CN112011261B - 一种双组份喷涂聚脲黏弹涂料及其应用 - Google Patents
一种双组份喷涂聚脲黏弹涂料及其应用 Download PDFInfo
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Abstract
本发明提供一种双组份喷涂聚脲黏弹涂料及其应用,基于本发明的涂料形成的涂膜,具有良好的耐温性、黏性、回弹性等综合性能。本发明提供一种双组份喷涂聚脲黏弹涂料,包括A组分和B组分,其中所述A组分为吸水性聚醚多元醇和MDI反应制得的含有NCO基团的预聚物,且所述预聚物中所述NCO基团的质量含量为4%~11%;所述B组分采用包括如下各组分的原料制得:二元胺类扩链剂,聚醚胺,增塑剂,偶联剂等;其中,所述二元胺类扩链剂为带有伯胺基的芳香扩链剂和带有仲胺基的芳香扩链剂的组合物;基于所述二元胺类扩链剂的总质量,所述带有伯胺基的芳香扩链剂的质量比为2%‑15%。
Description
技术领域
本发明涉及喷涂聚脲黏弹涂料领域,具体涉及一种双组份喷涂聚脲黏弹涂料及其应用。
背景技术
喷涂聚脲黏弹涂料是双组份、无溶剂、快固化的厚涂涂料,具有黏弹性能,被广泛用于建筑防水。
现有的喷涂聚脲涂料作为防水涂料,在应用中暴露出许多缺点:
1)本身内应力大,结构性裂缝导致其断裂。
2)对基材表面强度要求高,易剥落。
3)对基材含水量要求高,否则不粘合。
4)对所用喷涂设备要求高,投资大;喷涂需要高压设备加热,进行热喷涂。
5)对施工操作人员素质要求高,与从业人员实情不相符。由于传统聚脲的喷涂需要高压喷涂机,设备复杂精密故障点多,需要培训高素质人员操作。
以上这些缺点,都是导致喷涂聚脲应用于防水工程失败的原因。也是以上原因造成喷涂聚脲防水的成本居高不下,难以推广应用。
发明内容
有鉴于此,本发明提供一种双组份喷涂聚脲黏弹涂料,基于该涂料形成的涂膜,具有良好的耐温性、粘性、回弹性等综合性能。
本发明为达到其目的,提供如下技术方案:
本发明提供一种双组份喷涂聚脲黏弹涂料,包括A组分和B组分,其中所述A组分为吸水性聚醚多元醇和MDI反应制得的含有NCO基团的预聚物,且所述预聚物中所述NCO基团的质量含量为4%~11%;
所述B组分采用包括如下质量百分比的各组分制得:二元胺类扩链剂19.5%~48%,聚醚胺30%~55%,增塑剂15%~22.5%,偶联剂1.5%~2.5%,抗氧剂0.1%~0.3%,消泡剂0.2%~0.5%,抗紫外线剂0~0.2%;
其中,所述二元胺类扩链剂为带有伯胺基的芳香族扩链剂和带有仲胺基的芳香族扩链剂的组合物;基于所述二元胺类扩链剂的总质量,所述带有伯胺基的芳香族扩链剂的质量比为2%-15%;所述偶联剂优选为表面能rc≥40达因/厘米的硅烷偶联剂。
一些实施方案中,所述硅烷偶联剂选自γ-巯丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷中的至少一种。
一些实施方案中,所述聚醚胺的重均分子量≥5000。
一些实施方案中,所述带有伯胺基的芳香族扩链剂选自二甲硫基甲苯二胺、二乙基甲苯二胺中的至少一种,所述带有仲胺基的芳香族扩链剂选自4,4'-双(仲丁基氨基)-二苯基甲烷。
一些实施方案中,所述吸水性聚醚多元醇选自聚醚二元醇,优选重均分子量为3000以上,例如重均分子量为3000-5000等;
一些实施方案中,所述MDI为MDI-50(二苯基甲烷二异氰酸酯,为2.4’-MDI与4.4’-MDI混合物),可商购获得;
一些实施方案中,所述增塑剂选自邻苯二甲酸酯类、氯化石蜡(如长链氯化石蜡类增塑剂)等增塑剂中的一种或多种;
一些实施方案中,所述抗氧剂选自受阻酚类抗氧剂,如IRGANOX 245;
一些实施方案中,所述消泡剂选自脂肪族矿油类,如BYK-031;
一些实施方案中,所述抗紫外线剂选自甲脒类化合物,如Givsor6 UV-2。
一些实施方案中,所述A组分中,所述吸水性聚醚多元醇和所述MDI的质量比为3.2:1~1.5:1。
