CN106892941A - 一种利用工业副产松油烯制备含氟脱模添加剂的方法 - Google Patents
一种利用工业副产松油烯制备含氟脱模添加剂的方法 Download PDFInfo
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Abstract
本发明公开了一种利用工业副产松油烯制备含氟脱模添加剂的方法,其特征是:将松油烯中的α-蒎烯、双戊烯和异松油烯异构化成α-松油烯,松油烯中的主要成分α-松油烯和不断异构化而来的松油烯均与(甲基)烯基酸进行加成反应,生成的(甲基)烯基酸松油烯加成化合物,与过氧化氢进行环氧化反应,生成环氧化(甲基)烯基酸松油烯加成化合物,再进行水解,生成双羟基产物,双羟基产物均与六氟丙烯齐聚体进行亲核取代反应,得到六氟丙烯齐聚体取代的产物,六氟丙烯齐聚体取代的产物与二乙醇胺进行酰胺化反应,制得酰胺化产物,最后,酰胺化产物与磷酸进行酯化反应制得酯化产物;即为利用工业副产松油烯制备含氟脱模添加剂。
Description
技术领域
本发明涉及脱模添加剂合成技术领域,尤指一种利用工业副产松油烯制备含氟脱模添加剂的方法。
背景技术
脱模剂是一种介于模具与有机高分子物质或其他制品之间的功能性物质,是防止橡胶、塑料和聚氨酯等弹性体物质及其他材料的模制品、层压制品、纺丝件等物质粘结到模具或金属板面上,起到易于脱离作用的一类加工助剂,在高分子聚合物加工领域内,脱模剂的使用是必不可少的,通常用作主要脱模剂的活性物质主要为碳氢类化合物或聚硅氧烷类有机硅化合物,碳氢类化合物配制的脱模剂来源丰富,价格便宜,脱模后的产品可以直接进行二次加工,但是,长期使用会造成模具表面形成棕色结焦物质进而污染模具,聚硅氧烷类有机硅化合物配制的脱模剂,其脱模效果较碳氢类化合物配制的脱模剂优越,但是,脱模后的产品表面上会产生一定的油状物,产品的二次加工性能差。
氟脱模剂是以主体含氟化合物和其他辅助物料混合配制而成的一种混合物,与其他类型的脱模剂相比较,氟脱模剂的优点主要有:脱模剂本身质量稳定、产品储存周期长;使用浓度低,效果好,寿命长,一次喷涂可多次使用;对高粘度原料有良好的脱模性,脱模后对制品的污染小,不影响产品的二次加工;脱模效果是一般有机硅系列脱模剂的3-5倍,一些国外的公司和研究机构对氟脱模剂进行了大量的研究,国内对此研究和开发的报道较少,现有的高效氟脱模剂基本上依赖进口。随着社会和环境要求的提高,传统的全氟辛磺酰类化合物和全氟辛酸类化合物因对环境和生物体有危害而加以限用或禁用。
以松节油为原料合成松油醇,会产生大量副产松油烯,副产松油烯约占松油醇产量的20%~30%,我国松脂资源丰富,是松脂香和松节油产量最大的国家之一,每年因合成松油醇而产生的副产松油烯数量巨大,松油烯是多种性质极其相似的同分异构体的混合物,分离是很困难的,所以只能作为低档溶剂使用,难以产生更大的经济效益。
针对国内现有脱模剂的不足,选择利用工业副产松油烯制备含氟脱模添加剂,提高高分子聚合物加工效率、满足市场的需要,具有良好的经济效益和社会效益。
发明内容
本发明的目的在于提供一种利用工业副产松油烯制备含氟脱模添加剂的方法。
