CN101528857A - 用于聚合物本体着色的单偶氮着色剂 - Google Patents
用于聚合物本体着色的单偶氮着色剂 Download PDFInfo
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- CN101528857A CN101528857A CN200780039532.4A CN200780039532A CN101528857A CN 101528857 A CN101528857 A CN 101528857A CN 200780039532 A CN200780039532 A CN 200780039532A CN 101528857 A CN101528857 A CN 101528857A
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Abstract
一种本体着色高分子量材料的方法,在该方法中在成型之前或者在成型过程中将式(I)的化合物或者其互变异构体掺入所述高分子量材料中,其中M1是H、1/2M2、1/3M3或者NR4R5R6R7,优选是H、1/2M2或者NR4R5R6R7,特别是H,M2是处于氧化态II的碱土金属或者过渡金属或者是处于氧化态IV的氧合金属,M3是Al(III)、处于氧化态III的过渡金属或者处于氧化态V的氧合金属,R1是H或者非离子取代基,R2是H或者是独立于R1的另外的非离子取代基,R3是H、C1-C6烷基、苯基、CO-C1-C6烷基或者CO-苯基,优选是H或者CO-C1-C6烷基,特别是H,且R4、R5、R6和R7彼此独立的是H或者未取代的或可由羟基或由卤素取代的苯基、苄基或者C1-C6烷基,并且在C3-C6烷基的情况中是未被中断的或者由O中断。所获得的着色具有良好的光稳定性和热稳定性,特别是在聚烯烃中时。
Description
颜色索引颜料黄191:2是一种具有优异的着色性的颜料,但是其必须在多个步骤中由碱性化学品制得。因此需要一种具有同样良好着色性的颜料,其易于制备并且在聚合物本体着色(mass-colouring)中表现出良好的用途相关的性能。
JP S34/000875公开了可以用作核酸新陈代谢的拮抗剂以及抗癌药物(或者作为其原料)的化合物,其包括下式的化合物:
DE-OS 1 445 982在实施例8中公开了制备下式的4-氨基-5-芳基偶氮-嘧啶衍生物的方法:
DE-OS 1 769 250公开了制备如下通式的水溶性偶氮嘧啶染料的方法:
并在实施例104中公开了制备下式的染料的方法:
DE-OS 23 51 294公开了下面的优选通式的偶氮颜料:其中X1可以是氨基,Y1和Z1是OH或者NH2,但是X1,Y1和Z1不同时全部为OH。R1,R2和R3的定义既不包括SO3H基团,也不包括它们的盐。
现在已经令人惊讶地发现用于本体着色聚合物的良好的着色剂可以通过一种非常简单的方式制得。本发明因此涉及一种本体着色高分子量材料的方法,在该方法中在成型之前或者在成型过程中将式(I)的化合物或者其互变异构体掺入所述高分子量材料中,
其中
M1是H,1/2M2,1/3M3或者NR4R5R6R7,优选是H,1/2M2或者NR4R5R6R7,特别是H,
M2是处于氧化态II的碱土金属或者过渡金属或者是处于氧化态IV的氧合金属(oxo-metal),
M3是Al(III),处于氧化态III的过渡金属或者处于氧化态V的氧合金属,
R1是H或者非离子取代基,
R2是H或者是独立于R1的另外的非离子取代基,
R3是H,C1-C6烷基,苯基,CO-C1-C6烷基或者CO-苯基,优选是H或者CO-C1-C6烷基,特别是H,且
