CN100572460C - 包含具有盐基的聚合物的防垢组合物 - Google Patents
包含具有盐基的聚合物的防垢组合物 Download PDFInfo
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- CN100572460C CN100572460C CNB2005800039833A CN200580003983A CN100572460C CN 100572460 C CN100572460 C CN 100572460C CN B2005800039833 A CNB2005800039833 A CN B2005800039833A CN 200580003983 A CN200580003983 A CN 200580003983A CN 100572460 C CN100572460 C CN 100572460C
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- salt
- polymkeric substance
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- monomer
- polymer
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- 125000003277 amino group Chemical group 0.000 claims abstract description 26
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Abstract
本发明涉及包含与聚合物骨架连接(侧接)的胺官能基团的盐和/或膦官能基团的盐的聚合物在防垢组合物中的用途,所述盐包含具有含至少5个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基作为相反离子。本发明还涉及包含这种聚合物的防垢组合物。
Description
本发明涉及尤其用于海洋应用的防垢漆。
浸入水中的人造结构体如船壳、浮标、钻井平台、石油生产钻塔和管道易于被水生生物如绿藻、褐藻、藤壶、贻贝等结垢。这类结构体通常是金属的,但也可能包含其它结构材料如混凝土。在船壳上的这种结垢是有害的,因为它增加了在水中移动时的摩擦阻力,结果是使速度降低并且增加了燃料成本。它在静态结构体如钻井平台和石油生产钻塔的支架上是有害的,首先因为厚的结垢层对浪和水流的阻力可在结构体中产生不可预测和潜在危险的应力,其次因为结垢使得难以检测结构体的缺陷如应力开裂和腐蚀。它在管道如冷却水的进口和出口中是有害的,因为结垢使有效的横截面积减小,结果是使流速下降。
已知将防垢漆例如作为船壳面漆用于抑制海洋生物如藤壶和藻类的定居和生长,通常通过释放用于海洋生物的生物杀伤剂而进行抑制。
防垢漆通常包含较惰性的粘合剂和从漆中浸出的生物杀伤颜料。已使用的粘合剂是乙烯基树脂和松香。乙烯基树脂不溶于海水并且基于它们的漆使用高颜料浓度,以使颜料颗粒之间接触而确保浸出。松香是在海水中的溶解度非常小的硬脆树脂。基于松香的防垢漆曾被称为可溶性基质或侵蚀漆。生物杀伤颜料从所用松香粘合剂基质中非常缓慢地浸出,留下松香骨架基质,从外壳表面洗刷掉该松香骨架基质使得生物杀伤颜料可从漆膜深处浸出。
