CN108137623A - 基于烷氧基硅烷烷基异氰酸酯的单脲基甲酸酯 - Google Patents
基于烷氧基硅烷烷基异氰酸酯的单脲基甲酸酯 Download PDFInfo
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
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- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及基于烷氧基硅烷‑烷基异氰酸酯的下式的新型单脲基甲酸酯及其用途。此外要求保护制造方法,其中将下面展示的两种组分混合:R6 m(OR5)3‑mSi‑R4‑NCO、Rn(OR1)3‑n Si‑R2‑NH‑(C=O)‑OR3。所要求保护的单脲基甲酸酯用作漆料组合物和胶粘剂组合物的添加剂。
Description
本发明涉及基于烷氧基硅烷烷基异氰酸酯的新型单脲基甲酸酯、制造方法和用途。
聚氨酯已确立作为漆料、胶粘剂、密封剂和塑料体系的高品质成分几十年。在此,额外的烷氧基硅烷基团可以在网络密度、耐化学品性和耐刮性方面起重要作用,主要通过形成硅氧烷结构。此类体系也是已知。
既具有烷氧基硅烷基团也具有异氰酸酯基团的分子提供了通过一种组分引入两种所述官能性,即硅氧烷和聚氨酯基团的可能性。此类物质,例如异氰酸根合烷基三烷氧基硅烷也已使用很久。由这些物质可以通过与多元醇反应而制造无异氰酸酯的湿固化型交联剂。原则上,此类“SiPUR”(含烷氧基硅烷的聚氨酯)可以与其它异氰酸酯反应产生脲基甲酸酯,以改进特定的材料性能,例如粘度。
例如DE102005041953A1描述了平均分子量为3000-20000 g/mol的多元醇与过量的异氰酸根合丙基三甲氧基硅烷的反应,以使得在形成聚氨酯之后进行脲基甲酸酯反应。
在DE102005041954A1中,向来自多元醇和二异氰酸酯(例如IPDI,异佛尔酮二异氰酸酯)的聚氨酯加入异氰酸根合丙基三甲氧基硅烷并加热直至形成脲基甲酸酯结构。
EP2089444A1要求保护含脲基甲酸酯的聚氨酯,其除了不饱和官能性外还具有含硅烷基团的组分。
在EP2089445A1中看起来也类似;但是在此,这些聚氨酯还必须额外地含有分散活性的组分,以将其变得与水相容(wassergängig)。
US20140097392A1中也谈及了含脲基甲酸酯和烷氧基硅烷的聚合物,其在这一情况中与染料混合。
J. Kozakiewicz等人在Progress in Organic Coatings 72 (2011) 120-130中发表了用于多异氰酸酯的含硅烷的封端剂,其通过脲基甲酸酯基团引入。显然需要带有烷氧基硅烷基团的其它化合物尤其用于耐刮应用。但是,所有迄今实例的共同点是,在此始终是既具有高粘度也难以清洁或分离的聚合物和/或聚氨酯。
本发明的目的是提供具有耐刮性能的带有烷氧基硅烷基团的新型化合物,其不具有现有技术的缺点,但特别是易于制造、具有低粘度并通过较少支出就可清洁。
令人惊讶地已发现,由异氰酸酯改性的含烷氧基硅烷基团的单氨基甲酸酯构成的单脲基甲酸酯具有所需性能。
本发明的主题因此是具有式1的单脲基甲酸酯:
其中R、R1-R6彼此独立地是相同或不同的具有1-8个碳原子的烃基,其中它们可以是支化或环状的或可以相互合并成环状,并且m和n彼此独立地是0-2。
优选地,m和n是0。
R1和R5彼此独立地优选为甲基或乙基。
R2和R4优选彼此独立地是甲基或丙基。
更优选地,R1 = R5且R2 = R4。
优选为m和n是0、R1和R5是甲基或乙基且R2和R4是甲基或丙基的化合物。
非常特别优选为m和n是0、R1 = R5 =甲基且R2 = R4 =丙基的化合物。
主题还是通过A)与B)在20至220℃的温度下的反应制造本发明的单脲基甲酸酯的方法,
A) 含烷氧基硅烷基团的异氰酸酯,
B) 含烷氧基硅烷基团的单氨基甲酸酯。
含烷氧基硅烷基团的异氰酸酯A)具有式2:
R6 m (OR5)3-mSi-R4-NCO
其中R6、R5和R4彼此独立地是相同或不同的具有1-8个碳原子的烃基,其中它们可以是支化或环状的或可以相互合并成环状,并且m是0-2。
优选地,m = 0。
R4优选为甲基或丙基。
R5优选为甲基或乙基。
优选为m是0且R4是甲基或丙基且R5是甲基或乙基的化合物。
特别优选为异氰酸根合丙基三甲氧基硅烷。
含烷氧基硅烷基团的单氨基甲酸酯B)具有式3:
