CN103396513B - 一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用 - Google Patents
一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用 Download PDFInfo
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- CN103396513B CN103396513B CN201310314516.9A CN201310314516A CN103396513B CN 103396513 B CN103396513 B CN 103396513B CN 201310314516 A CN201310314516 A CN 201310314516A CN 103396513 B CN103396513 B CN 103396513B
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Abstract
本发明公开了一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用，该方法是将环状单体、乙烯基单体、乙烯基硅烷酯单体按配比混和在溶剂中，然后加入单体总量质量百分比为0.01～5%的复合引发剂，在温度为25～150℃，氩气或氮气保护的条件下反应制备；以质量百分比计，单体组成为：环状单体5～95%、乙烯基单体0～90%和乙烯基硅烷酯5～95%；本发明所得到的树脂除了侧链硅烷酯在海水的作用下能水解之外，主链聚酯链段在海水的作用下也能发生断链，解决了传统自抛光材料对航速的依赖性，有效调控防污剂以恒定速率释放，保证了活性物质在船舶涂层表面的保持，很好的满足低航速的船舶，潜艇以及海上采油平台设施的防污要求。
Description
技术领域
本发明涉及一种硅烷酯树脂，特别是涉及一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用；该应用主要是海洋防污材料技术领域。
背景技术
海洋生物污损是指海洋微生物、植物和动物在船舶和海中设施表面的附着,生长所形成的生物垢，它对海洋运输和海洋资源的勘探、开发、利用造成危害。在国防领域,也长期受到海洋生物污损的困扰,例如海洋生物污损会加速舰艇船底钢板的腐蚀，降低武器装备的使用寿命，同时引起的腐蚀破坏需要人力进行频繁的周期性维护，严重影响海军的战斗力并造成巨大的经济损失。此外，海洋生物污损会增加舰船自重和航行的阻力，增加燃油消耗，严重影响舰船的作战性能。尤其对于舰船或潜艇来说，长期处于苛刻的海洋环境中，船底部分受到海洋生物的污损严重。防污涂料是目前解决舰艇海洋生物污损最常用的方法。但海军军舰和一般民用船相比，具有停泊时间长,航行频率相对较低,跨海域机动性强等特点。目前现有自抛光技术主要针对远洋船舶设计，其性能的发挥对航期和航速都有一定的要求。在静止阶段，仅靠海水自流很难达到理想的自抛光效果。实际上，如何解决静止状态下长效防污一直是一个世界性的难题，对于舰船，潜艇，海上采油平台都具有重要的战略意义。
发明内容
本发明的目的是针对现有材料和技术的不足，提供一种主链含有聚酯链段，侧链含有硅烷酯的主链断裂型聚丙烯酸类硅烷酯树脂及其制备方法。
本发明另一目的在于提供一种可满足静态防污的主链断裂型聚丙烯酸类硅烷酯树脂在制备海洋防污涂料的应用。
