CN102300907B - 聚苯胺加成预聚物、聚苯胺加成预聚物的制备方法、聚苯胺接枝聚合物、聚苯胺接枝聚合物的制备方法、交联材料和油漆 - Google Patents
聚苯胺加成预聚物、聚苯胺加成预聚物的制备方法、聚苯胺接枝聚合物、聚苯胺接枝聚合物的制备方法、交联材料和油漆 Download PDFInfo
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- CN102300907B CN102300907B CN201080005982.3A CN201080005982A CN102300907B CN 102300907 B CN102300907 B CN 102300907B CN 201080005982 A CN201080005982 A CN 201080005982A CN 102300907 B CN102300907 B CN 102300907B
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- polyaniline
- methyl
- acrylate
- polymkeric substance
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
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Abstract
将聚苯胺加入含缩水甘油基或含异氰酸酯基团的(甲基)丙烯酸酯中以得到聚苯胺加成预聚物,然后使所得聚苯胺加成预聚物和含不饱和基团的另一种单体经受在它们各自的双键处加成共聚合以得到重均分子量为1,000-100,000的聚苯胺接枝聚合物。
Description
发明背景
1.发明领域
本发明涉及新聚苯胺加成预聚物和制备聚苯胺加成预聚物的方法。另外,本发明涉及通过使聚苯胺加成预聚物加聚而得到的聚苯胺接枝聚合物和制备聚苯胺接枝聚合物的方法。另外,本发明涉及聚苯胺接枝聚合物的三维交联材料。此外,本发明涉及含有聚苯胺接枝聚合物或聚苯胺接枝聚合物的三维交联材料作为涂料组分的油漆。
2.相关技术描述
聚苯胺(PANI)也称为苯胺黑,为以这种方式得到的黑色粉状聚合物质:使苯胺经受氧化化学聚合或电化学聚合。聚苯胺为导电聚合物,所以,近年来,已研究了聚苯胺作为新电子材料或传导材料应用于广泛领域中,例如在电池组用的电极材料、抗静电材料、电磁波屏蔽材料、光电子转换装置、光储存器、各种传感器的功能器件等,显示设备、各种混合材料、透明导体和各种终端设备中。
然而,聚苯胺通常具有高度发达的p-共轭体系。聚合物主链为刚性的且分子链之间的相互作用强。另外,大量强氢键存在于分子链之间,所以聚苯胺不溶于几乎所有有机溶剂中。另外,甚至当将它加热时,聚苯胺也不熔融,所以,它具有差的可成形性,并且难以将它制成膜等。因此,根据相关技术,将单体浸入基础原料如具有所需形状的纤维或聚合材料的多孔体中,然后使单体与足够的聚合催化剂接触以通过电解氧化聚合,或单体在热塑性聚合物粉末的存在下聚合以得到导电性复合材料。
J.Chem.Soc.,Chem.Commun.,1989,1736描述了通过选择聚合催化剂和反应温度而合成且可溶于N-甲基-2-吡咯烷酮中的聚苯胺。然而,该聚苯胺也几乎不溶于其它通常的有机溶剂中,且聚苯胺的适用范围有限。另外,各种聚苯胺衍生物用于合成可溶于有机溶剂中的聚苯胺衍生物;然而,仍未制得具有充分挠性的膜。此外,还已研究了取代基,例如烷基链的引入;然而,这导致引入这些取代基的聚苯胺的耐热性降低。
