CN114790162B - 一种低雾化度环保增塑剂 - Google Patents
一种低雾化度环保增塑剂 Download PDFInfo
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Abstract
本发明公开了一种低雾化度环保增塑剂,该环保增塑剂的相对分子量大,使得该环保增塑剂不易出现挥发析出显现,且目前汽车内饰件选用的材料多为PP材料,在PP材料与环保增塑剂共混接枝过程中,环保增塑剂侧链的双键能够与PP材料主链接枝,进而避免了环保增塑剂的析出和雾化,同时面对高温也不会析出,同时环保增塑剂侧链含有大量的长链烷基,在寒冷情况下长链烷基能够保持聚合物分子链间的运动,使得环保增塑剂具有很好的耐寒效果,该环保增塑剂分子上含有柠檬酸结构,使得该增塑剂对环境污染小,具有降解能力。
Description
技术领域
本发明涉及增塑剂制备技术领域,具体涉及一种低雾化度环保增塑剂。
背景技术
增塑剂是现代塑料工业最大的助剂品种,对促进塑料工业特别是聚氯乙烯工业的发展起着决定性作用,随着各种塑胶原料制品的迅猛发展,在塑料产品加工工艺中,增塑剂已经是不可缺少的辅助原料助剂之一,增塑剂大多是一种高沸点的液态酯类,按一定的比例加入树脂中,可以改变树脂的性质,例如增加塑料的柔软性、提高耐温性、提升塑料制品在低温下的使用性和降低熔融料的黏度等,以使树脂变得容易加工成型;
目前,增塑剂的生产主要以普通增塑剂的生产为主,普通增塑剂的原料是石油化工的提炼副产物乙烯、丙烯再经过加氢的合成醇,化工合成物在自然环境中不易降解,对环境造成污染,近年来,保护环境已成为人们研发催化新工艺的重要动力,增塑剂在塑料制品、以及线缆、皮革制品中不可或缺的添加剂,因此研发对环境减少污染、容易降解的生物基增塑剂变得势在必行。
发明内容
本发明的目的在于提供一种低雾化度环保增塑剂,解决了现阶段增塑剂易析出、易雾化、耐低温效果差,且不易降解的问题。
本发明的目的可以通过以下技术方案实现:
一种低雾化度环保增塑剂,由如下步骤制成:
步骤A1:将1H-吡咯-2,5-二甲酸、氯甲酸苄酯、碳酸钠、三氯甲烷、水混合均匀,在转速为150-200r/min,温度为50-60℃的条件下,进行反应5-7h后,调节反应液pH值为6,制得中间体1,将中间体1、二氯亚砜、氯仿混合均匀,在温度为70-80℃的条件下,回流反应2-3h,减压回流收集二氯亚砜和氯仿,制得中间体2;
反应过程如下:
步骤A2:将腰果酚、三乙胺、二氯甲烷混合均匀,在转速为200-300r/min,温度为0-3℃的条件下,进行搅拌并加入中间体2,升温至温度为40-50℃,进行反应5-7h,过滤去除水相,将有机相洗涤至中性,制得中间体3,将中间体3、间氯过氧苯甲酸、二氯甲烷混合均匀,在转速为150-200r/min,温度为30-40℃的条件下,进行反应2-4h后,调节反应液为中性,分层去除上层液,制得中间体4;
反应过程如下:
步骤A3:将柠檬酸、三甲基氯硅烷、三乙胺、四氢呋喃混合均匀,在转速为200-300r/min,温度为70-80℃的条件下,进行搅拌回流3-5h后,蒸馏去除溶剂,再过滤,将滤饼、十二醇、浓硫酸混合均匀,在转速为300-500r/min,温度为100-110℃的条件下,进行反应6-8h,制得中间体5,将中间体5、四氢呋喃、四丁基氟化铵溶液混合搅拌,制得中间体6;
反应过程如下:
步骤A4:将中间体6、中间体4、三甲胺、N,N-二甲基甲酰胺混合均匀,在转速为200-300r/min,温度为100-110℃的条件下,进行反应3-5h,制得中间体7,将中间体7、钯炭、四氢呋喃加入反应釜中,通入氢气,在温度为40-50℃的条件下,进行反应5-7h后,过滤去除滤渣,将滤液蒸馏去除溶剂,制得中间体8;