一些实施方案中,所述A组分的制备包括如下步骤:将所述MDI在氮气气氛下加热升温至75-83℃,然后加入所述吸水性聚醚多元醇,在80℃±5℃的温度范围内反应至NCO基团质量含量为4%~11%;
所述组分B的制备:通过将所述B组分的各组分混合均匀获得。
一些实施方案中,所述A组分和所述B组分的质量比为1:1~0.80:1。
本发明的双组份喷涂聚脲黏弹涂料,在需要使用涂料前,只需将所述A组分和B组分按照配比在混合器中完成混合即可获得所述涂料。
本发明还提供上文所述的双组份喷涂聚脲黏弹涂料的应用,所述双组份喷涂聚脲黏弹涂料用于喷涂于混凝土基材表面,例如用于喷涂于混凝土基材表面以起到防水-作用。
本发明提供的技术方案具有如下有益效果:
本发明提供的双组份喷涂聚脲黏弹涂料,
①选用吸水性聚醚多元醇与MDI-50反应,所得预聚物中分子中有亲水基团,在与B组份反应中,可以吸收环境中的水份,使A组份NCO与B组份中的-NH2、-NHR基团反应,阻断水份参与反应可能性,避免涂层发泡或失粘的发生。
②预聚体分子中与B组份反应后亲水性基团(例如-(CH2-CH2-O-CH2-CH2)n-)增加了聚脲高分子的柔性及粘性。
③A组份水中NCO含量高低直接影响聚脲黏弹体的柔粘性,NCO越低,成品越柔越粘,易蠕变,耐温性下降。NCO越高,成品硬度增加,粘性减低,或失去粘性,失去蠕变特性,耐温性提高。本申请发明人发现,将A组份NCO含量控制在4~11%,可以良好的兼顾耐温性、粘性、硬度和蠕变性等综合性能。
④B组份中选用芳香族仲胺与位阻芳香族伯胺组合使用来调整反应速度,控制成品的柔性、粘性及弹性。发明人发现,仲胺占比越大反应越慢,涂层柔性越好,利于粘性及蠕变性。伯胺越多反应越快,涂层硬度大,回弹性好,柔性差不利于蠕变。本发明两种不同胺的比例控制为伯胺扩链剂2%-15%,其余为仲胺扩链剂(85%-98%),可以使得上述性能得到良好的兼顾,从而获得综合性能优异的产品。
⑤选择高分子量(大于等于5000)聚醚胺,分子量越大涂层柔性越大,反之涂层硬度增加。
⑥偶联剂改善涂层与基材粘着效果,本发明主要用于混凝土基材上,发明人发现选择表面能rc≥40达因/厘米的硅烷偶联剂,可提高涂层与潮湿基材的粘合力。
本发明的涂料,A组份在合成中选用3000以上分子量的亲水性聚醚多元醇为反应物,控制A组份的NCO含量(4%~11%),以及B组份中扩链剂二元胺选用特定配比的带伯胺的芳香扩链剂和带仲胺的芳香扩链剂组合使用,同时选择表面能rc≥40达因/厘米的硅烷偶联剂,所得的喷涂聚脲黏弹涂料具有优异的性能,可以消除传统聚脲存在的一些缺点,是用于防水领域的颠覆性新产品技术。
本发明的涂料可以用低压设备进行涂覆,可无需加热进行冷喷涂,所需设备简单,对操作人员素质要求低。
本发明“聚脲黏弹体”具有如下特点与优势:
(1)100%固含量,为环保型新材料;
(2)具有蠕变弹性双重性能,既有蠕变性能又能在弹性范围内恢复原状;
(3)本发明的“聚脲黏弹体”具有高伸长率,可抵抗基材热胀冷缩或局部开裂;发明人在实验中测试发现,本发明的“聚脲黏弹体”500%伸长内体现回弹性,超过5000%伸长量后体现蠕变性;
(4)伤口自愈合修复功能,即使是局部人为穿刺、割裂,本材料能自愈合修复,因而能避免局部破损漏水现象;
(5)与各种基材如钢铁、混凝土、木质材料、PVC、石材、瓷砖等粘着力好,能自粘复合,附着力大于自身强度,可以应对不同应用环境,抵抗相应老化破坏,例如利用本发明的涂料可以在表面自粘氟碳膜,带来颜色不变且自净的效果;例如利用本发明的涂料可以在表面自粘粘瓷砖,行人或车辆可以在其上行走;例如利用本发明的涂料可以在表面刷涂真石漆,起到装饰功能等等;
(6)高黏弹低模量,即使基材断裂其断裂应力沿着涂层厚度方向递减传导,不因结构断裂应力而发生极限断裂;
(7)对混凝土,即使是潮湿混凝土的表面也具有优异的粘着力,能与混凝土基材粘合一体,不存在传统防水材料与基层剥离而窜水、漏水现象;
(8)对基材表面缺陷具有广泛适应性;如对混凝土的针眼、裂纹、潮湿等具有适应性。
(9)-40℃无脆裂,大于65℃不流淌;
(10)对表面有水、冰、油污基材,仍具有优异粘着力。
具体实施方式