日本专利申请出版物No.6-100691(JP-A-6-100691)描述了具有接枝结构的聚苯胺衍生物。使聚苯胺与在末端具有与氨基反应的基团的聚硅氧烷反应。因此,聚苯胺衍生物能在有机溶剂中溶解或溶胀,并能形成具有高耐热性的挠性自支撑膜或纤维。然而,形成该聚苯胺衍生物,使得苯醌二亚胺(quinodiimine)结构单元和亚氨基-1,4-亚苯基结构单元中任一个或二者随意地与N-聚硅氧烷接枝-亚氨基-1,4-亚苯基结构单元组合。因此,制备聚苯胺的方法是复杂的,另外,聚苯胺不具有当用于油漆等时所需的溶剂分散性和长期分散稳定性。
另一方面,聚苯胺具有钝化铁表面的功能。关注该功能,还已研究了聚苯胺应用于防腐漆。然而,如上所述,聚苯胺为不溶性聚合物,且除部分溶剂(N-甲基-2-吡咯烷酮等)外,基本不溶于溶剂中。于是,主要使用这一方法:当应用于防腐漆时,将聚合物本体物理地压碎以降低粒径,然后与油漆混合。然而,通过物理压碎聚合物本体而降低粒径是有限的。因此,聚苯胺的稳定性在油漆中降低,粒子最后沉淀而从油漆中分离。此外,聚苯胺的分散体在涂料中是不足的。
如上所述,聚苯胺为当用作油漆时难以处理的材料。
发明概述
本发明提供一种在制备聚苯胺接枝聚合物中作为中间体的合成原料。本发明提供长期稳定地分散或溶解在各种溶剂中且能形成涂层或自支撑膜的聚苯胺接枝聚合物。另外,本发明提供一种含有利用这些性能作为涂料组分的聚苯胺接枝聚合物的油漆。
即,本发明提供一种新聚苯胺加成预聚物和一种制备聚苯胺加成预聚物的方法,通过将聚苯胺加成聚合物加聚得到的聚苯胺接枝聚合物,和一种制备聚苯胺接枝聚合物的方法,和含聚苯胺接枝聚合物作为涂料组分的油漆。
本发明第一方面涉及包含含有缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯并向其中加入聚苯胺的聚苯胺加成预聚物。
在根据以上方面的聚苯胺加成预聚物中,含缩水甘油基的(甲基)丙烯酸酯为(甲基)丙烯酸缩水甘油酯,含异氰酸酯基团的(甲基)丙烯酸酯为(甲基)丙烯酸-2-异氰酸酯基乙酯(2-isocyanate ethyl(meth)acrylate)。
本发明第二方面涉及一种制备聚苯胺加成预聚物的方法。该方法包括将聚苯胺加入含有缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯中。
在根据以上方面的方法中,含缩水甘油基的(甲基)丙烯酸酯为(甲基)丙烯酸缩水甘油酯,含异氰酸酯基团的(甲基)丙烯酸酯为(甲基)丙烯酸-2-异氰酸酯基乙酯。
本发明第三方面涉及聚苯胺接枝聚合物。聚苯胺接枝聚合物包含:包含含有缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯并向其中加入聚苯胺的聚苯胺加成预聚物;和含不饱和基团且与聚苯胺加成预聚物进行加成共聚合的另一种单体。在根据以上方面的聚苯胺接枝聚合物中,加成共聚合在缩水甘油基或异氰酸酯基团的双键与不饱和基团的双键之间进行。
根据以上方面的聚苯胺接枝聚合物的重均分子量可为1,000-100,000。
在聚苯胺接枝聚合物中,含缩水甘油基的(甲基)丙烯酸酯为(甲基)丙烯酸缩水甘油酯,含异氰酸酯基团的(甲基)丙烯酸酯为(甲基)丙烯酸-2-异氰酸酯基乙酯。
在以上方面的聚苯胺接枝聚合物中,另一种单体选自(甲基)丙烯酸-2-羟基乙酯(HE(M)A)、(甲基)丙烯酸甲酯(M(M)A)、(甲基)丙烯酸丁酯(B(M)A)和丙烯酸(AA)。