反应过程如下:
步骤A5:将中间体8、4,4'-二溴二苯甲酮、三乙胺、N,N-二甲基甲酰胺混合均匀,在转速为200-300r/min,温度为60-70℃的条件下,进行反应3-5h,制得中间体9,将中间体9、盐酸羟胺、乙醇、氢氧化钠混合均匀,在转速为150-200r/min,温度为80-90℃的条件下,进行反应10-15min后,加入浓盐酸和去离子水,晶体析出,过滤去除滤液,制得中间体10;
反应过程如下:
步骤A6:将中间体10、氢氧化钠溶液、锌粉混合均匀,在转速为150-200r/min,温度为100-110℃的条件下,进行反应1-2h后,过滤去除滤渣,将滤液调节至中性,加入乙酸钠、乙酸酐混合均匀,在温度为100-110℃的条件下,进行反应2-3h后,调节反应液pH值为中性后,在温度为150-160℃的条件下,蒸馏制得低雾化度环保增塑剂。
反应过程如下:
进一步的,步骤A1所述的1H-吡咯-2,5-二甲酸和氯甲酸苄酯的用量比为1:1,中间体1和二氯亚砜的用量比为0.01mol:10mL。
进一步的,步骤A2所述的腰果酚、三乙胺、中间体2的用量摩尔比为1:2:2,中间体3和间氯过氧苯甲酸的用量质量比为13.5:12.3。
进一步的,步骤A3所述的柠檬酸、三甲基氯硅烷、十二醇的用量摩尔比为1:1:3.2,中间体5和四丁基氟化铵溶液的用量比为1g:5mL,四丁基氟化铵溶液的质量分数为25%。
进一步的,步骤A4所述的中间体6和中间体4的用量摩尔比为1:4。
进一步的,步骤A5所述的中间体8和4,4'-二溴二苯甲酮的用量摩尔比为2:1,中间体9、盐酸羟胺、乙醇、氢氧化钠、浓盐酸、去离子水的用量比为2.5g:1g:20mL:0.7g:8mL:50mL,浓盐酸质量分数为36%。
进一步的,步骤A6所述的中间体10、氢氧化钠溶液、锌粉、乙酸钠、乙酸酐的用量比为0.25:250:18:7.9:100,氢氧化钠溶液的质量分数为20%。
本发明的有益效果如下:
本发明制备的低雾化度环保增塑剂以1H-吡咯-2,5-二甲酸为原料用氯甲酸苄酯进行仲胺保护,制得中间体1,将中间体1与二氯亚砜反应,使得中间体1上的羧基与二氯亚砜反应形成酰氯,制得中间体2,将腰果酚和中间体2反应,使得腰果酚上的酚羟基与中间体2上的酰氯反应,制得中间体3,将中间体3用间氯过氧苯甲酸处理,使得中间体3的双键环氧化制得中间体4,将柠檬酸用三甲基氯硅烷进行羟基保护,再与十二醇进行酯化反应,制得中间体5,将中间体5进行脱保护,制得中间体6,将中间体6和中间体4进行反应,使得中间体6上的醇羟基与中间体4上的环氧基进行反应,制得中间体7,在用钯炭和氢气对中间体7进行脱保护,制得中间体8,将中间体8与4,4'-二溴二苯甲酮在三乙胺的作用下,使得中间体8的仲胺与4,4'-二溴二苯甲酮上的溴原子位点反应,制得中间体9,将中间体9用盐酸羟胺处理,制得中间体10,将中间体10用锌粉还原后,再与乙酸酐反应,制得低雾化度环保增塑剂,该环保增塑剂的相对分子量大,使得该环保增塑剂不易出现挥发析出显现,目前汽车内饰件选用的材料多为PP材料,在PP材料与环保增塑剂共混接枝过程中,环保增塑剂侧链的双键能够与PP材料主链接枝,进而避免了环保增塑剂的析出和雾化,同时面对高温也不会析出,同时环保增塑剂侧链含有大量的长链烷基,在寒冷情况下长链烷基能够保持聚合物分子链间的运动,使得环保增塑剂具有很好的耐寒效果,该环保增塑剂分子上含有柠檬酸结构,使得该增塑剂对环境污染小,具有降解能力。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一种低雾化度环保增塑剂,由如下步骤制成:
