CN107522845A - 一种聚天门冬氨酸酯脲胶黏剂及其施工工艺 - Google Patents

一种聚天门冬氨酸酯脲胶黏剂及其施工工艺 Download PDF

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CN107522845A
CN107522845A CN201710774758.4A CN201710774758A CN107522845A CN 107522845 A CN107522845 A CN 107522845A CN 201710774758 A CN201710774758 A CN 201710774758A CN 107522845 A CN107522845 A CN 107522845A
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薛隽
鲁晓东
邬茳
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Shenzhen Flying Wing Chun Research New Material Ltd By Share Ltd
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Abstract

本发明公开了一种聚天门冬氨酸酯脲胶黏剂及其施工工艺,该胶黏剂由主剂和固化剂组成,主剂与固化剂的当量比为1:0.9‑1.1,以重量份计,主剂由80‑90份聚天门冬氨酸酯树脂、2‑5份噁唑烷吸收剂、8‑12份分子筛、0.1‑0.5份消泡剂、0.1‑0.5份基材润湿剂组成。胶黏剂中不含有游离TDI等毒性成分,同时不含有有机溶剂和邻苯二甲酸酯类增塑剂,属于无溶剂体系,不含有重金属,绿色环保,无毒无害,同时该胶黏剂还具有良好的物理性能:耐候性能良好,不易变色,拉伸强度、断裂伸长率高、回弹性良好,易于施工,其可操作性和物理性能与常规的聚氨酯胶黏剂相当,兼具了优异的环保安全性和物理特性。制备工艺流程简单、条件温和,施工性能良好,易于涂布,适宜于批量化工业生产。

Description

一种聚天门冬氨酸酯脲胶黏剂及其施工工艺
技术领域
本发明属于胶黏剂生产技术领域,具体地说涉及一种用于透水型塑胶跑道的聚天门冬氨酸酯脲胶黏剂及其施工工艺。
背景技术
随着人们生活水平的日渐提高,休闲运动越来越受到大家的喜爱,塑胶跑道由于平整度好、硬度弹性适中、有利于运动人员速度和技术的发挥,也能降低摔伤率,因而广泛应用于各类学校及体育场、全民健身路径、游乐场道路铺面、室内外跑道、球场、公园、居民小区等活动场地。
塑胶跑道一般由合成材料铺装而成,主要制作方法是利用单组份潮气固化聚氨酯胶水混合三元乙丙橡胶(EPDM)颗粒,满铺成厚度为10mm左右的弹性层,作为制备弹性塑胶跑道的主要工艺步骤,最后还会在弹性层表面施工一层保护面漆。其中弹性层所使用胶水的品质优劣直接决定了整个塑胶跑道的使用性能,更重要的是决定了塑胶跑道的安全性、是否无毒环保。
目前塑胶跑道用胶水一般由二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)和聚醚多元醇的预聚物与大量增塑剂混合制得,但是以常规的生产工艺,塑胶跑道中存在超标量游离的TDI,难以去除,而TDI是一类毒性很强的化学物质,是产生毒跑道的一个重要因素,而在生产过程中加入的增塑剂也是一类潜在的有害物质,目前使用最多的是邻苯二甲酸脂类物质,其存在容易迁移到涂层表面且其本身具有毒性的问题,同时受光照后易降解,会产生复杂的有毒有害烟气成分。对于这种常用的塑胶跑道用胶水,其具备良好的回弹性、伸长率、拉伸强度等使用性能;另一方面,环保性能上,一般只能尽量降低这两类有害原料的含量,将其控制在一个相对安全的水平,但是无法完全杜绝其毒害风险。
发明内容
为此,本发明所要解决的技术问题在于现有塑胶跑道用胶水存在有毒有害成分、安全环保性能差,从而提出一种兼具优异的物理性能和环保安全性能的用于透水型塑胶跑道的聚天门冬氨酸酯脲胶黏剂及其施工工艺。
为解决上述技术问题,本发明的技术方案为:
