CN101687957B - 基于烯丙基醚和乙烯基醚的非离子水溶性添加剂 - Google Patents
基于烯丙基醚和乙烯基醚的非离子水溶性添加剂 Download PDFInfo
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Abstract
本发明涉及可以通过单体(A)、(B)和(C)的聚合获得的共聚物,其中(A)是式(I)的单体,其中A是C2-C4亚烷基,B是不同于A的C2-C4亚烷基,k相应于数0或1,m是0至500的数,n是0至500的数,在此m+n的总和等于1至1000;(B)含芳族基团的烯属不饱和单体;和(C)含烷基的烯属不饱和单体。根据本发明的共聚物适合作为颜料的分散剂。
Description
技术领域
本发明涉及可用作水基颜料制剂的分散剂的新型非离子共聚物和这些共聚物的制备方法。
背景技术
迄今常用的酚醛清漆基非离子分散剂含有由于它们的生产过程引起的烷基酚(经常是壬基酚)和其乙氧基化物的残余物。因为烷基酚乙氧基化物或它们的降解产物在环境中几乎不经历任何降解,所以它们积聚。这是成问题的,因为它们对水生生物具有激素影响。因此,许多国家中已经公布了限制或禁止在开放的物质循环中使用含烷基酚或其乙氧基化物的物质的法规(例如2003/53/EC)。
US 2005 085 563描述了通过乙烯基官能化聚醚和氧化苯乙烯的共聚获得的分散剂。EP-A-0 894 811和EP-A-0 736 553描述了基于不饱和羧酸衍生物和氧亚烷基二醇烷基醚以及二羧酸衍生物的适用于水硬性粘结剂,尤其是水泥中的共聚物。DE-A-100 17 667描述了此类共聚物用于制备水性颜料制剂的用途。
到目前为止的研究已经表明,仍极其难以合成等效于非离子酚醛清漆体系的分散剂。因此需要能够将浓度大于40%的高浓度有机颜料分散成低粘度形式的新型分散剂。这些分散体必须可容易地制备,即颜料必须可容易地被润湿和可容易地被引入到水性介质中。分散体必须具有高和可再现的着色强度并且这种着色强度必须保持稳定数年的时间。同样地,所有其它色彩参数例如色调角和纯净度应该是可再现和稳定的。另外,分散体必须具有低粘度;颜料既不允许附聚也不允许絮凝,又不允许它们浮起或沉降。分散体应该不起泡或在应用介质中不引起或加速泡沫形成。另外,分散剂应该有助于分散体在各种应用介质中的宽的相容性。此外,分散体必须剪切稳定,即在剪切作用下着色强度或色彩性能不允许改变,并且分散体在这些条件下必须保持絮凝稳定。
发明内容
现已令人惊奇地发现,利用由聚乙二醇/聚丙二醇单乙烯基醚或单烯丙基醚组成的大分子单体制备的特定非离子梳状共聚物达到这一目的。
本发明因此提供可通过单体(A)、(B)和(C)的聚合获得的共聚物,其中
(A)是式(I)的单体
其中
A表示C2-C4-亚烷基,
B表示不同于A的C2-C4-亚烷基,
k相应于数0或1,
m是0-500的数,优选0-50;
n是0-500的数,优选0-50;
在此m+n的总和是1-1000;
(B)是含芳族基团的烯属不饱和单体;和
(C)是含烷基的烯属不饱和单体。
本发明的共聚物具有常见的末端基团,这些末端基团通过引发自由基聚合或通过链转移反应或通过链终止反应而形成,例如质子、衍生自自由基引发剂的基团或衍生自链转移剂的含硫基团。
单体的摩尔比例优选是1-80%单体(A),0.1-80%单体(B)和0.1-80%单体(C)。尤其优选单体的摩尔比例是10-70%单体(A),10-60%单体(B)和10-60%单体(C)。
在优选的单体(A)中,A表示亚乙基,B表示亚丙基,或A表示亚丙基,B表示亚乙基。氧化亚烷基单元(A-O)m和(B-O)n可以以无规排列形式存在,或如在优选的实施方案的情况下,以嵌段状排列形式存在。氧化亚烷基单元的总和原则上可以是n+m=1-1000,1-500是优选的,2-100是尤其优选的,5-100是更优选的。