步骤A1:将1H-吡咯-2,5-二甲酸、氯甲酸苄酯、碳酸钠、三氯甲烷、水混合均匀,在转速为150r/min,温度为50℃的条件下,进行反应5h后,调节反应液pH值为6,制得中间体1,将中间体1、二氯亚砜、氯仿混合均匀,在温度为70℃的条件下,回流反应2h,减压回流收集二氯亚砜和氯仿,制得中间体2;
步骤A2:将腰果酚、三乙胺、二氯甲烷混合均匀,在转速为200r/min,温度为0℃的条件下,进行搅拌并加入中间体2,升温至温度为40℃,进行反应5h,过滤去除水相,将有机相洗涤至中性,制得中间体3,将中间体3、间氯过氧苯甲酸、二氯甲烷混合均匀,在转速为150r/min,温度为30℃的条件下,进行反应2h后,调节反应液为中性,分层去除上层液,制得中间体4;
步骤A3:将柠檬酸、三甲基氯硅烷、三乙胺、四氢呋喃混合均匀,在转速为200r/min,温度为70℃的条件下,进行搅拌回流3h后,蒸馏去除溶剂,再过滤,将滤饼、十二醇、浓硫酸混合均匀,在转速为300r/min,温度为100℃的条件下,进行反应6h,制得中间体5,将中间体5、四氢呋喃、四丁基氟化铵溶液混合搅拌,制得中间体6;
步骤A4:将中间体6、中间体4、三甲胺、N,N-二甲基甲酰胺混合均匀,在转速为200r/min,温度为100℃的条件下,进行反应3h,制得中间体7,将中间体7、钯炭、四氢呋喃加入反应釜中,通入氢气,在温度为40℃的条件下,进行反应5h后,过滤去除滤渣,将滤液蒸馏去除溶剂,制得中间体8;
步骤A5:将中间体8、4,4'-二溴二苯甲酮、三乙胺、N,N-二甲基甲酰胺混合均匀,在转速为200r/min,温度为60℃的条件下,进行反应3h,制得中间体9,将中间体9、盐酸羟胺、乙醇、氢氧化钠混合均匀,在转速为150r/min,温度为80℃的条件下,进行反应10min后,加入浓盐酸和去离子水,晶体析出,过滤去除滤液,制得中间体10;
步骤A6:将中间体10、氢氧化钠溶液、锌粉混合均匀,在转速为150r/min,温度为100℃的条件下,进行反应1h后,过滤去除滤渣,将滤液调节至中性,加入乙酸钠、乙酸酐混合均匀,在温度为100℃的条件下,进行反应2h后,调节反应液pH值为中性后,在温度为150℃的条件下,蒸馏制得低雾化度环保增塑剂。
实施例2
一种低雾化度环保增塑剂,由如下步骤制成:
步骤A1:将1H-吡咯-2,5-二甲酸、氯甲酸苄酯、碳酸钠、三氯甲烷、水混合均匀,在转速为180r/min,温度为55℃的条件下,进行反应6h后,调节反应液pH值为6,制得中间体1,将中间体1、二氯亚砜、氯仿混合均匀,在温度为75℃的条件下,回流反应2.5h,减压回流收集二氯亚砜和氯仿,制得中间体2;
步骤A2:将腰果酚、三乙胺、二氯甲烷混合均匀,在转速为200r/min,温度为2℃的条件下,进行搅拌并加入中间体2,升温至温度为45℃,进行反应6h,过滤去除水相,将有机相洗涤至中性,制得中间体3,将中间体3、间氯过氧苯甲酸、二氯甲烷混合均匀,在转速为180r/min,温度为35℃的条件下,进行反应3h后,调节反应液为中性,分层去除上层液,制得中间体4;
步骤A3:将柠檬酸、三甲基氯硅烷、三乙胺、四氢呋喃混合均匀,在转速为300r/min,温度为75℃的条件下,进行搅拌回流4h后,蒸馏去除溶剂,再过滤,将滤饼、十二醇、浓硫酸混合均匀,在转速为500r/min,温度为105℃的条件下,进行反应7h,制得中间体5,将中间体5、四氢呋喃、四丁基氟化铵溶液混合搅拌,制得中间体6;
