CN113896846B - 一种加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体及制备方法 - Google Patents
一种加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体及制备方法 Download PDFInfo
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- CN113896846B CN113896846B CN202111251173.7A CN202111251173A CN113896846B CN 113896846 B CN113896846 B CN 113896846B CN 202111251173 A CN202111251173 A CN 202111251173A CN 113896846 B CN113896846 B CN 113896846B
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- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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Abstract
本发明公开了一种加氢聚异戊二烯‑嵌‑间规聚多氟代苯乙烯基疏水弹性体及制备方法,将异戊二烯与多氟代苯乙烯类化合物在催化体系的作用下进行共聚反应;所述催化体系由有机硼盐化合物、有机铝化合物和如式(Ⅰ)所示的稀土金属配合物组成;本申请在制备聚异戊二烯‑嵌‑间规聚多氟代苯乙烯的过程中,采用的催化剂体系为稀土金属配合物、有机硼盐化合物和有机铝化合物的组合物,在烃类等良溶剂中可以催化异戊二烯和多氟代苯乙烯的共聚合。将聚异戊二烯‑嵌‑间规聚多氟代苯乙烯经催化加氢可得到加氢聚异戊二烯‑嵌‑间规聚多氟代苯乙烯基疏水弹性体。本发明提供的制备工艺简单,制备的聚合物材料有良好的弹性和疏水特性。
Description
技术领域
本发明涉及烯烃共聚物技术领域,尤其涉及一种加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯的制备方法。
背景技术
高分子材料由于其特有的性能在生物材料领域有着广泛应用,例如在人工心脏、人工血管以及血袋等方面的应用,这些与人类健康息息相关。目前,在生物材料领域使用最为广泛的高分子材料是聚氯乙烯(PVC),但由于PVC容易析出对人体有害的增塑剂,耐辐照性能差,灭菌受限等缺点,国内外在开发医用PVC替代材料方面做了大量工作。
最近的研究发现在聚烯烃中引入氟元素可以改善聚烯烃的细胞毒性、血液相容性。CN 107722155 A公开了一种α-烯烃-氟苯乙烯共聚物及其制备方法,其利用主催化剂和助催化剂使α-烯烃单体和氟苯乙烯单体进行共聚反应,得到了α-烯烃-氟苯乙烯共聚物,所得共聚物中氟苯乙烯含量较高(大于30mol%),从而使得材料不能获得较好的韧性,限制了其应用。CN 113136001 A公开了一种乙烯-氟苯乙烯共聚物的制备方法,其利用主催化剂和助催化剂使乙烯单体和苯乙烯单体进行共聚反应,得到了乙烯-苯乙烯共聚物,得到的共聚物中氟苯乙烯结构单元的含量较低,且存在连续的结晶性聚乙烯乙烯链段,起物理交联点作用,从而使得到的乙烯-氟苯乙烯共聚物的韧性、弹性,拉伸强度有较大提高,且具有良好的生物相容性。因此,通过简单的共聚反应引入带有含氟功能基团的改性聚合物,仍是目前含氟改性聚烯烃材料研究领域关注的热点。
发明内容
本发明的目的在于提供一种加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备方法,本申请制备的加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯中多氟代苯乙烯含量可调且制备工艺简单,所得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体有良好的弹性和疏水特性。
本发明的技术方案:
一种加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体,该加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的结构如下:
其中,x/(x+y)=0.1~0.7,y/(x++y)=0.3~0.9;R为引入的含氟功能基团,为全氟甲基、全氟乙基、全氟正丙基、全氟异丙基、全氟正丁基、全氟叔丁基、全氟正戊基、全氟正己基、全氟正庚基或全氟正辛基。
本申请提供了一种聚异戊二烯-嵌-间规聚多氟代苯乙烯的制备方法,即将异戊二烯与多氟代苯乙烯类化合物在催化体系的作用下进行共聚反应,所述催化体系由有机硼盐化合物、有机铝化合物和稀土金属配合物组成;本申请提供的催化剂组合物具有较高的催化活性,在较短时间内得到的聚异戊二烯-嵌-间规聚多氟代苯乙烯,该制备方法工艺简单,制备的聚合物经加氢反应后所得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体有良好的弹性和较高的疏水特性。
一种加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备方法,步骤如下:
(1)聚异戊二烯-嵌-间规聚多氟代苯乙烯的合成:惰性气体保护下,加入稀土金属配合物和有机硼盐化合物,再加入溶剂A,搅拌t1分钟;然后加入有机铝化合物,继续搅拌t2分钟;然后加入异戊二烯,继续搅拌t3分钟;然后加入多氟代苯乙烯类化合物,继续搅拌t4分钟;加入链终止剂,使反应中止;将反应液用溶剂B进行沉降,析出固体聚合物,过滤、洗涤、干燥,得到聚异戊二烯-嵌-间规聚多氟代苯乙烯;共聚反应的温度为-20~100℃;
所述的溶剂A为石油醚、正戊烷、正己烷、环己烷、正庚烷、正辛烷、苯、甲苯、对二甲苯、间二甲苯、邻二甲苯、氯苯、对二氯苯、间二氯苯、邻二氯苯或溴苯中的一种或两种以上混合;优选正庚烷、甲苯或环己烷;
所述的溶剂B为乙酸乙酯、甲醇、乙醚、乙醇、正丙醇、异丙醇中的一种或两种以上混合;优选甲醇、乙醇或异丙醇;
所述的链终止剂为甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己醇、环己醇、正辛醇中的一种或两种以上混合;
所述的有机硼盐化合物和稀土金属配合物的摩尔比为1:200~200:1;
所述有机铝化合物和稀土金属配合物的摩尔比为1:200~200:1;
所述的稀土金属配合物与多氟代苯乙烯化合物的摩尔比为1:100~1:1500;
所述的异戊二烯与多氟代苯乙烯类化合物的摩尔比为10:1~1:10;
所述的异戊二烯在反应体系中的浓度为0.05~50mol/L;
所述的搅拌时间t1为2~600min,其中优选5~120min;
所述的搅拌时间t2为2~600min,其中优选5~120min;
所述的搅拌时间t3为30~1200min,其中优选120~360min;
所述的搅拌时间t4为2~600min,其中优选5~120min;
所述聚异戊二烯-嵌-间规聚多氟代苯乙烯的数均分子量为5000~100000,分子量分布为1~5。
(2)加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备:将聚异戊二烯-嵌-间规聚多氟代苯乙烯溶于溶剂C中,通过催化体系加氢对碳碳双键位点进行还原,后将聚合物反应液倒入沉淀剂D中,过滤、洗涤、干燥,即得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体;加氢反应的反应时间为2~120h;反应温度为20~150℃;
所述的溶剂C为三氟甲苯、氟苯、邻二氟苯、五氟苯、六氟苯中的一种或两种以上混合;
所述的沉淀剂D为乙醚、水、乙醇、乙酸乙酯、丙酮、甲醇中的一种或两种以上混合。
步骤(1)中将异戊二烯与多氟代苯乙烯类化合物在催化体系的作用下进行共聚反应;所述催化体系由有机硼盐化合物、有机铝化合物和如式(Ⅰ)所示的稀土金属配合物组成;
其中,Cp选自取代的或非取代的环戊二烯基、取代的或非取代的茚基、取代的或非取代的芴基中的一种;
Ln选自Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu。
具体为:所述稀土金属配合物的结构式具体如下所示:
步骤(1)中所述有机硼盐化合物为[Ph3C][B(C6F5)4]、[PhNMe2H][BPh4]、[NEt3H][BPh4]、[PhNMe2H][B(C6F5)4]、B(C6F5)3中的一种或两种以上组合;所述有机铝化合物为二乙基氢化铝、二正丙基氢化铝、二正丁基氢化铝、二异丁基氢化铝、二苯基氢化铝、二对甲苯基氢化铝、二苄基氢化铝、苯基乙基氢化铝、苯基正丙基氢化铝、对甲苯基乙基氢化铝、对甲苯基正丙基氢化铝、对甲苯基异丙基氢化铝、苄基乙基氢化铝、苄基正丙基氢化铝、苄基异丙基氢化铝、乙基二氢化铝、丁基二氢化铝、异丁基二氢化铝、辛基二氢化铝、戊基二氢化铝、二乙基乙醇铝、二丙基乙醇铝、三甲基铝、三乙基铝、三正丙基铝、三异丙基铝、三正丁基铝、三异丁基铝、三戊基铝、三己基铝、三环己基铝、三辛基铝、三苯基铝、三对甲苯基铝、三苄基铝、乙基二苯基铝、乙基二对甲苯基铝、乙基二苄基铝、二乙基苯基铝、二乙基对甲苯基铝二乙基苄基铝中的一种或两种以上组合。
所述多氟代苯乙烯类化合物的结构式具体如下所示:
本发明的有益效果:
本申请提供的催化剂组合物具有较高的催化活性,在较短时间内得到聚异戊二烯-嵌-间规聚多氟代苯乙烯,该制备方法工艺简单,制备的聚合物经加氢反应后所得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体有良好的弹性和较高的疏水特性,为优良的带有含氟功能基团的改性聚烯烃材料。
附图说明
图1是聚异戊二烯-嵌-间规聚多氟代苯乙烯的核磁谱图。
图2是加氢聚异戊二烯烯-嵌-间嵌-间规聚多氟代苯乙烯基疏水弹性体的拉伸强度和断裂伸长率曲线图。
图3是加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的水接触角度示意图。
具体实施方式
以下结合实施案例对本发明做进一步详细的描述,但是本发明的实施方式并不仅限于此。
实施例1
(1)聚异戊二烯-嵌-间规聚多氟代苯乙烯的制备:惰性气体保护下,向反应瓶中加入式2结构的稀土金属配合物(10μmol)和有机硼盐化合物(10μmol),加入5mL甲苯,搅拌5分钟;然后加入三异丁基铝(10μmol),继续搅拌5分钟;然后加入异戊二烯(0.238g,3.5mmol),继续搅拌240分钟;然后加入式2结构的多氟代苯乙烯(0.525g,1.5mmol),继续搅拌60分钟;加入甲醇,使反应中止;将反应液用甲醇进行沉降,析出固体聚合物,过滤、洗涤、干燥,得到聚异戊二烯嵌-间规聚多氟代苯乙烯;
(2)加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备:耐压反应器中,将3g聚异戊二烯-嵌-间规聚多氟代苯乙烯溶于三氟甲苯中,加入雷尼镍,催化加氢,100℃反应3天,将聚合物反应液倒入甲醇中,过滤、洗涤、真空烘干至恒重,即可得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体。
本实例所得到的加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的结构如下:
实施例2
(1)聚异戊二烯-嵌-间规聚多氟代苯乙烯的制备:惰性气体保护下,向反应瓶中加入式3结构的稀土金属配合物(10μmol)和有机硼盐化合物(10μmol),加入10mL甲苯,搅拌10分钟;然后加入三异丁基铝(10μmol),继续搅拌10分钟;然后加入异戊二烯(0.170g,2.5mmol),继续搅拌240分钟;然后加入式3结构的多氟代苯乙烯(1.125g,2.5mmol),继续搅拌90分钟;加入乙醇,使反应中止;将反应液用乙醇进行沉降,析出固体聚合物,过滤、洗涤、干燥,得到聚异戊二烯-嵌-间规聚多氟代苯乙烯;
(2)加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备:耐压反应器中,将2g聚异戊二烯-嵌-间规聚多氟代苯乙烯溶于五氟苯中,加入雷尼镍,催化加氢,90℃反应3天,将聚合物反应液倒入乙醇中,过滤、洗涤、真空烘干至恒重,即可得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体。
本实例所得到的加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的结构如下:
实施例3
(1)聚异戊二烯-嵌-间规聚多氟代苯乙烯的制备:惰性气体保护下,向反应瓶中加入式4结构的稀土金属配合物(10μmol)和有机硼盐化合物(10μmol),加入15mL甲苯,搅拌20分钟;然后加入三异丁基铝(10μmol),继续搅拌20分钟;然后加入异戊二烯(0.102g,1.5mmol),继续搅拌240分钟;然后加入式4结构的多氟代苯乙烯(1.926g,3.5mmol),继续搅拌120分钟;加入异丙醇,使反应中止;将反应液用异丙醇进行沉降,析出固体聚合物,过滤、洗涤、干燥,得到聚异戊二烯-嵌-间规聚多氟代苯乙烯;
