CN107001817B - 含有dcoit的控制释放组合物 - Google Patents

含有dcoit的控制释放组合物 Download PDF

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CN107001817B
CN107001817B CN201580064214.8A CN201580064214A CN107001817B CN 107001817 B CN107001817 B CN 107001817B CN 201580064214 A CN201580064214 A CN 201580064214A CN 107001817 B CN107001817 B CN 107001817B
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dcoit
coating
activated carbon
marine
microns
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B·阿雅伊
D·M·拉根艾拉
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Nutrition And Biotechnology Usa Second Ltd
DDP Specialty Electronic Materials US LLC
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Abstract

一种含有4，5‑二氯‑2‑正辛基异噻唑啉‑3‑酮、表面积为至少700m2/g的活性碳以及固化异氰酸酯的组合物。

Description

含有DCOIT的控制释放组合物
技术领域
本发明涉及含有4，5-二氯-2-正辛基异噻唑啉-3-酮(DCOIT)的控制释放组合物。
背景技术
含有DCOIT的控制释放组合物和活性碳公开于WO2014/074376中。然而，需要从涂料调配物吸收较少粘结剂和/或溶剂同时维持DCOIT的控制释放的控制释放组合物。
发明内容
本发明涉及包含4，5-二氯-2-正辛基异噻唑啉-3-酮、表面积为至少700m2/g的活性碳以及固化异氰酸酯的组合物。
具体实施方式
除非另外规定，否则温度以摄氏度(℃)计，百分比的提及是重量百分比(wt％)，且DCOIT的量和比率是按活性成分计。除非另外规定，否则所有操作均在室温(20-25℃)和正常大气压(101kPa)下进行。如本文所使用，术语「异氰酸酯」是指具有异氰酸酯官能基的化合物或预聚物。如本文所使用，当粒子集具有某一值的D50时，那么50体积百分比的粒子具有小于或等于所述值的直径。对于非球形粒子来说，直径是最大尺寸。船舶涂料组合物是能够在船舶物件的表面上形成干燥涂层的涂料组合物。在形成干燥涂层之后，即使当一些或全部经涂布的表面保持在水下大量的时间(即每天至少一个小时)时，干燥涂层也将粘着于表面持续有用地长的时间。船舶物件是在其中一些或全部物件在水下持续大量的时间的环境中投入使用的那些物件。船舶物件的实例包括船、码头、船坞、桩、鱼网、热交换器、水坝以及管道结构，如进口滤网。优选地，衬底是船舶物件。
海水是来自大海或海洋的水。平均来说，世界海洋中的海水具有约3.5wt％的盐度和1.025g/ml的海洋表面平均密度。人工海水是水与溶解的矿物质盐的混合物，其模拟海水。人工海水的实例是可购自RICCA(ASTM D1141)的合成海水。
优选地，DCOIT和活性碳存在于船舶涂料中，即涂布于船舶物件上。优选地，在涂布于船舶物件表面上之前，将DCOIT和活性碳添加到液体船舶涂料调配物中。在本发明的一个优选实施例中，将DCOIT和活性碳分别添加到液体船舶涂料组合物中。在本发明的一个优选实施例中，DCOIT和活性碳在添加到液体船舶涂料组合物中之前组合。通过将呈熔融物或溶液形式的DCOIT与活性碳混合，DCOIT可以吸附在活性碳上。对于DCOIT来说适合的溶剂是溶解DCOIT、不使其去稳定化且不与活性碳反应的任何溶剂。适合的溶剂包括醇，如甲醇、乙醇以及丙醇；酯，如乙酸乙酯和乙酸丁酯；酮，如丙酮、甲基异丁基酮以及甲基异戊基酮；二甲苯；矿油精；以及腈，如乙腈。优选的溶剂是(C1-C4)醇、二甲苯以及矿油精。优选地，使DCOIT在与活性碳或液体船舶涂料混合之前在溶剂中溶解或成浆液。
