CN109517514B - 一种石墨烯改性抗穿刺重防腐喷涂材料及其制备方法 - Google Patents
一种石墨烯改性抗穿刺重防腐喷涂材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种石墨烯改性抗穿刺重防腐喷涂材料及其制备方法,该材料包括主剂A组分和辅剂B组分,A组分与B组分质量比为1:1;其中,A组分由包括如下重量份数的原料制成:二苯基甲烷二异氰酸酯,异佛尔酮二异氰酸酯,2,2,4‑三甲基己二异氰酸酯,端氨基聚醚二元醇,聚醚多元醇,聚碳酸酯二元醇;B组分由包括如下重量份数的原料制成:抗氧化剂,胺扩链剂,N,N,‑二烷基甲基二胺,DETDA,端氨基聚醚多元醇,活性纳米石墨烯因子,纳米二氧化钛,煅烧高岭土,纳米二氧化硅,滑石粉,沉淀硫酸钡,氧化锌,消泡剂,分散剂。该材料延长了管廊、管线使用寿命,增加了植被根系的抗穿刺性能,防止了因外界环境造成的腐蚀及其渗漏。
Description
技术领域
本发明属于防腐材料技术领域,尤其是涉及一种石墨烯改性抗穿刺重防腐喷涂材料及其制备方法。
背景技术
随着国民社会经济的迅猛发展,立足于城市建设的理念不断兴起,不同城市都有其特色化的东西和建设存在,日益发生着翻天覆地的变化,随着城市现代化和信息化的建设发展,市政建设可能还存在少许落后的方式与社会发展方向相互无法协调,不能紧跟城市化快速发展的脚步。故市政建设中的地下管网建设、市政市政管线设施建设、市政管廊建设等能更好的满足城市交通、城市景观的发展需求。
目前,应用于地下管网、市政管线和市政管廊上的防腐材料在制备过程中大多会引入含有VOCS以及重金属离子的原料,使整个生产过程会产生对环境有危害的物质排出。而且,现有市政管线等大多都是埋设在低下,往往会出现植被根系对管线穿刺,造成管线渗漏;同时,现有的市政管线等应用的防腐材料的防腐效果一般,经常会发生管线的腐蚀,从而降低了这些管线的使用寿命。
发明内容
有鉴于此,本发明旨在提出一种耐腐蚀、耐穿刺且抗渗透的石墨烯改性抗穿刺重防腐喷涂材料及其制备方法。
为达到上述目的,本发明的技术方案是这样实现的:
一种石墨烯改性抗穿刺重防腐喷涂材料,包括主剂A组分和辅剂B组分,A组分与B组分质量比为1:1;
其中,A组分由包括如下重量份数的原料制成:
B组分由包括如下重量份数的原料制成:
进一步,所述端氨基聚醚二元醇的官能度f=2,分子量M=2000-4000;
所述聚醚多元醇的官能度f=2-3,分子量M=1000-6000;
所述聚碳酸酯二元醇的官能度f=2,分子量M=2000。
进一步,所述端氨基聚醚多元醇为端氨基聚醚多元醇1、端氨基聚醚多元醇2、端氨基聚醚多元醇3和端氨基聚醚多元醇4;
其中,所述端氨基聚醚多元醇1的官能度f=2,分子量M=1000-3000,重量份数为20-50;
所述端氨基聚醚多元醇2的官能度f=2,分子量M=1000-2000,重量份数为15-30份;
所述端氨基聚醚多元醇3的官能度f=2,分子量M=200-1000,重量份数为1-5份;
所述端氨基聚醚多元醇4的官能度f=3,分子量M=2000-5000,重量份数为1-10份。
进一步,所述抗氧化剂为Zrganox245或抗氧剂Zrganox1076中的一种或两种;
所述胺扩链剂为TX-2;
所述消泡剂为BYK-141;
所述分散剂为BYK-183。
