CN107163224B - 一种生物降解型高分子海洋防污材料及其制备与应用 - Google Patents

一种生物降解型高分子海洋防污材料及其制备与应用 Download PDF

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CN107163224B
CN107163224B CN201710353247.5A CN201710353247A CN107163224B CN 107163224 B CN107163224 B CN 107163224B CN 201710353247 A CN201710353247 A CN 201710353247A CN 107163224 B CN107163224 B CN 107163224B
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acid
preparation
marine antifouling
diisocyanate
antifouling material
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CN107163224A (zh
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张广照
马春风
潘健森
谢庆宜
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South China University of Technology SCUT
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Abstract

本发明属于海洋防污材料的技术领域，公开了一种生物降解型高分子海洋防污材料及其制备与应用。方法为：(1)聚氨酯的制备：将可控降解多元醇进行脱水处理，得到脱水产物；在惰性气体和搅拌的条件下，向脱水产物中加入溶剂和二异氰酸酯进行反应，再加入扩链剂和催化剂，继续反应，得到含有主链降解型聚氨酯的溶液；(2)向溶液中加入金属化合物、水解性单体和溶剂，于80～140℃反应，得到生物降解型高分子海洋防污材料。本发明的材料具有良好的表面自更新性能和力学性能，在静态或低航速条件下可保持较高的自更新速率；该材料是一种绿色环保的防污材料，用于制备海洋防污涂层。本发明的方法简单，成本较低，适合工业化生产。

Description

一种生物降解型高分子海洋防污材料及其制备与应用
技术领域
本发明属于海洋防污材料的技术领域，具体涉及一种生物降解的聚氨酯海洋防污材料及其制备方法与应用。
背景技术
海洋生物污损，即海洋微生物、植物、动物在浸没于海水的设施表面附着繁殖而成的生物垢，给航海事业和海洋资源的勘探、开发、利用等造成巨大的危害。例如在船舶上附着的海生物会增加船体重量和粗糙度，造成燃料消耗和二氧化碳排放量大大增加，对军舰而言严重影响其机动性和隐身功能；在海产养殖的网箱上附着繁殖的海生物堵塞网孔，降低氧气和营养物质的交换效率。解决此问题最经济有效的方法是涂装海洋防污涂料。随着海洋环保法规的日趋完善，曾被广泛应用的有机锡自抛光防污材料因其长期的生物毒性已被禁用，目前已被无锡自抛光防污材料取代。
与含锡涂料相比，无锡自抛光涂料毒性小，主要包括丙烯酸铜聚合物，丙烯酸锌聚合物和丙烯酸硅烷酯聚合物基自抛光涂料。但是这类材料对航速有一定依赖性，在静态条件下因水流冲刷作用弱，水解抛光慢，导致防污效果不理想，因此对长期停泊或低航速的舰艇，采油平台等静态海洋设备的防污能力仍有待提高。另外它仍需要配合氧化亚铜防污剂一同使用。尽管铜的毒性低于锡，但仍会在海洋中大量积聚，导致海藻等生物的大量死亡，破坏海洋生态的平衡。同时，即使聚合物侧链水解后，主体的材料无法降解仍存在于海洋环境中，造成海洋微塑料污染。随着人们环保意识的增强和法律法规的完善，有毒的海洋防污涂料将逐渐被淘汰，发展环境友好型防污材料对于国防建设、海洋资源开发和环境保护都有着重要的军事、经济和社会意义。
发明内容
本发明的目的是针对现有材料和技术的不足，提供一种生物降解型高分子海洋防污材料的制备方法。本发明首先通过可控生物降解多元醇、二异氰酸酯和扩链剂反应得到聚合物，再通过酸碱反应或酯交换反应在聚合物侧链引入水解性功能单元，从而得到生物降解型高分子海洋防污材料。通过本发明方法所得到的材料具有优异的降解性能，特别是可控生物降解的主链；该主链与后接枝的水解性功能单元，赋予材料静态条件下的高抛光速率。此外，该防污材料的聚酯主链在海水中可降解成无毒的小分子，解决了传统自抛光防污材料因主链无法降解而造成的海洋微塑料污染问题。