用于船舶涂料的衬底可以是未经涂布的表面，例如船舶物件或船舶物件表面上的另一种涂层，例如表面上的底涂剂或涂料的底层。优选地，船舶涂层是环氧树脂涂层、自抛光涂层(例如金属丙烯酸酯共聚物涂料，典型地并有锌或铜羧酸盐基团，或硅烷基丙烯酸酯共聚物涂料)或污损释放涂层(例如硅酮涂料)。船舶涂料组合物包含粘合剂和溶剂以及任选地其它成分。所述溶剂可以是有机溶剂或水。其它成分可以包括无机颜料、有机颜料或染料以及天然树脂。水基涂料还可以含有聚结剂、分散剂、表面活性剂、流变改性剂或粘着促进剂。溶剂基涂料还可以包括增量剂、塑化剂或流变改性剂。典型的船舶涂料组合物包含5％到30％的粘合剂，至多15％的松香/改性松香，0.5％到5％的塑化剂，0.1％到2％的防沉剂，5％到60％的溶剂，至多65％的氧化亚铜，至多30％的颜料(不同于氧化亚铜)以及至多15％的船舶防污剂(包括DCOIT)。优选地，船舶涂料含有至少0.5wt％的DCOIT，优选是至少0.8wt％，优选是至少1wt％，优选是至少1.2wt％，优选是至少1.4wt％，优选是至少1.6wt％，优选是至少1.8wt％，优选是至少2wt％；优选地，船舶涂料含有不超过8wt％的DCOIT，优选是不超过6wt％，优选是不超过5wt％，优选是不超过4.5wt％，优选是不超过4wt％，优选是不超过3.5wt％，优选是不超过3wt％，优选是不超过2.5wt％，优选是不超过2wt％，优选是不超过1.8wt％。优选地，船舶涂料含有至少1wt％的活性碳，优选是至少1.5wt％，优选是至少2wt％，优选是至少2.5wt％，优选是至少3wt％，优选是至少3.5wt％；优选地，船舶涂料含有不超过24wt％的活性碳，优选是不超过20wt％，优选是不超过16wt％，优选是不超过14wt％，优选是不超过12wt％，优选是不超过10wt％，优选是不超过8wt％。
优选地，固化异氰酸酯为固化芳香族异氰酸酯，优选包含二苯基甲烷二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)，优选MDI。MDI可为4，4′和2，4′异构体的混合物。优选地，异氰酸酯为MDI与二醇的异氰酸酯封端的预聚物。优选地，二醇具有62到200，优选90到155的分子量。优选地，预聚物的异氰酸酯当量为135到220，优选160到200。尤其优选的二醇包括二乙二醇、二丙二醇、三乙二醇以及三丙二醇。优选地，聚合二醇单元为5到25wt％的预聚物，优选是8到18wt％。
固化异氰酸酯为含有由异氰酸酯基与水、羟基或胺的反应产生的基团的聚合物。优选地，聚合物具有已知由异氰酸酯基反应产生的脲、胺基甲酸酯、碳化二亚胺或其他基团。优选地，固化异氰酸酯为由异氰酸酯基与水，优选环境湿气的反应形成的聚脲。优选地，本发明的组合物包含：包含4，5-二氯-2-正辛基异噻唑啉-3-酮的粒子、表面积为至少700m2/g的活性碳以及固化异氰酸酯。优选地，粒子包含固化异氰酸酯囊封的活性碳和DCOIT。优选地，粒子含有小于20％的反应性异氰酸酯基，优选小于10％。优选地，将异氰酸酯与DCOIT混合，且随后与活性碳接触。优选地，异氰酸酯与DCOIT的重量比为1∶1到10∶1，优选2∶1到5∶1
优选地，活性碳与DCOIT的重量比是至少1∶1，优选是至少1.5∶1，优选是至少2∶1，优选是至少2.5∶1，优选是至少3∶1；优选地，所述重量比不超过12∶1，优选是不超过10∶1，优选是不超过8∶1，优选是不超过6∶1，优选是不超过5∶1，优选是不超过4.5∶1。优选地，自抛光涂层中活性碳与DCOIT的重量比是1.5∶1到5∶1，优选是2∶1到4∶1。优选地，污损释放涂层中活性碳与DCOIT的重量比是2∶1到10∶1，优选是2∶1到8∶1，优选是3∶1到8∶1。