步骤A4:将中间体6、中间体4、三甲胺、N,N-二甲基甲酰胺混合均匀,在转速为300r/min,温度为105℃的条件下,进行反应4h,制得中间体7,将中间体7、钯炭、四氢呋喃加入反应釜中,通入氢气,在温度为45℃的条件下,进行反应6h后,过滤去除滤渣,将滤液蒸馏去除溶剂,制得中间体8;
步骤A5:将中间体8、4,4'-二溴二苯甲酮、三乙胺、N,N-二甲基甲酰胺混合均匀,在转速为300r/min,温度为65℃的条件下,进行反应4h,制得中间体9,将中间体9、盐酸羟胺、乙醇、氢氧化钠混合均匀,在转速为180r/min,温度为85℃的条件下,进行反应13min后,加入浓盐酸和去离子水,晶体析出,过滤去除滤液,制得中间体10;
步骤A6:将中间体10、氢氧化钠溶液、锌粉混合均匀,在转速为180r/min,温度为105℃的条件下,进行反应1.5h后,过滤去除滤渣,将滤液调节至中性,加入乙酸钠、乙酸酐混合均匀,在温度为105℃的条件下,进行反应2.5h后,调节反应液pH值为中性后,在温度为155℃的条件下,蒸馏制得低雾化度环保增塑剂。
实施例3
一种低雾化度环保增塑剂,由如下步骤制成:
步骤A1:将1H-吡咯-2,5-二甲酸、氯甲酸苄酯、碳酸钠、三氯甲烷、水混合均匀,在转速为200r/min,温度为60℃的条件下,进行反应7h后,调节反应液pH值为6,制得中间体1,将中间体1、二氯亚砜、氯仿混合均匀,在温度为80℃的条件下,回流反应3h,减压回流收集二氯亚砜和氯仿,制得中间体2;
步骤A2:将腰果酚、三乙胺、二氯甲烷混合均匀,在转速为300r/min,温度为3℃的条件下,进行搅拌并加入中间体2,升温至温度为50℃,进行反应7h,过滤去除水相,将有机相洗涤至中性,制得中间体3,将中间体3、间氯过氧苯甲酸、二氯甲烷混合均匀,在转速为200r/min,温度为40℃的条件下,进行反应4h后,调节反应液为中性,分层去除上层液,制得中间体4;
步骤A3:将柠檬酸、三甲基氯硅烷、三乙胺、四氢呋喃混合均匀,在转速为300r/min,温度为80℃的条件下,进行搅拌回流5h后,蒸馏去除溶剂,再过滤,将滤饼、十二醇、浓硫酸混合均匀,在转速为500r/min,温度为110℃的条件下,进行反应8h,制得中间体5,将中间体5、四氢呋喃、四丁基氟化铵溶液混合搅拌,制得中间体6;
步骤A4:将中间体6、中间体4、三甲胺、N,N-二甲基甲酰胺混合均匀,在转速为300r/min,温度为110℃的条件下,进行反应5h,制得中间体7,将中间体7、钯炭、四氢呋喃加入反应釜中,通入氢气,在温度为50℃的条件下,进行反应7h后,过滤去除滤渣,将滤液蒸馏去除溶剂,制得中间体8;
步骤A5:将中间体8、4,4'-二溴二苯甲酮、三乙胺、N,N-二甲基甲酰胺混合均匀,在转速为300r/min,温度为70℃的条件下,进行反应5h,制得中间体9,将中间体9、盐酸羟胺、乙醇、氢氧化钠混合均匀,在转速为200r/min,温度为90℃的条件下,进行反应15min后,加入浓盐酸和去离子水,晶体析出,过滤去除滤液,制得中间体10;
步骤A6:将中间体10、氢氧化钠溶液、锌粉混合均匀,在转速为200r/min,温度为110℃的条件下,进行反应2h后,过滤去除滤渣,将滤液调节至中性,加入乙酸钠、乙酸酐混合均匀,在温度为110℃的条件下,进行反应3h后,调节反应液pH值为中性后,在温度为160℃的条件下,蒸馏制得低雾化度环保增塑剂。
对比例1
本对比例为中国专利CN110885519A制得的环保增塑剂。
对比例2
本对比例为中国专利CN112920394A制得的环保增塑剂。