近年来,许多成功的防垢漆为基于聚合物粘合剂的“自抛光共聚物”漆,其中生物杀伤三有机锡部分与该聚合物粘合剂化学连接,且生物杀伤部分通过海水由其逐渐水解。在这种粘合剂体系中,线性聚合物单元的侧基在第一步中通过与海水反应而断裂,结果是使剩余聚合物框架变为水溶性或水分散性。在第二步中,在船的漆层表面上的水溶性或水分散性框架被洗刷掉或被侵蚀。这类漆体系例如描述于GB-A-1 457 590中。
由于三有机锡已经在全世界禁止使用,需要可用于防垢组合物的替代防垢物质。释放非生物杀伤部分的自抛光共聚物漆描述于EP-A-69 559、EP-A-204 456、EP-A-529 693、EP-A-779 304、WO-A-91/14743、WO-A-91/09915、GB-A-231 070和JP-A-9-286933中。
US-A-4,675,051描述了一种逐渐溶于海水的海洋防垢漆,其包含通过使松香与含有至少一个伯氨基或仲氨基的脂族多胺反应而产生的树脂形式的粘合剂。EP-A-802 243描述了一种包含松香化合物、含有机硅酯基的聚合物和防垢剂的涂料组合物。
WO-A-02/02698描述了一种逐渐溶于海水的防垢漆。该漆包含粘合剂和具有海洋生物杀伤性能的成分。粘合剂包含松香材料和辅助成膜树脂。辅助成膜树脂包含非水解性、水不溶性成膜聚合物和酸官能成膜聚合物,酸官能成膜聚合物的酸基由季铵基或季鏻基保护。在第一步中,保护基团水解、离解或与海水物质交换,结果是使剩余聚合物框架变得可溶于或可分散于海水中。在第二步中,在船的漆层表面上的水溶性或水分散性框架被洗刷掉或被侵蚀。
周作酸官能聚合物上的保护基团的季铵基或季鏻基的结构影响了漆溶解或侵蚀速率。尽管较长链季铵基确保漆降解慢,但这些基团的毒性随着尺寸增加而更强。该毒性例如用于在JP-A-2-120372中所述的防霉涂料组合物中。
GB-A-2 273 934描述了一种替换基于有机锡的防垢体系的粘合剂体系。所述可水解的聚合物粘合剂之一包含与聚合物骨架连接的含卤化铵盐的基团。这种聚合物粘合剂通过使包含(甲基)丙烯酰胺官能的卤化铵盐单体共聚而制备。由于卤化铵盐基,这些聚合物粘合剂部分溶于海水。然而,由于整个粘合剂开始就在一定程度上溶于海水,漆侵蚀较快。
JP-A-07 082511描述了替换基于有机锡的防垢体系的另一粘合剂体系。所述可水解的聚合物粘合剂之一包含与聚合物骨架连接的鏻盐基。鏻离子的相反离子是小基团如卤离子,甲酸、乙酸或草酸的残基,硫酸根离子或者磷酸离子。由于小鏻盐基,这些聚合物粘合剂部分溶于海水。然而,由于整个粘合剂开始就在一定程度上溶于海水,漆侵蚀较快。
上述包含盐基的粘合剂是锡体系的替代物,但那些体系的侵蚀速率较快。因此,需要一种开始在海水中溶解较差的包含盐基的粘合剂聚合物,而相反离子可水解、可离解或可与海水物质交换,结果是使剩余的聚合物框架变得可溶于或可分散于海水中。
本发明涉及可解决上述问题/缺点的聚合物在防垢组合物中的用途、包含聚合物的防垢组合物以及这类防垢组合物保护浸入水中的人造结构体如船壳、浮标、钻井平台、石油生产钻塔和管道的用途。
用于本发明的粘合剂聚合物为包含与聚合物骨架连接(侧接)的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物,所述盐包含具有含至少5个,优选至少6个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基作为相反离子。所述粘合剂聚合物包含由式(I)基团组成或包含式(I)基团的一种或多种与聚合物骨架连接的胺官能基团的盐和/或一种或多种膦官能基团的盐:
其中
Y为O或NH,Z为N或P,R1为氢原子或C1-C4烷基,优选氢或C1-C2烷基。
R2为C2-C12二价烃基,优选C2-C8二价烃基,更优选C2-C4二价烃基。