本发明提供的一种主链断裂型聚丙烯酸类硅烷酯树脂是由环状单体、乙烯基单体、乙烯基硅烷酯单体在复合引发剂下共聚合而成，其结构是由聚酯链段和乙烯基硅烷酯链段组成的无规共聚物。本发明在传统的自抛光树脂中引入主链聚酯链段，使所涉及的材料除了侧链硅烷酯在海水的作用下能水解之外，主链聚酯在海水的作用下也能发生断链，从而满足静态防污的应用需要。本发明中主链断裂型聚丙烯酸类硅烷酯树脂包括主链断裂型聚丙烯酸硅烷酯树脂和主链断裂型聚甲基丙烯酸硅烷酯树脂。
本发明的目的通过以下技术方案实现：
一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法：将环状单体、乙烯基单体、乙烯基硅烷酯单体按配比混和在溶剂中，然后加入单体总量质量百分比为0.01～5%的复合引发剂，在温度为25～150℃，氩气或氮气保护的条件下反应制备；以质量百分比计，单体组成为：环状单体5～95%、乙烯基单体0～90%和乙烯基硅烷酯5～95%；所述溶剂为四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、乙酸丁酯、甲苯、二甲苯、丙酮和正丁醇中的一种或多种；
所述环状单体为丙交酯、乙交酯、己内酯、2‐甲基‐ε‐己内酯、2‐氯‐ε‐己内酯、丁内酯、戊内酯、2-亚甲基-1,3-二氧杂环庚烷、碳酸乙烯酯、碳酸丙烯酯、三亚甲基环碳酸酯、2，2‐二甲基三亚甲基环碳酸酯、二甲氨基三亚甲基环碳酸酯、2‐乙基‐2‐恶唑啉、2‐甲基‐2‐恶唑啉、五元环磷酸酯、六元环磷酸酯、环氧乙烷、环氧丙烷、环氧氯丙烷和γ‐缩水甘油醚氧丙基三甲氧基硅烷中的一种或多种；
所述乙烯基单体为丙烯酸，甲基丙烯酸，甲基丙烯酸甲酯，甲基丙烯酸乙酯，甲基丙烯酸丁酯，甲基丙烯酸辛酯，丙烯酸甲酯，丙烯酸乙酯，丙烯酸丁酯，丙烯酸辛酯，甲基丙烯酸十二氟庚酯，丙烯酰胺，甲基丙烯酰胺，羟甲基丙烯酰胺，异丙基丙烯酰胺，甲基丙烯酸乙二醇酯，丙烯酸羟乙酯，甲基丙烯酸羟乙酯，甲基丙烯酸缩水甘油醚，苯乙烯，甲基丙烯酸二甲氨基乙酯，甲基丙烯酸二乙氨基乙酯，乙烯基吡咯烷酮，四乙烯基吡啶，丙烯酰氧乙基二甲基苄基氯化铵，甲基丙烯酰氧基乙基苄基二甲基氯化铵，甲基丙烯酰氧乙基三甲基氯化铵，聚磺酸甜菜碱甲基丙烯酸甲酯和聚羧酸甜菜碱甲基丙烯酸甲酯中的一种或多种；
所述乙烯基硅烷酯单体为丙烯酸三甲基硅烷酯、丙烯酸三乙基硅烷酯、丙烯酸三异丙基硅烷酯、丙烯酸三苯基硅烷酯、丙烯酸三丁基硅烷酯、丙烯酸三正辛基硅烷酯、甲基丙烯酸三甲基硅烷酯、甲基丙烯酸三乙基硅烷酯、甲基丙烯酸三异丙基硅烷酯、甲基丙烯酸三苯基硅烷酯、甲基丙烯酸三丁基硅烷酯、甲基丙烯酸三正辛基硅烷酯中的一种或任意几种以任意比例组成的混合物；
所述复合引发剂为低分子醇，低分子胺，硫醇，磷腈、磷腈盐、氧化磷腈、偶氮二异丁腈、过氧化苯甲酰中的两种或者两种以上组成的混合物。
优选地，所述单体总量与溶剂的质量比为(50～200)：100。所述低分子胺为含碳原子2～10的脂肪族胺中的至少一种。所述低分子醇为含碳原子2～10的脂肪族醇中的至少一种。
一种主链断裂型聚丙烯酸类硅烷酯树脂，由上述制备方法制得。
所述主链断裂型聚丙烯酸类硅烷酯树脂在制备海洋防污涂料中的应用：以重量份数计，将10～60份的所述主链断裂型聚丙烯酸类硅烷酯树脂、20～60份的氧化亚铜、3～15份的有机防污剂、10～40份的颜填料、0～5份的助剂和5～20份的有机溶剂混合搅拌均匀，制得海洋防污涂料；
所述有机防污剂为吡啶硫酮铜、吡啶硫酮锌、吡啶三苯基硼烷、4,5‐二氯代‐2‐正辛基‐4‐异噻唑啉‐3‐酮、米托咪啶、2‐(对‐氯苯基)‐3‐氰基‐4‐溴基‐5‐三氟甲基‐吡咯和2,4,6‐三氯苯基‐N‐苯基马来酰亚胺中的一种或多种；
所述颜填料为氧化锌、氧化铁红、碳酸钙和硫酸钡中的一种或多种；
所述助剂为氯化石蜡、松香、邻苯二甲酸二辛酯、蓖麻油、膨润土、聚酰胺蜡和气相二氧化硅中的一种或多种。
所述有机溶剂为二甲苯、正丁醇、甲基异丁基酮、丁酮、二丙酮醇和醋酸乙烯酯中的一种或多种。
