CN108690473B - 松香酸改性醇酸树脂锌盐防污涂料的制备方法 - Google Patents
松香酸改性醇酸树脂锌盐防污涂料的制备方法 Download PDFInfo
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Abstract
本发明涉及涂料制备领域，特别涉及一种松香酸改性醇酸树脂锌盐防污涂料的制备方法，按重量份数计，所述松香酸改性醇酸树脂锌盐防污涂料由以下组分组成：松香酸改性醇酸树脂锌盐900~1100份，混合防锈颜料40~50份，涂料助剂1~3份，以上各组分在配有高速分散器的搅拌罐中或砂磨机中进行高速分散或砂磨后即得到松香酸改性醇酸树脂锌盐防污涂料。在本发明中引入改性松香酸结构，与一般涂料相比，具有附着力强、柔韧性好、内聚性能优、快干等特点,而且对海洋环境的污染极小，比较环保。含锌盐涂料在海水中将会发生置换性电离反应，游离生成松香酸的钠盐和锌离子，对海洋微小寄生生物有抑制生长作用，对船舶、堤防、岸基也有显而易见的清洁保护。
Description
技术领域
本发明涉及涂料制备领域，特别涉及一种松香酸改性醇酸树脂锌盐防污涂料的制备方法。
背景技术
目前船体、码头、钻井平台等位于吃水线下的部分易受到细菌和海洋生物的附着污损，大量的附着污损物不仅增加船舶的自重、减少船舶的载重，同时将大大增加船体的阻力，造成船舶的航速降低和燃油消耗的增加，而且污损生物死亡后脱落，还可能被吸入设备的管道内，造成管道的堵塞，污损生物的繁殖也会引起船舶或海上建筑的防腐蚀保护层的损坏，加速金属构件的腐蚀，降低了船舶和海上建筑物的使用寿命，通常都是在这些部分涂防污涂料来防止海洋生物附着，传统的锡系的海洋防污涂料由于对海洋生态环境污染较大，已经禁止使用，松香作为一种重要的化工原料被广泛应用于肥皂、造纸、油漆和橡胶等行业，松香的改性，一般利用松香分子结构中的共轭双键、羧基等反应活性基团，通过加成、歧化、氢化、聚合、氨解、成盐、酯化等反应制成马来松香、歧化松香、氢化松香、聚合松香、松香胺、松香盐及各种松香酯等深加工产品。
发明内容
为了弥补以上不足，本发明公开一种松香酸改性醇酸树脂锌盐防污涂料的制备方法，松香改性醇酸树脂是指在醇酸树脂的制备过程中添加改性剂松香，经化学反应制成的改性树脂，由于松香的改性，使该树脂易溶于酯类溶剂，能增加漆膜的附着力，减少漆膜起皱，提高漆膜的耐久性、耐碱性和光泽，降低黏度；漆膜释放溶剂也较快，干率提高，干透加快，而且对海洋环境的污染较小。
本发明是通过如下技术方案实现的：一种松香酸改性醇酸树脂锌盐防污涂料的制备方法，按下述工艺步骤进行制备：
步骤一：松香酸的精制
在松香中加入乙醇水溶液，再加入氢氧化钠的水溶液，加热至沸腾，回流搅拌反应3～4小时，加入活性炭脱色，过滤，滤液冷却到0～4℃，缓慢滴入盐酸水溶液，再次过滤，得到略带黄色固体，用水洗至中性；
步骤二：松香酸改性醇酸树脂锌盐的制备
在反应釜中加入精制的松香酸、多元醇、含油酸的物质以及溶剂，升温至90～100℃，反应0.5～1h，然后加入烷基二羧酸和无水氧化锌搅拌均匀，加热至沸腾，脱水反应1h；升高温度至210～220℃，反应2～4h，测定酸值为80以下，即得松香酸改性醇酸树脂锌盐；
步骤三：松香酸改性醇酸树脂锌盐防污涂料的制备
将所述松香酸改性醇酸树脂锌盐900～1100份、混合防锈颜料40～50份、涂料助剂1～3份，分散或砂磨至粒度40μm以下，即得。