本发明第四方面涉及一种制备聚苯胺接枝聚合物的方法。方法包括:通过将聚苯胺加入含有缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯中而合成聚苯胺加成预聚物;以及合成的聚苯胺加成预聚物与含不饱和基团的另一种单体进行加成共聚合。在该方法中,加成共聚合在缩水甘油基或异氰酸酯基团的双键与不饱和基团的双键之间进行。
在根据以上方面的方法中,含缩水甘油基的(甲基)丙烯酸酯为(甲基)丙烯酸缩水甘油酯,含异氰酸酯基团的(甲基)丙烯酸酯为(甲基)丙烯酸-2-异氰酸酯基乙酯。
在根据以上方面的方法中,另一种单体选自(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯和丙烯酸。
本发明第五方面涉及包含根据第三方面的聚苯胺接枝聚合物的交联材料,其通过二异氰酸酯化合物交联。以以上配置,交联材料具有对THF等改善的耐溶剂性。
根据第三方面的聚苯胺接枝聚合物或根据第五方面的交联材料可含在油漆的涂料形成组分(coating forming component)中。以以上配置,可提供显示聚苯胺的防腐性能的油漆。
根据本发明方面的聚苯胺接枝聚合物能形成可分散或溶于各种溶剂中的长期稳定且自支撑的膜。因此,特别地,聚苯胺接枝聚合物可用作防腐漆的涂料组分。另外,由聚苯胺接枝聚合物形成的涂料和膜通过掺杂显示出高导电率,所以涂料和膜显著用于各种应用,例如电子材料和传导材料中。
附图简述
本发明的前述和其它目的、特征和优点将由以下实施例实施方案描述,参考附图而变得清晰,其中类似的数用于表示类似的元件且其中:
图1显示仅PANI的NMR;
图2显示仅GMA的NMR;
图3显示PANI-GMA-7的NMR;
图4显示PANI-GMA/HEMA的NMR;
图5显示PANI-GMA/MMA的NMR;
图6显示PANI-GMA/BMA的NMR;
图7显示PANI-MOI的NMR;
图8显示当DN-981用作交联剂时,反应以前和以后的IR;
图9显示当DN-980用作交联剂时,反应以前和以后的IR;
图9显示当DN-750用作交联剂时,反应以前和以后的IR。
实施方案详述
发明人使用聚苯胺加成预聚物作为中间体制备具有特殊结构的聚苯胺接枝聚合物。
将描述根据本发明实施方案的聚苯胺加成预聚物。在本发明实施方案中,“聚苯胺加成预聚物”为通过将聚苯胺加成在含缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯中而得到的物质。“加成”意指(甲基)丙烯酸酯和聚苯胺通过共价键合而化学连接。具体而言,在含缩水甘油基的(甲基)丙烯酸酯的情况下,加成意指(甲基)丙烯酸酯的缩水甘油基通过反应连接在聚苯胺的氨基(NH2基团)和/或亚氨基(-NH-基团)上。另外,在含异氰酸酯基团的(甲基)丙烯酸酯的情况下,(甲基)丙烯酸酯的异氰酸酯基团通过反应连接在聚苯胺的氨基和/或亚氨基上。根据本发明实施方案的聚苯胺加成预聚物用作稍后描述的合成聚苯胺接枝聚合物的中间体。
根据本发明实施方案,“含缩水甘油基的(甲基)丙烯酸酯”例如为(甲基)丙烯酸缩水甘油酯(G(M)A)。
另外,根据本发明实施方案,“含异氰酸酯基团的(甲基)丙烯酸酯”可例如为(甲基)丙烯酸-2-异氰酸酯乙酯或2-甲基丙烯酰氧基乙基异氰酸酯(MO1)。
用根据本发明的聚苯胺加成预聚物,可提供一种合成原料作为制备根据本发明实施方案的聚苯胺接枝聚合物的中间体。另外,根据本实施方案的聚苯胺加成预聚物可溶于N-甲基-2-吡咯烷酮(NMP)或二甲亚砜(DMSO)中,如在稍后实施例中所述。该优点使制备容易,且在稍后将描述的聚苯胺接枝聚合物的情况下,聚苯胺加成预聚物可用作防腐漆或导电油漆的涂料组分。
