CN113501786B - 尼龙单体及其制备方法 - Google Patents
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Abstract
本发明提供了四种尼龙单体及其制备方法,在已内酰胺或庚二酸的3位和5位引入苯基形成尼龙单体,其制备方法是以查尔酮、乙酰乙酸乙酯为原料,经迈克尔加成串联分子内羟醛缩合反应、酯基脱除、与盐酸羟胺缩合、贝克曼重排反应或在强碱条件下发生开环反应制得。本发明通过在已内酰胺或庚二酸的3位和5位引入两个苯环,由于苯环具有良好的疏水性和稳定性等,特别是苯环之间可存在较强的π‑π相互作用,有望合成出在强度、稳定性、疏水性、硬度及耐热耐腐蚀性等方面均有更为优良的性能的新型尼龙材料。
Description
技术领域
本发明涉及有机合成化学及高分子材料化学技术领域,具体涉及四种新型尼龙单体及其制备方法。
背景技术
尼龙,即聚酰胺类化合物,是工程塑料中最重要的品种,被广泛应用于交通运输、机械工业、电子电器、家电、仪器仪表等领域。内酰胺或二酸与二胺类化合物是合成各种尼龙材料的单体,现有的最重要的尼龙材料为尼龙6或尼龙66,其合成单体分别为己内酰胺或己二酸与己二胺。由于这些单体疏水性较差,分子内除了酰胺基,再也没有可显著提高分子间相互作用的基团,因此以这些单体合成的现有尼龙产品存在弹性模量小、制品的尺寸稳定性不好、产品在干态和低温下的抗冲击性能较差、刚性、耐热性不佳及等问题。特别是疏水性较差的及强度较低等缺陷,限制了它们的进一步广泛应用。
尽管通过掺杂改性方式可获得在相关性能上获得显著提升的尼龙材料,但仅通过掺杂改性的方式还是无法从根本上显著提升尼龙材料的性能。因此,通过对合成出新型尼龙单体,直接在单体上引入有助于显著提高尼龙材料的强度、稳定性、疏水性、硬度及耐热耐腐蚀性的结构单元,然后以这种新型尼龙单体为原料,有望合成出在性能有显著提升的新型尼龙材料。
发明内容
本发明提供了一种尼龙单体及其制备方法,在已内酰胺或庚二酸的3位和5位引入两个苯环,由于苯环具有良好的疏水性和稳定性等,而用引入了苯环的这些新型单体来合成尼龙材料,将有望合成出在强度、稳定性、疏水性、硬度及耐热耐腐蚀性等方面均有更为优良的性能的新型尼龙材料。
为实现上述目的,本发明的技术方案为:
一种尼龙单体,在已内酰胺的4位和6位引入苯基,或在庚二酸的3位和5位引入苯基,形成尼龙单体。
进一步的,在已内酰胺的4位和6位引入苯基具体为:
进一步的,在庚二酸的3位和5位引入苯基具体为:
本发明进一步提供了尼龙单体A和尼龙单体B的制备方法,包括以下步骤:
S4.化合物5a或5b,经贝克曼重排反应,得到对应的尼龙单体A或尼龙单体B。
优选的,所述步骤S1中,迈克尔加成反应加入K2CO3作为催化剂,加入无水甲醇作为溶剂;
分子内羟醛缩合反应加入Pd/C作为催化剂,加入乙酸乙酯作为溶剂。
优选的,所述步骤S2中,中间体3a或3b,加入NaCl、H2O和DMSO脱除酯基。
优选的,所述步骤S3中,化合物4a和盐酸羟胺,加入氢氧化钠、水和无水乙醇进行缩合反应;
所述步骤S4中,化合物5a,加入三氟乙酸-乙腈溶液和三聚氯氰进行贝克曼重排反应。
本发明进一步提供了尼龙单体C和尼龙单体D的制备方法,包括以下步骤:
A2.中间体3a或3b,在强碱条件下发生开环反应,得到对应的尼龙单体C或尼龙单体D。
优选的,所述步骤A2中,开环反应加入氢氧化钠作为催化剂,加入甲醇作为溶剂。