与现有技术相比，本发明具有以下优点和有益效果：
（1）本发明通过环状单体和乙烯基硅烷酯单体的共聚合反应，制备了主链含有聚酯链段，侧链含有硅烷酯的主链断裂型自抛光树脂材料。所得到的树脂除了侧链硅烷酯在海水的作用下能水解之外，主链聚酯链段在海水的作用下也能发生断链，从而解决了传统自抛光材料对航速的依赖性，在静态海水中也能通过水解作用更新出新的表面，从而有效调控防污剂以恒定速率释放，保证了活性物质在船舶涂层表面的保持，很好的满足低航速的船舶，潜艇以及海上采油平台设施的防污要求；
（2）本发明提供的材料由于主侧链在海水中均可发生水解，能均匀和彻底水解抛光，使得船舶在航行期间涂层表面光滑，从而降低表面粗糙度，减少航行阻力，赋予材料优异的减阻性能；
（3）本发明还可以在共聚合中加入乙烯基单体以调控材料的力学性能和粘附力，同时改善材料在船舶涂料常规溶剂中的溶解性，具有优异的力学性能和粘附力。
（4）本发明树脂在船舶涂料常规溶剂中的溶解性好，合成工艺简单，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。
附图说明
图1为实施例1所得聚(己内酯‐甲基丙烯酸三甲基硅烷酯)的红外图谱；
图2为实施例1所得聚(己内酯‐甲基丙烯酸三甲基硅烷酯)的核磁图谱；
图3为实施例1所得聚(己内酯‐甲基丙烯酸三甲基硅烷酯)的降解图谱。
具体实施方式
为更好地理解本发明，下面结合实施例对本发明作进一步地详细说明，但本发明的实施方式不限于此。
实施例1
在干燥的250mL带有搅拌器和温度计的三口瓶中加入50g已内酯，50g甲基丙烯酸三甲基硅烷酯、0.1g甲醇和100mL二甲苯，加入100μL磷腈(t‐BuP4)的正已烷溶液，在25℃条件下反应6h后，在甲醇沉淀，真空干燥，得到聚(己内酯‐甲基丙烯酸三甲基硅烷酯)，其产率为90%。从图1红外谱图中出现1730cm‐1(对应己内酯的酯基吸收峰)，2860cm‐1(对应己内酯的CH2的吸收峰)以及2950cm‐1(对应硅烷酯的CH3的吸收峰)，说明成功合成目标产物。图2核磁谱图中化学位移δ=0.87(对应硅烷酯的CH3的吸收峰)以及δ=1.32‐1.45ppm、1.55‐1.72ppm、2.25‐2.40ppm、3.98‐4.17ppm出现了四个峰(对应己内酯的CH2吸收峰)，进一步说明合成了聚(己内酯‐甲基丙烯酸三甲基硅烷酯)。
通过凝胶渗透色谱仪检测其数均分子量为2.0×104g/mol。由于本实施例1所得产物中主链含有聚酯链段，其在酶的作用下可发生降解作用。通过石英晶体微天平表征该聚合物的主链是否可断裂。如图3所示。石英晶体微天平可以原位检测材料的质量损失行为，频率变化对应与质量变化，且成反比。可以看到，当加入酶溶液后，频率发生上升，说明有质量损失。由于材料中硅烷脂在酶的作用下不能发生水解，质量损失是有主链段发生断裂造成的。因而证明该材料是主链断裂型的。
将合成的30g聚(己内酯‐甲基丙烯酸三甲基硅烷酯)、40g氧化亚铜、5g吡啶硫酮铜、10g氧化锌以及15g二甲苯搅拌混合，制成海洋防污涂料。通过喷涂200g制备的涂料在环氧树脂板上成膜，按照GB/T5370‐2007《防污漆样板浅海浸泡试验方法》，在厦门海域进行了浅海挂板实验(2012.4‐2013.4)，12个月无海洋生物生长，说明基于该材料制备的防污涂料具有很好的防污效果，同时不依赖于航速。
实施例2
