CN111777934B - 一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法 - Google Patents
一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法 Download PDFInfo
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Abstract
本发明涉及环氧氯丙烷生产废料的利用,针对环氧氯丙烷生产废料甘油沥青需作危废处置成本高的问题,提供一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,先将环氧氯丙烷生产过程中产生的精馏高沸物蒸馏得甘油沥青;然后取50份甘油沥青与10‑20份异氰酸酯、40‑50份重钙混匀后60‑100℃下搅拌反应1‑5 h,得到反应混合物;反应混合物降至50‑70℃后加入增塑剂5‑10份、填料15‑20份、助剂0.1‑2份和溶剂20‑30份搅拌均匀,出料,制得聚氨酯防水涂料。本发明将环氧氯丙烷生产废料甘油沥青用作制备聚氨酯防水涂料的主要原料,变废为宝,减少了危废处置。
Description
技术领域
本发明涉及环氧氯丙烷生产废料的利用,尤其是涉及一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法。
背景技术
甘油法生产环氧氯丙烷主要分为氯化反应和环化反应两个步骤,氯化反应时甘油和氯化氢气体在酸性催化剂作用下得到二氯丙醇。二氯丙醇往往需要精制后再进行环化反应。二氯丙醇通过精馏精制后会产生塔釜残液,根据《国家危险废物名录(2016年版)》,塔釜残液属于危险废物,若不将塔釜残液加工成其他产品,则需作危废处置,处置成本较高。此塔釜残液为精馏高沸物,蒸馏处理后会留下高沸点甘油沥青(以下简称甘油沥青),外观是黑色或暗黑色粘稠状物,闭杯闪点139℃(难燃,通过做燃烧实验,打火机明火烧灼只能液体沸腾,最后残留灰渣,液体无法点燃)。通过分析,此甘油沥青中的主要成分为缩合甘油和混合甘油脂肪酸脂。甘油沥青不能直接做为副产品进行销售,须加工成符合国标、行标或地方标准的产品才能进入市场。为降低三废处置成本,提高产品附加值,需要对甘油沥青进行综合利用。
聚氨酯防水涂料是一种性能优异的化学反应型高分子防水涂料,施工固化前为无定形液体,故有“液体橡胶”之称,施工后固化成膜,可形成一层连续、柔韧性好、无接缝的整体橡胶防水膜。该防水膜具有力学性能优异、耐磨性突出、耐化学腐蚀性好、整体防水效果佳等优点,被广泛应用于建筑物的屋面、地下室、厕浴间、沟池及化工厂地面的防潮、防水、防渗等。但是,聚氨酯防水涂料的涂刷与地面基层状况有很大关系,基层越不平整,使用的涂料就越多。在涂刷防水涂料之前,需要将基层进行处理,使基层处理平整,保证基面无尘、无土、无油,如处理不当,则会引起防水涂料的开裂掉皮,影响防水效果。据此需要对聚氨酯防水涂料进行改进。
发明内容
本发明为了克服环氧氯丙烷生产废料甘油沥青需作危废处置成本较高的问题,提供一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,将环氧氯丙烷生产废料甘油沥青用作制备聚氨酯防水涂料的主要原料,变废为宝,减少了危废处置。
为了实现上述目的,本发明采用以下技术方案:一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,包括以下步骤:
(1)将环氧氯丙烷生产过程中产生的精馏高沸物蒸馏得甘油沥青;