Rn (OR1)3-n Si-R2-NH-(C=O)-OR3
其中R、R1、R2和R3各自独立地是相同或不同的具有1-8个碳原子的烃基,其中它们可以是支化或环状的或可以相互合并成环状,并且n是0-2。
优选地,n = 0。
R1优选是甲基或乙基。
R2优选是甲基或丙基。
优选地,R3 = R1。
优选为n是0且R2是甲基或丙基且R1是甲基或乙基且R3 = R1的化合物。
特别优选为N-三甲氧基甲硅烷基丙基氨基甲酸甲酯。
本发明的单脲基甲酸酯的制造通常在无溶剂的情况下或在使用非质子溶剂的情况下进行,其中该反应可以不连续或连续地进行。该反应在合适的装置,例如搅拌釜、挤出机、静态混合机、捏合室中进行。该反应可以在室温下,即在20至22℃的温度下进行,但是优选使用80至220℃,更优选80至120℃的更高温度。为了加速该反应,可以有利地使用氨基甲酸酯化学中已知的催化剂,例如金属有机化合物,如含锡或锌的化合物,盐,例如氯化锌(II)和/或碱。合适的是例如Sn、Bi、Zn和其它金属的羧酸盐, 例如二月桂酸二丁基锡、辛酸锡、新癸酸铋、叔胺例如1,4-二氮杂双环[2.2.2]辛烷(DABCO)、三乙胺、脒和胍以及季铵盐,优选四烷基铵盐,和/或季鏻盐。可考虑的催化剂包括金属乙酰丙酮化物。对此的实例是单独或混合物形式的乙酰丙酮锌、乙酰丙酮锂、乙酰丙酮铁和乙酰丙酮锡。优选地使用乙酰丙酮锌。可考虑的催化剂此外是季铵乙酰丙酮化物或季鏻乙酰丙酮化物。
该反应在排除水的情况下进行。优选地,该反应在无溶剂的情况下进行。
本发明的主题还是本发明的单脲基甲酸酯用于金属、塑料、玻璃、木材、MDF(中密度纤维板)或皮革基材或其它耐热基底的漆料组合物中的用途。
本发明的主题还是本发明的单脲基甲酸酯用于胶粘金属、塑料、玻璃、木材、MDF或皮革基材或其它耐热基底的胶粘剂组合物的用途。
本发明此外通过下列不受限的实施例说明,从中可以获知本发明的其它特征、实施方案、方面和优点。
实施例
1)
制造本发明的单脲基甲酸酯
a)
将236 g(1 mol)三甲氧基甲硅烷基丙基氨基甲酸甲酯(Evonik Industries AG)和205g异氰酸根合丙基三甲氧基硅烷(Evonik Industries AG)相互混合并加热到175℃ 2 h。然后,在100℃和 0.3 mbar下经短程蒸馏分离出输出产物(Ausgangsprodukt)。留下183 g(41.5%)的纯净无色透明(wasserklar)液体。
在CDCl3中的C13-NMR (ppm): 156.9 (1); 154.4 (1); 53.5 (1); 50.5 (10);46.3 (1); 43.2 (1); 23.2 (1); 22.6 (1). 6.7 (1); 6.5 (1).
粘度为大约200 mPas,因此是非常低粘性的。
b)
将236 g(1 mol)三甲氧基甲硅烷基丙基氨基甲酸甲酯(Evonik Industries AG)、205g异氰酸根合丙基三甲氧基硅烷(Evonik Industries AG)和0.4 g氯化锡(II)相互混合并加热到150℃ 1 h。然后,在90℃和0.3 mbar下经短程蒸馏分离出输出产物。留下339 g(76.9%)的纯净无色透明液体(NMR见上)。
c)
将236 g(1 mol)三甲氧基甲硅烷基丙基氨基甲酸甲酯(Evonik Industries AG)、205g异氰酸根合丙基三甲氧基硅烷(Evonik Industries AG)和1 g乙酰丙酮铁(III)相互混合并加热到90℃ 3 h。然后,在90℃和0.3 mbar下经短程蒸馏分离出输出产物。留下184 g(41.5%)的纯净无色透明液体(NMR见上)。
2)
配制漆料
将44.5 g Setalux 1760(OH官能的丙烯酸酯,Nuplex industries)和30 g本发明产物a)与25 g乙酸丁酯/二甲苯(1:1)混合并加入0.5 g催化剂(VESTANAT EP-CAT 11,EvonikIndustries AG)。将该混合物通过120 µm螺旋刮刀刮涂到钢板上并在140℃下烧制22 min。涂层(30 µm层厚度)具有176 s摆撞硬度和> 150 MEK双冲程的耐化学品性。因此,其完全固化。
耐刮性:
起始光泽度为86刻度分度(Skt.)(20°)。在刷擦测试(Bürstentest)后,光泽度降至84Skt.。摩擦掉色(Crockmeter)测试导致光泽度为83 Skt.。光泽度损失因此为2或3 Skt.,因此耐刮性是极好的!