本发明进一步提供了以上所述的尼龙单体在合成尼龙方面的应用。
具体的合成路线如Schme 1所示:
本发明合成得到了四种新的尼龙单体,成功地在已内酰胺和庚二酸尼龙单体上引入了两个苯环。由于苯环具有良好的疏水性和稳定性等,且苯环之间还可通过π-π相互作用,增大单体之间的相互作用,因此有利于改善尼龙性能,如本发明的两个带苯基的环己内酰胺尼龙单体和两个带苯基的庚二酸尼龙单体,因引入了两苯环,显著增大了单体的疏水性,使得这四个单体均是完全不溶于水的,而现用的跟它们相对应的环己内酰胺尼龙单体和己二酸及庚二酸均是水溶性的;更重要的是,由于苯环之间存在较强的π-π相互作用,使得本发明中两个新的苯基的环己内酰胺尼龙单体的熔点分别到达了170和183℃,远高于环己内酰胺的68℃;另外两个带苯基的庚二酸尼龙单体,熔点也分别达到了174℃和196℃,远高于庚二酸的103℃,这均表明单体之间因苯环的引入而显著增强了它们之间的相互作用力;因此,用这些新型单体来合成尼龙材料,将有望合成出在强度、稳定性、疏水性、硬度及耐热耐腐蚀性等方面均有更为优良的性能的新型尼龙材料。
具体实施方式
以下结合具体实施例对本发明作进一步说明,但本发明的保护范围不限于以下实施例。
实施例1尼龙单体A的合成:
S1.将查尔酮(32g,150mmol)、乙酰乙酸乙酯(24mL,185mmol)、K2CO3(0.9g,6.3mmol)、无水甲醇(100mL)加入圆底烧瓶中,在N2保护下、电磁搅拌下,将圆底烧瓶置于80℃中回流反应2h(TLC监测反应进程,展开剂:VPE:VEA=6:1)。确认原料已经反应完,减压蒸发所有溶剂,加入200毫升冰水搅拌,抽滤,固体粗产物用400mL乙醇中重结晶,抽滤得化合物2白色固体,产量为42.33g,产率为89%,m.p.112–114℃。
在30g化合物2中加入250mL的乙酸乙酯和0.2g 10%Pd/C,于50℃、1atm氢气搅拌,反应20h后,TLC(VPE:VEA=4:1)检测确定其反应完毕。滤去Pd/C催化剂,减压除去溶剂,所得产物在乙醇中结晶,抽滤得到大部分的白色固体3a。滤液旋干后经硅胶柱层析提纯(洗脱剂VPE:VEA=100:1),又得到化合物另一部分的白色固体3a和无色粘稠状液体3b,3a的总量为12.83g,产率43%,m.p.130–132℃。另一个差向异构体3b总产量为11.52g,产率39%。
S2.将化合物3a(10g,31mmol)、NaCl(7g,mmol)、H2O(4mL)、DMSO(20mL)加入至圆底烧瓶中,在N2保护和电磁搅拌下,将烧瓶置于180℃的电热套中回流反应8h(TLC监测反应进程,展开剂VPE:VEA=6:1)。确认原料已经反应完,放置一段时间冷却至室温后,加入100mL水洗涤除去溶剂并静置数小时,抽滤,所得粗产物用20mL乙醇洗涤,抽滤得到白色固体6.92g,产率为89%,m.p.138–139℃。
S3.将化合物4a(6.5g,26mmol)、盐酸羟胺(2.3g,30mmol)、氢氧化钠(1.3g,30mmol)、水(6mL)、无水乙醇(60mL)置于圆底烧瓶中,在N2保护与电磁搅拌下,于100℃的油浴锅中回流反应0.5h(TLC监测反应进程,展开剂VPE:VEA=8:1)。确认原料已经反应完毕,停止加热冷却至室温,减压除去溶剂,用50mL饱和NaHCO3水溶液洗涤瓶中混合物,搅拌片刻,抽滤得到白色化合物5a,产量为6.10g,产率93%,m.p.212–213℃。