优选的单体(B)可以由式(IIa)或式(IIb)描述:
其中
Xa表示含3-30个碳原子的芳族或芳脂族基团,该基团任选地含有N、O和S杂原子中的一种或多种,
Za表示H或(C1-C4)-烷基,
Zb表示H或(C1-C4)-烷基,
Zc表示H或(C1-C4)-烷基;
其中
R1表示氢或甲基,
Xb表示含3-30个碳原子的芳族或芳脂族基团,该基团任选地含有N、O和S杂原子中的一种或多种,
Wa表示氧或NH基。
单体(B)包括例如丙烯酸和甲基丙烯酸的以下酯和酰胺:苯基、苄基、甲苯基、2-苯氧基乙基、苯乙基。其它单体(B)是乙烯基芳族单体例如苯乙烯和其衍生物,例如乙烯基甲苯,α-甲基苯乙烯。芳族单元还可以是指杂芳族单元,例如在1-乙烯基咪唑中。尤其优选的单体(B)可以是:苯乙烯、1-乙烯基咪唑、甲基丙烯酸苄基酯、甲基丙烯酸2-苯氧基乙酯和甲基丙烯酸苯乙酯。
优选的单体(C)可以由式(IIIa)或式(IIIb)描述:
其中
R2表示氢或甲基,
Y表示含1-30个碳原子,优选6-30,尤其是9-20个碳原子的脂族烃基,该基团可以是直链或支化或环状的,并且可以含有杂原子O、N和/或S,并也可以是不饱和的,
Wb表示氧或NH基;
其中
R3表示含1-30个碳原子,优选6-20,尤其8-12个碳原子的脂族烃基,该基团可以是直链或支化或环状的,并且可以含有杂原子O、N和/或S并且也可以是不饱和的。
单体(C)包括例如丙烯酸和甲基丙烯酸的以下酯和酰胺:甲基、乙基、丙基、异丙基、正丁基、异丁基、叔丁基、戊基、己基、2-乙基己基、3,3-二甲基丁基、庚基、辛基、异辛基、壬基、月桂基、鲸蜡基、硬脂基、二十二烷基、环己基、三甲基环己基、叔丁基环己基、冰片基、异冰片基、金刚烷基、(2,2-二甲基-1-甲基)丙基、环戊基、4-乙基-环己基、2-乙氧基乙基、四氢糠基和四氢吡喃基。单体(C)还包括羧酸的乙烯基酯,例如月桂酸乙烯酯、肉豆蔻酸乙烯酯、硬脂酸乙烯酯、山萮酸乙烯酯、新戊酸乙烯酯、新己酸乙烯酯、新庚酸乙烯酯、新辛酸乙烯酯、新壬酸乙烯酯、新癸酸乙烯酯和新十一烷酸乙烯酯。在此同样可以使用由这些羧酸的混合物得到的乙烯基酯。
优选的单体(C)是丙烯酸和甲基丙烯酸的以下烷基酯或烷基酰胺:甲基、乙基、丙基、丁基、异丁基、2-乙氧基乙基、肉豆蔻基、十八烷基,更优选2-乙基己基和月桂基。
本发明的共聚物具有103g/mol-109g/mol,更优选103-107g/mol,甚至更优选103-105g/mol的分子量。
通过单体(A)与芳族和脂族单体(B)和(C)的结合成功实现模拟酚醛清漆型分散剂的性能,以致获得非常类似的性能分布。
本发明的共聚物可以利用自由基聚合制备。聚合反应可以连续、间歇或半连续地进行。聚合反应有利地作为沉淀聚合、乳液聚合、溶液聚合、本体聚合或凝胶聚合进行。溶液聚合对于本发明共聚物的性能分布尤其有利。
可用作聚合反应的溶剂的是对自由基聚合反应很大程度上表现为惰性的所有有机或无机溶剂,实例是乙酸乙酯、乙酸正丁酯或乙酸1-甲氧基-2-丙酯,以及醇,例如乙醇、异丙醇、正丁醇、2-乙基己醇或1-甲氧基-2-丙醇,此外还有二醇例如乙二醇和丙二醇。同样可以使用酮例如丙酮、丁酮、戊酮、己酮和甲基乙基酮,乙酸、丙酸和丁酸的烷基酯例如乙酸乙酯、乙酸丁酯和乙酸戊酯,醚例如四氢呋喃、二乙醚和乙二醇单烷基醚、乙二醇二烷基醚、聚乙二醇单烷基醚和聚乙二醇二烷基醚。同样可以使用芳族溶剂例如甲苯、二甲苯或更高沸点的烷基苯。溶剂混合物的使用同样是可想得到的,在这种情况下,溶剂的选择取决于本发明共聚物的预期用途而定。优选使用水;低级醇;优选甲醇,乙醇,丙醇,异-、仲-和叔-丁醇,2-乙基己醇,丁基乙二醇和丁基二甘醇,更优选异丙醇,叔丁醇,2-乙基己醇,丁基乙二醇和丁基二甘醇;含5-30个碳原子的烃和上述化合物的混合物和乳液。甲基乙基酮、甲基异丁基酮和异丙醇是尤其优选的溶剂。