R4,R5,R6和R7彼此独立的是H或者未取代的或可由羟基或由卤素取代的苯基,苄基或者C1-C6烷基,并且在C3-C6烷基的情况中是未被中断的或者由O中断。
M2优选是Ca,Co,Cu,Fe,Mg,Mn,Sr,TiO,Zn或者ZrO。M3优选是Al,Ce,Co,Cr,Fe或者VO。分数1/2和1/3表示金属原子M2或者M3分别与两个或者三个磺酸盐分子形成盐。
R1优选是对位哈米特常数σp为-0.3至0.6,特别是-0.3至0.3的非离子取代基。R2优选是H或者是独立于R1的对位哈米特常数σp为-0.3至0.6,特别是-0.3至0.3的另外的非离子取代基,但是R2非常特别是H。
对位哈米特常数σp为-0.3至0.6的非离子性取代基是例如OCH3(σp=-0.27),叔C4H9(σp=-0.20),CH3(σp=-0.17),NHCOCH3(σp=-0.01),C6H5(σp=-0.01),F(σp=0.06),I(σp=0.18),Cl(σp=0.22),Br(σp=0.23),CO2C2H5(σp=0.45)和CF3(σp=0.54)。
通常的取代基的哈米特常数可以以表格形式在例如的百科全书(www.roempp.com)中找到。另外的取代基的哈米特常数可以根据Chem.Rev.17,125-136[1935]确定。但是,例如COO-或者SO3 -等离子性取代基,和例如N(CH3)3(σp=-0.83),NH2(σp=-0.66),OH(σp=-0.37),CN(σp=0.66)或者NO2(σp=0.78)等强极化取代基经常产生不期望的不太有利的性能。
式(I)的化合物还可以为与其它盐(例如与碱金属盐)的混合物或者固溶体的形式。根据反应和干燥参数,还可能存在结晶水。
C1-C6烷基是例如甲基,乙基,正丙基,异丙基,正丁基,仲丁基,异丁基,叔丁基,正戊基,2-戊基,3-戊基,2,2-二甲基丙基或者正己基。卤素是氯,溴,氟或者碘,优选氟或者氯,特别是烷基上的氟(例如三氟甲基,α,α,α-三氟乙基或者例如七氟丙基等全氟烷基基团)和苯基上的氯。
特别优选的R1是C1-C6烷基,OC1-C6烷基,NHCOC1-C6烷基,苯基或者C1,更特别的是C1-C4烷基,例如叔丁基或者非常特别的是甲基,特别优选的R2和R3是氢。磺基基团SO3M优选位于偶氮桥的邻位。
特别的,许多特别令人感兴趣的化合物是新颖的。本发明因此还涉及一种下式(II)的化合物或者其互变异构体,
其中
M1是H,1/2M2,1/3M3或者NR4R5R6R7,优选是H,1/2M2或者NR4R5R6R7,特别是H,
R8是对位哈米特常数σp为-0.3至0.6,优选-0.3至0.3的非离子取代基,
R9是H或者是独立于R8的另外的对位哈米特常数σp为-0.3至0.6,优选-0.3至0.3的非离子取代基,
R10是H,C1-C6烷基,苯基,CO-C1-C6烷基或者CO-苯基,优选是H或者CO-C1-C6烷基,特别是H,且
R4,R5,R6和R7彼此独立的是H或者未取代的或可由羟基或由卤素取代的苯基,苄基或者C1-C6烷基,并且在C3-C6烷基的情况中是未被中断的或者由O中断。
优选下式的化合物,它们还可以以互变异构体而存在,例如作为磺基甜菜碱(当M1 +是H)而存在:
通常,磺基甜菜碱有利地以特别高的着色强度和具有良好的不褪色性能的比橙色稍红的色调而著名。
在式(II),(III)和(IV)中,与式(I)中的R1,R2和R3相同的其它的优选项分别适用于R8,R9和R10。
特别优选下式的化合物:
当用于本体着色高分子量材料,特别是塑料和塑料纤维时,式(I),(II),(III),(IV),(V)和(VI)的化合物产生令人惊讶的高温稳定不褪色且强着色的着色。