本发明的另一目的在于提供由上述制备方法得到的生物降解型高分子海洋防污材料。
本发明的再一目的在于提供上述生物降解型高分子海洋防污材料的应用。所述生物降解型高分子海洋防污材料用于制备海洋防污涂料。
本发明的目的通过以下技术方案实现：
一种生物降解型高分子海洋防污材料的制备方法，包括以下步骤：
(1)聚氨酯的制备：将可控降解多元醇进行脱水处理，得到脱水产物；在惰性气体和搅拌的条件下，向脱水产物中加入溶剂和二异氰酸酯，于50～120℃反应1～3h，再加入扩链剂和催化剂，于50～120℃反应3～5h，得到含有主链降解型聚氨酯的产物；
(2)向步骤(1)的含有主链降解型聚氨酯的产物中加入金属化合物、水解性单体和溶剂，于80～140℃反应，得到生物降解型高分子海洋防污材料。所述金属化合物、水解性单体反应完全。
步骤(1)中所述脱水处理是指于80～150℃真空脱水2～3h，优选为120℃真空脱水2h。
步骤(1)中所述惰性气体为氮气或氩气。
步骤(1)中所述可控降解多元醇、二异氰酸酯和扩链剂的用量以重量百分比计：可控降解多元醇15～90％，优选40～80％；二异氰酸酯5～85％，优选10～50％；扩链剂5～50％，优选5～20％。
所述二异氰酸酯与(可控降解多元醇+扩链剂)的摩尔比为(1～1.3):1。
步骤(1)中所述可控降解多元醇均含端羟基，具体为聚甲基乙撑碳酸酯、聚(1,3-三亚甲基碳酸酯)、聚(己内酯-乙交酯)、聚(己内酯-丙交酯)、聚(己内酯-乙二醇)、聚(丙交酯-乙交酯)、聚(丙交酯-乙二醇)、聚3-羟基丁酸酯、聚(3-羟基丁酸酯-co-3-羟基戊酸酯)、聚己二酸乙二醇酯、聚己二酸二乙二醇酯、聚己二酸丁二醇酯、聚己二酸己二醇酯、聚丁二酸丁二醇酯、聚原酸酯、聚酸酐、聚磷酸酯、聚乙二醇、聚己内酯、聚丙交酯和聚乙交酯中的一种以上；所述可控降解多元醇的分子量为1×102～1×106g/mol，优选为1×103～1×105g/mol。
步骤(1)中所述二异氰酸酯为二苯基甲烷二异氰酸酯(MDI)、赖氨酸二异氰酸酯(LDI)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)或二环己基甲烷二异氰酸酯(HMDI)中的一种以上。
步骤(1)中所述扩链剂为含羧基的小分子醇、含羧基的小分子醇与小分子胺的混合物、含羧基的小分子醇与无羧基的小分子醇的混合物或含羧基小分子醇与小分子胺和无羧基的小分子醇的混合物中一种；
所述小分子醇为含碳原子2～10的脂肪族醇中的至少一种；所述含羧基的小分子醇优选为2,2-二羟甲基丙酸、二羟甲基丁酸中一种以上，所述无羧基的小分子醇优选为乙二醇、1,4-丁二醇、1,3-丙二醇、甲基二乙醇胺中一种以上。
所述小分子胺为含碳原子2～10的脂肪族胺中的至少一种；优选为乙二胺、1,4-丁二胺、乙二胺基乙磺酸钠、二乙烯三胺中一种以上。
所述含羧基的小分子醇的用量为扩链剂总质量的0～100％，优选为5～80％。
步骤(1)和(2)中所述溶剂相同或不同，所述溶剂为四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、乙酸乙酯、甲苯、二甲苯、丙酮、丁酮或正丁醇中的一种以上。
步骤(1)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡、三亚乙基二胺的一种以上。
步骤(1)中所述催化剂和扩链剂可以以溶液的形式加入，即以催化剂、扩链剂和溶剂的混合物形式加入，此处溶剂与其他溶剂(步骤(1)和(2)中溶剂)相同或不同。
步骤(2)中所述水解性单体为天然松香(松香)、氢化松香、歧化松香、松香酸、甲酸、乙酸、丙酸、苯甲酸、正辛酸、异辛酸、硬脂酸、异硬脂酸、环烷酸、环己甲酸、衣康酸、马来酸、油酸、棕榈酸、亚麻酸、亚油酸中的一种以上。
步骤(2)中所述金属化合物为氧化铜、氧化锌、氧化镁、乙酸铜、乙酸锌、乙酸镁、丙酸铜、丙酸锌、丙酸镁、氢氧化铜、氢氧化锌或氢氧化镁中的至少一种。
所述金属化合物是利用聚氨酯侧链的羧基以及水解性单体的羧基与金属化合物反应，得到水解性的铜酯键或锌酯键或镁酯键。
步骤(2)中所述金属化合物、水解性单体与步骤(1)中主链降解型聚氨酯侧链羧基(侧链羧基，是由含羧基的小分子扩链剂引入的，聚氨酯中的侧链羧基以投料比计算得到)的摩尔比为1:1:1。
所述生物降解型高分子海洋防污材料由上述制备方法得到。