为了更好的理解本发明的技术方案,下面结合实施例进一步阐述本发明的内容,但本发明的内容并不仅仅局限于以下实施例。
实施例中所用原料若未特别说明,均为本领域常规试剂,可商购获得。
实施例1
1、合成A组份(目标:制备NCO含量=9wt%预聚体)
原料选用:MDI-50(2.4’-MDI与4.4’-MDI混合物)(万华化学);聚醚二元醇(恒丰HT-3681,重均分子量约3500)
合成步骤:
将500克的MDI-50投入反应烧瓶中,充氮气加热升温至75~83℃之间,慢慢将1050克的聚醚二元醇HT-3681加入,控制温度在80℃±5℃,2小时内加完,保持反应2小时,降温至40℃左右,包装。分析结果:NCO=8.92%(依照标准:HG/T 2409-92检测NCO含量)
2、B组份
B组分原料组成和配比(基于B组分各原料总质量为100%计):
将B组分的上述原料混合均匀获得B组分。
3、喷涂聚脲黏弹涂料的制备
在使用涂料前,将上述A组分和B组分按照质量比1:1在混合器中完成混合,从而获得所需涂料。
实施例2
1、合成A组份(目标:制备NCO含量=6.5wt%预聚体)
原料选用:MDI-50(2.4’-MDI与4.4’-MDI混合物)(万华化学);聚醚二元醇(恒丰HT-3681,重均分子量约3500)
合成步骤:
将500克的MDI-50投入反应烧瓶中,充氮气加热升温至75~83℃之间,慢慢将1575克的聚醚二元醇HT-3681加入,控制温度在80℃±5℃,2小时内加完,保持反应2小时,降温至40℃左右,包装。分析结果:NCO=6.5%(依照标准:HG/T 2409-92检测NCO含量)
2、B组份
B组分原料组成和配比(基于B组分各原料总质量为100%计):
将B组分的上述原料混合均匀获得B组分。
3、喷涂聚脲黏弹涂料的制备
在使用涂料前,将上述A组分和B组分按照质量比1:1在混合器中完成混合,从而获得所需涂料。
产品性能检测:
将实施例1的喷涂聚脲黏弹涂料进行如下性能检测:
(1)粘合力
要求:粘结强度在0.4-0.9MPa,100%内聚破坏。
测试结果:
干(即干的混凝土基材):粘结强度为0.95MPa,内聚力100%破坏(按GB/T1677-2018中7A测试);
湿(即湿的混凝土基材):粘结强度为0.55MPa,内聚力100%破坏(按GB/T1677-2008中7.1.1.4测试);
结果:涂层粘连在混凝土表面,在干的或湿的混凝土上实施例1的喷涂聚脲黏弹涂料形成的涂层100%粘在混凝土上。
此外,发明人还对实施例1的喷涂聚脲黏弹涂料在PVC、木板、钢板、瓷砖表面进行粘结力测试,其粘结强度依次分别为0.55、0.57、0.57、0.57MPa,100%内聚力破坏。
将实施例2的喷涂聚脲黏弹涂料进行如下性能检测:
(1)粘合力
测试结果:
干(即干的混凝土基材):粘结强度为0.72MPa,内聚力100%破坏(按GB/T1677-2018中7A);(要求:粘结强度在0.79-0.82MPa,100%内聚破坏)。
湿(即湿的混凝土基材):粘结强度为0.43MPa,内聚力100%破坏(按GB/T1677-2008中7.1.1.4);
结果:涂层粘连在混凝土表面,在干的或湿的混凝土上实施例2的喷涂聚脲黏弹涂料形成的涂层100%粘在混凝土上。
(2)自愈合:
自愈合测试方法和结果:
a)将实施例1和实施例2的得到的聚脲粘弹体试棒用刀割断分离,再把分离开来的断开面对接,瞬间粘合一起;
b)用锋利的锥尖穿刺涂有实施例1和实施例2聚脲粘弹体的泡沫箱,用刀片割透箱底,然后装水,箱体不漏水;由于割***的聚脲粘弹体自愈合,从而未漏水。
(3)耐热性:
测试方法及结果:将实施例1和实施例2的聚脲粘涂料分别喷涂于混凝土基材表面,65℃下分别加热2小时、8小时,均不流淌且没有鼓包,无滴落;在85℃下加热2h、8h均不流淌。
(4)耐低温:
耐低温-40℃,无断裂;
测试方法:将实施例1和实施例2的涂料分别制成试片(尺寸150mm*20mm,厚度2mm),将试片和Φ20mm的塑料棒,放入-40℃冰柜中,冷冻1小时,然后在冰柜中将试片缠绕在Φ20mm塑料棒上,试片无脆裂、无裂纹。