S4.将化合物5a(6.0g,7.2mmol)、三氟乙酸-乙腈溶液(5:4,54mL)、三聚氯氰(50mg)加入圆底烧瓶中,在N2保护与电磁搅拌下,于80℃的油浴锅中回流反应2h(TLC监测反应进程,展开剂VPE:VEA=4:1,VPE:VEA=1:1)。确认原料已经反应完毕,停止加热稍冷却,减压除去大部分有机溶剂.加入50mL饱和碳酸氢钠溶液洗涤反应物,搅拌片刻,抽滤,所得固体用10mL乙醇洗涤,抽滤得到白色的尼龙单体A,产量4.81g,产率79%。
m.p.170-171℃;1H NMR(400MHz,CDCl3)δ7.22-7.08(m,10H),6.88(s,1H),3.60-3.53(m,1H),3.25-3.19(m,1H),3.03-2.96(m,2H),2.88-2.79(m,1H),2.64-2.57(m,1H),2.20-2.16(d,1H),2.00-1.89(m,1H).13C NMR(101MHz,CDCl3)δ176.01,145.54,143.05,127.73,127.64,125.79,125.57,125.52,125.28,47.33,46.66,46.12,42.41,39.86.
实施例2尼龙单体B的合成:
步骤S1同实施例1。
S2.将化合物3b(9.0g,28mmol)、NaCl(4.5g,75mmol)、H2O(1.0mL)、DMSO(30mL)加入圆底烧瓶中,在N2保护下,将烧瓶置于200℃的电热套中搅拌回流反应4.0h(TLC监测反应进程,展开剂VPE:VEA=6:1)。反应完成后冷却至室温后,加入300mL水,静置数小时,抽滤,固体用乙醇洗涤,抽滤得到白色固体,产量为6.98g,产率为76%,m.p.74–76℃。
S3.依次将化合物4b(5.6g,22mmol)、盐酸羟胺(1.9g,25mmol)、氢氧化钠(1.2g,30mmol)、水(2.5mL)、无水乙醇(50mL)加入圆底烧瓶中,在N2保护下,于100℃的油浴锅中搅拌回流1h(TLC监测反应进程,展开剂VPE:VEA=8:1)。反应完毕,冷却至室温,减压除去溶剂,加入用饱和NaHCO3溶液搅拌3-5分钟,抽滤得到白色化合物5b,产量为4.22g,产率91%,m.p.154–155℃。
S4.依次将化合物5b(4.0g,29mmol)、三氟乙酸-乙腈溶液(5:4,36mL)、三聚氯氰(40mg)加入圆底烧瓶中,N2保护,于85℃的油浴锅中搅拌回流2.5h(TLC监测反应进程,展开剂VPE:VEA=4:1,VPE:VEA=1:1)。反应完毕后,冷却,减压除去大部分溶剂。加入50mL饱和碳酸氢钠溶液,搅拌20分钟后静置,抽滤,固体用少量乙醇洗涤,抽滤得到白色尼龙单体B,产量为2.45g,产率61%。
m.p.183-184℃;1H NMR(400MHz,CDCl3)δ7.34-7.22(m,10H),6.50(s,1H),3.65-3.53(m,2H),3.38-3.32(m,1H),3.17-3.12(m,1H),3.08-3.03(m,1H),2.86-2.82(dd,1H),2.38-2.35(t,1H).13C NMR(101MHz,CDCl3)δ176.48,144.59,142.83,128.82,128.71,127.34,126.93,126.73,126.54,47.18,42.95,41.92,41.30,36.48.