进一步,所述活性纳米石墨烯因子由包括如下步骤的方法制备得到:将石墨烯与端氨基聚醚多元醇搅拌混合,石墨烯和端氨基聚醚多元醇的质量比为1:20,并在混合过程中加入消泡剂以及配方量2/3的分散剂,之后将该混合浆料导入纳米研磨机研磨备用。
进一步,所述搅拌条件是:1200-1800r/min下搅拌60min,研磨的条件是:研磨8-10h直至粒径≤10nm。
本发明还提供了一种上述的石墨烯改性抗穿刺重防腐喷涂材料的制备方法,该方法包括如下步骤:
A、制备A组分:
(1)将端氨基聚醚二元醇、聚醚多元醇、聚碳酸酯二元醇分别脱水;
(2)向脱水后的聚醚多元醇、聚碳酸酯二元醇加入二苯基甲烷二异氰酸酯并搅拌;之后加入2,2,4-三甲基己二异氰酸酯并搅拌;
(3)向所述步骤(2)得到的产物中加入端氨基聚醚二元醇,并搅拌;之后在0-10℃的温度下将异佛尔酮二异氰酸酯滴加其中;
(4)测量反应后得到的浅黄色至无色透明液体的NCO含量,之后脱气、降温、密封保存;
B、制备B组分:
(1)活性纳米石墨烯因子的制备:将石墨烯与端氨基聚醚多元醇搅拌混合,石墨烯和端氨基聚醚多元醇的质量比为1:20,并在混合过程中加入消泡剂以及配方量2/3的分散剂,之后将该混合浆料导入纳米研磨机研磨备用;
(2)将抗氧化剂和与抗氧剂等量的端氨基聚醚多元醇共同加热溶解后备用;
(3)将煅烧高岭土、纳米二氧化钛、纳米二氧化硅、滑石粉、沉淀硫酸钡、氧化锌、配方量1/3的分散剂和端氨基聚醚多元醇搅拌混合,其中,端氨基聚醚多元醇的用量与煅烧高岭土、纳米二氧化钛、纳米二氧化硅、滑石粉、沉淀硫酸钡、氧化锌和分散剂的用量相等,之后加入纳米研磨机中研磨备用;
(4)将所述步骤(2)得到的混合物、胺扩链剂、N,N,-二烷基甲基二胺、DETDA和剩余的端氨基聚醚多元醇混合均匀;
(5)将所述步骤(3)得到的浆料加入到所述步骤(4)的混合液中混合均匀;
(6)将所述步骤(1)得到的活性纳米石墨烯因子加入到所述步骤(5)的混合液中混合均匀;
(7)向所述步骤(6)得到的液体抽真空,出料密封保存;
C、按配方比例混合A组分和B组分即可得到所述防腐喷涂材料。
进一步,所述A组分制备方法中,所述步骤(1)脱水的条件是:-0.1MPa、真空、110℃脱水2-3h;
所述步骤(2)中,加入二苯基甲烷二异氰酸酯的反应条件是:先反应20min后将温度升至80±5℃反应再3h,加入2,2,4-三甲基己二异氰酸酯的反应条件是:80±5℃反应0.5h。
进一步,所述A组分制备方法中,所述步骤(3)滴加完异佛尔酮二异氰酸酯后,将温度升至30±5℃反应30min,后将温度升至70±5℃保温5h后出料。
进一步,所述B组分制备方法中,所述步骤(1)中搅拌的条件是:1200-1800r/min下搅拌60min,研磨的条件是:研磨8-10h直至粒径≤10nm;
所述步骤(2)中的搅拌的条件是:800r/min下搅拌120min,研磨的条件是:研磨至粒径≤15nm;
所述步骤(5)中所述步骤(3)得到的浆料在400-500r/min下加入;
所述步骤(6)中活性纳米石墨烯因子在800r/min的条件下匀速加入;
所述步骤(7)中在50±5℃的条件下抽真空2h,使真空度达到-0.1MPa。
相对于现有技术,本发明所述的石墨烯改性抗穿刺重防腐喷涂材料及其制备方法具有以下优势:
1、本发明所述的石墨烯改性抗穿刺重防腐喷涂材料在传统的HSPT喷涂材料的基础上,在材料本体上引入大分子量聚醚多元醇,而大分子量的聚醚多元醇会使材料的硬度下降,断裂延伸率增加,整体的弹性变好,从而增加材料体系整体的柔顺性,也因此增加材料的抗穿刺性能。同时,利用纳米石墨烯因子对其进行化学改性,以此增加材料的综合机械性能以及重防腐性能。由于考虑到现今社会对环保性的特殊要求,故本材料的制备全过程均采用高固体分原材料进行合成,制备过程中不会引入任何含有VOCS以及重金属离子的原料,整个生产过程没有对环境有危害的物质排出。本发明所述的石墨烯改性抗穿刺重防腐喷涂材料延长了管廊、管线体系的使用寿命,增加了植被根系的抗穿刺性能,防止了因外界环境造成的腐蚀及其渗漏,降低道路建设及养护成本,节约社会资源。
2、本发明的所述A组分中加入端氨基聚醚二元醇、聚醚多元醇和聚碳酸酯二元醇,主要作用是增加材料本身的柔顺性,进而达到刚柔并进的效果。
3、本发明的所述B组分中的端氨基聚醚多元醇采用不同品种,增加体系的柔顺性。端氨基聚醚多元醇2主要增加材料的防腐性能,端氨基聚醚多元醇3和端氨基聚醚多元醇4主要增加材料的韧性,端氨基聚醚多元醇1主要增加材料的弹性。
4、本发明所采用的活性纳米石墨烯因子主要增加材料的机械性能、防腐性能和抗穿刺性能;纳米二氧化钛、纳米二氧化硅主要增加材料的机械性能和耐候性能;煅烧高岭土属于颜填料,主要增加材料的白度以及遮盖力;滑石粉属于填料,主要作用是抗粉化且降低成本;沉淀硫酸钡、氧化锌主要增加防腐性能。
具体实施方式
需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
下面将结合实施例来详细说明本发明。
实施例1
一种石墨烯改性抗穿刺重防腐喷涂材料,包括主剂A组分和辅剂B组分A组分与B组分质量比为1:1;
其中,A组分由包括如下重量份数的原料制成:
制得的A组分的异氰酸集团含量为17.00%。
B组分由包括如下重量份数的原料制成:
实施例2
一种石墨烯改性抗穿刺重防腐喷涂材料,包括主剂A组分和辅剂B组分A组分与B组分质量比为1:1;
其中,A组分由包括如下重量份数的原料制成:
制得的A组分的异氰酸集团含量为18.8%。
B组分由包括如下重量份数的原料制成:
实施例3
一种石墨烯改性抗穿刺重防腐喷涂材料,包括主剂A组分和辅剂B组分A组分与B组分质量比为1:1;
其中,A组分由包括如下重量份数的原料制成:
制得的A组分的异氰酸集团含量为14.00%。
B组分由包括如下重量份数的原料制成:
实施例1-3所述的石墨烯改性抗穿刺重防腐喷涂材料的制备方法,该方法包括如下步骤:
A、制备A组分:
(1)将端氨基聚醚二元醇、聚醚多元醇、聚碳酸酯二元醇分别在-0.1MPa、真空、110℃脱水2-3h;
(2)脱水后的聚醚多元醇、聚碳酸酯二元醇温度降至50±5℃时,加入二苯基甲烷二异氰酸酯反应20min后将温度升至80±5℃反应3h;之后加入2,2,4-三甲基己二异氰酸酯80±5℃反应0.5h后备用;
(3)向所述步骤(2)得到的产物中加入端氨基聚醚二元醇,并搅拌;之后在0-10℃的温度下将异佛尔酮二异氰酸酯滴加其中,注意滴加全程注意温升情况,待滴加完毕后,将温度慢慢升至30±5℃反应30min,后将温度升至70±5℃保温5h后出料备用;
(4)取样分析反应后得到的浅黄色至无色透明液体的NCO含量达到理论值后,脱气,降温分装密封保存;其中,NCO含量即是异氰酸基团含量,本材料NCO含量理论值≤20%(质量百分数)。
B、制备B组分:
(1)活性纳米石墨烯因子的制备:将石墨烯与任一种端氨基聚醚多元醇在200-1800r/min下搅拌分散60min,石墨烯和端氨基聚醚多元醇的质量比为1:20,并在混合过程中加入消泡剂以及配方量2/3的分散剂,之后将该混合浆料导入纳米研磨机研磨8-10h,直至粒径≤10nm备用;
(2)将抗氧化剂和与抗氧剂等量的端氨基聚醚多元醇1共同加热溶解后备用;
(3)将煅烧高岭土、纳米二氧化钛、纳米二氧化硅、滑石粉、沉淀硫酸钡、氧化锌、配方量1/3的分散剂和端氨基聚醚多元醇1在800r/min下搅拌分散120min,其中,端氨基聚醚多元醇1的用量与煅烧高岭土、纳米二氧化钛、纳米二氧化硅、滑石粉、沉淀硫酸钡、氧化锌和分散剂的用量相等,之后加入纳米研磨机中研磨至粒径≤15nm备用;
(4)将所述步骤(2)得到的混合物、胺扩链剂、N,N,-二烷基甲基二胺、DETDA和剩余的端氨基聚醚多元醇1以及其他3种端氨基聚醚多元醇混合均匀;
(5)将所述步骤(3)得到的浆料在400-500r/min的条件下加入到所述步骤(4)的混合液中混合均匀;
(6)将所述步骤(1)得到的活性纳米石墨烯因子在800r/min的条件下加入到所述步骤(5)的混合液中混合均匀;
(7)向所述步骤(6)得到的液体在50±5℃的条件下抽2h真空,真空度为-0.1MPa,出料密封保存;
C、按配方比例混合A组分和B组分即可得到所述防腐喷涂材料。
将实施例1-3得到的3种材料在标准环境下用喷涂机喷涂制件,喷涂的厚度为1.5±0.2mm,在标准环境下养护168h后测性能如下表1-3。
表1实施例1得到的防腐喷涂材料的测试性能
表2实施例2得到的防腐喷涂材料的测试性能
表3实施例3得到的防腐喷涂材料的测试性能
对比例:
在实施例1的基础上A组分不添加端氨基聚醚二元醇、聚醚多元醇和聚碳酸酯二元醇,B组分不添加端氨基聚醚多元醇和活性纳米石墨烯因子,并对最终得到的材料进行性能测试,如下表。
表4对比例得到的防腐涂料材料的测试性能
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的石墨烯改性抗穿刺重防腐喷涂材料,其特征在于:所述端氨基聚醚二元醇的官能度f=2,分子量M=2000-4000;所述聚醚多元醇的官能度f=2-3,分子量M=1000-6000;所述聚碳酸酯二元醇的官能度f=2,分子量M=2000。
3.根据权利要求1所述的石墨烯改性抗穿刺重防腐喷涂材料,其特征在于:所述端氨基聚醚多元醇为端氨基聚醚多元醇1、端氨基聚醚多元醇2、端氨基聚醚多元醇3和端氨基聚醚多元醇4;其中,所述端氨基聚醚多元醇1的官能度f=2,分子量M=1000-3000,重量份数为20-50;所述端氨基聚醚多元醇2的官能度f=2,分子量M=1000-2000,重量份数为15-30份;所述端氨基聚醚多元醇3的官能度f=2,分子量M=200-1000,重量份数为1-5份;所述端氨基聚醚多元醇4的官能度f=3,分子量M=2000-5000,重量份数为1-10份。
4.根据权利要求1所述的石墨烯改性抗穿刺重防腐喷涂材料,其特征在于:所述抗氧化剂为Zrganox245或抗氧剂Zrganox1076中的一种或两种;所述胺扩链剂为TX-2;所述消泡剂为BYK-141;所述分散剂为BYK-183。
5.根据权利要求1所述的石墨烯改性抗穿刺重防腐喷涂材料,其特征在于:所述活性纳米石墨烯因子由包括如下步骤的方法制备得到:将石墨烯与端氨基聚醚多元醇搅拌混合,石墨烯和端氨基聚醚多元醇的质量比为1:20,并在混合过程中加入消泡剂以及配方量2/3的分散剂,之后将该混合浆料导入纳米研磨机研磨备用。