本发明提供的生物降解型海洋防污材料，首先由可控降解多元醇，二异氰酸酯和扩链剂聚合得到聚氨酯产物，随后接枝水解性功能单体得到。所述海洋防污材料是由具有生物降解性的主链和水解性侧链组成的聚合物。本发明赋予材料可控水解-降解性，所制备的材料能在海水中发生水解-降解从而更新出新的表面，使在旧表面粘附的海生物脱落，尤其在静态或低航速条件下可保持较高的自更新速率。更为重要的是，该材料由于主链的降解性可在海水中降解成无毒小分子，避免海洋微塑料污染，是一种绿色环保的防污材料。通过调节聚氨酯的组成和配比来控制多元醇的结晶性从而有效的对其降解性能进行调控，特别是水解性单体的种类和含量能有效调控其亲、疏水性，从而控制材料的自更新速率。二异氰酸酯和扩链剂的引入可保证材料具有优秀的成膜性和附着力。本发明提供的主链降解型海洋防污材料可溶于常规的二甲苯或者醇类溶剂中，具有良好的表面自更新性能和力学性能，同时不含任何防污剂。该方法工艺简单，成本较低，适合工业化生产，该材料在制备海洋防污涂层领域具有很好的应用前景。
与现有技术相比，本发明具有如下优点及有益效果：
(1)本发明提供的降解型海洋防污材料能在海水中降解，不断更新表面，使其表面的海生物脱离，特别是侧链引入的水解性单体，通过铜/锌/镁酯键的水解，可以调节材料的自抛光速率，在静态条件下仍能快速水解抛光，尤其适合长期处于低航速或静态的海上设备。
(2)本发明提供的降解型海洋防污材料可以通过调节聚合物主链的组成、含量和水解性单体的种类和含量，可有效控制可控降解多元醇的结晶性、亲/疏水性从而有效调控其降解性能。
(3)本发明提供的降解型海洋防污材料可溶于常用的二甲苯或者醇类溶剂中，具有良好的力学性能。
(4)本发明提供的降解型海洋防污材料在海水中可降解成无毒的小分子，避免了海洋塑料污染问题，且不含任何防污剂，环境友好。
(5)本发明提供的降解型海洋防污材料制备方法工艺简单，成本较低，适合工业化生产，该材料在环境友好型海洋防污领域具有广阔的应用前景。
具体实施方式
下面结合具体实施例对本发明作进一步详细描述，但本发明的实施方式不限于此。
实施例1
(1)将分子量2000g/mol的聚甲基乙撑碳酸酯12.5g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至70℃，加入二甲苯40mL和二苯基甲烷二异氰酸酯(MDI)12.0g，氮气保护下搅拌反应1h；然后加入1,4-丁二醇1.6g，2,2-二羟甲基丙酸3.2g和辛酸亚锡0.1g，升温至80℃，继续搅拌反应3h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入氢氧化镁1.4g、硬脂酸6.8g和二甲苯10mL，100℃下搅拌至收集到0.8g水时，出料，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在预先涂有环氧防腐底漆的钢板上，浅海挂板实验表明6个月内无海洋生物在其表面生长。
实施例2
(1)将分子量2000g/mol的聚(己内酯-丙交酯)50.0g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至60℃，加入二甲基甲酰胺80.0mL和赖氨酸二异氰酸酯(LDI)15.1g，氮气保护下搅拌反应1h；然后加入1,4丁二醇1.6g、2,2-二羟甲基丙酸3.2g和二月桂酸二丁基锡0.2g，70℃下继续搅拌反应3h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入氢氧化锌2.3g,、乙酸1.5g和二甲基甲酰胺10.0mL，110℃下搅拌至收集到0.8g水时，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在环氧纤维板上，浅海挂板实验表明8个月无海洋生物生长。
实施例3
(1)将分子量10000g/mol的聚3-羟基丁酸酯30.0g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至60℃，加入二甲基乙酰胺60.0mL和二苯基甲烷二异氰酸酯(MDI)10.0g，氩气氛围下搅拌反应2h；加入2,2-二羟甲基丙酸5.0g和二月桂酸二丁基锡0.6g，升温到70℃，保持搅拌反应3h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入乙酸镁5.3g、环烷酸(酸值165)12.7g和二甲基乙酰胺30.0mL，140℃下搅拌至收集到4.4g乙酸时，出料，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在环氧纤维板上，浅海挂板实验表明6个月无海洋生物生长。
