CN103275607A - 含磷醇酸树脂电缆防火涂料及其制备方法 - Google Patents
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Abstract
含磷醇酸树脂电缆防火涂料及其制备方法，按质量百分数计，含磷醇酸树脂电缆防火涂料配方为：含磷醇酸树脂30%～45%，聚磷酸铵11%～18%，三聚氰胺5.5%～7.5%，季戊四醇4%～6%，硼酸锌3%～4.5%，膨润土3%～4.5%，钛白粉4%～6%，三氧化二钼1%～1.5%，二甲基硅油0.1%～0.15%，催干剂0.9%～1.35%，溶剂30%～45%；其制备步骤为：将配方量溶剂、聚磷酸铵、三聚氰胺、季戊四醇、硼酸锌、膨润土、钛白粉、三氧化二钼依次加入多用分散研磨机中进行高速分散30～60min，降低搅拌速度加入含磷醇酸树脂再分散20～40min，加入二甲基硅油，用锥形磨研磨至所需的细度，然后在多用分散研磨机中分散10～20min后加入催干剂分散均匀即得产品。
Description
技术领域
本发明涉及含磷醇酸树脂电缆防火涂料及其制备方法，属于高分子化学及聚合物涂料组合物技术领域。
背景技术
电线电缆是电力电讯事业的重要材料，国内外大量电缆火灾的发生，以及由此而造成的大面积停电或者因此而引起连锁灾难，导致重大的人员伤亡和巨大的财产损失，使人们意识到电缆火灾危害极大，防止电缆着火，阻止电缆延燃，非常必要。其中，电缆防火涂料是在饰面型防火涂料基础上发展起来集装饰和防火于一体的新型防火涂料品种。当它涂覆于普通电缆表面时，平时可起一定的装饰和保护作用，一旦火灾发生则具有阻止火焰蔓延，防止火灾发展的作用，从而达到保护电缆的目的。
CN102746775A公开了溴碳醇酸树脂电缆防火涂料及其制备方法，防火涂料的组分为：溴碳醇酸树脂，聚磷酸铵，三聚氰胺，季戊四醇，三氧化二锑，硼酸锌，膨润土，钛白粉，氯化石蜡，三氧化二钼，二甲基硅油，催干剂，溶剂；其制备步骤为：将配方量溶剂、聚磷酸铵、三聚氰胺、季戊四醇、三氧化二锑、硼酸锌、膨润土、钛白粉、氯化石蜡、三氧化二钼依次加入多用分散研磨机中进行高速分散30～60min，降低搅拌速度加入溴碳醇酸树脂再分散20～40min，加入二甲基硅油，用锥形磨研磨至所需的细度，然后在多用分散研磨机中分散10～20min后加入催干剂分散均匀即得产品。
目前使用广泛的是溶剂型电缆防火涂料，且以膨胀型防火涂料为主，但由于在涂料体系中添加大量无机阻燃助剂，导致涂层抗弯性变差而引起脱落，同时也存在外界因素作用下的迁移、析出等不足。
发明内容
本发明的目的是提供一种含磷醇酸树脂电缆防火涂料及其制备方法。
本发明是含磷醇酸树脂电缆防火涂料及其制备方法，含磷醇酸树脂电缆防火涂料，基于含磷醇酸树脂电缆防火涂料的总质量，按质量百分数计， 含磷醇酸树脂电缆防火涂料配方为：
含磷醇酸树脂30%~45%，聚磷酸铵11%~18%，三聚氰胺5.5%~7.5%，季戊四醇4%~6%，硼酸锌3%~4.5%，膨润土3%~4.5%，钛白粉4%~6%，三氧化二钼1%~1.5%，二甲基硅油0.1%~0.15%，催干剂0.9%~1.35%，溶剂30%~45%；
基于制备含磷醇酸树脂的总质量，按质量百分数计，含磷醇酸树脂配方为：
豆油酸50.8%~60.5%，季戊四醇11.6%~17.8%，邻苯二甲酸酐0%~15.5%，DOPOMA9.5%~20.9% ，带水剂5.1%~7%；
基于制备催干剂各组分的总质量，按质量百分数计，制备催干剂各组分的组成为：
异辛酸钴3.60%，异辛酸锰14.83%，异辛酸锆14.71%，200#溶剂油66.57%。
含磷醇酸树脂电缆防火涂料的制备方法，按权利要求1所述组分及其配比进行配料，其特征在于：