为了实现上述目的,本发明的技术解决方案为:将松油烯中的α-蒎烯、双戊烯和异松油烯异构化成α-松油烯,松油烯中的主要成分α-松油烯和不断异构化而来的松油烯均与(甲基)烯基酸进行加成反应,生成的(甲基)烯基酸松油烯加成化合物,与过氧化氢进行环氧化反应,生成环氧化(甲基)烯基酸松油烯加成化合物,再进行水解,生成双羟基产物,双羟基产物均与六氟丙烯齐聚体进行亲核取代反应,得到六氟丙烯齐聚体取代的产物,六氟丙烯齐聚体取代的产物与二乙醇胺进行酰胺化反应,制得酰胺化产物,最后,酰胺化产物与磷酸进行酯化反应制得酯化产物,具体制备方法包含以下步骤:
1).在对甲苯磺酸和氨基磺酸作用下,松油烯体系中的α-蒎烯(ⅠA)、双戊烯(ⅠB)和异松油烯(ⅠC)异构化成α-松油烯(Ⅱ),松油烯中的主要成分α-松油烯(Ⅱ)和不断异构化而来的α-松油烯(Ⅱ)均与(甲基)烯基酸(Ⅲ)于150℃~180℃下回流反应4~6小时,生成(甲基)烯基酸松油烯加成化合物(ⅣA)和(ⅣB),其主要化学反应为:
2).冰醋酸和浓硫酸作用下,(甲基)烯基酸松油烯加成化合物(ⅣA)和(ⅣB)均与过氧化氢于60~80℃下环氧化反应4~5小时,生成环氧化(甲基)烯基酸松油烯加成化合物(ⅤA)和(ⅤB),其主要化学反应为:
3).环氧化(甲基)烯基酸松油烯加成化合物(ⅤA)和(ⅤB),用3倍体积的热水进行水解,静置,取油层,得到双羟基产物(ⅥA)和(ⅥB),其主要化学反应为:
4).以甲苯为溶剂,N,N-二甲基环己胺存在下,于20℃~35℃下,双羟基产物(ⅥA)和(ⅥB)均与六氟丙烯齐聚体(Ⅶ)进行亲核取代反应6~8小时后,蒸馏出甲苯,得到六氟丙烯齐聚体取代的产物(ⅧA)和(ⅧB),其主要化学反应为:
5).六氟丙烯齐聚体取代的产物(ⅧA)和(ⅧB)均与二乙醇胺(Ⅸ),于85℃~105℃温度下进行酰胺化反应,制得酰胺化产物(ⅩA)和(ⅩB),冷却至10℃~30℃,其主要化学反应为:
6).以N,N-二甲基亚砜为溶剂,在五氧化二磷存在下,酰胺化产物(ⅩA)和(ⅩB)均与磷酸,水浴加热于85℃~95℃进行酯化反应3~4小时后,冷却至10℃~30℃,制得酯化产物(ⅫA)和(ⅫB),用水稀释酯化产物(ⅫA)和(ⅫB),过滤,取滤饼,即为利用工业副产松油烯制备含氟脱模添加剂,其主要化学反应为:
进一步的是,上述各反应式中的R是氢、甲基、乙基或丙基;
上述各反应式中的Rf是具有如下化学结构的化合物:
失去一个氟原子后形成的基团,其中,n = 2,3,4;
所述的松油烯、(甲基)烯基酸、过氧化氢、六氟丙烯齐聚体、二乙醇胺和磷酸的质量比为1﹕0.6~0.8﹕0.7~0.9﹕3.5~4.0﹕0.8~1.0﹕1.4~1.6;
所述的对甲苯磺酸和氨基磺酸,其用量分别为松油烯质量的0%~6%,其总用量为松油烯质量的6%~10%;
所述的冰醋酸和浓硫酸,其用量分别是过氧化氢质量的20%~30%和2%~3%;
所述的N,N-二甲基环己胺,其用量为松油烯质量的3%~5%。
本发明一种利用工业副产松油烯制备含氟脱模添加剂的方法,其特点和优点是:选择利用工业副产松油烯制备含氟脱模添加剂,原料来源充足,成本较低;合成物是一种含氟酰胺基二元磷酸酯脱模添加剂,属于含氟高端脱模剂添加剂,可提高高分子聚合物加工效率、满足市场的需要;具有良好的经济效益和社会效益;反应操作简单易行,适合工业化生产。