R3和R4独立地代表氢原子或烷基,优选C1-C6烷基,更优选甲基,或者代表任选取代的苯基。
X为具有含至少5个,优选至少6个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基。
因此,聚合物包含伯胺和/或仲胺和/或叔胺的盐,和/或伯膦和/或仲膦和/或叔膦的盐。这类聚合物例如描述于JP63-273609中。该日本文献描述了这类聚合物作为用于含大量有机材料的废水的凝结处理剂的用途。
制备用于本发明的含盐基的聚合物的方法可包括下列步骤:
-使长链酸与式(II)的胺官能单体或膦官能单体反应:
其中
Y为O或NH,Z为N或P,R1为氢原子或C1-C4烷基,优选氢或C1-C2烷基。
R2为C2-C12二价烃基,优选C2-C8二价烃基,更优选C2-C4二价烃基。
R3和R4独立地代表氢原子或C1-C6烷基,优选甲基,或者代表任选取代的苯基。
该反应产生包含胺官能基团的盐和/或膦官能基团的盐的单体,所述盐包含具有含至少5个,优选至少6个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基作为相反离子(见上述式(I))。该反应没有形成季铵基或季鏻基。
-使至少一种含盐单体聚合,所述单体包含根据如上定义的式(I)的胺官能基团的盐和/或膦官能基团的盐。
具有含5个或更多个,优选6个或更多个碳原子的脂族、芳族或烷芳烃基的酸可作为长链酸用于首先提及的方法步骤中。例如,酸可以为碳酸、磺酸或硫酸。酸优选包含5个或更多个,更优选6个或更多个,甚至更优选8个或更多个碳原子。酸可以支化。酸可包含环状基团。合适的酸例如为棕榈酸、硬脂酸(steric acid)、乙基己酸、松香和酸官能的松脂酸盐的衍生物。酸优选包含至多50个,更优选至多30个,甚至更优选至多20个,最优选16个碳原子。任选地,酸为具有海洋生物杀伤性能的酸官能的化合物,例如(9E)-4-(6,10-二甲基辛-9,11-二烯基)呋喃-2-甲酸或对(磺基氧基(sulphooxy))肉桂酸(zosteric acid)。
含盐单体或含盐单体混合物的聚合可使用各种共聚单体,任选共聚单体混合物进行。例如,可用不饱和单体进行加成共聚合,该不饱和单体通过使烷基、烷氧基烷基、碳环或杂环醇或胺的酯或酰胺与不饱和羧酸反应而制备,例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸异冰片酯或甲基丙烯酸异冰片酯。或者,不饱和共聚单体可以为乙烯基化合物,例如苯乙烯、乙烯基吡咯烷酮或乙酸乙烯酯。
可使用长链、酸封端的季铵官能单体和/或长链、酸封端的季鏻官能单体进行含盐单体的聚合。这类单体及其聚合描述于WO 2004/018533中。这种单体的季铵官能基团和/或季鏻官能基团为“长链、酸封端”,即其由相反离子中和,该相反离子由具有含6个或更多个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基组成。因此所得聚合物包含伯胺和/或仲胺和/或叔胺的盐,和/或伯膦和/或仲膦和/或叔膦的盐并且它为季铵官能和/或季膦官能。这种体系可称作混合体系。
优选使用至少5摩尔%,更优选至少10摩尔%的含盐单体进行含盐单体的聚合。优选使用小于40摩尔%,更优选小于30摩尔%的含盐单体进行聚合。如果使用含盐单体和季官能单体进行聚合,则含盐单体加上季官能单体的总量优选为至少5摩尔%,更优选至少10摩尔%且优选小于40摩尔%,更优选小于30摩尔%。