在制备根据本发明实施方案的聚苯胺加成预聚物中,用作起始原料的聚苯胺可通过已知方法得到。例如聚苯胺可以以这种方式得到:过硫酸铵等用作氧化剂以使苯胺在低温,例如在-20至50℃的温度下氧化聚合。
在制备根据本发明第一实施方案的聚苯胺加成预聚物中,聚苯胺加入含缩水甘油基的(甲基)丙烯酸酯中通过含缩水甘油基的(甲基)丙烯酸酯的缩水甘油基与聚苯胺的氨基和/或亚氨基之间的反应实现。在该反应中,可加入相对于聚苯胺过量的含缩水甘油基的(甲基)丙烯酸酯。两种化合物之间的具体混合摩尔比例如使得含缩水甘油基的(甲基)丙烯酸酯与聚苯胺之比理想地为500至2500∶1,更理想地为1000至2000∶1或1500至1800∶1。反应温度理想地为80-120℃,更理想地为90-110℃,进一步理想地为95-100℃。另外,反应持续时间理想地为1-6小时,更理想地为2-5小时。其后,收集沉淀物并浸入醇(甲醇、乙醇)等中,然后保持静止半天至一周。这样做,除去混入沉淀物中的多余含缩水甘油基的(甲基)丙烯酸酯。其后,通常在20-70℃,理想地30-60℃的温度下将沉淀物干燥。然后可收集聚苯胺加成预聚物。
以下反应式显示根据本实施方案的聚苯胺加成预聚物的制备方案。
[化学式1]
反应式显示一种反应,使得将聚苯胺(PANI)加入用作含缩水甘油基的(甲基)丙烯酸酯的甲基丙烯酸缩水甘油酯(GMA)中以合成聚苯胺加成甲基丙烯酸缩水甘油酯(PANI-GMA),其为聚苯胺加成预聚物。
另外,在制备根据本发明第二实施方案的聚苯胺加成预聚物中,聚苯胺加入含异氰酸酯基团的(甲基)丙烯酸酯中通过含异氰酸酯基团的(甲基)丙烯酸酯的异氰酸酯基团与聚苯胺的氨基和/或亚氨基之间的反应实现。在该反应中,理想地加入相对于聚苯胺过量含异氰酸酯基团的(甲基)丙烯酸酯。两种化合物之间的具体混合物摩尔比例如使得含异氰酸酯基团的(甲基)丙烯酸酯与聚苯胺之比理想地为1000至2000∶1,更理想地为1200至1800∶1,进一步理想地为1300至1700∶1。反应温度理想地为80-120℃,更理想地为90-110℃,进一步理想地为95-100℃。另外,反应持续时间理想地为1-6小时,更理想地为2-5小时。
以下反应式显示根据本实施方案的聚苯胺加成预聚物的制备方案。
[化学式2]
反应式显示一种反应,使得将聚苯胺(PANI)加入用作含异氰酸酯基团的(甲基)丙烯酸酯的甲基丙烯酸-2-异氰酸酯乙酯(MOI)中以合成聚苯胺加成甲基丙烯酸-2-异氰酸酯乙酯(PANI-MOI),其为聚苯胺加成预聚物。
将描述根据本发明实施方案的聚苯胺接枝聚合物。在本发明实施方案中,“聚苯胺接枝聚合物”意指通过根据本发明实施方案的聚苯胺加成预聚物和含不饱和基团的另一种单体在各自双键处加成共聚合而得到的化合物(共聚物)。因此,根据本发明实施方案的聚苯胺接枝聚合物通常具有一种结构,使得含聚苯胺且源自聚苯胺加成预聚物的侧链和源自含不饱和基团的另一种单体的侧链由主要由碳组成的线性主链分支。
在本发明实施方案中,“含不饱和基团的另一种单体”不受具体限制,条件是它为含不饱和键,即双键或三键的化合物。例如,含不饱和烃基(例如乙烯基、烯丙基(2-丙烯基)、异丙烯基)的化合物对应于以上“含不饱和基团的另一种单体”。具体而言,该化合物可以为含丙烯酸系不饱和基团的单体。其中,(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯和丙烯酸是特别合适的。另外,多个不饱和键可包含在含不饱和基团的另一种单体中。
根据本发明实施方案的聚苯胺接枝聚合物可以为通过两种或更多种根据本发明实施方案的聚苯胺加成预聚物和两种或更多种含不饱和基团的另一种单体在各自的双键处加成共聚合而得到的化合物。具体而言,聚苯胺加成(甲基)丙烯酸缩水甘油酯(PANI-G(M)A)、(甲基)丙烯酸-2-羟基乙酯和(甲基)丙烯酸甲酯对应于以上化合物。