6.根据权利要求5所述的石墨烯改性抗穿刺重防腐喷涂材料,其特征在于:所述搅拌条件是:1200-1800r/min下搅拌60min,研磨的条件是:研磨8-10h直至粒径≤10nm。
7.一种权利要求1-6任一项所述的石墨烯改性抗穿刺重防腐喷涂材料的制备方法,其特征在于:该方法包括如下步骤:
A、制备A组分:
(1)将端氨基聚醚二元醇、聚醚多元醇、聚碳酸酯二元醇分别脱水;
(2)向脱水后的聚醚多元醇、聚碳酸酯二元醇加入二苯基甲烷二异氰酸酯并搅拌;之后加入2,2,4-三甲基己二异氰酸酯并搅拌;
(3)向所述步骤(2)得到的产物中加入端氨基聚醚二元醇,并搅拌;之后在0-10℃的温度下将异佛尔酮二异氰酸酯滴加其中;
(4)测量反应后得到的浅黄色至无色透明液体的NCO含量,之后脱气、降温、密封保存;
B、制备B组分:
(1)活性纳米石墨烯因子的制备:将石墨烯与端氨基聚醚多元醇搅拌混合,石墨烯和端氨基聚醚多元醇的质量比为1:20,并在混合过程中加入消泡剂以及配方量2/3的分散剂,之后将该混合浆料导入纳米研磨机研磨备用;
(2)将抗氧化剂和与抗氧剂等量的端氨基聚醚多元醇共同加热溶解后备用;
(3)将煅烧高岭土、纳米二氧化钛、纳米二氧化硅、滑石粉、沉淀硫酸钡、氧化锌、配方量1/3的分散剂和端氨基聚醚多元醇搅拌混合,其中,端氨基聚醚多元醇的用量与煅烧高岭土、纳米二氧化钛、纳米二氧化硅、滑石粉、沉淀硫酸钡、氧化锌和分散剂的用量相等,之后加入纳米研磨机中研磨备用;
(4)将所述步骤(2)得到的混合物、胺扩链剂、N,N,-二烷基甲基二胺、DETDA和剩余的端氨基聚醚多元醇混合均匀;
(5)将所述步骤(3)得到的浆料加入到所述步骤(4)的混合液中混合均匀;
(6)将所述步骤(1)得到的活性纳米石墨烯因子加入到所述步骤(5)的混合液中混合均匀;
(7)向所述步骤(6)得到的液体抽真空,出料密封保存;
C、按配方比例混合A组分和B组分即可得到所述防腐喷涂材料。
8.根据权利要求7所述的石墨烯改性抗穿刺重防腐喷涂材料的制备方法,其特征在于:所述A组分制备方法中,所述步骤(1)脱水的条件是:-0.1MPa、真空、110℃脱水2-3h;所述步骤(2)中,加入二苯基甲烷二异氰酸酯的反应条件是:先反应20min后将温度升至80±5℃反应再3h,加入2,2,4-三甲基己二异氰酸酯的反应条件是:80±5℃反应0.5h。
9.根据权利要求7所述的石墨烯改性抗穿刺重防腐喷涂材料的制备方法,其特征在于:所述A组分制备方法中,所述步骤(3)滴加完异佛尔酮二异氰酸酯后,将温度升至30±5℃反应30min,后将温度升至70±5℃保温5h后出料。
10.根据权利要求7所述的石墨烯改性抗穿刺重防腐喷涂材料的制备方法,其特征在于:所述B组分制备方法中,所述步骤(1)中搅拌的条件是:1200-1800r/min下搅拌60min,研磨的条件是:研磨8-10h直至粒径≤10nm;所述步骤(2)中的搅拌的条件是:800r/min下搅拌120min,研磨的条件是:研磨至粒径≤15nm;所述步骤(5)中所述步骤(3)得到的浆料在400-500r/min下加入;所述步骤(6)中活性纳米石墨烯因子在800r/min的条件下匀速加入;所述步骤(7)中在50±5℃的条件下抽真空2h,使真空度达到-0.1MPa。
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