本发明涉及包含与聚合物骨架连接(侧接)的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物在防垢涂料组合物中的用途,所述盐包含具有含至少5个,优选至少6个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基作为相反离子。所述粘合剂聚合物包含与聚合物的骨架连接的由如上定义的式(I)基团组成或包含如上定义的式(I)基团的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐。
以构造聚合物的单体总量计算,优选使用的包含与聚合物骨架连接(侧接)的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物构造有至少5摩尔%含盐单体。更优选聚合物包含至少10摩尔%的含盐单体结构单元。优选使用的聚合物包含小于40摩尔%,更优选小于30摩尔%的含盐单体结构单元。
还优选使用的聚合物包含一种或多种含盐单体结构单元以及一种或多种季官能单体结构单元,其中含盐单体结构单元加上季官能单体结构单元的总量为至少5摩尔%,更优选至少10摩尔%且优选小于40摩尔%,更优选小于30摩尔%。
还优选使用包含一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物与任选的包含与聚合物骨架连接(侧接)的一种或多种季铵官能基团和/或季鏻官能基团的聚合物的混合物。以构造混合物中的聚合物的单体总量计算,所述混合物包含的含盐单体结构单元加上(任选存在的)季官能单体结构单元优选为至少5摩尔%。混合物包含的含盐单体结构单元加上季官能单体结构单元更优选为至少10摩尔%。优选使用的聚合物混合物包含的含盐单体结构单元加上季官能单体结构单元小于40摩尔%,更优选小于30摩尔%。
本发明还涉及包含含有与聚合物骨架连接(侧接)的胺官能基团的盐和/或膦官能基团的盐的聚合物的防垢涂料组合物,所述盐包含具有含至少5个,优选至少6个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基作为相反离子。所述粘合剂聚合物包含与聚合物的骨架连接的由如上定义的式(I)基团组成的或包含如上定义的式(I)基团的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐。
涂料组合物优选包含含有与聚合物骨架连接(侧接)的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物,所述聚合物包含至少5摩尔%,更优选至少10摩尔%的含盐单体结构单元。涂料组合物优选包含含有小于40摩尔%,更优选小于30摩尔%的含盐单体结构单元的聚合物。
还优选涂料组合物包含含有一种或多种含盐单体结构单元和一种或多种季官能单体结构单元的聚合物,其中含盐单体结构单元加上季官能单体结构单元的总量为至少5摩尔%,更优选至少10摩尔%且优选小于40摩尔%,更优选小于30摩尔%。
还优选涂料组合物包含含有一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物与任选的包含与聚合物骨架连接(侧接)的一种或多种季铵官能基团和/或季鏻官能基团的聚合物的混合物,所述混合物包含的含盐单体结构单元加上(任选存在的)季官能单体结构单元为至少5摩尔%,更优选至少10摩尔%。涂料组合物优选包含的聚合物混合物包含的含盐单体结构单元加上季官能单体结构单元小于40摩尔%,更优选小于30摩尔%。
在优选实施方案中,在包含一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物中的盐的相反离子一般为低毒性的或甚至为非生物杀伤的。此时本发明防垢涂料组合物应包含具有海洋生物杀伤性能的单独成分。