实施例4
(1)将分子量约4000g/mol的聚(己内酯-乙二醇)100.0g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至降温至60℃，加入正丁醇150.0mL和六亚甲基二异氰酸酯(HDI)15.7g，在氩气氛围下搅拌反应2h；加入乙二胺1.6g、2,2-二羟甲基丙酸5.6g和二月桂酸二丁基锡1.0g，升温到70℃，继续搅拌反应3h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入氢氧化铜4.0g,天然松香(酸值165)14.2g和丁酮30.0mL，110℃下搅拌至收集到1.5g水时，出料，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在环氧纤维板上，浅海挂板实验表明8个月无海洋生物生长。
实施例5
(1)将分子量约6000g/mol的聚己二酸丁二醇酯60.0g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至降温至60℃，加入二甲苯100.0mL和异佛尔酮二异氰酸酯(IPDI)14.6g，氮气保护下搅拌反应2h；加入2,2-二羟甲基丙酸7.5g，辛酸亚锡0.4g，升温到80℃，继续搅拌反应2h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入氧化锌4.5g、松香酸16.9g和二甲苯30.0mL，110℃下搅拌至收集到1.0g水时，出料，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在环氧纤维板上，浅海挂板实验表明6个月无海洋生物生长。
实施例6
(1)将分子量约4000g/mol的聚丁二酸丁二醇酯和聚乙二醇(两者的质量比为2:1)共500.0g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至60℃，加入丙酮800.0mL和甲苯二异氰酸酯(TDI)274.0g，氮气保护下搅拌反应2h；加入1,4-丁二胺88.2g、2,2-二羟甲基丙酸60.0g、二甲苯200mL和二月桂酸二丁基锡2.0g，升温到70℃，继续搅拌反应3h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入氧化铜35.5g、苯甲酸54.6g和丙酮100.0mL，100℃下搅拌至收集到8.0g水时，出料，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在环氧纤维板上，浅海挂板实验表明6个月无海洋生物生长。
实施例7
(1)将分子量约2000g/mol的聚(1,3-三亚甲基碳酸酯)60.0g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至60℃，加入四氢呋喃90.0mL和异佛尔酮二异氰酸酯(IPDI)20.0g，氮气保护下搅拌反应1h；加入乙二醇1.9g、2,2-二羟甲基丙酸4.0g、二月桂酸二丁基锡0.2g和二甲基甲酰胺10.0mL，70℃下继续搅拌反应3h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入乙酸铜5.4g、环烷酸(酸值165)10.2g和二甲基甲酰胺20.0mL，130℃下搅拌至收集到3.5g乙酸时，出料，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在环氧纤维板上，浅海挂板实验表明12个月无海洋生物生长。
实施例8
(1)将分子量2000g/mol的聚丁二酸丁二醇酯70.0g于120℃下真空除水2h，得到脱水产物；
(2)将脱水产物降温至60℃，加入乙酸乙酯100.0mL和二环己基甲烷二异氰酸酯(HMDI)25.0g，氮气保护下搅拌反应1h；加入2,2-二羟甲基丙酸8.1g、三亚乙基二胺0.2g，70℃下继续搅拌反应3h，得到含有聚氨酯的产物；
(3)向步骤(2)中含有聚氨酯的产物中加入乙酸锌11.0g、异辛酸8.7g和二甲基甲酰胺20.0mL，140℃下搅拌至收集到7.2g乙酸时，出料，得到生物降解型高分子海洋防污材料。将海洋防污材料涂刷在环氧纤维板上，浅海挂板实验表明10个月无海洋生物生长。