（1）DOPOMA的制备步骤为：
①在装有搅拌器、温度计、回流冷凝管的三口烧瓶中，加入等质量的四氢呋喃和甲苯混合溶液；
②DOPO和顺丁烯二酸酐以1:1.05的物质的量比投入，搅拌加热，温度为84℃时开始出现回流，体系稳定反应9h后颜色逐渐加深变为绿色，继续反应24h后体系颜色为墨绿色，保温反应24h后停止反应并冷却至室温；
③向溶液中加入适量的二甲苯并不断搅拌，体系分层，下层为墨绿色粘稠液体，上层为淡黄色澄清液体，分离得到下层粘稠液体，用二甲苯多次洗涤后放置于120℃的烘箱中干燥48h，取出冷却至室温淡黄色结晶固体；
（2）含磷阻燃醇酸树脂的制备步骤为：
①在100ml的四口烧瓶中加入豆油酸，季戊四醇，邻苯二甲酸酐和少许二甲苯，通氮气，开搅拌，缓慢升温，在30-40min内加热至180℃保温反应40min，保温结束后10min内分批加入的DOPOMA，加料完毕后缓慢升温至200℃保温反应30min；
②再缓慢升温至210℃，最终的保温反应温度为210-220℃，随着反应的进行，体系颜色逐渐加深，最终变为橙红色，保温反应2h后每隔半小时测量酸价，当酸价为10mgKOH/g左右时停止加热、降温、出料即可得到含磷醇酸树脂；
（3）催干剂的制备步骤为：
在200#溶剂油中，加入异辛酸钴、异辛酸锰、异辛酸锆，在3500r/min条件下高速分散2h即可得到含磷醇酸树脂饰面型防火涂料用催干剂；
（4）含磷醇酸树脂电缆防火涂料的制备步骤为：
将配方量溶剂、聚磷酸铵、三聚氰胺、季戊四醇、硼酸锌、膨润土、钛白粉、三氧化二钼依次加入多用分散研磨机中进行高速分散30～60min，降低搅拌速度加入含磷醇酸树脂再分散20～40min，加入二甲基硅油，用锥形磨研磨至所需的细度，然后在多用分散研磨机中分散10～20min后加入催干剂分散均匀即得产品。
本发明的有益之处是：通过分子设计首先采用9，10一二氢一9一氧杂一10一磷杂菲一10一氧化物(DOPO)和马来酸酐（MA）以1:1的摩尔比反应得到DOPOMA，并以此为原料来合成醇酸树脂，其在高分子链中引入了具有阻燃性能的元素磷，合成了具有阻燃性能的醇酸树脂，以合成的含磷醇酸树脂为涂料基体树脂，辅以膨胀阻燃体系及其它助剂，得到含磷醇酸树脂电缆防火涂料，应用于电线电缆阻燃防火涂装，可有效提高电线电缆的防火性能，赢得火灾条件下受灾人员的安全逃生和灭火救灾时间，减少人、财、物损失。
具体实施方式
本发明由以下技术方案完成，DOPO与MA以1:1的摩尔比来合成原料DOPOMA，季戊四醇经豆油酸封端得到两官能度的二元醇，然后与邻苯二甲酸酐进行酯化反应合成醇酸树脂，最后加入DOPOMA缩聚得到含磷阻燃醇酸树脂，以合成含磷醇酸树脂为基体树脂，加入催干助剂，在溶剂中分散均匀即得电缆防火涂料。
含磷醇酸树脂合成工艺路线如下：
其中
R为脂肪碳链，
基于含磷醇酸树脂电缆防火涂料的总质量，按质量百分数计，含磷醇酸树脂电缆防火涂料配方为：
含磷醇酸树脂30%~45%，聚磷酸铵11%~18%，三聚氰胺5.5%~7.5%，季戊四醇4%~6%，硼酸锌3%~4.5%，膨润土3%~4.5%，钛白粉4%~6%，三氧化二钼1%~1.5%，二甲基硅油0.1%~0.15%，催干剂0.9%~1.35%，溶剂30%~45%；
其中溶剂由200#溶剂油与环己酮组成，其重量比为1：1，聚磷酸铵聚合度为1000，DOPOMA是由9，10一二氢一9一氧杂一10一磷杂菲一10一氧化物(DOPO)和马来酸酐以1:1的摩尔比反应得到。
基于制备含磷醇酸树脂的总质量，按质量百分数计，含磷醇酸树脂配方为：
豆油酸50.8%~60.5%，季戊四醇11.6%~17.8%，邻苯二甲酸酐0%~15.5%，DOPOMA9.5%~20.9% ,带水剂5.1%~7%。