在另一优选实施方案中,在包含一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物中的盐包含具有海洋生物杀伤性能的成分作为相反离子。此时本发明防垢涂料组合物可包含具有海洋生物杀伤性能的单独成分作为辅助生物杀伤剂。在聚合物的盐基团中掺入生物杀伤剂的优点在于内置生物杀伤剂的释放速率取决于离子交换速率,这比取决于扩散速率的释放速率更可控。用作相反离子的酸官能生物杀伤剂可以为天然或合成化合物并且可源于天然产物。例如,用作相反离子的酸官能生物杀伤剂可以为源于海洋生物的材料。生物杀伤剂优选可易于在海洋环境中降解。
(在水解、离解或与相反离子的海水物质交换之后或过程中)溶于海水或分散于海水中的聚合物框架,即粘合剂优选为低毒性,最优选为非生物杀伤的。
由本发明防垢涂料组合物制备的固化涂层在海水中的溶解速率或侵蚀速率可通过长链酸残基相反离子基团的结构来调节,基本不会有涉及释放基团毒性的问题。长链酸残基相反离子基团例如可以包含长链,和/或可以支化,和/或可包含环状基团。通过改变长链酸残基相反离子基团的疏水性可调节涂层在海水中的溶解或侵蚀速率。用于制备包含一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐的聚合物的盐单体的实际量也可用于调节涂层在海水中的溶解或侵蚀速率。相反离子基团优选包含一种或多种具有包含5-50个,更优选6-50个,甚至更优选6-20个碳原子的脂族烃基的酸的阴离子残基。相反离子例如可由松香或其它松脂酸盐衍生材料的阴离子残基组成。
根据本发明的另一实施方案,除包含与聚合物骨架连接(侧接)的胺官能基团的盐和/或膦官能基团的盐的聚合物外,本发明防垢组合物还包含松香材料作为粘合剂材料,其中所述盐包含具有含至少5个,优选至少6个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基作为相反离子。所述含有盐基团的粘合剂聚合物包含与聚合物的骨架连接的由如上定义的式(I)基团组成或包含如上定义的式(I)基团的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐。松香不是非常好的成膜剂,在基于松香的防垢漆中加入其它成膜树脂是已知的。因此包含松香材料作为粘合剂材料(任选地,松香也可作为相反离子存在于包含胺官能基团的盐和/或膦官能基团的盐的聚合物中)的本发明防垢涂料组合物优选另外包含非水解性、水不溶性成膜聚合物。松香粘合剂材料与包含胺官能基团的盐和/或膦官能基团的盐的聚合物以及任选一种或多种其它成膜树脂的比例影响了漆膜的强度和/或基于松香的漆基质的可靠侵蚀。
根据本发明的优选实施方案,防垢漆具有的粘合剂包含松香材料与辅助成膜树脂的重量比为20∶80-95∶5的共混物,辅助成膜树脂包含20-100重量%的成膜聚合物(A)和至多80%的非水解性、水不溶性成膜聚合物(B),聚合物(A)为具有与聚合物骨架连接(侧接)的胺官能基团的盐和/或膦官能基团的盐的含有盐基团的聚合物,所述盐包含具有含至少5个,优选至少6个碳原子的脂族、芳族或烷芳烃基的酸的阴离子残基作为相反离子。
可作为粘合剂材料加入包含含有胺官能基团的盐和/或膦官能基团的盐的聚合物的组合物中的松香材料优选为松香(rosin),更特别为木松香或者松浆油松香(tall rosin)或脂松香(gum rosin)。松香的主要化学成分为松香酸。松香可以为任何市售品级,优选以WW(水白色)松香出售的松香。松香材料或者可以为松香衍生物,例如马来酸化松香、富马酸化松香、氢化松香、甲酰化松香或聚合松香,或者松香金属盐如松脂酸钙、松香酸镁、松香酸铜或松香酸锌。