本发明提供一种聚天门冬氨酸酯脲胶黏剂,其由主剂和固化剂组成,所述主剂与固化剂的当量比为1:0.9-1.1,以重量份计,所述主剂由80-90份聚天门冬氨酸酯树脂、2-5份吸收剂、8-12份分子筛、0.1-0.5份消泡剂、0.1-0.5份基材润湿剂组成。
作为优选,所述固化剂由HDI三聚体、HDI酮二脲和羟基树脂改性固化剂组成,所述HDI三聚体、HDI酮二脲和羟基树脂改性固化剂的质量比为1-3:1-2:4-6。
作为优选,所述羟基树脂改性固化剂为聚醚多元醇或聚酯多元醇与IPDI、HMDI、HDI中的一种或多种预聚反应得到的NCO含量在3-12%的树脂改性固化剂。
作为优选,所述聚天门冬氨酸酯树脂为N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四乙酯、N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四丁酯、N,N'-(亚甲基二-(1-甲基-4,1-环己烷二基))二天冬氨酸四乙酯、N,N'-(聚氧(甲基-1,2-亚乙基)二基)二天冬氨酸四乙酯中的一种或多种。
作为优选,所述羟基树脂改性固化剂采用如下工艺制备:将聚醚多元醇、聚酯多元醇、聚己内酯中的一种与IPDI、HMDI、HDI中的一种在60℃下反应5h,然后升温至90℃,反应4h后降温至50℃,测定NCO含量降至符合设计要求,即得羟基树脂改性固化剂。
本发明还提供一种所述的天冬聚脲胶黏剂的施工工艺,其包括如下步骤:将主剂与固化剂按照当量比1:0.9-1.1的比例混合均匀,得到胶黏剂,向所述胶黏剂中加入三元乙丙橡胶颗粒,得到涂布混合物,然后将所述涂布混合物在跑道基面上涂布10-15mm。
作为优选,所述胶黏剂与所述三元乙丙橡胶颗粒的质量比为1:6-10。
本发明的上述技术方案相比现有技术具有以下优点:
(1)本发明所述的聚天门冬氨酸酯脲胶黏剂,其由主剂和固化剂组成,所述主剂与固化剂的当量比为1:0.9-1.1,以重量份计,所述主剂由80-90份聚天门冬氨酸酯树脂、2-5份吸收剂、8-12份分子筛、0.1-0.5份消泡剂、0.1-0.5份基材润湿剂组成。主剂中不含有机溶剂和邻苯二甲酸酯类增塑剂,属于无溶剂体系,也不含有重金属,绿色环保,无毒无害;同时该胶黏剂还具有良好的物理性能:耐候性能良好,不易变色,拉伸强度、断裂伸长率高、回弹性良好,易于施工,其可操作性和物理性能与常规的聚氨酯胶黏剂相当,兼具了优异的环保安全性和物理特性。
(2)本发明所述的聚天门冬氨酸酯脲胶黏剂,所述固化剂由HDI三聚体、HDI酮二脲和羟基树脂改性固化剂组成,所述HDI三聚体、HDI酮二脲和羟基树脂改性固化剂的质量比为1-3:1-2:4-6,用HMDI或者IPDI单体替换TDI、MDI单体制备羟基树脂改性固化剂,避免了游离TDI的挥发毒性,采用低粘度天冬树脂N,N'-(聚氧(甲基-1,2-亚乙基)二基)二天冬氨酸四乙酯降低体系粘度,确保具备合适的施工粘度的同时,避免了采用有机溶剂和领苯二甲酸酯类增塑剂,安全环保。另外N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四乙酯具备较快的反应速度和很好的粘结强度,而树脂改性的IPDI固化剂反应速度较慢,与反应快速的HDI三聚体搭配使用,可以调节合适的可使用时间。
(3)本发明所述的聚天门冬氨酸酯脲胶黏剂的施工工艺,主剂和固化剂制备工艺流程简单,操作方便,条件温和,适宜于批量化工业生产。聚天门冬氨酸酯脲胶黏剂施工性能良好,易于涂布,固化干燥时间短、可使用时间长,操作性与聚氨酯胶黏剂一致。
具体实施方式
为了使本发明的内容更容易被清楚的理解,下面根据本发明的具体实施例对本发明作进一步详细的说明。
实施例1
本实施例提供一种双组份聚天门冬氨酸酯脲胶黏剂,所述胶黏剂由主剂和固化剂组成,二者当量比为1:1.1,其中以重量份计,所述主剂组分如下:
N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四乙酯 47.5份;
N,N'-(聚氧(甲基-1,2-亚乙基)二基)二天冬氨酸四乙酯 40份;
噁唑烷吸收剂 3份;
A3分子筛 10份;
消泡剂BYK085(毕克化学) 0.3份;
润湿剂BorchiGol1375(欧蒽吉) 0.2份;
以重量份计,所述固化剂组分如下:
拜耳三聚体N3900 30份;