在250mL封管中加入10g丙交酯，90g丙烯酸三异丙基硅酯，0.01g二乙二醇和100mL四氢呋喃，液氮冷冻，置换氮气三次后在氮气气氛下注入70μL的t‐BuP4的正己烷溶液，熔融封管，60℃条件下反应2h，然后沉淀在100mL甲醇中，真空干燥12h，产率为94%，通过凝胶渗透色谱仪检测其数均分子量为1.5×104g/mol。将该聚合物20g，与120g氧化亚铜，20g吡啶三苯基硼烷，10g氧化铁红以及30g甲基异丁基酮搅拌混合，制成海洋防污涂料。通过刷涂的方式，在环氧树脂板上成膜，在厦门海域进行了浅海挂板实验(2012.4‐2013.2)，10个月无海洋生物生长。
实施例3
在500mL三口瓶中加入180g碳酸乙烯酯，10g丙烯酸三正丁基硅酯，10g甲基丙烯酸甲酯，甲醇0.02g，液氮冷冻，置换氮气三次后在氮气气氛下迅速注入70μL的t‐BuP4的正己烷溶液，150℃条件下反应12h。反应结束后沉淀在甲醇中，过滤，真空干燥，产率为90%，通过凝胶渗透色谱仪检测其数均分子量为2.4×104g/mol。将该聚合物30g，与40g氧化亚铜，7g4,5‐二氯代‐2‐正辛基‐4‐异噻唑啉‐3‐酮，7g氧化锌，6g碳酸钙，3g膨润土，以及7g丁酮搅拌混合，制成海洋防污涂料。通过刷涂的方式，在环氧树脂板上成膜，在厦门海域进行了浅海挂板实验(2012.4‐2013.4)，12个月无海洋生物生长。
实施例4
在250mL三口瓶中加入80g2-亚甲基-1,3-二氧杂环庚烷，20g甲基丙烯酸甲酯，20g丙烯酸三正丁基硅酯，0.5g偶氮二异丁腈和100mL甲苯溶液，50℃反应12h。反应结束后用正己烷沉淀，过滤，真空干燥12h，产率为90%，通过凝胶渗透色谱仪检测其数均分子量为1.3×104g/mol。将该聚合物60g，与20g氧化亚铜，3g米托咪啶，12g氧化锌以及5g二甲苯搅拌混合，制成海洋防污涂料。通过刷涂的方式，在环氧树脂板上成膜，在厦门海域进行了浅海挂板实验(2012.4‐2013.4)，12个月无海洋生物生长。
实施例5
在100mL三口瓶中加入50g2‐甲基‐ε‐己内酯，25g甲基丙烯酸甲酯，25g甲基丙烯酸三异丙基硅酯，0.1g过氧化苯甲酰和100mL二甲苯溶液，70℃反应24h。反应结束后用水沉淀，过滤，真空干燥12h，产率为80%，通过凝胶渗透色谱仪检测其数均分子量为2.3×104g/mol。将该聚合物10g，与30g氧化亚铜，5g2,4,6‐三氯苯基‐N‐苯基马来酰亚胺，30g氧化锌，5g氧化铁红，5g聚酰胺蜡以及15g二甲苯搅拌混合，制成海洋防污涂料。通过喷涂的方式，在环氧树脂板上成膜，在厦门海域进行了浅海挂板实验(2012.4‐2013.6)，14个月无海洋生物生长。
实施例6
在250mL三口瓶中加入40g2‐氯‐ε‐己内酯，60g甲基丙烯酸三甲基硅烷，0.1g乙醇以及100mL甲苯溶液，液氮冷冻，置换氮气三次后在氮气气氛下注入7μL的t‐BuP4的正己烷溶液，25℃反应12h，在甲醇沉淀，过滤，真空干燥，产率90%，通过凝胶渗透色谱仪检测其数均分子量为5.5×104g/mol。将该聚合物30g，与30g氧化亚铜，10g吡啶硫酮锌，7g硫酸钡，3g膨润土以及20g正丁醇搅拌混合，制成海洋防污涂料。通过刷涂的方式，在环氧树脂板上成膜，在厦门海域进行了浅海挂板实验(2012.4‐2013.4)，12个月无海洋生物生长。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (4)
1.一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法，其特征在于，将环状单体、乙烯基单体、乙烯基硅烷酯单体按配比混和在溶剂中，然后加入单体总量质量百分比为0.01～5％的复合引发剂，在温度为25～150℃，氩气或氮气保护的条件下反应制备；以质量百分比计，单体组成为：环状单体5～95％、乙烯基单体0～90％和乙烯基硅烷酯5～95％；所述溶剂为四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、乙酸丁酯、甲苯、二甲苯、丙酮和正丁醇中的一种或多种；