非水解性、水不溶性成膜聚合物(B)例如可以为乙烯基醚聚合物如聚(乙烯基烷基醚)或者乙烯基烷基醚与乙酸乙烯酯或氯乙烯的共聚物;丙烯酸酯聚合物如一种或多种优选在烷基中含1-6个碳原子的丙烯酸烷基酯或甲基丙烯酸烷基酯的均聚物或共聚物,其中所述均聚物或共聚物可含有共聚单体如丙烯腈或苯乙烯;或者乙酸乙烯酯的聚合物如聚乙酸乙烯酯或乙酸乙烯酯/氯乙烯共聚物。聚合物(B)或者可以为聚胺,尤其是具有增塑作用的聚酰胺如脂肪酸二聚物的聚酰胺或以商标“Santiciser”出售的聚酰胺。
我们已经发现当非水解性、水不溶性成膜聚合物(B)存在于组合物中时,本发明漆具有成膜和侵蚀性能的最优组合。最优选松香与所有辅助成膜树脂的重量比为25∶75,50∶50或55∶45至至多80∶20。水解或离解的成膜聚合物(A)优选形成至少30重量%,最优选至少50重量%,至多80或90重量%的辅助成膜树脂,剩下的为非水解性、水不溶性聚合物(B)。
可将松香和形成辅助成膜树脂的聚合物在普通溶剂中混合,所述溶剂形成至少部分漆溶剂,例如芳烃如二甲苯、甲苯或三甲基苯,醇如正丁醇,醚醇如丁氧基乙醇或甲氧基丙醇,酯如乙酸丁酯或乙酸异戊酯,醚酯如乙酸乙氧基乙酯或乙酸甲氧基丙酯,酮如甲基·异丁基酮或甲基·异戊基酮,脂族烃如石油溶剂,或者两种或更多种这些溶剂的混合物。
含有或不含松香的本发明防垢漆可包括非聚合物增塑剂。这种增塑剂基于所有粘合剂聚合物例如可以至多50重量%存在,更优选基于粘合剂聚合物为至少10重量%且至多35重量%。这类增塑剂的实例为邻苯二甲酸酯如邻苯二甲酸二丁酯、邻苯二甲酸丁苄酯或邻苯二甲酸二辛酯,磷酸三酯如磷酸三甲苯基酯或磷酸三(异丙基)苯酯,或者氯化石蜡。
具有海洋生物杀伤性能的成分通常为用于水生生物的生物杀伤剂或颜料,或者它们的混合物。可用常规的混合漆的技术将该生物杀伤剂和/或颜料与粘合剂混合。当具有海洋生物杀伤性能的成分为颜料时,它可以是漆的颜料的全部或部分。涂料组合物的颜料体积浓度例如优选为15-55%。
当具有海洋生物杀伤性能的成分为颜料时,颜料可包含含金属颜料,例如在海水中的溶解度为0.5-10重量ppm的含金属颜料。这类也作为水生生物杀伤剂的颜料的实例包括铜或锌化合物,如氧化亚铜、硫氰酸亚铜、硫酸亚铜、亚乙基双二硫代氨基甲酸锌、二甲基二硫代氨基甲酸锌、2-巯基吡啶氧化锌、2-巯基吡啶氧化铜、二乙基二硫代氨基甲酸锌、松脂酸铜或亚乙基双二硫代氨基甲酸亚铜。在海水中的溶解度为0.5-10ppm的其它微溶颜料包括硫酸钡、硫酸钙、白云石和氧化锌。可以使用微溶颜料的混合物:例如为高效生物杀伤颜料额氧化亚铜、硫氰酸亚铜或亚乙基双二硫代氨基甲酸锌可以与不是有效的生物杀伤剂但更迅速地微溶于海水的氧化锌混合。铜金属例如可以薄片或粉末形式作为水生生物杀伤剂存在。
防垢涂料组合物可以含有用于海洋生物的不含金属的生物杀伤剂,即具有海洋生物杀伤性能的成分,该成分为生物杀伤剂但不是颜料。这类化合物的实例为二硫化四甲基秋兰姆、亚甲基二硫氰酸酯、克菌丹、吡啶三苯基硼,取代的异噻唑啉酮(isothiazolone)如4,5-二氯-2-正辛基-4-异噻唑啉-3-酮,2-甲硫基-4-叔丁氨基-6-环丙基氨基均三嗪,N-3,4-二氯苯基-N′,N′-二甲基脲(″敌草隆″),2-(氰硫基甲硫基)苯并噻唑,2,4,5,6-四氯间苯二甲氰,dichlorofluanide,对甲抑菌灵,2-(对氯苯基)-3-氰基-4-溴-5-三氟甲基吡咯,3-苯并(b)噻吩-2-基-5,6-二氢-1,4,2-噁噻嗪4-氧化物,3-丁基-5-(二溴代亚甲基)-2(5H)-呋喃酮以及2,3,5,6-四氯-4-(甲基硫酰基)吡啶,5-甲基-2-(1-甲基乙基)环己醇(L-薄荷醇),薄荷醇丙二醇碳酸酯。这类不含金属的生物杀伤剂可作为涂料的仅有的生物杀伤剂用于不含铜,或甚至不含金属或不含颜料的防垢涂料中。