本发明的着色剂可以根据本身已知的方法或者与其类似的方法制备,并且以纯净物形式分离和干燥,然后它们易于分散于塑料,表面涂料和印刷油墨中,例如使用球磨机或珠磨机。它们还可以以湿的压缩饼的形式直接用于生产颜料分散体。为了提高用途相关的性能,常规的添加剂可以任选地在沉淀或者分离之前或者在沉淀或者分离过程中以常规的浓度加入本发明的着色剂中。
本发明因此还涉及一种本体着色的高分子量材料,其包含基于总的着色高分子量材料0.01-70重量%的式(I),(II),(III),(IV),(V)或(VI)的化合物,所述化合物以分布于高分子量材料中的固体粒子的形式或者以溶解的形式均匀渗透高分子量材料。
本发明还涉及式(I),(II),(III),(IV),(V)或(VI)的化合物在高分子量材料的本体着色中的用途。
所述高分子量材料优选是聚烯烃,例如高密度、中密度或者低密度聚乙烯(HDPE,HDPE-HMW,HDPE-UHMW,LDPE,LLDPE,VLDPE,ULDPE),聚丙烯或者聚异丁烯,实现了令人惊讶的程度的高温稳定性,这甚至对于在聚酰胺中的应用也是令人感兴趣的。
虽然本发明的着色剂特别适于本体着色聚烯烃,更特别的是聚乙烯,但是它们还可以有利地用于本体着色其它聚合物。
本发明的待着色的高分子量有机材料可以是天然或者合成来源的,并且通常具有103-108g/mol的分子量。例如,其可以是天然树脂或者干性油,橡胶或者干酪素,或者是改性的天然物质,例如氯化橡胶,油改性的醇酸树脂,纤维胶,或者纤维素醚或酯,例如醋酸纤维素酯,丙酸纤维素酯,乙酰丁酸纤维素酯或者硝基纤维素,但特别的是通过聚合、缩聚或者加成聚合而获得的完全合成的有机聚合物(热固性塑料或者热塑性塑料),例如聚碳酸酯,聚酯,例如聚对苯二甲酸乙二酯或者聚对苯二甲酸丁二酯,聚烯烃,例如聚乙烯,聚丙烯或者聚异丁烯,取代的聚烯烃,例如氯乙烯、醋酸乙烯酯、苯乙烯、丙烯腈或者丙烯酸酯和/或甲基丙烯酸酯或者丁二烯的聚合产物,聚苯乙烯或者聚甲基丙烯酸甲酯,以及所述单体的共聚产物,特别是丙烯腈/丁二烯/苯乙烯(ABS),苯乙烯/丙烯腈(SAN)或者EVA。
在加聚树脂和缩聚树脂的范围中,可以提到甲醛与酚的缩聚产物,所谓的酚醛塑料,和甲醛与脲、硫脲和三聚氰胺的缩聚产物,所谓的氨基塑料,用作表面涂料树脂的聚酯,该聚酯是饱和的例如醇酸树脂,或者是不饱和的例如马来树脂,以及线性聚酯和聚酰胺或者硅树脂。
此外,所述高分子量有机材料可以是用于表面涂料或者印刷油墨的粘合剂,例如煮沸的亚麻子油,硝基纤维素,醇酸树脂,三聚氰胺树脂,脲醛树脂,丙烯酸树脂或者其它可硬化的或者可聚合的前体。
所述的高分子量化合物可以单独使用或者混合使用,以塑料组合物、溶液或者熔融物的形式,可以任选地将该高分子量化合物纺纱以形成纤维。其可以是准备使用的组合物或者由其形成的制品,或者是母炼料,例如颗粒形式的母炼料。任选地,还可以将常规的添加剂根据本发明的着色高分子量有机材料,该添加剂可以包含在未着色的有机材料和着色剂中或者可以在混合过程中加入。
这样的添加剂的例子是稳定剂,例如抗氧化剂,UV稳定剂或者光稳定剂,表面活性剂,润湿剂,增塑剂或者结构改进剂。当需要结构改进剂时,任选将其在合成过程中或在后处理过程中尽早加入,优选加入到本发明的着色剂中。
结构改进剂是例如具有至少12个碳原子的脂肪酸,例如特别是硬脂酸或者山萮酸,硬脂酸酰胺或者山萮酸酰胺,硬脂酸或者山萮酸的盐,例如硬脂酸或者山萮酸的镁、锌或者铝盐,以及季铵化合物,例如特别是三(C1-C4)烷基苄基铵盐,例如三甲基-,三乙基-,三正丙基-,三异丙基-,三正丁基-,三仲丁基-和三叔丁基-苄基铵盐,以及增塑剂,例如环氧化大豆油,蜡,例如聚乙烯蜡,树脂酸,例如松香酸,松香皂,氢化或者二聚松香,(C12-C18)-石蜡二磺酸,烷基酚和醇,例如十八烷醇,以及月桂胺或者硬脂胺,和/或脂族1,2-二醇,例如1,2-十二烷二醇。