优选地，船舶涂层的湿膜厚度是至少25微米，优选是至少50微米，优选是至少100微米，优选是至少200微米；优选是不超过500微米，优选是不超过400微米，优选是不超过300微米。预期湿涂层固化后所形成的干膜的厚度将比湿厚度小对应于湿涂层材料的溶剂含量的量。优选地，船舶涂层的干(固化)膜厚度是至少20微米，优选是至少40微米，优选是至少80微米，优选是至少160微米；优选是不超过400微米，优选是不超过320微米，优选是不超过240微米。
适合的活性碳包括例如碳，如衍生自煤、木材、椰子壳、木质素或动物骨的碳。活性碳可以通过物理处理或化学处理产生。物理处理需要以下过程的组合：在600℃到900℃范围内的温度下在缺氧条件下使碳碳化、热解；以及在高于250℃的温度下用氧化气氛(二氧化碳、氧气或蒸汽)暴露碳化的碳。化学活化需要在碳化之前用以下特定化学物质浸渍原材料：酸、强碱或盐(例如磷酸、氢氧化钾、氢氧化钠、氯化钙以及氯化锌25％)；继而在较低温度(450℃到900℃)下进行碳化。特别优选的是高表面积“活性”碳，如通过直接化学活化制备的碳。关于这些活性碳和其制备方法的其它一般和具体细节可以查询石油衍生碳(Petroleum Derived Carbons)(T.M.奥格雷迪(T.M.O′Grady)和A.N.温涅伯格(A.N.Wennerberg)著)，美国化学学会讨论会丛刊(American Chemical SocietySymposiumSeries)，第303卷，J.D.巴夏(J.D.Bacha)等人编，美国化学学会出版物(AmericanChemical Society Publications)，华盛顿哥伦比亚特区(Washington，D.C.)，(1986)。优选地，活性碳的表面积是至少750m2/g(通过BET方法测量)，优选是至少800m2/g，优选是至少900m2/g，优选是至少1000m2/g，优选是至少1200m2/g；优选是不超过2500m2/g，优选是不超过2200m2/g。
优选地，仅在与DCOIT或船舶涂料调配物组合之前，活性碳的平均粒度(例如D50)是不超过100微米(0.1mm)，优选是不超过50微米，优选是不超过40微米，优选是不超过35微米，优选是不超过30微米，优选是不超过25微米，优选是不超过20微米；优选是至少5微米，优选是至少10微米。
实例
经GERSTEL TWISTER聚二甲基硅氧烷(polydimethylsiloxane，PDMS)涂布的搅拌棒购自格斯特尔股份有限公司(Gerstel Gmbh)。所用的涂料是商购获得的InterluxMICRON66涂料(“M66”)、INTERSLEEK 970涂料(“P970”)以及INTERSLEEK 731(“P731”)，且除了添加如下文所描述的DCOIT之外，根据制造商的说明将其混合。
使用定轨振荡器(美国红魔鬼公司(Red Devil Inc，USA))将涂料与DCOIT和吸附剂混合且使用不锈钢量规将其涂覆在玻璃显微镜载玻片上(湿膜厚度500微米)。使涂料干燥过夜。
将显微镜载玻片浸没到含有100ml人工海水的120ml玻璃瓶中，插入Twister搅拌棒，且将瓶子放置在搅拌混合器上。搅拌速率是600-800rpm。在第1天、第4天、第7天、第14天以及第21天、第28天、第35天、第42天，将TWISTER棒从瓶子中移出，用纸巾擦拭且放置到含有1ml乙腈的HPLC小瓶中。在40-50℃下萃取吸附的杀生物剂30min。在萃取之后，再次擦拭棒且将其放回具有海水/MAF涂料的瓶子中。通过HPLC测量杀生物剂的浓度。通过化学工作站(Chemstation)软件控制装备有自动进样器、柱加热器以及二极管阵列检测器的安捷伦(Agilent)1200HPLC。使用Ultra C18柱150×4.6cm(瑞斯泰克公司(Restek Inc))分析DCOIT。使用等度条件(70％乙腈，2.3ml/min)。在280nm下检测到DCOIT。使用外部标准技术来对所释放的杀生物剂进行定量。基于先前校准，估计Twister搅拌棒容量是400微克。通过测定微克数且将此值除以表面积和从放入先前样品开始的天数来计算DCOIT释放。
用于测定吸油量的方法如下：
将0.5g待测试材料称量到小盘中。
在天平上称量第二小容器的亚麻籽油的皮重
逐滴添加亚麻籽油直到粉末变成可涂抹的膏状物为止。记录所添加的亚麻籽油重量。