作为优选方案，在步骤一中：所述乙醇的体积分数为75%～90%，所述氢氧化钠水溶
液和盐酸的浓度是1～3mol/L，所述松香、氢氧化钠和盐酸的摩尔比为10:1:1.2，松香、乙醇和活性炭的质量比为100:150～170:1～3。
作为优选方案，在步骤二中：所述溶剂为甲苯或正丁醇中的一种，所述多元醇为季
戊四醇、丙三醇或三羟基甲基丙烷中的一种，所述含油酸的物质为豆油酸、蓖麻油、葵花籽油、棕榈油、棉籽油或菜籽油中的一种，所述烷基二羧酸为丁二酸、马来酸、富马酸或草酸中的一种或多种；所述松香酸、多元醇、含油酸的物质、烷基二羧酸和无水氧化锌的重量比为100：35～45：45～55：25～35：0.02～0.03。
本发明的有益效果是：本发明中引入改性松香酸结构，与一般涂料相比，具有附着力强、柔韧性好、内聚性能优、快干等特点,而且对海洋环境的污染极小，比较环保；含锌盐涂料在海水中将会发生置换性电离反应，游离生成松香酸的钠盐和锌离子，对海洋微小寄生生物有抑制生长作用，对船舶、堤防、岸基也有显而易见的清洁保护。
附图说明
图1是本发明实施例1的挂片试验。
具体实施方式
下面通过实施例对本发明做进一步说明，但本发明范围不受此限制。
实施例1：
松香酸的精制：在300g松香中加入体积分数为75%的乙醇800ml，再加入50ml的2mol/L氢氧化钠水溶液，加热至沸腾，回流搅拌反应3.5小时，加入6g活性炭脱色，过滤，滤液冷却到0～4℃，缓慢滴入60ml2mol/L盐酸水溶液，再次过滤，得到略带黄色固体，用水洗至中性。
松香酸改性醇酸树脂锌盐的制备：向配有搅拌器、温度计、直管冷凝管、油水分离器的反应釜中加入1013g松香酸、421g丙三醇和506g豆油酸，升温至95℃，反应35分钟，然后加入320g富马酸、2.3g草酸和0.253g无水氧化锌搅拌均匀，加热至沸腾，脱水反应1h；升高温度至220℃，再反应3h，测定酸值为80以下,即得松香酸改性醇酸树脂锌盐。
松香酸改性醇酸树脂锌盐防污涂料的制备：向配有高速分散机的涂料生产罐中加入松香酸改性醇酸树脂锌盐1000g，混合防锈颜料45g，涂料助剂2g，进行高速分散，测细度在40μm以下，即得。
性能测试：
附着力（级）：按GB/T1720-1989标准评价为1；
柔韧性（mm）：按GB/T1731-1993标准评价为1；
粘度（Pa.s）：按GB/T1723-1993标准评价为40～50；
冲击强度（kg.cm）：按GB/T1732-1993标准评价为45±5；
耐人工老化（600h）：按GB/T1865-2009标准评价，无起泡、剥落、裂纹；
盐雾试验（1000h）：按GB/T1771-2007标准评价，无起泡、无开裂、无锈斑；
固化时间(25C˚，相对湿度70％)：表干≦0.5h；实干≦4h；
挂片试验情况
如图1所示，以改性松香酸锌盐复合聚丙烯酸树脂为基料生产的环保防污涂料经对日照海域码头做挂片试验7次，每片涂装2平方米，存放三年，未见微生物附着，临近海洋水域生物未见生长异常。
实施例2：
松香酸的精制：在300g松香中加入体积分数为85%的乙醇715ml，再加入100ml的1mol/L氢氧化钠水溶液，加热至沸腾，回流搅拌反应3小时，加入3g活性炭脱色，过滤，滤液冷却到0～4℃，缓慢滴入120ml的1mol/L盐酸水溶液，再次过滤，得到略带黄色固体，用水洗至中性。