其中带水剂是二甲苯。
基于制备催干剂各组分的总质量，按质量百分数计，制备催干剂各组分的组成为：
异辛酸钴3.60%，异辛酸锰14.83%，异辛酸锆14.71%，200#溶剂油66.57%。
DOPOMA的制备步骤为：
在装有搅拌器、温度计、回流冷凝管的三口烧瓶中，加入等质量的四氢呋喃和甲苯混合溶液，DOPO和顺丁烯二酸酐以1:1.05的物质的量比投入，搅拌加热，温度为84℃时开始出现回流，体系稳定反应9h后颜色逐渐加深变为绿色，继续反应24h后体系颜色为墨绿色，保温反应24h后停止反应并冷却至室温，向溶液中加入适量的二甲苯并不断搅拌，体系分层，下层为墨绿色粘稠液体，上层为淡黄色澄清液体，分离得到下层粘稠液体，用二甲苯多次洗涤后放置于120℃的烘箱中干燥48h，取出冷却至室温淡黄色结晶固体。
含磷阻燃醇酸树脂的制备步骤为：
在100ml的四口烧瓶中加入豆油酸，季戊四醇，邻苯二甲酸酐和少许二甲苯，通氮气，开搅拌，缓慢升温。在30-40min内加热至180℃保温反应40min，保温结束后10min内分批加入的DOPOMA，加料完毕后缓慢升温至200℃保温反应30min，再缓慢升温至210℃，最终的保温反应温度为210-220℃，随着反应的进行，体系颜色逐渐加深，最终变为橙红色，保温反应2h后每隔半小时测量酸价，当酸价为10mgKOH/g左右时停止加热、降温、出料即可得到含磷醇酸树脂。
催干剂的制备步骤为：
在200#溶剂油中，加入异辛酸钴、异辛酸锰、异辛酸锆，在3500r/min条件下高速分散2h即可得到含磷醇酸树脂电缆防火涂料用催干剂;
含磷醇酸树脂电缆防火涂料的制备步骤为：
将配方量溶剂、聚磷酸铵、三聚氰胺、季戊四醇、硼酸锌、膨润土、钛白粉、三氧化二钼依次加入多用分散研磨机中进行高速分散30～60min，降低搅拌速度加入含磷醇酸树脂再分散20～40min，加入二甲基硅油，用锥形磨研磨至所需的细度，然后在多用分散研磨机中分散10～20min后加入催干剂分散均匀即得产品。
以下是本发明的实施例，但本发明不局限于下列实施例中。
实施例1.
在装有搅拌器、温度计、回流冷凝管的500ml的三口烧瓶中，加入100g四氢呋喃和100g甲苯混合溶液，162gDOPO和77g顺丁烯二酸酐，搅拌加热。温度为84℃时开始出现回流，体系稳定反应9h后颜色逐渐加深变为绿色，反应24h后体系颜色为墨绿色。保温反应24h后停止反应并冷却至室温，向溶液中加入适量的二甲苯并不断搅拌，体系分层，下层为墨绿色粘稠液体，上层为淡黄色澄清液体。分离得到下层粘稠液体，用二甲苯多次洗涤后放置120℃的烘箱中干燥48h，取出冷却至室温得到淡黄色结晶固体。
实施例2.
在100ml的四口烧瓶中加入豆油酸28份，季戊四醇7.6份，邻苯二甲酸酐4.8份和3份二甲苯。通氮气，开搅拌，缓慢升温。（在30-40min内加热至180℃）。160℃时开始有油溅的声音，并出现回流现象。体系为浑浊液。温度170℃以后反应20min体系变为微黄澄清液。当体系温度到达180℃时开始保温40min。保温结束后10min内分批加入4.9份的DOPOMA。加料完毕后缓慢升温至200℃保温反应30min，再缓慢升温至210℃，最终的保温反应温度为210-220℃（不可快速升温至220℃，以免发生爆沸现象）。随着反应的进行，体系颜色逐渐加深，最终变为橙红色。保温反应2h后每隔半小时进行测量酸价，当酸价为10mgKOH/g左右时停止加热、降温、出料即得含磷阻燃醇酸树脂。
实施例3.
在50g200#溶剂油中，加入3g异辛酸钴、11g异辛酸锰、11g异辛酸锆，在3500r/min条件下高速分散2h即可得到含磷醇酸树脂电缆防火涂料用催干剂。
实施例4.