任选地,防垢组合物包含一种或多种酸官能的生物杀伤剂,例如(9E)-4-(6,10-二甲基辛-9,11-二烯基)呋喃-2-甲酸和对(磺基氧基)肉桂酸(zosteric acid)。这类不含金属的酸官能的生物杀伤剂(混合物)可作为涂料的仅有的生物杀伤剂用于不含铜,或甚至不含金属或不含颜料的防垢涂料中。
作为替换或另外,可将酸官能的生物杀伤剂掺入包含胺官能基团的盐和/或膦官能基团的盐的聚合物中,即聚合物中的一种或多种相反离子可以为酸官能生物杀伤剂的阴离子残基。如果在包含胺官能基团的盐和/或膦官能基团的盐的聚合物中掺入足够的酸官能生物杀伤剂,则不需要单独的具有生物杀伤性能的成分。
除通常为用于水生生物的生物杀伤剂或颜料或其混合物,或者掺入聚合物的生物杀伤剂的具有海洋生物杀伤性能的成分外,涂料组合物还可含有(其它)颜料。例如,不与海水反应并可高度不溶于海水(溶解度低于0.5重量ppm)的颜料如二氧化钛或氧化铁,或有机颜料如酞菁或偶氮颜料。这类高度不溶的颜料的用量优选小于漆的所有颜料组分的60重量%,最优选小于40重量%。
涂料组合物可另外含有其它添加剂,例如常规增稠剂,尤其是触变胶如二氧化硅或膨润土和/或稳定剂如沸石或者脂族胺或芳族胺如脱氢枞胺。
参考如下实施例阐述本发明。这些实施例意欲阐述本发明而不是理解为以任何方式限制其范围。
实施例1(制备棕榈酸盐封端的单体)
为得到N-[3-(二甲基铵)丙基]甲基丙烯酰胺棕榈酸盐,使N-[3-(二甲氨基)丙基]甲基丙烯酰胺与棕榈酸以如下方式反应。
将N-[3-(二甲氨基)丙基]甲基丙烯酰胺(20g,0.1175摩尔)溶于甲醇(400mL)并置于1L三颈圆底烧瓶中。使用漏粉斗并在N2的持续吹扫下将固体棕榈酸(30.13g,0.1175摩尔)加入该搅拌的溶液中。将反应混合物在室温下搅拌过夜。
过滤无色液体以除去任何残留颗粒并在减压下除去溶剂。将所得粘稠液体用1H nmr分析并且没有进一步纯化就使用。
在该反应经常使用的条件下进行上述试验。可以变化这些反应条件。例如,可使用替代的溶剂如乙醇、丙醇、异丙醇、丁醇或者这些溶剂与甲苯的共混物产生单体溶液,该单体溶液可直接转入(没有分离)聚合步骤。此外,反应可在升高温度下进行以缩短周期。
实施例2(制备松香酸(松香)封端的单体)
为得到N-[3-(二甲基铵)丙基]甲基丙烯酰胺松脂酸盐,使N-[3-(二甲氨基)丙基]甲基丙烯酰胺与松香酸以如下方式反应。
将N-[3-(二甲氨基)丙基]甲基丙烯酰胺(20g,0.1175摩尔)溶于甲醇(400mL)并置于1L三颈圆底烧瓶中。使用漏粉斗并在N2的持续吹扫下将固体松香酸(35.54g,0.1175摩尔)加入该搅拌的溶液中。将反应混合物在室温下搅拌过夜。
过滤稻草色液体以除去任何残留颗粒并在减压下除去溶剂。将所得深色粘稠液体用1H nmr分析并且没有进一步纯化就使用。
实施例3(制备聚合物)
将在实施例1中制备的N-[3-(二甲基铵)丙基]甲基丙烯酰胺棕榈酸盐与甲基丙烯酸异冰片酯(iBoMA)(20∶80)聚合而得到50%固体的聚合物溶液。