松香酸改性醇酸树脂锌盐的制备：向配有搅拌器、温度计、直管冷凝管、油水分离器的反应釜中加入1013g松香酸、355g丙三醇和456g蓖麻油，升温至90℃，反应30分钟，然后加入304g马来酸和0.203g无水氧化锌搅拌均匀，加热至沸腾，脱水反应1h；升高温度至210℃，再反应2h，测定酸值为80以下，即得松香酸改性醇酸树脂锌盐。
松香酸改性醇酸树脂锌盐防污涂料的制备：向砂磨机中加入松香酸改性醇酸树脂锌盐900g，混合防锈颜料40g，涂料助剂1g，进行砂磨，测细度在40μm以下，即得。
实施例3：
松香酸的精制：在300g松香中加入体积分数为90%的乙醇676ml，再加入33ml的3mol/L氢氧化钠水溶液，加热至沸腾，回流搅拌反应4小时，加入9g活性炭脱色，过滤，滤液冷却到0～4℃，缓慢滴入40ml的3mol/L盐酸水溶液，再次过滤，得到略带黄色固体，用水洗至中性。
松香酸改性醇酸树脂锌盐的制备：向配有搅拌器、温度计、直管冷凝管、油水分离器的反应釜中加入1013g松香酸、455g三羟基甲基丙烷和557g菜籽油，升温至100℃，反应1h，然后加入354g丁二酸和0.304g无水氧化锌搅拌均匀，加热至沸腾，脱水反应1h；升高温度至215℃，再反应4h，测定酸值为80以下，即得松香酸改性醇酸树脂锌盐。
松香酸改性醇酸树脂锌盐防污涂料的制备：向配有高速分散机的涂料生产罐中加入松香酸改性醇酸树酯锌盐1100g，混合防锈颜料50g，涂料助剂3g，进行高速分散，测细度在40μm以下，即得。
除说明书所述技术特征外，其余技术特征均为本领域技术人员已知技术。
Claims (3)
1.一种松香酸改性醇酸树脂锌盐防污涂料的制备方法，其特征在于，按下述工艺步骤进行制备：
步骤一：松香酸的精制
在松香中加入乙醇水溶液，再加入氢氧化钠的水溶液，加热至沸腾，回流搅拌反应3～4小时，加入活性炭脱色，过滤，滤液冷却到0～4℃，滴入盐酸水溶液，再次过滤，得到略带黄色固体，用水洗至中性，即得；
步骤二：松香酸改性醇酸树脂锌盐的制备
向反应釜中加入精制的松香酸、多元醇、含油酸的物质以及溶剂，升温至90～100℃，反应0.5～1h，然后加入烷基二羧酸和无水氧化锌搅拌均匀，加热至沸腾，脱水反应1h，再升高温度至210～220℃，反应2～4h，测定酸值为80以下，即得松香酸改性醇酸树脂锌盐；
步骤三：松香酸改性醇酸树脂锌盐防污涂料的制备
将所述松香酸改性醇酸树脂锌盐900～1100份、混合防锈颜料40～50份、涂料助剂1～3份，分散或砂磨至粒度40µm以下，即得。
2.根据权利要求1所述的松香酸改性醇酸树脂锌盐防污涂料的制备方法，其特征在于，在步骤一中：所述乙醇水溶液的体积分数为75%～90%，所述氢氧化钠水溶液和盐酸水溶液的浓度是1～3mol/L，所述松香、氢氧化钠和盐酸的摩尔比为10:1:1.2，松香、乙醇和活性炭的质量比为100:150～170:1～3。
3.根据权利要求1所述的松香酸改性醇酸树脂锌盐防污涂料的制备方法，其特征在于，在步骤二中：所述溶剂为甲苯或正丁醇中的一种，所述多元醇为季戊四醇、丙三醇或三羟基甲基丙烷中的一种，所述含油酸的物质为豆油酸、蓖麻油、葵花籽油、棕榈油、棉籽油或菜籽油中的一种，所述烷基二羧酸为丁二酸、马来酸、富马酸或草酸中的一种或多种；所述松香酸、多元醇、含油酸的物质、烷基二羧酸和无水氧化锌的重量比为100：35～45：45～55：25～35：0.02～0.03。
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