将实施例1-3和对比例1-2制得的环保增塑剂依照DIN75201/B检测雾化度,依照ASTM D1043的标准检测低温韧性,依照ASTM D746的标准检测脆化温度,结果如下表所示:
由上表可知实施例1-3制得的环保增塑剂的雾化度为0.1-0.15mg,低温韧性为零下48.6-48.9℃,催化温度为零下51.8-52.3℃,表明本发明具有很好的耐析出耐雾化效果,且耐低温效果好。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (7)
1.一种低雾化度环保增塑剂,其特征在于:由如下步骤制成:
步骤A1:将1H-吡咯-2,5-二甲酸、氯甲酸苄酯、碳酸钠、三氯甲烷、水混合反应后,调节反应液pH值,制得中间体1,将中间体1、二氯亚砜、氯仿混合回流反应,减压回流收集二氯亚砜和氯仿,制得中间体2;
反应过程如下:
步骤A2:将腰果酚、三乙胺、二氯甲烷混合搅拌并加入中间体2,升温反应,过滤去除水相,将有机相洗涤至中性,制得中间体3,将中间体3、间氯过氧苯甲酸、二氯甲烷混合反应后,调节反应液为中性,分层去除上层液,制得中间体4;
反应过程如下:
步骤A3:将柠檬酸、三甲基氯硅烷、三乙胺、四氢呋喃混合搅拌回流后,蒸馏去除溶剂,再过滤,将滤饼、十二醇、浓硫酸混合反应,制得中间体5,将中间体5、四氢呋喃、四丁基氟化铵溶液混合搅拌,制得中间体6;
反应过程如下:
步骤A4:将中间体6、中间体4、三甲胺、N,N-二甲基甲酰胺混合反应,制得中间体7,将中间体7、钯炭、四氢呋喃加入反应釜中,通入氢气,进行反应后,过滤去除滤渣,将滤液蒸馏去除溶剂,制得中间体8;
反应过程如下:
步骤A5:将中间体8、4,4'-二溴二苯甲酮、三乙胺、N,N-二甲基甲酰胺混合反应,制得中间体9,将中间体9、盐酸羟胺、乙醇、氢氧化钠混合反应后,加入浓盐酸和去离子水,晶体析出,过滤去除滤液,制得中间体10;
反应过程如下:
步骤A6:将中间体10、氢氧化钠溶液、锌粉混合反应后,过滤去除滤渣,将滤液调节至中性,加入乙酸钠、乙酸酐混合反应后,调节反应液pH值为中性后,蒸馏制得低雾化度环保增塑剂;
反应过程如下:
2.根据权利要求1所述的一种低雾化度环保增塑剂,其特征在于:步骤A1所述的1H-吡咯-2,5-二甲酸和氯甲酸苄酯的用量比为1:1,中间体1和二氯亚砜的用量比为0.01mol:10mL。
3.根据权利要求1所述的一种低雾化度环保增塑剂,其特征在于:步骤A2所述的腰果酚、三乙胺、中间体2的用量摩尔比为1:2:2,中间体3和间氯过氧苯甲酸的用量质量比为13.5:12.3。
4.根据权利要求1所述的一种低雾化度环保增塑剂,其特征在于:步骤A3所述的柠檬酸、三甲基氯硅烷、十二醇的用量摩尔比为1:1:3.2,中间体5和四丁基氟化铵溶液的用量比为1g:5mL,四丁基氟化铵溶液的质量分数为25%。
5.根据权利要求1所述的一种低雾化度环保增塑剂,其特征在于:步骤A4所述的中间体6和中间体4的用量摩尔比为1:4。
6.根据权利要求1所述的一种低雾化度环保增塑剂,其特征在于:步骤A5所述的中间体8和4,4'-二溴二苯甲酮的用量摩尔比为2:1,中间体9、盐酸羟胺、乙醇、氢氧化钠、浓盐酸、去离子水的用量比为2.5g:1g:20mL:0.7g:8mL:50mL,浓盐酸质量分数为36%。
7.根据权利要求1所述的一种低雾化度环保增塑剂,其特征在于:步骤A6所述的中间体10、氢氧化钠溶液、锌粉、乙酸钠、乙酸酐的用量比为0.25:250:18:7.9:100,氢氧化钠溶液的质量分数为20%。
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