聚酯多元醇及改性芳香族聚酯多元醇中的一种或多种。
3.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述A组分中的醇胺选取甘油、三乙醇胺、1,4丁二醇，二乙醇胺，二甘醇，三甘醇中的一种或多种。
4.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述A组分中的阻燃剂选取TCPP、TCEP、TEP、TDCPP、三（二溴丙基）磷酸酯、四（2-氯乙基）亚乙基二磷酸酯、DMMP及DEEP中的一种或多种。
5.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述A组分中的催化剂体系由胺类催化剂与有机金属类催化剂复合而成，复配比例为1：1或1：2，其中胺类催化剂选取脂肪胺类、脂环胺类、芳香胺类和醇胺类中的一种或多种；有机金属催化剂选取羧酸盐和锡、钾、铅、汞、锌、钛、铋中的一种或多种。
6.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述A组分中的发泡剂可选用化学发泡剂、物理发泡剂或二者的混合物；所选用化学发泡剂为水，物理发泡剂为二氯一氟乙烷、戊烷、五氟丙烷、二氯甲烷中的一种或多种。
7.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述A组分配方中水的用量范围在10～60wt%。
8.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述B组分中的多异氰酸酯化合物选取多苯基多异氰酸酯、异氰酸酯预聚体或碳化二亚胺改性二异氰酸酯中的一种或多种。
9.根据权利要求1所述的一种煤矿用高水含量低发热聚氨酯充填材料，其特征在于，所述B组分中的添加剂选取醋酸酯、碳酸酯、磷酸三氯丙酯中的一种或多种。
10.一种权利要求1～9任一所述的煤矿用高水含量低发热聚氨酯充填材料的制备方法，具体步骤如下：
A组分的制备：将聚醚或聚酯多元醇、醇胺、催化剂、发泡剂、乳化剂和水加入反应釜，在温度5～35℃下，搅拌速度50～400r/min的条件混合2～4h，抽样检验合格后出料，密闭包装；
B组分的制备：将多异氰酸酯及添加剂加入反应釜，在室温条件下,搅拌速度50～400r/min的条件下混合1～3h，整个操作过程为无水环境，经抽样检验合格后出料，氮气置换包装。
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