具体实施方式
实施例1
在装有搅拌装置、回流冷凝装置和温度计的四口瓶中,加入30克松油烯、1.5克甲基苯磺酸和0.5克浓硫酸,搅拌0.5~1小时后,加入21克2-甲基-2-戊烯酸,升温至170℃~180℃进行回流反应5小时,生成甲基戊烯酸松油烯加成化合物,降温至60~70℃,加入25克过氧化氢,5克冰醋酸和0.5克浓硫酸,进行环氧化反应4小时,生成环氧化2-甲基-2-戊烯酸松油烯加成化合物,然后用3倍体积的热水进行水解,静置,取油层,生成双羟基产物,加入150mL甲苯和120克六氟丙烯齐聚体,开启搅拌,缓慢加入1.5克N,N-二甲基环己胺,20℃~35℃的温度下进行亲核取代反应6~8小时后,蒸馏出甲苯,得到六氟丙烯齐聚体取代的产物,向四口瓶中加入30克二乙醇胺,于95℃~105℃温度下进行酰胺化反应,制得酰胺化产物,冷却至10℃~30℃,最后向四口瓶中加入65克N,N-二甲基亚砜、4克五氧化二磷和48克磷酸,水浴加热于85℃~95℃下进行酯化反应3小时后,冷却至10℃~30℃,制得酯化产物,用水稀释酯化产物,过滤,取滤饼,即为利用工业副产松油烯制备含氟脱模添加剂。
实施例2
在装有搅拌装置、回流冷凝装置和温度计的四口瓶中,加入30克松油烯、1.8克对甲苯磺酸和1.2克氨基磺酸,搅拌0.5~1小时后,加入18克丁烯酸,升温至150℃~160℃进行回流反应4小时,生成丁烯酸松油烯加成化合物,降温至65~75℃,加入21克过氧化氢,5.5克冰醋酸和0.6克浓硫酸,进行环氧化反应3小时,生成环氧化丁烯酸松油烯加成化合物,然后用3倍体积的热水进行水解,静置,取油层,生成双羟基产物,加入120mL甲苯和110克六氟丙烯齐聚体,开启搅拌,缓慢加入2克N,N-二甲基环己胺,20℃~35℃的温度下进行亲核取代反应6~8小时后,蒸馏出甲苯,得到六氟丙烯齐聚体取代的产物,向四口瓶中加入27克二乙醇胺,于85℃~95℃温度下进行酰胺化反应,制得酰胺化产物,冷却至10℃~30℃,最后向四口瓶中加入80克N,N-二甲基亚砜、5克五氧化二磷和45克磷酸,水浴加热于85℃~95℃下进行酯化反应4小时后,冷却至10℃~30℃,制得酯化产物,用水稀释酯化产物,过滤,取滤饼,即为利用工业副产松油烯制备含氟脱模添加剂。
实施例3
在装有搅拌装置、回流冷凝装置和温度计的四口瓶中,加入30克松油烯、1克对甲苯磺酸和1.5克氨基磺酸,搅拌0.5~1小时后,加入24克2-己烯酸,升温至160℃~170℃进行回流反应6小时,生成己烯酸松油烯加成化合物,降温至70~80℃,加入24克过氧化氢,6.5克冰醋酸和0.7克浓硫酸,进行环氧化反应5小时,生成环氧化2-己烯酸松油烯加成化合物,然后用3倍体积的热水进行水解,静置,取油层,生成双羟基产物,加入100mL甲苯和105克六氟丙烯齐聚体,开启搅拌,缓慢加入1克N,N-二甲基环己胺,20℃~35℃的温度下进行亲核取代反应6~8小时后,蒸馏出甲苯,得到六氟丙烯齐聚体取代的产物,向四口瓶中加入24克二乙醇胺,于95℃~105℃温度下进行酰胺化反应,制得酰胺化产物,冷却至10℃~30℃,最后向四口瓶中加入70克N,N-二甲基亚砜、6克五氧化二磷和42克磷酸,水浴加热于85℃~95℃下进行酯化反应3.5小时后,冷却至10℃~30℃,制得酯化产物,用水稀释酯化产物,过滤,取滤饼,即为利用工业副产松油烯制备含氟脱模添加剂。