所述环状单体为2-亚甲基-1,3-二氧杂环庚烷；
所述乙烯基单体为丙烯酸，甲基丙烯酸，甲基丙烯酸甲酯，甲基丙烯酸乙酯，甲基丙烯酸丁酯，甲基丙烯酸辛酯，丙烯酸甲酯，丙烯酸乙酯，丙烯酸丁酯，丙烯酸辛酯，甲基丙烯酸十二氟庚酯，丙烯酰胺，甲基丙烯酰胺，羟甲基丙烯酰胺，异丙基丙烯酰胺，甲基丙烯酸乙二醇酯，丙烯酸羟乙酯，甲基丙烯酸羟乙酯，甲基丙烯酸缩水甘油醚，苯乙烯，甲基丙烯酸二甲氨基乙酯，甲基丙烯酸二乙氨基乙酯，乙烯基吡咯烷酮，四乙烯基吡啶，丙烯酰氧乙基二甲基苄基氯化铵，甲基丙烯酰氧基乙基苄基二甲基氯化铵和甲基丙烯酰氧乙基三甲基氯化铵中的一种或多种；
所述乙烯基硅烷酯单体为丙烯酸三甲基硅烷酯、丙烯酸三乙基硅烷酯、丙烯酸三异丙基硅烷酯、丙烯酸三苯基硅烷酯、丙烯酸三丁基硅烷酯、丙烯酸三正辛基硅烷酯、甲基丙烯酸三甲基硅烷酯、甲基丙烯酸三乙基硅烷酯、甲基丙烯酸三异丙基硅烷酯、甲基丙烯酸三苯基硅烷酯、甲基丙烯酸三丁基硅烷酯、甲基丙烯酸三正辛基硅烷酯中的一种或任意几种以任意比例组成的混合物；
所述复合引发剂为偶氮二异丁腈和过氧化苯甲酰组成的混合物。
2.根据权利要求1所述的主链断裂型聚丙烯酸类硅烷酯树脂的制备方法，其特征在于，所述单体总量与溶剂的质量比为(50～200)：100。
3.一种主链断裂型聚丙烯酸类硅烷酯树脂，其特征在于，其由权利要求1或2所述制备方法制得。
4.权利要求3所述主链断裂型聚丙烯酸类硅烷酯树脂在制备海洋防污涂料中的应用，其特征在于，以重量份数计，将10～60份的所述主链断裂型聚丙烯酸类硅烷酯树脂、20～60份的氧化亚铜、3～15份的有机防污剂、10～40份的颜填料、0～5份的助剂和5～20份的有机溶剂混合搅拌均匀，制得海洋防污涂料；
所述有机防污剂为吡啶硫酮铜、吡啶硫酮锌、吡啶三苯基硼烷、4,5‐二氯代‐2‐正辛基‐4‐异噻唑啉‐3‐酮、米托咪啶、2‐(对‐氯苯基)‐3‐氰基‐4‐溴基‐5‐三氟甲基‐吡咯和2,4,6‐三氯苯基‐N‐苯基马来酰亚胺中的一种或多种；
所述颜填料为氧化锌、氧化铁红、碳酸钙和硫酸钡中的一种或多种；
所述助剂为氯化石蜡、松香、邻苯二甲酸二辛酯、蓖麻油、膨润土、聚酰胺蜡和气相二氧化硅中的一种或多种，
所述有机溶剂为二甲苯、正丁醇、甲基异丁基酮、丁酮和二丙酮醇中的一种或多种。
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| US20240166315A1 (en) | 2021-03-23 | 2024-05-23 | Jotun A/S | Monitoring the cleanliness of an underwater surface of a stationary object |
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| CN102718919A (zh) * | 2012-06-29 | 2012-10-10 | 华南理工大学 | 一种水解速度可控防污硅酯材料及其制备方法与应用 |
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| CN103396513A (zh) | 2013-11-20 |
| WO2015010390A1 (zh) | 2015-01-29 |
| US9701794B2 (en) | 2017-07-11 |
| US20160185913A1 (en) | 2016-06-30 |
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