聚合反应优选在0-180℃,更优选10-100℃的温度范围中,不但在常压下而且在升高的或降低的压力下进行。如果需要的话,聚合也可以在惰性气体气氛下,优选在氮气下进行。
可以使用高能电磁辐射、机械能或常用的化学聚合引发剂,例如有机过氧化物,例如过氧化苯甲酰、氢过氧化叔丁基、过氧化甲基乙基酮、过氧化枯酰、过氧化二月桂酰(DLP),或偶氮引发剂,例如偶氮二异丁腈(AIBN)、偶氮双酰氨基丙基盐酸盐(ABAH)和2,2′-偶氮双(2-甲基丁腈)(AMBN),引发聚合。同样适合的是无机过氧化合物,例如(NH4)2S2O8、K2S2O8或H2O2,非必要地与还原剂(例如亚硫酸氢钠、抗坏血酸、硫酸铁(II))或含脂族或芳族磺酸(例如苯磺酸、甲苯磺酸)作为还原性组分的氧化还原体系结合使用。
使用常用的化合物作为分子量调节剂。适合的已知调节剂是例如醇,例如甲醇、乙醇、丙醇、异丙醇、正丁醇、仲丁醇和戊醇,醛,酮,烷基硫醇,例如十二烷基硫醇和叔十二烷基硫醇,巯基乙酸,巯基乙酸异辛酯和一些卤素化合物,例如四氯化碳、氯仿和二氯甲烷。
本发明进一步提供本发明的共聚物作为尤其用于颜料和填料,例如在水性颜料浓缩物制备中的分散剂的用途,所述水性颜料浓缩物用于将乳胶漆和油光漆(Lackfarben)、油漆、涂料和印刷油墨着色,此外还用于将纸、卡纸和纺织品着色。
具体实施方式
合成实施例
合成规程1
初始在氮气导入下将在溶剂中的单体A、单体C和非必要的分子量调节剂装入配备有搅拌器、回流冷凝器、内部温度计和氮气入口的烧瓶。然后,在搅拌下使温度达到80℃并在一小时的过程中计量添加引发剂的溶液。同时,开始计量添加单体B,其在3小时之后结束。接着在该温度下另外进一步搅拌2小时,然后在减压下除去溶剂。
合成规程2
初始在氮气导入下将在溶剂中的单体A、单体C和非必要的分子量调节剂和氧化还原引发剂体系的组分1(抗坏血酸)装入配备有搅拌器、回流冷凝器、内部温度计和氮气入口的烧瓶。然后,在搅拌下使温度达到80℃并在三小时的过程中计量添加氧化还原引发剂体系的组分2(t-BuOOH)的溶液。同时,开始计量添加单体B,其在3小时之后结束。接着在该温度下另外进一步搅拌2小时,然后在减压下除去溶剂。
以下三个表含有类似于上述两个一般合成规程进行的合成实施例。
AMBN=2,2′-偶氮双(2-甲基丁腈)
表1-3中的单体A的组成:
聚二醇1
聚亚烷基二醇单乙烯基醚(式(I),k=0,n=0,m=11.5;(A-O)对应于(CH2CH2O)),摩尔质量大约550g/mol
聚二醇2
聚亚烷基二醇单乙烯基醚(式(I),k=0,n=0,m=24;(A-O)对应于(CH2CH2O)),摩尔质量大约1100g/mol
聚二醇3
聚亚烷基二醇单乙烯基醚(式(I),k=0,n=0,m=44.5;(A-O)对应于(CH2CH2O)),摩尔质量大约2000g/mol
聚二醇4
聚亚烷基二醇单乙烯基醚(式(I),k=0,n=0,m=135.4;(A-O)对应于(CH2CH2O)),摩尔质量大约6000g/mol
聚二醇5
聚亚烷基二醇单烯丙基醚(式(I),k=1,n=0,m=6.6;(A-O)对应于(CH2CH2O)),摩尔质量大约350g/mol
聚二醇6
聚亚烷基二醇单烯丙基醚(式(I),k=1,n=0,m=10;(A-O)对应于(CH2CH2O)),摩尔质量大约500g/mol
聚二醇7
聚亚烷基二醇单烯丙基醚(式(I),k=1,n=0,m=21.4;(A-O)对应于(CH2CH2O)),摩尔质量大约1000g/mol
聚二醇8
聚亚烷基二醇单烯丙基醚(式(I),k=1,氧化亚乙基/氧化亚丙基比6∶4(无规聚合的),摩尔质量大约500g/mol
聚二醇9
聚亚烷基二醇单烯丙基醚(式(I),k=1,氧化亚乙基(B-O)/氧化亚丙基(A-O)比11∶4(嵌段共聚物),摩尔质量大约750g/mol
聚二醇10
聚亚烷基二醇单烯丙基醚(式(I),k=1,氧化亚乙基(B-O)/氧化亚丙基(A-O)比20∶10(嵌段共聚物),摩尔质量大约1500g/mol