制备了包含在(3∶1)二甲苯∶丁醇(50g)中的N-[3-(二甲基铵)丙基]甲基丙烯酰胺棕榈酸盐(50.14g,0.1175摩尔)、iBoMA(104.50g,0.47摩尔)和2,2′-偶氮二(2-甲基丁腈)AMBN引发剂(1.13g,0.0059摩尔,1摩尔%)的进料溶液。在机械搅拌和在N2气氛下,将该进料溶液经3.5小时滴加至85℃的含有(3∶1)甲苯∶丁醇(156g)的反应容器中。在单体加完后,将温度升至95℃并加入辅助量的AMBN(0.56g,0.0029摩尔)。在该升高温度下维持反应1小时。将聚合物溶液转移至储存容器中进行冷却。
在该反应经常使用的条件下进行上述试验,但可以变化这些反应条件。可将其它溶剂或由普通漆溶剂组成的溶剂共混物用来替换。其它共聚单体例如为(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、丙烯酸异冰片酯、苯乙烯和其它乙烯基单体。单体的比例也可以改变。胺-酸盐单体的存在量优选为5-40摩尔%,更优选10-30摩尔%。聚合物溶液的粘度使材料配制成固体百分数为45-65%。此外,可使用替代引发剂如αα’-偶氮异丁腈(AIBN)。
实施例4(涂料组合物)
使用高速分散机以所述重量百分数混合下列材料而形成本发明含铜防垢漆。
实施例5(不含铜的涂料组合物)
使用高速分散机以所述重量百分数混合下列材料而形成本发明不含铜的防垢漆。
实施例6(不含铜的涂料组合物)
使用高速分散机以所述重量百分数混合下列材料而形成本发明不含铜的防垢漆。
实施例7(不含铜的涂料组合物)
使用高速分散机以所述重量百分数混合下列材料而形成本发明不含铜的防垢漆。
实施例8(不含锌和铜的涂料组合物)
使用高速分散机以所述重量百分数混合下列材料而形成本发明不含锌和铜的防垢漆。
Claims (10)
2.根据权利要求1的涂料组合物,其特征在于所述阴离子残基包含5-50个碳原子。
3.根据权利要求1或2的涂料组合物,其特征在于所述聚合物或者所述聚合物与存在于组合物中的其它聚合物的混合物,以构造所述聚合物或所述聚合物混合物的单体总量计算包含的含盐单体结构单元加上季官能单体结构单元的总量为5-40摩尔%,其中所述其它聚合物包含与聚合物骨架连接的一种或多种胺官能基团的盐和/或一种或多种膦官能基团的盐和/或一种或多种季铵官能基团和/或一种或多种季鏻官能基团。
4.根据权利要求1或2的涂料组合物,其特征在于所述涂料组合物具有的粘合剂包含松香材料与辅助成膜树脂的重量比为20∶80-95∶5的共混物,辅助成膜树脂包含20-100重量%的成膜聚合物(A)和至多80%的非水解性、水不溶性成膜聚合物(B),聚合物(A)为所述含有盐基团的聚合物。
5.根据权利要求4的涂料组合物,其特征在于所述粘合剂包含松香材料与辅助成膜树脂的重量比为55∶45-80∶20的共混物。
6.根据权利要求4的涂料组合物,其特征在于所述辅助成膜树脂包含30-90重量%的可水解或离解为溶于海水的聚合物的成膜聚合物(A)以及70-10重量%的非水解性、水不溶性成膜聚合物(B)。
7.根据权利要求4的涂料组合物,其特征在于非水解性、水不溶性成膜聚合物(B)为丙烯酸酯聚合物或乙烯基醚聚合物。
8.根据权利要求4的涂料组合物,其特征在于所述粘合剂包括非聚合物增塑剂,该增塑剂的存在量基于所有粘合剂聚合物为至多50重量%。
9.根据权利要求1-8中任一项的涂料组合物用于保护浸入水中的人造结构体如船壳、浮标、钻井平台、石油生产钻塔和管道的用途。
10.根据权利要求9的用途,其中所述人造结构体选自船壳、浮标、钻井平台、石油生产钻塔和管道。
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2005
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