(2)按重量份计,取50份甘油沥青与10-20份异氰酸酯、40-50份重钙混匀后60-100℃下搅拌反应1-5h,得到反应混合物;
(3)将步骤(2)得到的混合物降温至50-70℃后,加入增塑剂5-10份、填料15-20份、助剂0.1-2份和溶剂20-30份搅拌均匀,出料,制得聚氨酯防水涂料,即可刮涂或喷涂施工。
甘油法生产环氧氯丙烷主要分为氯化反应和环化反应两个步骤,氯化反应时甘油和氯化氢气体在酸性催化剂作用下得到二氯丙醇。二氯丙醇需要精制后再进行环化反应。二氯丙醇通过精馏精制后会产生塔釜残液,塔釜残液即为步骤(1)的精馏高沸物,蒸馏后留下的残渣为甘油沥青,此甘油沥青中的主要成分为缩合甘油和混合甘油脂肪酸脂,含有大量的羟基。本发明将环氧氯丙烷生产废料甘油沥青用作制备聚氨酯防水涂料的主要原料,变废为宝,减少了危废处置。甘油沥青聚合过程中含有羟基的缩合甘油和混合甘油脂肪酸脂会参与聚合,其他杂质不会参与反应,所以甘油沥青无需提纯即可投入反应,节省成本。
作为优选,步骤(1)精馏高沸物在130-150℃下蒸馏得甘油沥青。
作为优选,步骤(2)在反应混合物中加入10-15份环氧氯丙烷在80-100℃反应2-3h。聚合生成聚氨酯时增加环氧氯丙烷作为单体,合成的聚合物中除了甘油沥青带的羟基,还增加了环氧基,使制得的聚氨酯防水涂料具有很高的粘结力和反应活性,可以适应多种材料的基层,对于略微不平整或不干净的基层,聚氨酯防水涂料也能吸附牢。
作为优选,步骤(3)的填料包括膨润土。聚氨酯防水涂料涂覆到基层后,靠空气中的湿气固化成膜,即—NCO与H2O反应生成氨基甲酸(—NHCOOH),—NHCOOH不稳定,会分解产生CO2气体,导致膜表面和截面容易产生针孔、气泡等缺陷,影响防水性。膨润土作为填料充当体架材料,增加聚氨酯防水涂料成膜后的性能。另外,膨润土具有吸水膨胀的特性,可以在接触水汽后膨胀,弥补针孔或气泡缺陷;而且,对于不平整的基层,膨润土也可以在聚氨酯防水涂料吸附牢基层的基础上朝基层的凹陷处膨胀,填充聚氨酯防水涂料和基层之间的细微空隙,增强聚氨酯防水涂料的防水性。
作为优选,步骤(3)的填料还包括改性膨润土,膨润土和改性膨润土的质量比为3:(1-2),改性膨润土由所述膨润土经过下述改性步骤得到:按重量份计,将3-4份膨润土、1份十二烷基三甲基氯化铵和60-80份去离子水混合,50-60℃、1000-2000MHz微波照射、搅拌条件下反应3-5h,抽滤分离、水洗,产物120℃下烘干、研磨得到改性膨润土。通过改性,膨润土的层间阳离子由金属阳离子变成季铵盐阳离子,表面由亲水性变成亲油性,可以吸附基层表面的油性物质,增强聚氨酯防水涂料与有油基层的结合强度。改性膨润土的表面亲油,和聚氨酯性质不同,所以改性膨润土会发生贴壁的切肤效应,向聚氨酯防水涂料的表层迁移,使得改性膨润土更容易与外界接触。而膨润土表面亲水,所以膨润土和改性膨润土配合使用充当体架材料时,对聚氨酯防水涂料的支撑更均匀。
作为优选,助剂为消泡剂、分散剂、流平剂、防沉剂、偶联剂、抗氧剂和缓凝剂中的至少一种。
作为优选,步骤(3)在出料前经过脱气步骤:在-0.09--0.1MPa的真空条件下脱气泡20-30min。搅拌过程会引入气泡,对聚氨酯防水涂料的性能有影响,所以出料前需要脱气泡。
作为优选,步骤(3)的溶剂选自甲苯或乙酸乙酯。
因此,本发明具有如下有益效果:(1)本发明将环氧氯丙烷生产废料甘油沥青用作制备聚氨酯防水涂料的主要原料,变废为宝,减少了危废处置;(2)聚合生成聚氨酯时增加环氧氯丙烷作为单体,合成的聚合物中除了甘油沥青带的羟基,还增加了环氧基,使制得的聚氨酯防水涂料具有很高的粘结力和反应活性,可以适应多种材料的基层,对于略微不平整或不干净的基层,聚氨酯防水涂料也能吸附牢;(3)作为填料的膨润土具有吸水膨胀的特性,可以在接触水汽后膨胀,弥补针孔或气泡缺陷;而且,对于不平整的基层,膨润土也可以在聚氨酯防水涂料吸附牢基层的基础上朝基层的凹陷处膨胀,填充聚氨酯防水涂料和基层之间的细微空隙,增强聚氨酯防水涂料的防水性。