(5)拉伸强度(GB/T 528-1998):
测试结果:实施例1拉伸强度为2.24MPa;实施例2拉伸强度为1.72MPa;
(6)伸长率(GB/T528-1998)
实施例1伸长率为1060%;实施例2伸长率为1150%;
(7)延伸性测试
实验方法:将两块120mm×50mm×(2~4)mm的铝板沿短边对接成一整体,两块铝板之间的缝隙不得大于0.05mm,黏弹体涂覆在两块铝板中间,涂覆面积(150×50)mm,厚度(2.0±0.2)mm,共制备3个试件,并在标准条件(25℃)下养护168h。将试件加持在拉力机的夹具中心,并不得歪扭变形,记录此时延伸尺指针所示数值L0,开动拉力机,拉伸速度为10mm/min,使试件受拉至裂口边缘开裂或收缩至10mm时为止,记录此时延伸尺指针所示值L1,精确到1mm。经测试延伸性结果为:实施例1为55mm;实施例2为59mm。
本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (12)
1.一种双组份喷涂聚脲黏弹涂料,其特征在于,包括A组分和B组分,其中所述A组分为吸水性聚醚多元醇和MDI反应制得的含有NCO基团的预聚物,且所述预聚物中所述NCO基团的质量含量为4%~11%;
所述B组分采用包括如下质量百分比的各组分制得:二元胺类扩链剂19.5%~48%,聚醚胺30%~55%,增塑剂15%~22.5%,偶联剂1.5%~2.5%,抗氧剂0.1%~0.3%,消泡剂0.2%~0.5%,抗紫外线剂0~0.2%;
其中,所述二元胺类扩链剂为带有伯胺基的芳香族扩链剂和带有仲胺基的芳香族扩链剂的组合物;基于所述二元胺类扩链剂的总质量,所述带有伯胺基的芳香族扩链剂的质量比为2%-15%;所述偶联剂为表面能rc≥40达因/厘米的硅烷偶联剂。
2.根据权利要求1所述的双组份喷涂聚脲黏弹涂料,其特征在于,
所述硅烷偶联剂选自γ-巯丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷中的至少一种。
3.根据权利要求1-2任一项所述的双组份喷涂聚脲黏弹涂料,其特征在于,所述聚醚胺的重均分子量≥5000。
4.根据权利要求3所述的双组份喷涂聚脲黏弹涂料,其特征在于,所述带有伯胺基的芳香族扩链剂选自二甲硫基甲苯二胺、二乙基甲苯二胺中的至少一种,所述带有仲胺基的芳香族扩链剂选自4,4'-双(仲丁基氨基)-二苯基甲烷。
5.根据权利要求4所述的双组份喷涂聚脲涂料,其特征在于,
所述吸水性聚醚多元醇选自聚醚二元醇;
所述MDI为MDI-50;
所述增塑剂选自邻苯二甲酸酯类和氯化石蜡增塑剂中的一种或多种。
6.根据权利要求5所述的双组份喷涂聚脲涂料,其特征在于,所述吸水性聚醚多元醇的重均分子量为3000以上。
7.根据权利要求1-2、4-6任一项所述的双组份喷涂聚脲黏弹涂料,其特征在于,所述A组分中,所述吸水性聚醚多元醇和所述MDI的质量比为3.2:1~1.5:1。
8.根据权利要求7所述的双组份喷涂聚脲黏弹涂料,其特征在于,所述A组分的制备包括如下步骤:将所述MDI在氮气气氛下加热升温至75-83℃,然后加入所述吸水性聚醚多元醇,在80℃±5℃的温度范围内反应至NCO基团质量含量为4%~11%;
所述B组分通过将所述B组分的各组分混合均匀获得。
9.根据权利要求1-2、4-6、8任一项所述的双组份喷涂聚脲黏弹涂料,其特征在于,所述A组分和所述B组分的质量比为1:1~0.80:1。
10.根据权利要求9所述的双组份喷涂聚脲黏弹涂料,其特征在于:在使用所述涂料前,将所述A组分和B组分按照配比在混合器中混合即可获得所述涂料。
11.权利要求1-10任一项所述的双组份喷涂聚脲黏弹涂料的应用,其特征在于,所述双组份喷涂聚脲黏弹涂料用于喷涂于混凝土基材表面。
12.根据权利要求11所述的双组份喷涂聚脲黏弹涂料的应用,其特征在于,所述双组份喷涂聚脲黏弹涂料用于喷涂于混凝土基材表面以起到防水作用。
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