(2)加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备:耐压反应器中,将2g聚异戊二烯-嵌-间规聚多氟代苯乙烯溶于六氟苯中,加入雷尼镍,催化加氢,90℃反应3天,将聚合物反应液倒入乙酸乙酯中,过滤、洗涤、真空烘干至恒重,即可得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体。
本实例所得到的加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的结构如下:
Claims (10)
2.一种加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备方法,其特征在于,步骤如下:
(1)聚异戊二烯-嵌-间规聚多氟代苯乙烯的合成:惰性气体保护下,加入稀土金属配合物和有机硼盐化合物,再加入溶剂A,搅拌t1分钟;然后加入有机铝化合物,继续搅拌t2分钟;然后加入异戊二烯,继续搅拌t3分钟;然后加入多氟代苯乙烯类化合物,继续搅拌t4分钟;加入链终止剂,使反应中止;将反应液用溶剂B进行沉降,析出固体聚合物,过滤、洗涤、干燥,得到聚异戊二烯-嵌-间规聚多氟代苯乙烯;共聚反应的温度为-20~100℃;
所述的溶剂A为石油醚、正戊烷、正己烷、环己烷、正庚烷、正辛烷、苯、甲苯、对二甲苯、间二甲苯、邻二甲苯、氯苯、对二氯苯、间二氯苯、邻二氯苯、溴苯中的一种或两种以上混合;
所述的溶剂B为乙酸乙酯、甲醇、乙醚、乙醇、正丙醇、异丙醇中的一种或两种以上混合;
所述的链终止剂为甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己醇、环己醇、正辛醇中的一种或两种以上混合;
所述的有机硼盐化合物和稀土金属配合物的摩尔比为1:200~200:1;
所述有机铝化合物和稀土金属配合物的摩尔比为1:200~200:1;
所述的稀土金属配合物与多氟代苯乙烯化合物的摩尔比为1:100~1:1500;
所述的异戊二烯与多氟代苯乙烯类化合物的摩尔比为10:1~1:10;
所述的异戊二烯在反应体系中的浓度为0.05~50mol/L;
(2)加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体的制备:将聚异戊二烯-嵌-间规聚多氟代苯乙烯溶于溶剂C中,通过催化体系加氢对碳碳双键位点进行还原,后将聚合物反应液倒入沉淀剂D中,过滤、洗涤、干燥,即得加氢聚异戊二烯-嵌-间规聚多氟代苯乙烯基疏水弹性体;加氢反应的反应时间为2~120h;反应温度为20~150℃;
所述的溶剂C为三氟甲苯、氟苯、邻二氟苯、五氟苯、六氟苯中的一种或两种以上混合;
所述的沉淀剂D为乙醚、水、乙醇、乙酸乙酯、丙酮、甲醇中的一种或两种以上混合。
4.根据权利要求2或3所述的制备方法,其特征在于,步骤(1)中所述有机硼盐化合物为[Ph3C][B(C6F5)4]、[PhNMe2H][BPh4]、[NEt3H][BPh4]、[PhNMe2H][B(C6F5)4]、B(C6F5)3中的一种或两种以上组合;所述有机铝化合物为二乙基氢化铝、二正丙基氢化铝、二正丁基氢化铝、二异丁基氢化铝、二苯基氢化铝、二对甲苯基氢化铝、二苄基氢化铝、苯基乙基氢化铝、苯基正丙基氢化铝、对甲苯基乙基氢化铝、对甲苯基正丙基氢化铝、对甲苯基异丙基氢化铝、苄基乙基氢化铝、苄基正丙基氢化铝、苄基异丙基氢化铝、乙基二氢化铝、丁基二氢化铝、异丁基二氢化铝、辛基二氢化铝、戊基二氢化铝、二乙基乙醇铝、二丙基乙醇铝、三甲基铝、三乙基铝、三正丙基铝、三异丙基铝、三正丁基铝、三异丁基铝、三戊基铝、三己基铝、三环己基铝、三辛基铝、三苯基铝、三对甲苯基铝、三苄基铝、乙基二苯基铝、乙基二对甲苯基铝、乙基二苄基铝、二乙基苯基铝、二乙基对甲苯基铝二乙基苄基铝中的一种或两种以上组合。
10.根据权利要求2、3、6、8或9所述的制备方法,其特征在于,步骤(1)中,
所述的搅拌时间t1为2~600min;
所述的搅拌时间t2为2~600min;
所述的搅拌时间t3为30~1200min;
所述的搅拌时间t4为2~600min。
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