优选的结构改进剂是月桂胺和硬脂胺,脂族1,2-二醇,硬脂酸及其酰胺、盐和酯,环氧化大豆油,蜡和树脂酸。
这样的添加剂可以例如有利的以基于本发明组合物0.05-25重量%,优选0.5-15重量%的量在本发明的组合物制备之前、制备过程中或之后加入。
用本发明的着色剂对高分子量有机物质的着色是例如通过使用辊炼机或者混合或研磨设备将任选的母炼料形式的这样的着色剂与基底混合进行。然后通常将着色的材料通过本身已知的方法转化为期望的最终形式,例如通过压延、压塑、挤出、涂覆、喷涂、浇铸、印刷或者通过注塑。为了制造非刚性的模塑品或者降低它们的脆性,将所谓的增塑剂在成型之前掺入高分子量化合物常常是合意的。可以使用例如磷酸、苯二甲酸或者癸二酸的酯作为增塑剂。在本发明的方法中,增塑剂可以在颜料染料掺入之前或者之后掺入聚合物中。为了得到不同的颜色色调,还可以将除了颜料组合物之外的填料或者其它覆色成分(例如白色、彩色或者黑色颜料以及效应颜料)以各自所需的量加入高分子量有机材料。
着色剂的混合还可以在即将进行实际的加工步骤之前,例如通过将本发明的粉状着色剂与颗粒状高分子量有机材料以及任选的另外的成分(例如诸如添加剂)同时直接连续进料到挤出机的入口区进行,其中混合在即将加工之前进行。但是,通常优选预先将着色剂混入高分子量有机材料,因为这样可以实现更均匀的结果。
对于着色表面涂料和印刷油墨,高分子量有机材料和本发明的着色剂通常任选地和添加剂一起细微分散或者溶解在有机和/或水性溶剂或者溶剂混合物中,所述的添加剂是例如稳定剂,分散剂,光泽改进剂,填料,其它颜料,干燥剂或者增塑剂。可以使用一种程序,其中单个组分分别分散或者溶解或者多个组分一起分散或者溶解,并且仅仅随后合并全部组分。
表面涂料例如通过浸涂、刀涂、拉膜、刷涂或者喷涂施用,本发明的涂层在干燥和硬化之后形成,干燥和硬化有利地通过热或者通过照射进行。另外的产生涂膜的施涂方法是粉末涂覆和绕线涂覆方法,其全部的详细内容本身是本领域技术人员已知的。
当待着色的高分子量材料是表面涂料时,它可以是常规的涂料或者特殊的涂料,例如汽车罩面漆。
通常已知的组合物的印刷油墨是通过常规的方法,例如通过凸版印刷(苯胺印刷),平版印刷(胶印,石版印刷),凹版印刷(照相凹版,钢板雕刻),丝网印刷或者喷墨印刷(压电(piezo)或者蒸汽气泡方法),而施用到例如纸张、纸板、金属、木头、皮革、塑料或者纺织品上,用于出版物、图表、包装、钞票、物流单证或者装饰品。另外的油墨组合物可以用于圆珠笔和毡尖笔以及用于墨垫,墨带和墨盒中。
对于本领域技术人员可取的是例行尝试任何他已知的塑料、表面涂料或者印刷油墨组合物,例如公开专利申请的主题的那些或者市售的那些,甚至当他不准确的了解其组成时。
除了本体着色塑料、表面涂料和印刷油墨形式的高分子量有机材料之外,本发明的着色剂还适于例如生产固体调色剂,蜡转印带或者彩色滤光片。
下面的实施例说明本发明而非限制其范围(除非另有指示,“%”总是表示重量%):
实施例1:将7.56g的4-甲基苯胺-2-磺酸(99%)在160ml水中搅拌并用4ml的30%氢氧化钠溶液溶解。然后加入14ml的37%盐酸(工业级)。将该混合物冷却至0-5℃并逐滴加入10ml的4N亚硝酸钠水溶液。2小时之后,将4ml的1N氨基磺酸水溶液加入到该重氮悬浮液中。
将5.55g的2,4-二氨基-6-羟基嘧啶溶解在120ml的含有30%氢氧化钠溶液的水中,然后在30分钟内逐滴加入到冷却的重氮盐悬浮液中。用30%氢氧化钠溶液将pH调节到pH 5.5。将该反应混合物在23℃下搅拌另外18小时。然后将该悬浮液分为两个样品,每个大约300ml。