以上所述,实施方式仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明技术的精神的前提下,本领域工程技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明的权利要求书确定的保护范围内。
Claims (2)
1.一种利用工业副产松油烯制备含氟脱模添加剂的方法,其特征是:将松油烯中的α-蒎烯、双戊烯和异松油烯异构化成α-松油烯,松油烯中的主要成分α-松油烯和不断异构化而来的松油烯均与(甲基)烯基酸进行加成反应,生成的(甲基)烯基酸松油烯加成化合物,与过氧化氢进行环氧化反应,生成环氧化(甲基)烯基酸松油烯加成化合物,再进行水解,生成双羟基产物,双羟基产物均与六氟丙烯齐聚体进行亲核取代反应,得到六氟丙烯齐聚体取代的产物,六氟丙烯齐聚体取代的产物与二乙醇胺进行酰胺化反应,制得酰胺化产物,最后,酰胺化产物与磷酸进行酯化反应制得酯化产物;具体包含以下步骤:
1).在对甲苯磺酸和氨基磺酸作用下,松油烯体系中的α-蒎烯、双戊烯和异松油烯异构化成α-松油烯,松油烯中的主要成分α-松油烯和不断异构化而来的α-松油烯均与(甲基)烯基酸于150℃~180℃下回流反应4~6小时,生成(甲基)烯基酸松油烯加成化合物;
2).冰醋酸和浓硫酸作用下,(甲基)烯基酸松油烯加成化合物与过氧化氢于60~80℃下环氧化反应4~5小时,生成环氧化(甲基)烯基酸松油烯加成化合物;
3).环氧化(甲基)烯基酸松油烯加成化合物,用3倍体积的热水进行水解,静置,取油层,得到双羟基产物;
4).以甲苯为溶剂,N,N-二甲基环己胺存在下,于20℃~35℃下,双羟基产物与六氟丙烯齐聚体进行亲核取代反应6~8小时后,蒸馏出甲苯,得到六氟丙烯齐聚体取代的产物;
5).六氟丙烯齐聚体取代的产物与二乙醇胺,于85℃~105℃温度下进行酰胺化反应,制得酰胺化产物,冷却至10℃~30℃;
6).以N,N-二甲基亚砜为溶剂,在五氧化二磷存在下,酰胺化产物与磷酸,水浴加热于85℃~95℃进行酯化反应3~4小时后,冷却至10℃~30℃,制得酯化产物,用水稀释酯化产物,过滤,取滤饼,即为利用工业副产松油烯制备含氟脱模添加剂。
2.根据权利要求1所述的一种利用工业副产松油烯制备含氟脱模添加剂的方法,其特征是:所述的松油烯、(甲基)烯基酸、过氧化氢、六氟丙烯齐聚体、二乙醇胺和磷酸的质量比为1﹕0.6~0.8﹕0.7~0.9﹕3.5~4.0﹕0.8~1.0﹕1.4~1.6;所述的对甲苯磺酸和氨基磺酸,其用量分别为松油烯质量的0%~6%,其总用量为松油烯质量的6%~10%;所述的冰醋酸和浓硫酸,其用量分别是过氧化氢质量的20%~30%和2%~3%;所述的N,N-二甲基环己胺,其用量为松油烯质量的3%~5%。
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