拜耳酮二脲N3400 20份;
羟基改性固化剂1# 50份;
三者质量比为3:2:5。
其中,羟基改性固化剂1#制备方法如下:
羟基树脂改性固化剂为聚醚多元醇与IPDI预聚反应得到的NCO含量在3-12%的树脂改性固化剂,其制备工艺如下:将100gIPDI反应釜中,加热到60℃,滴加PPG-2000树脂453g,保温反应5h,慢慢升高温度到90℃下反应4h,测定NCO含量降低至3.45%,降温到50℃出料,即得羟基树脂改性固化剂。
本实施例还提供一种所述的聚天门冬氨酸酯脲胶黏剂的施工工艺,其包括如下步骤:将主剂与固化剂按照当量比1:1.1的比例混合均匀,得到胶黏剂,向所述胶黏剂中加入三元乙丙橡胶颗粒,胶黏剂与所述三元乙丙橡胶颗粒的质量比为1:6,得到涂布混合物,然后将所述涂布混合物在跑道基面上铺设12mm,即完成施工。
实施例2
本实施例提供一种双组份聚天门冬氨酸酯脲胶黏剂,所述胶黏剂由主剂和固化剂组成,二者当量比为1:1,其中以重量份计,所述主剂组分如下
N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四丁酯 55份;
N,N'-(聚氧(甲基-1,2-亚乙基)二基)二天冬氨酸四乙酯 30份;
噁唑烷吸收剂 3份;
消泡剂BYK085(毕克化学) 0.4份;
基材润湿剂Borchi Gol 1375(欧蒽吉) 0.3份;
A3分子筛 11.6份。
以重量份计,所述固化剂组分如下:
拜耳三聚体N3900 20份;
拜耳酮二脲N3400 17份;
羟基改性固化剂2# 53份;
三者质量比为2:1.7:5.3。
其中,羟基改性固化剂制备方法如下:
羟基树脂改性固化剂为聚醚多元醇与HMDI预聚反应得到的NCO含量在3-12%的树脂改性固化剂,其制备工艺如下:将100gHMDI反应釜中,加热到60℃,滴加PPG-2000树脂249g,保温反应5h,慢慢升高温度到90℃下反应4h,测定NCO含量降低至5.1%,降温到50℃出料,即得羟基树脂改性固化剂。
本实施例还提供一种所述的聚天门冬氨酸酯脲胶黏剂的施工工艺,其包括如下步骤:将主剂与固化剂按照质量比1:1的比例混合均匀,得到胶黏剂,向所述胶黏剂中加入三元乙丙橡胶颗粒,胶黏剂与所述三元乙丙橡胶颗粒的质量比为1:8,得到涂布混合物,然后将所述涂布混合物在跑道基面上铺设10mm,即完成施工。
实施例3
本实施例提供一种双组份聚天门冬氨酸酯脲胶黏剂,所述胶黏剂由主剂和固化剂组成,二者当量比为1:0.9,其中以重量份计,所述主剂组分如下:
N,N'-(亚甲基二-(1-甲基-4,1-环己烷二基))二天冬氨酸四乙酯 30份;
N,N'-(聚氧(甲基-1,2-亚乙基)二基)二天冬氨酸四乙酯 30份;
N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四丁酯 30份;
噁唑烷吸收剂 5份;
有机硅消泡剂BYK085(毕克化学) 0.5份;
基材润湿剂Borchi Gol 1375(欧蒽吉) 0.5份;
A3分子筛 12份。
以重量份计,所述固化剂组分由30份HDI三聚体N3900(拜耳)、20份HDI酮二脲N3400(拜耳)、60份羟基树脂改性固化剂组成,三种组分的质量比为3:2:6。
混合使用时,按主剂:固化剂=1:0.9的质量比计入。
其中,羟基树脂改性固化剂为聚酯多元醇与HDI预聚反应得到的NCO含量在3-12%的树脂改性固化剂,其制备工艺如下:将100gIPDI反应釜中,加热到60℃,滴加PG树脂173g,保温反应5h,慢慢升高温度到90℃下反应4h,测定NCO含量降低至11.55%,降温到50℃出料,即得羟基树脂改性固化剂。
本实施例还提供一种所述的聚天门冬氨酸酯脲胶黏剂的施工工艺,其包括如下步骤:将主剂与固化剂按照质量比1:0.9的比例混合均匀,得到胶黏剂,向所述胶黏剂中加入三元乙丙橡胶颗粒,胶黏剂与所述三元乙丙橡胶颗粒的质量比为1:10,得到涂布混合物,然后将所述涂布混合物在跑道基面上铺设15mm,即完成施工。
实施例4
本实施例提供一种双组份聚天门冬氨酸酯脲胶黏剂,所述胶黏剂由主剂和固化剂组成,其中以重量份计,所述主剂组分如下:
N,N'-(亚甲基二-(1-甲基-4,1-环己烷二基))二天冬氨酸四乙酯 80份;