1)将一部分悬浮液加热至60℃并搅拌另外1小时。然后将该黄色悬浮液通过硬质过滤器过滤,用250ml水清洗并在90℃/5·103Pa下干燥,产生6.2g的下式的产物:当该产物用于本体着色PVC(压延机)和HDPE(注塑)时,产生热稳定的黄色着色。
分析:C H N S Na
[%] 40.0 3.92 6.1 9. 5<1ppm
计算:40.7 3.72 5.9 9.9 -
2)将第二部分悬浮液用在10ml水中的1g的单月桂酸山梨糖醇酯处理。将该混合物加热至60℃并搅拌另外1小时。然后将该黄色悬浮液通过硬质过滤器过滤,残留物用250ml水清洗并在90℃/5·103Pa下的真空舱内干燥,产生7.4g的产物,当该产物用于本体着色PVC(压延机)和HDPE(注塑)时,产生热稳定的黄色着色。
分析:C H N S Na
[%] 43.3 4.5 23.3 8.4 <1ppm
实施例2:将22.7g的4-甲基苯胺-2-磺酸(99%)在450ml水中搅拌。然后加入30ml的37%盐酸(工业级)。将该混合物冷却至0-5℃并逐滴加入40ml的4N的亚硝酸钠水溶液。1.5小时之后,将6ml的1N的氨基磺酸水溶液加入到该重氮盐悬浮液中。
将16.6g的2,4-二氨基-6-羟基嘧啶溶解在360ml的含有30%氢氧化钠溶液的水中,然后用乙酸沉淀并冷却至0-5℃。然后在30分钟内向其中逐滴加入冷却的重氮盐悬浮液,同时用30%氢氧化钠溶液将pH保持在5.5。将该橙色悬浮液在23℃下搅拌另外18小时,然后加热至85℃并搅拌2小时,最后通过硬质过滤器过滤,用1200ml水清洗并在90℃/5·103Pa下干燥,产生37.7g(理论值的96.3%)的产物,当该产物用于本体着色PVC(压延机)和HDPE(注塑)时,产生热稳定的黄色着色。
分析:C H N S Na
[%] 40.4 3.9 26.2 9.6 <1ppm
计算:40.7 3.7 25.9 9.9 -
通过改变pH值还可以获得在一些情况下包含碱金属离子作为M1 +(例如Na+,Li+,K+)的颜料混合物或者固溶体。
实施例3-5:进行类似实施例2的程序,但是当偶合完成时,将磺酸用醋酸钙、醋酸锶或者醋酸铵中和,产生具有下面的结构的化合物,当该化合物用于本体着色PVC(压延机)和HDPE(注塑)时,产生热稳定的黄色着色:
实施例7-10:进行类似于实施例2-5的程序,但是使用等价量的2-甲基苯胺-4-磺酸代替4-甲基苯胺-2-磺酸。结果非常类似于实施例2-5的那些结果。
实施例11-14:进行类似于实施例2-5的程序,但是使用等价量的苯胺-4-磺酸代替4-甲基苯胺-2-磺酸。结果非常类似于实施例2-5的那些结果,但是具有稍微更淡绿的色调。
实施例15-16:进行类似于实施例2-3的程序,但是使用等价量的苯胺-3-磺酸代替4-甲基苯胺-2-磺酸,这里另外加入了20重量%(基于理论上可获得的颜料的量)的松香树脂来改进结构。
实施例17-20:进行类似于实施例2-5的程序,但是使用等价量的2-氨基-5-氯-4-乙基苯磺酸代替4-甲基苯胺-2-磺酸:
结果非常类似于实施例2-5的那些。
实施例21-24:进行类似于实施例2-5的程序,但是使用等价量的2-氨基-5-甲氧基苯磺酸代替4-甲基苯胺-2-磺酸:
结果非常类似于实施例2-5的那些,但是具有更淡红到橙色的颜色。
实施例25-28:进行类似于实施例2-5的程序,但是使用等价量的5-乙酰氨基-2-氨基苯磺酸代替4-甲基苯胺-2-磺酸:
结果非常类似于实施例2-5的那些,但是具有更淡红到橙色的颜色。
实施例29-32:进行类似于实施例2-5的程序,但是使用等价量的4-乙酰氨基-2-氨基-5-(2′-磺苯基偶氮)-苯磺酸代替4-甲基苯胺-2-磺酸:
结果非常类似于实施例2-5的那些,但是具有更淡红到橙色的颜色。
实施例33-36:进行类似于实施例2-5的程序,但是使用等价量的4-氨基-2-二甲基氨基-6-羟基嘧啶代替2,4-二氨基-6-羟基嘧啶:
结果非常类似于实施例2-5的那些,但是具有更淡红到橙色的颜色。
实施例37-66:将根据实施例7-36获得的颜料用于本体着色在压延机上的PVC,产生具有良好的光稳定性的均匀着色。
实施例67-96:将根据实施例7-36获得的颜料用于本体着色在注塑法中的HDPE,产生具有良好的光稳定性的均匀着色。
实施例97-122:将0.2重量%的根据实施例7-32获得的颜料依照实施例6掺入聚酰胺6中,此后通过在240℃下注塑生产测试板(例如30×50×2mm)。获得具有良好的光稳定性的均匀着色。
Claims (11)
1.一种本体着色高分子量材料的方法,在该方法中在成型之前或者在成型过程中将式(I)的化合物或者其互变异构体掺入所述高分子量材料中,
其中
M1是H、1/2M2、1/3M3或者NR4R5R6R7,优选是H、1/2M2或者NR4R5R6R7,特别是H,
M2是处于氧化态II的碱土金属或者过渡金属或者是处于氧化态IV的氧合金属,
M3是Al(III)、处于氧化态III的过渡金属或者处于氧化态V的氧合金属,
R1是H或者非离子取代基,
R2是H或者是独立于R1的另外的非离子取代基,
R3是H、C1-C6烷基、苯基、CO-C1-C6烷基或者CO-苯基,优选是H或者CO-C1-C6烷基,特别是H,且
R4、R5、R6和R7彼此独立的是H或者未取代的或可由羟基或由卤素取代的苯基、苄基或者C1-C6烷基,并且在C3-C6烷基的情况中是未被中断的或者由O中断。
2.根据权利要求1的方法,其中M2是Ca、Co、Cu、Fe、Mg、Mn、Sr、TiO、Zn或者ZrO,或者M3是Al、Ce、Co、Cr、Fe或者VO。
3.根据权利要求1或者2的方法,其中R1是对位哈米特常数σp为-0.3至0.6的非离子取代基,且R2是H或者是独立于R1的对位哈米特常数σp为-0.3至0.6的另外的非离子取代基。
4.根据权利要求1、2或者3的方法,其中在式(I)中,SO3M处于偶氮桥的邻位。
5.一种式(II)的化合物或者其互变异构体,
其中
M1是H、1/2M2、1/3M3或者NR4R5R6R7,优选是H、1/2M2或者NR4R5R6R7,特别是H,
R8是对位哈米特常数σp为-0.3至0.6,优选-0.3至0.3的非离子取代基,
R9是H或者是独立于R8的对位哈米特常数σp为-0.3至0.6,优选-0.3至0.3的另外的非离子取代基,
R10是H、C1-C6烷基、苯基,CO-C1-C6烷基或者CO-苯基,优选是H或者CO-C1-C6烷基,特别是H,且
R4、R5、R6和R7彼此独立的是H或者未取代的或可由羟基或由卤素取代的苯基、苄基或者C1-C6烷基,并且在C3-C6烷基的情况中是未被中断的或者由O中断。
9.一种本体着色的高分子量材料,其包含基于总的着色的高分子量材料0.01-70重量%的根据权利要求1-7的任一项的式(I),(II),(III),(IV),(V)或(VI)的化合物,或者根据权利要求8的混合物或者固溶体,其是以分布在高分子量材料中的固体粒子的形式或者以溶解的形式均匀渗透高分子量材料。
10.根据权利要求9的本体着色的高分子量材料,其中该高分子量材料是聚烯烃。
11.根据权利要求1-7的任一项的式(I),(II),(III),(IV),(V)或者(VI)的化合物,或者根据权利要求8的混合物或者固溶体在高分子量材料的本体着色中的用途。
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