Claims (9)

1.一种生物降解型高分子海洋防污材料的制备方法，其特征在于：包括以下步骤：
(1)聚氨酯的制备：将可控降解多元醇进行脱水处理，得到脱水产物；在惰性气体和搅
拌的条件下，向脱水产物中加入溶剂和二异氰酸酯，于50～120℃反应1～3h，再加入扩链剂和催化剂，于50～120℃反应3～5h，得到含有主链降解型聚氨酯的产物；
(2)向步骤(1)的含有主链降解型聚氨酯的产物中加入金属化合物、水解性单体和溶剂，于80～140℃反应，得到生物降解型高分子海洋防污材料；
步骤(2)中所述金属化合物为乙酸铜、乙酸锌、乙酸镁、丙酸铜、丙酸锌或丙酸镁中的至少一种；
步骤(1)中所述扩链剂为含羧基的小分子醇、含羧基的小分子醇与小分子胺的混合物、含羧基的小分子醇与无羧基的小分子醇的混合物或含羧基小分子醇与小分子胺和无羧基的小分子醇的混合物中一种；所述小分子醇为含碳原子2～10的脂肪族醇中的至少一种；所述小分子胺为含碳原子2～10的脂肪族胺中的至少一种；
所述含羧基的小分子醇为2 ,2-二羟甲基丙酸、二羟甲基丁酸中一种以上；
步骤 (2)中所述水解性单体为天然松香、氢化松香、歧化松香、松香酸、苯甲酸、正辛酸、异辛酸、硬脂酸、异硬脂酸、环烷酸、环己甲酸、衣康酸、马来酸、油酸、棕榈酸、亚麻酸、亚油酸中的一种以上；
步骤(1)和(2)中所述溶剂相同或不同，所述溶剂为四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、乙酸乙酯、甲苯、二甲苯、丙酮、丁酮或正丁醇中的一种以上。
2.根据权利要求1所述生物降解型高分子海洋防污材料的制备方法，其特征在于：所述无羧基的小分子醇为乙二醇、1 ,4-丁二醇、1 ,3-丙二醇、甲基二乙醇胺中一种以上；
所述小分子胺为乙二胺、1 ,4-丁二胺、乙二胺基乙磺酸钠、二乙烯三胺中一种以上。
3.根据权利要求1所述生物降解型高分子海洋防污材料的制备方法，其特征在于：
步骤(1)中所述可控降解多元醇均含端羟基，为聚甲基乙撑碳酸酯、聚(1 ,3-三亚甲基碳酸酯)、聚(己内酯-乙交酯)、聚(己内酯-丙交酯)、聚(己内酯-乙二醇)、聚(丙交酯-乙交酯)、聚(丙交酯-乙二醇)、聚3-羟基丁酸酯、聚(3-羟基丁酸酯-co-3-羟基戊酸酯)、聚己二酸乙二醇酯、聚己二酸二乙二醇酯、聚己二酸丁二醇酯、聚己二酸己二醇酯、聚丁二酸丁二醇酯、聚原酸酯、聚酸酐、聚磷酸酯、聚乙二醇、聚己内酯、聚丙交酯、聚乙交酯中的一种以上；
步骤(1)中所述二异氰酸酯为二苯基甲烷二异氰酸酯、赖氨酸二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的一种以上。
4.根据权利要求1所述生物降解型高分子海洋防污材料的制备方法，其特征在于：
步骤(1)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡、三亚乙基二胺的一种以上；
步骤(1)中所述可控降解多元醇的分子量为1×102～1×106g/mol。
5.根据权利要求1所述生物降解型高分子海洋防污材料的制备方法，其特征在于：步骤(1)中所述可控降解多元醇、二异氰酸酯和扩链剂的用量以重量百分比计：可控降解多元醇15～90％；二异氰酸酯5～85％；扩链剂5～50％；
步骤(1)中所述扩链剂中含羧基的小分子醇的用量为扩链剂总质量的5～100％；
步骤(2)中所述金属化合物、水解性单体与步骤(1)中主链降解型聚氨酯侧链羧基的摩尔比为1:1:1。
6.根据权利要求5所述生物降解型高分子海洋防污材料的制备方法，其特征在于：所述二异氰酸酯与(可控降解多元醇+扩链剂)的摩尔比为(1～1 .3):1；
所述可控降解多元醇、二异氰酸酯和扩链剂的用量以重量百分比计：可控降解多元醇40～80％；二异氰酸酯10～50％；扩链剂5～20％；
所述扩链剂中含羧基的小分子醇的用量为扩链剂总质量的5～80％。
7.根据权利要求1所述生物降解型高分子海洋防污材料的制备方法，其特征在于：步骤(1)中所述脱水处理是指于80～150℃真空脱水2～3h；步骤(1)中所述惰性气体为氮气或氩气。
8.一种由权利要求1～7任一项所述制备方法得到的生物降解型高分子海洋防污材料。
9.根据权利要求8所述生物降解型高分子海洋防污材料的应用，其特征在于：所述生物降解型高分子海洋防污材料用于制备海洋防污涂料。
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