％吸油量＝(吸收的油克数/待测试材料的克数)×100
注意：100％的吸油量是指1g材料吸收1g亚麻籽油DCOIT的释放速率(在指定天测 量的DCOIT的μg/cm2/天)
涂料/DCOIT/碳：DCOIT 1 4 7 14 21 28 35 43
MM175/1％-对照 5.38 2.27 1.76 0.885 0.679 0.802 0.845 0.535
MM175/1％/2∶1(1) 1.77 0.757 0.888 0.403 0.297 0.305 0.471 0.339
MM175/1％/3∶1(2) 2.04 0.722 0.722 0.268 0.289 0.225 0.258 0.231
1 3 7 14 20 28 35 42
M 66/1％-对照 5.66 2.22 1.35 0.635 0.788 0.601 0.583 0.655
M 66/1％/2∶1(1) 3.32 1.44 0.708 0.456 0.420 0.362 0.222 0.314
M 66/1％/3∶1(2) 3.78 1.99 0.718 0.488 0.499 0.314 0.354 0.339
Jotun/1％-对照 1.22 1.81 0.842 0.467 0.470 0.385 0.313 0.300
Jotun/1％/2∶1(1) 0.570 0.631 0.317 0.179 0.197 0.101 0.121 0.083
Jotun/1％/3∶1(2) 0.482 0.595 0.416 0.252 0.236 0.190 0.162 0.175
I970/1％-对照 7.51 4.33 1.63 0.889 0.805 0.624 0.517 0.464
I970/1％/2∶1(1) 1.79 1.09 0.391 0.217 0.174 0.117 0.104 0.139
I970/1％/3∶1(2) 3.32 1.41 0.604 0.150 0.196 0.099 0.092 0.080
活性碳为纽恰尔(NUCHAR)HD(MWV公司)，表面积1600-1700m2/g
来自SEANINE 211N杀生物剂(陶氏化学公司)的对照物中的DCOIT，二甲苯中的30％DCOIT；样品(1)中的DCOIT源为伊索内特(ISONATE)181预聚物(陶氏化学公司)中的25％DCOIT，且样品(2)中的DCOIT源为100％DCOIT
“MM175”涂料为来自阿西马(ACIMA)(陶氏)的_MetaMare 175
“M 66”涂料为MICRON 66绿色涂料(国际涂料(International Paints))
“Jotun”为JOTUN SEAQUANTUM传统涂料(Jotun)
“I970”为INTERSLEEK 970FRC涂料(国际涂料)
调配物的吸油量
样品 吸油量
典型的＞700m2/g活性碳-对照 280％
1％DCOIT/3∶1 C：DCOIT 189％
1％DCOIT/2∶1 C：DCOIT(来自伊索内特181预聚物中的25％DCOIT) 90％
数据表明以下出人意料的结果：添加伊索内特181预聚物不实质上改变来自活性碳的DCOIT的控制释放，但确实降低粒子的吸油量。

Claims (6)

1.一种包含4,5-二氯-2-正辛基异噻唑啉-3-酮、表面积为至少700m2/g的活性碳以及固化异氰酸酯的组合物，所述固化异氰酸酯是MDI和二醇的异氰酸酯封端的预聚物。
2.根据权利要求1所述的组合物，其中所述组合物包含：包含吸收的4,5-二氯-2-正辛基异噻唑啉-3-酮以及MDI和二醇的异氰酸酯封端的预聚物的活性碳粒子。
3.根据权利要求1所述的组合物，其为包含0.5wt％到8wt％4,5-二氯-2-正辛基异噻唑啉-3-酮和1.5wt％到24wt％活性碳的船舶涂料。
4.根据权利要求3所述的组合物，其中所述活性碳具有800m2/g到2500m2/g的表面积。
5.根据权利要求4所述的组合物，所述船舶涂料是污损释放涂层。
6.根据权利要求4所述的组合物，其中所述船舶涂料是自抛光涂层。
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