噁唑烷吸收剂 2份;
有机硅消泡剂BYK085(毕克化学) 0.1份;
基材润湿剂Borchi Gol 1375(欧蒽吉) 0.1份;
A3分子筛 8份。
以重量份计,所述固化剂组分由10份HDI三聚体N3900(拜耳)、10份HDI酮二脲N3400(拜耳)、40份羟基树脂改性固化剂组成,三种组分的质量比为1:1:4。
混合使用时,按主剂:固化剂=1:1质量比计入。
其中,羟基树脂改性固化剂为聚己内酯多元醇与HDI预聚反应得到的NCO含量在3-12%的树脂改性固化剂,其制备工艺如下:将100gIPDI反应釜中,加热到60℃,滴加PCL320g,保温反应5h,慢慢升高温度到90℃下反应4h,测定NCO含量降低至6.7%,降温到50℃出料,即得羟基树脂改性固化剂。
本实施例还提供一种所述的聚天门冬氨酸酯脲胶黏剂的施工工艺,其包括如下步骤:将主剂与固化剂按照质量比1:1的比例混合均匀,得到胶黏剂,向所述胶黏剂中加入三元乙丙橡胶颗粒,胶黏剂与所述三元乙丙橡胶颗粒的质量比为1:9,得到涂布混合物,然后将所述涂布混合物在跑道基面上铺设13mm,即完成施工。
实验例
测试实施例1-2所述的天冬聚脲胶黏剂的性能:挥发性有机化合物(VOC)含量、游离TDI含量、重金属含量、阻燃等级、断裂伸长率和拉伸强度,测试结果如表1所示。
表1
检测项目 实施例1 实施例2
VOC含量(g/L) 30 32
游离TDI(mg/KG) 未检出 未检出
重金属(铅、锡、铬) 未检出 未检出
邻苯二甲酸酯类增塑剂总量(mg/KG) 未检出 未检出
断裂伸长率(%) 300 280
拉伸强度(MPa) 4.0 5.2
上述测试结果表明,实施例1-2所述的天冬聚脲胶黏剂性质优良:极低VOC含量、无游离TDI、重金属和邻苯二甲酸酯类增塑剂等毒害成分、绿色环保,断裂伸长率在300%左右,拉伸强度4MPa以上,回弹性良好,兼具了优异的环保安全性和物理性能。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (7)

1.一种聚天门冬氨酸酯脲胶黏剂,其特征在于,由主剂和固化剂组成,所述主剂与固化剂的当量比为1:0.9-1.1,以重量份计,所述主剂由80-90份聚天门冬氨酸酯树脂、2-5份吸收剂、8-12份分子筛、0.1-0.5份消泡剂、0.1-0.5份基材润湿剂组成。
2.根据权利要求1所述的聚天门冬氨酸酯脲胶黏剂,其特征在于,所述固化剂由HDI三聚体、HDI酮二脲和羟基树脂改性固化剂组成,所述HDI三聚体、HDI酮二脲和羟基树脂改性固化剂的质量比为1-3:1-2:4-6。
3.根据权利要求1所述的聚天门冬氨酸酯脲胶黏剂,其特征在于,所述羟基树脂改性固化剂为聚醚多元醇或聚酯多元醇与IPDI、HMDI、HDI中的一种或多种预聚反应得到的NCO含量在3-12%的树脂改性固化剂。
4.根据权利要求3所述的聚天门冬氨酸酯脲胶黏剂,其特征在于,所述聚天门冬氨酸酯树脂为N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四乙酯、N,N'-(亚甲基二-4,1-环己烷二基)二天冬氨酸四丁酯、N,N'-(亚甲基二-(1-甲基-4,1-环己烷二基))二天冬氨酸四乙酯、N,N'-(聚氧(甲基-1,2-亚乙基)二基)二天冬氨酸四乙酯中的一种或多种。
5.根据权利要求4所述的聚天门冬氨酸酯脲胶黏剂,其特征在于,所述羟基树脂改性固化剂采用如下工艺制备:将聚醚多元醇、聚酯多元醇、聚己内酯中的一种与IPDI、HMDI、HDI中的一种在60-80℃下反应5h,然后升温至90℃,反应4h后降温至50℃,测定NCO含量符合设计要求,即得羟基树脂改性固化剂。
6.一种如权利要求1-5任一项所述的聚天门冬氨酸酯脲胶黏剂的施工工艺,其特征在于,包括如下步骤:将主剂与固化剂按照当量比1:0.9-1.1的比例混合均匀,得到胶黏剂,向所述胶黏剂中加入三元乙丙橡胶颗粒,得到涂布混合物,然后将所述涂布混合物在跑道基面上涂布10-15mm。
7.根据权利要求6所述的聚天门冬氨酸酯脲胶黏剂的施工工艺,其特征在于,所述胶黏剂与所述三元乙丙橡胶颗粒的质量比为1:6-10。
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