根据本发明实施方案的聚苯胺接枝聚合物理想地具有1,000-100,000的重均分子量。这是由于,当聚合物具有大于或等于1,000的重均分子量时,聚合物具有对溶剂的高长期分散性,当聚合物具有小于或等于100,000的重均分子量时,聚合物具有低粘度,并且类似地,具有对溶剂的高分散性。
根据本发明实施方案的聚苯胺接枝聚合物能在各种有机溶剂中溶解或溶胀。根据本发明实施方案的聚苯胺接枝聚合物能以其中聚苯胺接枝在油漆树脂上的状态或以其中聚苯胺接枝聚合物与油漆树脂化合物交联的状态存在于油漆或涂料中。因此,可解决根据相关技术的聚苯胺的多个问题(不溶于通常的有机溶剂中,难以成形,在溶剂中差的分散性,在涂料中差的长期分散稳定性等)。因此,可容易地形成例如具有耐热性和长期稳定性的柔性和自支撑聚合膜,这是当使用相关技术的聚苯胺化合物时不可制备或难以制备的。
特别地,根据溶剂分散性和长期分散稳定性,根据本发明实施方案的聚苯胺接枝聚合物显著用作防腐漆的涂料组分。另外,由根据本发明实施方案的聚苯胺接枝聚合物形成的涂料和膜通过掺杂显示出高导电率,所以涂料或膜可用于各种应用中,例如电子材料和传导材料。
下面将描述根据本发明实施方案的聚苯胺接枝聚合物的制备方法。制备方法包括(1)聚苯胺加成预聚物合成步骤和(2)聚苯胺加成预聚物加聚步骤。下文中将描述那些步骤。
(1)聚苯胺加成预聚物合成步骤通过将聚苯胺加入含有缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯中而合成聚苯胺加成预聚物。该步骤类似于根据本发明实施方案的聚苯胺加成预聚物的制备方法,所以省略其描述。
(2)聚苯胺加成预聚物加聚步骤进行在步骤(1)中得到的聚苯胺加成预聚物与含不饱和基团的另一种单体在它们各自的双键处的加成共聚合。在该步骤中,首先将根据本发明实施方案的聚苯胺加成预聚物和含不饱和基团的另一种单体以足够的量加入溶剂中。含不饱和基团的另一种单体不受具体限制,条件是它为含有如聚苯胺接枝聚合物部分中所述的不饱和键的化合物。所述化合物理想地为(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸甲酯和/或(甲基)丙烯酸丁酯和/或丙烯酸。特别地,(甲基)丙烯酸-2-羟基乙酯是理想的。另外,溶剂可例如为有机溶剂,例如四氢呋喃(THF)。聚苯胺加成预聚物、含不饱和基团的另一种单体和溶剂的混合比不受具体限制。例如重量混合比理想地为1至5∶5至15∶20至100,更理想地为1至3∶7至12∶30至60。随后,聚合引发剂(自由基引发剂)可以例如为偶氮二异丁腈(AIBN)等。聚合引发剂可以以相对于含不饱和基团的另一种单体的摩尔%浓度,通常0.5-5摩尔%,理想地1-3摩尔%浓度添加。反应温度理想地为50-100℃,更理想地为60-90℃,进一步理想地为65-80℃。另外,反应持续时间理想地为5-24小时,更理想地为8-20小时,进一步更理想地为10-15小时。
以下反应式显示根据本发明第一实施方案的聚苯胺接枝聚合物的制备方案。
[化学式3]
反应式显示一种反应,使得用作聚苯胺加成预聚物的聚苯胺加成甲基丙烯酸缩水甘油酯(PANI-GMA)和为不饱和丙烯酸系单体的甲基丙烯酸2-羟基乙酯(HEMA)共聚以合成PANI-GMA-HEMA,其为根据本实施方案的聚苯胺接枝聚合物。
根据本发明第一实施方案的聚苯胺接枝聚合物可通过二异氰酸酯化合物交联以形成交联材料。二异氰酸酯化合物可例如为异氰脲酸酯化合物(由DIC制备的BURNOCK DN-980和/或DN-981)或加合物(D-750;由DIC制备的BURNOCK DN-981)。