具体实施方式
本发明中所用原料、设备,若无特别说明,均为本领域的常用原料、设备;本发明中所用方法,若无特别说明,均为本领域的常规方法。
下面结合具体实施方式对本发明做进一步的描述。
实施例1
一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,包括以下步骤:
(1)取甘油法生产环氧氯丙烷在氯化反应阶段的产物二氯丙醇精馏精制后产生的精馏高沸物,140℃下蒸馏得到高沸点的甘油沥青;
(2)按重量份计,取50份甘油沥青与10份异氰酸酯、40份重钙混匀后70℃下搅拌反应3h,然后加入15份环氧氯丙烷在100℃反应2h,得到反应混合物;
(3)将反应混合物降温至50℃后,加入增塑剂邻苯二甲酸二丁酯8份、填料石英粉20份、助剂聚二甲基硅氧烷消泡剂0.1份和溶剂甲苯30份搅拌均匀,出料,制得聚氨酯防水涂料,即可刮涂或喷涂施工。
实施例2
(1)取甘油法生产环氧氯丙烷在氯化反应阶段的产物二氯丙醇精馏精制后产生的精馏高沸物,130℃下蒸馏得到高沸点的甘油沥青;
(2)按重量份计,取50份甘油沥青与20份异氰酸酯、50份重钙混匀后60℃下搅拌反应5h,然后加入10份环氧氯丙烷在90℃反应2h,得到反应混合物;
(3)将反应混合物降温至60℃后,加入增塑剂邻苯二甲酸丁苄酯5份、填料膨润土17份、助剂异佛尔酮流平剂0.1份和溶剂乙酸乙酯20份搅拌均匀,在-0.09MPa的真空条件下脱气泡30min,出料,制得聚氨酯防水涂料,即可刮涂或喷涂施工。
实施例3
(1)取甘油法生产环氧氯丙烷在氯化反应阶段的产物二氯丙醇精馏精制后产生的精馏高沸物,150℃下蒸馏得到高沸点的甘油沥青;
(2)按重量份计,取50份甘油沥青,取50份脱水甘油沥青与15份异氰酸酯、45份重钙混匀后100℃下搅拌反应1h,然后加入12份环氧氯丙烷在80℃反应3h,得到反应混合物;
(3)将反应混合物降温至70℃后,加入增塑剂邻苯二甲酸二丁酯10份、填料膨润土和改性膨润土共15份、助剂聚丙烯酰胺分散剂2份和溶剂甲苯25份搅拌均匀,出料,制得聚氨酯防水涂料,即可刮涂或喷涂施工。其中膨润土和改性膨润土的质量比为3:1,改性膨润土由膨润土经过下述改性步骤得到:按重量份计,将3份膨润土、1份十二烷基三甲基氯化铵和70份去离子水混合,50℃、2000MHz微波照射、搅拌条件下反应3h,抽滤分离、水洗,产物烘干、研磨得到改性膨润土。
实施例4
同实施例3,区别在于膨润土和改性膨润土的质量比为3:2,改性膨润土的改性:按重量份计,将4份膨润土、1份十二烷基三甲基氯化铵和80份去离子水混合,55℃、1000MHz微波照射、搅拌条件下反应5h,抽滤分离、水洗,产物烘干、研磨得到改性膨润土。
实施例5
同实施例3,区别在于改性膨润土的改性:按重量份计,将3.5份膨润土、1份十二烷基三甲基氯化铵和60份去离子水混合,60℃、1500MHz微波照射、搅拌条件下反应4h,抽滤分离、水洗,产物烘干、研磨得到改性膨润土。
实施例6
同实施例1,区别在于步骤(2)为:按重量份计,取50份脱水甘油沥青与10份异氰酸酯、40份重钙混匀后70℃下搅拌反应3h得到反应混合物。
性能测试
将实施例1-6分别涂覆于聚苯乙烯材料表面,涂覆厚度均为3cm,涂覆面积为5cm×5cm,聚苯乙烯材料表面经过不同的处理。分别测试实施例1-6的剥离强度(单位N/cm),结果如下表所示:
由上表可知,实施例1相对于实施例6增加了环氧氯丙烷单体共聚形成聚氨酯,环氧基大大提高了聚氨酯防水涂料与基层的粘合力。对于表面平整、干净的基层,实施例1-5的剥离强度区别不是很大,只是聚氨酯防水涂料涂覆到基层后可能导致膜表面和截面容易产生针孔、气泡等缺陷,影响防水性,而膨润土具有吸水膨胀的特性,可以在接触水汽后膨胀,弥补针孔或气泡缺陷,所以实施例2-5的剥离强度会略高于实施例1。但是当表面不平整时,实施例2-5利用膨润土的优势体现出来,膨润土有朝凹坑膨胀的趋势,可以增强聚氨酯防水涂料涂和基层的粘结力,剥离强度均远优于未使用膨润土的实施例1。实际中一般不会使用有1mm凹坑的基层,本测试只是为了使对比效果更明显而设计的。当基层表面有油污时,有改性膨润土的实施例3-5剥离强度又优于实施例2,因为改性膨润土的表面亲油,可以吸附油污,增加聚氨酯防水涂料涂通过羟基、甲氧基和基层连接的接触点,提高剥离强度。另外实施例3-5同时利用膨润土和改性膨润土,比实施例2单独使用膨润土,得到的聚氨酯防水涂料强度更高。
通过上述比较可以看出本发明明显提高了环氧树脂改性聚氨酯防水涂料对非极性基材的粘附力,扩大了该防水涂料的应用范围。
以上所述,仅是本发明的较佳实施例,并非对本发明作任何限制,凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换,均仍属于本发明技术方案的保护范围。
Claims (5)
1.一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,包括以下步骤:
(1)甘油法生产环氧氯丙烷在氯化反应阶段的产物二氯丙醇精馏精制后产生的精馏高沸物,在130-150 ℃下蒸馏得到高沸点的甘油沥青;
(2)按重量份计,取50份脱水甘油沥青与10-20份异氰酸酯、40-50份重钙混匀后60-100℃下搅拌反应1-5 h,得到反应混合物;
(3)将步骤(2)得到的混合物降温至50-70 ℃后,加入增塑剂5-10份、填料15-20份、助剂0.1-2份和溶剂20-30份搅拌均匀,出料,制得聚氨酯防水涂料,刮涂或喷涂施工;所述填料包括膨润土和改性膨润土,膨润土和改性膨润土的质量比为3:(1-2),改性膨润土由膨润土经过下述改性步骤得到:按重量份计,将3-4份膨润土、1份十二烷基三甲基氯化铵和60-80份去离子水混合,50-60 ℃、1000-2000 MHz微波照射、搅拌条件下反应3-5 h,抽滤分离、水洗,产物烘干、研磨得到改性膨润土。
2.根据权利要求1所述的一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,其特征在于,步骤(2)在反应混合物中加入10-15份环氧氯丙烷在80-100 ℃反应2-3 h。
3.根据权利要求1所述的一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,其特征在于,助剂为消泡剂、分散剂、流平剂、防沉剂、偶联剂、抗氧剂和缓凝剂中的至少一种。
4.根据权利要求1所述的一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,其特征在于,步骤(3)在出料前经过脱气步骤:在-0.09 - -0.1 MPa的真空条件下脱气泡20-30 min。
5.根据权利要求1-4任一所述的一种环氧氯丙烷生产过程中精馏产生的高沸点甘油沥青的利用方法,其特征在于,步骤(3)的溶剂选自甲苯或乙酸乙酯。
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