评估:由于刮具的光泽度损失0-9 Skt.极好,10-20很好,21-34好,35-44中等,> 45差
相比而言,基于Setalux 1760的商购的双组份(2K)PUR漆料的光泽度损失为大约30Skt.。
刷擦测试(湿):
仪器: U 1 系列号003,制造商:BASF L + F,建造时间:1993
漆层表面由于承受质量(2 kg)的丝网(Siebgewebe)(尼龙丝网号11,网孔大小25 µm)而受损。该丝网和漆层表面使用洗涤剂溶液(在水中的0.25% Persil溶液)充分润湿。试验板借助发动机驱动以往复运动的形式在该丝网下面来回移动。在测试前和后测量光泽度。
摩擦掉色测试(干)
仪器:U 1 系列号003,制造商:BASF L + F,建造时间:1993
漆层表面由于承受质量(920 g)的织物(3M 281Q WetO干燥抛光纸)而受损。试验板借助发动机驱动以往复运动的形式在该织物下面来回移动。
Claims (15)
1.具有式1的单脲基甲酸酯:
其中R、R1-R6彼此独立地是相同或不同的具有1-8个碳原子的烃基,其中它们可以是支化或环状的或可以相互合并成环状,并且m和n彼此独立地是0-2。
2.根据权利要求1的具有式1的单脲基甲酸酯,其中m和n是0。
3.根据权利要求1的具有式1的单脲基甲酸酯,其中R1和R5彼此独立地是甲基或乙基。
4.根据权利要求1的具有式1的单脲基甲酸酯,其中R2和R4彼此独立地是甲基或丙基。
5.根据权利要求1的具有式1的单脲基甲酸酯,其中R1 = R5且R2 = R4。
6.根据权利要求1的具有式1的单脲基甲酸酯,其中m和n是0,R1和R5是甲基或乙基,且R2和R4是甲基或丙基。
7.根据权利要求1的具有式1的单脲基甲酸酯,其中m和n是0,R1 = R5 =甲基且R2 = R4 =丙基。
8.通过A)与B)在20至220℃的温度下的反应制造根据权利要求1-7的单脲基甲酸酯的方法,
A) 含烷氧基硅烷基团的异氰酸酯,
B) 含烷氧基硅烷基团的单氨基甲酸酯。
9.根据权利要求8的制造单脲基甲酸酯的方法,
其中含烷氧基硅烷基团的异氰酸酯A)具有式2:
R6 m (OR5)3-mSi-R4-NCO
其中R6、R5和R4彼此独立地是相同或不同的具有1-8个碳原子的烃基,其中它们可以是支化或环状的或可以相互合并成环状,并且m是0-2。
10.根据权利要求9的制造单脲基甲酸酯的方法,
其中m是0且R4是甲基或丙基,且R5是甲基或乙基。
11.根据权利要求9的制造单脲基甲酸酯的方法,其中使用异氰酸根合丙基三甲氧基硅烷。
12.根据权利要求8的制造单脲基甲酸酯的方法,
其中含烷氧基硅烷基团的单氨基甲酸酯B)具有式3:
Rn (OR1)3-n Si-R2-NH-(C=O)-OR3
其中R、R1、R2和R3彼此独立地是相同或不同的具有1-8个碳原子的烃基,其中它们可以是支化或环状的或可以相互合并成环状,并且n是0-2。
13.根据权利要求12的制造单脲基甲酸酯的方法,其中n是0且R2是甲基或丙基,且R1是甲基或乙基且R3 = R1。
14.根据权利要求12的制造单脲基甲酸酯的方法,其中使用N-三甲氧基甲硅烷基丙基氨基甲酸甲酯。
15.单脲基甲酸酯用于漆料组合物和胶粘剂组合物中的用途。
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CN101381443A (zh) * | 2007-07-13 | 2009-03-11 | 拜尔材料科学股份公司 | 包含脲基甲酸酯和硅烷基团的多异氰酸酯 |
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CN101381443A (zh) * | 2007-07-13 | 2009-03-11 | 拜尔材料科学股份公司 | 包含脲基甲酸酯和硅烷基团的多异氰酸酯 |
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