实施例3尼龙单体C的合成:
步骤A1同实施例1的步骤S1。
A2.将2.5g氢氧化钠,150mL的甲醇加入圆底烧瓶中,在90℃油浴中搅拌回流1h。稍冷,加入5g的化合物3a至圆底烧瓶内,继续在90℃油浴中加热2h。TLC(VPE:VEA=1:1)检测确定其反应完毕.减压除去大部分有机溶剂,然后加入40mL冷水,再用2M盐酸调pH至2-3,随后用80mL乙酸乙酯萃取,合并有机相并用无水硫酸钠干燥,硅胶柱色谱提纯(洗脱剂VPE:VEA=1:1),得到白色粘稠状尼龙单体C,2.52g,产率65%。
m.p.196-197℃;1H NMR(400MHz,CDCl3)δ7.15-6.96(m,10H),3.03-2.96(m,2H),2.69-2.55(m,4H),2.10-2.03(m,1H),1.97-1.90(m,1H).13C NMR(101MHz,CDCl3)δ178.46,143.37,128.65,127.29,126.77,42.27,40.67,39.43.
实施例4尼龙单体D的合成:
步骤A1同实施例1的步骤S1。
A2.将10g氢氧化钾,50mL的甲醇加入圆底烧瓶中,在90℃油浴下回流0.5h.稍冷,往其中缓慢滴加3b的甲醇溶液(2.0g3b溶解于20mL甲醇)至圆底烧瓶内,继续在90℃油浴中加热14h.TLC(VPE:VEA=4:1,VPE:VEA=1:1)检测确定其反应完成后,减压除去大部分溶剂,然后加入60mL冷水,再用6M盐酸溶液调pH至2-3,搅拌片刻有固体析出,静置后抽滤,得到淡黄色粉末状固体1.6g,产率80%。
m.p.174-176℃;1H NMR(400 MHz,DMSO-d6)δ11.91(s,2H),7.32-7.06(m,10H),2.64-2.56(m,2H),2.47-2.33(m,4H),1.99-1.95(m,2H).13C NMR(101 MHz,DMSO)δ172.81,143.39,128.28,127.78,126.38,42.16,41.14,39.31。
Claims (10)
1.一种尼龙单体,其特征在于:
在已内酰胺的4位和6位引入苯基,或在庚二酸的3位和5位引入苯基,形成尼龙单体。
6.根据权利要求4所述的制备方法,其特征在于:
所述步骤S2中,中间体3a或3b,加入NaCl、H2O和DMSO脱除酯基。
7.根据权利要求4所述的制备方法,其特征在于:
所述步骤S3中,化合物4a和盐酸羟胺,加入氢氧化钠、水和无水乙醇进行缩合反应;
所述步骤S4中,化合物5a,加入三氟乙酸-乙腈溶液和三聚氯氰进行贝克曼重排反应。
9.根据权利要求8所述的制备方法,其特征在于:
所述步骤A2中,开环反应加入氢氧化钠作为催化剂,加入甲醇作为溶剂。
10.权利要求1~3任一项所述的尼龙单体在合成尼龙方面的应用。
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GB1356220A (en) * | 1971-08-02 | 1974-06-12 | Ciba Geigy Ag | Amine salts of 3,5-dialkyl-4-hydroxyphenylcarboxylic acids and polyamide compositions stabilized therewith |
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GB1356220A (en) * | 1971-08-02 | 1974-06-12 | Ciba Geigy Ag | Amine salts of 3,5-dialkyl-4-hydroxyphenylcarboxylic acids and polyamide compositions stabilized therewith |
Non-Patent Citations (2)
Title |
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N-苯基马来酰亚胺-马来酸酐的合成及对尼龙6耐热性能的影响;张景中等;《高分子材料科学与工程》;20151231;第31卷(第6期);第22-26,33页 * |
尼龙66耐光、耐热性能研究;董国君等;《化学工程师》;20041231;第108卷(第9期);第61-62页 * |
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