将7份200#溶剂油、7份200#环己酮、6份聚磷酸铵、2.5份三聚氰胺、2份季戊四醇、1.5份硼酸锌、1.5份膨润土、2份钛白粉、1份三氧化二钼依次加入多用分散研磨机中进行高速分散30～60min，降低搅拌速度加入15份含磷醇酸树脂再分散20～40min，加入0.06份二甲基硅油，用锥形磨研磨至细度达90μm以下，然后在多用分散研磨机中分散10～20min后加入0.45份催干剂分散均匀即得产品。
经对所制备含磷醇酸树脂电缆防火涂料性能检测结果如表1。
表1：含磷醇酸树脂电缆防火涂料性能指标
Claims (5)
1.含磷醇酸树脂电缆防火涂料，其特征在于：基于含磷醇酸树脂电缆防火涂料的总质量，按质量百分数计， 含磷醇酸树脂电缆防火涂料配方为：
含磷醇酸树脂30%~45%，聚磷酸铵11%~18%，三聚氰胺5.5%~7.5%，季戊四醇4%~6%，硼酸锌3%~4.5%，膨润土3%~4.5%，钛白粉4%~6%，三氧化二钼1%~1.5%，二甲基硅油0.1%~0.15%，催干剂0.9%~1.35%，溶剂30%~45%；
基于制备含磷醇酸树脂的总质量，按质量百分数计，含磷醇酸树脂配方为：
豆油酸50.8%~60.5%，季戊四醇11.6%~17.8%，邻苯二甲酸酐0%~15.5%，DOPOMA9.5%~20.9% ，带水剂5.1%~7%；
基于制备催干剂各组分的总质量，按质量百分数计，制备催干剂各组分的组成为：
异辛酸钴3.60%，异辛酸锰14.83%，异辛酸锆14.71%，200#溶剂油66.57%。
2.根据权利要求1所述的含磷醇酸树脂电缆防火涂料，其特征在于溶剂由200#溶剂油与环己酮组成，其重量比为1：1，聚磷酸铵聚合度为1000。
3.根据权利要求1所述的含磷醇酸树脂电缆防火涂料，其特征在于所述的DOPOMA是由9，10一二氢一9一氧杂一10一磷杂菲一10一氧化物(DOPO)和马来酸酐以1:1的摩尔比反应得到。
4.根据权利要求1所述的含磷醇酸树脂电缆防火涂料，其特征在于带水剂为二甲苯。
5.含磷醇酸树脂电缆防火涂料的制备方法，按权利要求1所述组分及其配比进行配料，其特征在于：
（1）DOPOMA的制备步骤为：
①在装有搅拌器、温度计、回流冷凝管的三口烧瓶中，加入等质量的四氢呋喃和甲苯混合溶液；
②DOPO和顺丁烯二酸酐以1:1.05的物质的量比投入，搅拌加热，温度为84℃时开始出现回流，体系稳定反应9h后颜色逐渐加深变为绿色，继续反应24h后体系颜色为墨绿色，保温反应24h后停止反应并冷却至室温；
③向溶液中加入适量的二甲苯并不断搅拌，体系分层，下层为墨绿色粘稠液体，上层为淡黄色澄清液体，分离得到下层粘稠液体，用二甲苯多次洗涤后放置于120℃的烘箱中干燥48h，取出冷却至室温淡黄色结晶固体；
（2）含磷阻燃醇酸树脂的制备步骤为：
①在100ml的四口烧瓶中加入豆油酸，季戊四醇，邻苯二甲酸酐和少许二甲苯，通氮气，开搅拌，缓慢升温，在30-40min内加热至180℃保温反应40min，保温结束后10min内分批加入的DOPOMA，加料完毕后缓慢升温至200℃保温反应30min；
②再缓慢升温至210℃，最终的保温反应温度为210-220℃，随着反应的进行，体系颜色逐渐加深，最终变为橙红色，保温反应2h后每隔半小时测量酸价，当酸价为10mgKOH/g左右时停止加热、降温、出料即可得到含磷醇酸树脂；
（3）催干剂的制备步骤为：
在200#溶剂油中，加入异辛酸钴、异辛酸锰、异辛酸锆，在3500r/min条件下高速分散2h即可得到含磷醇酸树脂饰面型防火涂料用催干剂；
（4）含磷醇酸树脂电缆防火涂料的制备步骤为：
将配方量溶剂、聚磷酸铵、三聚氰胺、季戊四醇、硼酸锌、膨润土、钛白粉、三氧化二钼依次加入多用分散研磨机中进行高速分散30～60min，降低搅拌速度加入含磷醇酸树脂再分散20～40min，加入二甲基硅油，用锥形磨研磨至所需的细度，然后在多用分散研磨机中分散10～20min后加入催干剂分散均匀即得产品。
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Denomination of invention: Phosphorous alkyd resin cable fire-retardant coating and preparation method thereof Effective date of registration: 20190826 Granted publication date: 20150520 Pledgee: Lanzhou New District Klc Holdings Ltd. Pledgor: GANSU XIBEIZHIGUANG CABLE Co.,Ltd. Registration number: Y2019620000002 |
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Denomination of invention: Phosphorous alkyd resin cable fire-retardant coating and preparation method thereof Effective date of registration: 20200115 Granted publication date: 20150520 Pledgee: Lanzhou New District Klc Holdings Ltd. Pledgor: GANSU XIBEIZHIGUANG CABLE Co.,Ltd. Registration number: Y2020620000002 |
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Denomination of invention: Phosphorus containing alkyd resin cable fire retardant coating and its preparation method Effective date of registration: 20210220 Granted publication date: 20150520 Pledgee: Lanzhou New District Klc Holdings Ltd. Pledgor: GANSU XIBEIZHIGUANG CABLE Co.,Ltd. Registration number: Y2021620000003 |
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