聚二醇11
聚亚烷基二醇单烯丙基醚(式(I),k=1,氧化亚乙基/氧化亚丙基比20∶20(无规聚合的),摩尔质量大约2100g/mol
应用实施例
颜料制剂的制备:
将颜料以粉末、颗粒或滤饼形式与分散剂和其它添加剂一起在去离子水中调成糊剂,然后采用溶解器(例如得自于VMA-Getzmann GmbH公司,AE3-M1型)或者其它合适的设备将其均化和预分散。随后使用珠磨机(例如采用得自于VMA-Getzmann的AE3-M1)或者其它合适的分散设备组而进行细分散,其中在冷却下采用尺寸d=1mm的硅石英岩(Siliquarzit)珠粒或锆混合氧化物珠粒进行研磨,直到达到所希望的着色强度和色彩性能。此后,用去离子水将分散体调节至所希望的最终颜料浓度,将研磨介质分离出,并且将颜料制剂离析。
颜料制剂的评价:
着色强度和色调根据DIN 55986测定。为进行擦去试验(″Rub-Out-Test″),在与颜料分散体混合之后将乳胶漆施涂到漆卡上。随后在漆卡的底部上用手指后摩擦。如果经后摩擦的区域然后比邻接的未后处理的区域更艳地着色,则存在不相容性(该擦去试验描述于DE 2638946中)。使用用于外部涂漆的乳胶漆(水基,20%TiO2)测定着色强度和与待着色介质的相容性。
采用Haake公司的锥-板式粘度计(Roto Visco 1)在20℃下测定粘度(钛锥体:,1°),其中在0-200s-1的范围内研究粘度对剪切率的依赖关系。在60s-1的剪切率下测量粘度。为了评价分散体的存储稳定性,在制得制剂之后直接地测量粘度以及在50℃下存储四周之后测量粘度。
以下实施例中描述的颜料制剂根据上述方法制备,其中以下成分以给出的数量使用以致形成100份的颜料制剂。在下述实施例中份数是重量份:
50份 C.I.颜料黄1
6份 合成实施例3(表)的聚合物
1份 增湿剂
10份 丙二醇
0.2份 防腐剂
32.8份 水
该颜料制剂在白色分散体中具有高着色强度并且是稳定的。擦去试验表明与后摩擦区域相比没有任何着色强度差异。分散体经证实可良好流动并且储存稳定,因为在50℃下储存28天之后它同样仍可良好地流动。制成之后的粘度是494mPa·s。
Claims (11)
2.根据权利要求1的共聚物,其中单体(A)的摩尔比例是1-80%,单体(B)的摩尔比例是0.1-80%,单体(C)的摩尔比例是0.1-80%。
3.根据权利要求1或2的共聚物,其中单体(A)的摩尔比例是10-70%,单体(B)的摩尔比例是10-60%,单体(C)的摩尔比例是10-60%。
4.根据权利要求1或2的共聚物,其中氧化亚烷基单元(A-O)m和(B-O)n以嵌段状排列。
7.根据权利要求1或2的共聚物,其中单体(B)是苯乙烯、1-乙烯基咪唑、甲基丙烯酸苄基酯、甲基丙烯酸2-苯氧基乙酯或甲基丙烯酸苯乙酯。
8.根据权利要求1或2的共聚物,其中单体(C)是丙烯酸或甲基丙烯酸的烷基酯或烷基酰胺,其中所述烷基选自甲基、乙基、丙基、丁基、异丁基、2-乙基己基、2-乙氧基乙基、肉豆蔻基、月桂基和十八烷基。
9.根据权利要求1-8中任一项的共聚物的制备方法,其中将单体(A)、(B)和(C)自由基聚合。
10.根据权利要求1-8中任一项的共聚物作为分散剂的用途。
11.根据权利要求10的用途,其中所述分散剂是颜料和填料的分散剂。
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PCT/EP2008/006023 WO2009024235A1 (de) | 2007-08-23 | 2008-07-23 | Nichtionische wasserlösliche additive auf allyl- und vinyletherbasis |
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DE102007021867A1 (de) | 2007-05-10 | 2008-11-20 | Clariant International Limited | Pigmentpräparationen auf Wasserbasis |
DE102007039783A1 (de) * | 2007-08-23 | 2009-02-26 | Clariant International Ltd. | Wässrige Pigmentpräparationen mit anionischen Additiven auf Allyl- und Vinyletherbasis |
DE102007039781A1 (de) * | 2007-08-23 | 2009-02-26 | Clariant International Ltd. | Wässrige Pigmentpräparationen mit nichtionischen Additiven auf Allyl- und Vinyletherbasis |
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DE19513126A1 (de) | 1995-04-07 | 1996-10-10 | Sueddeutsche Kalkstickstoff | Copolymere auf Basis von Oxyalkylenglykol-Alkenylethern und ungesättigten Dicarbonsäure-Derivaten |
EP0921167A4 (en) * | 1996-08-22 | 2000-01-12 | Kaneka Corp | CURABLE COMPOSITION FOR EXTERIOR COATING AND ARTICLES THEREOF COVERED |
DE19834173A1 (de) | 1997-08-01 | 1999-02-04 | Sueddeutsche Kalkstickstoff | Copolymere auf Basis von ungesättigten Dicarbonsäure-Derivaten und Oxyalkylenglykol-Alkenylethern |
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US5157069A (en) * | 1991-08-07 | 1992-10-20 | Basf Corporation | Nonionic waterborne basecoat using metallic pigments and clear topcoat |
US5399618A (en) * | 1993-06-28 | 1995-03-21 | Union Carbide Chemical & Plastics Technology Corporation | Processes for preparing aqueous polymer emulsions |
US6777517B1 (en) * | 1999-06-11 | 2004-08-17 | Degussa Construction Chemicals Gmbh | Copolymers based on unsaturated mono-or dicarboxylic acid derivatives and oxyalkylene glycol alkenyl ethers, method for the production and use thereof |
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