交联反应通过以下反应式显示。
[化学式4]
【聚苯胺接枝共聚物的交联材料】
对于根据本实施方案的交联材料,通过二异氰酸酯化合物将聚苯胺接枝聚合物交联以改善耐溶剂性以及改善涂料物理性能。
请注意根据第二实施方案的聚苯胺接枝聚合物和交联材料可以以这种方式制备:在制备根据第一实施方案的聚苯胺接枝聚合物和交联材料中用PANI-MOI代替PANI-GMA。
根据本发明实施方案的油漆为含根据本发明上述实施方案的聚苯胺接枝聚合物作为部分或全部涂料形成组分的油漆,或含交联材料作为部分或全部涂料形成组分的油漆。
根据本发明实施方案的聚苯胺接枝聚合物可溶于酰胺溶剂如N-甲基-2-吡咯烷酮和N,N-二甲基乙酰胺,卤化烃溶剂如氯仿、二氯乙烷和二氯甲烷,醚溶剂如四氢呋喃,胺溶剂如吡啶,和极性溶剂如二甲亚砜中。涂料或自支撑膜可由以上溶液制备。此外,涂料或膜掺杂有受体掺杂剂以显示出10-3至10S/cm的高导电率。
这里所用掺杂剂不受具体限制。可使用任何掺杂剂,条件是当掺杂苯胺导电聚合物时它可用作掺杂剂。具体实例可以为各种化合物。所述化合物包括卤素,例如碘、溴、氯和碘三氯化物,质子酸如硫酸、盐酸、硝酸、高氯酸和氟硼酸,质子酸的各种盐,路易斯酸,例如三氯化铝、三氯化铁、氯化钼、氯化锑和五氟化砷,和有机酸如乙酸、三氟乙酸、苯磺酸和对甲苯磺酸。
掺杂这些化合物的方法不受具体限制。已知的方法可适用于掺杂方法。通常,仅需要使聚苯胺接枝聚合物的涂料或膜与掺杂剂化合物接触,接触可在蒸气相中或在液相中进行。作为选择,可使用在质子酸或质子酸盐的溶液中电化学掺杂聚苯胺接枝聚合物的涂料或膜的方法。
不同于含根据相关技术的聚苯胺的油漆,用根据本实施方案的油漆,可提供作为防腐漆和导电涂层形成油漆的具有高溶剂分散性和长期分散稳定性的油漆
下文将描述本发明的实施例;然而实施例仅为说明性的,不意欲限制本发明的范围。
第一实施例:PANI和GMA的预聚合
根据以下反应式所示的合成程序制备聚苯胺预聚物。
合成程序
i)将PANI和GMA以预定量(参见表1)装入烧瓶中。
ii)加入预定量(参见表1)的溶剂(DMF、NMP)。不存在溶剂时,省去该步骤。
iii)在表1所示的反应条件下进行反应。
iv)将沉淀物装入3L甲醇中,保持其静止3天。
v)在50℃的温度下将沉淀物干燥24小时。
[表1]
PANI和GMA的大分子单体化
*1:关于PA-GMA-2至5,加入GMA以检查反应。
*2:基于NMR中是否存在GMA的双键测定。
*3:PA-G-7为PA-G-6的再现性试验。
*4:PA-G-8为PA-G-7的尺度放大。
通过H-NMR评估沉淀物(检查苯环的C=C键为7ppm左右,检查C=C键为6ppm左右)。结果显示当GMA的加入量不足时,在NMR中没有识别GMA的双键的峰,当提高GMA的加入量时,识别GMA的双键。
图1-图3显示仅PANI、仅GMA和PANI-GMA-7的相应NMR。图3中7ppm左右的苯环峰表明每个C=C加入约13个苯环(51.61/4=12.7)。另外,用于合成的PANI的重均分子量为5000,PANI(5000)包括约55个苯环(5000/91=54.9)。假如PANI分子在反应期间不分解,则由NMR的结果预期每一个PANI分子键合约4个GMA分子(54.9/12.7=4.32)。推测GMA的缩水甘油基不与PANI的两端反应,而是与PANI中间的亚氨基(-NH-)反应以接枝GMA。
第二实施例:PANI-GMA和乙烯基单体的共聚
根据反应式所示的合成程序制备聚苯胺接枝聚合物。
合成程序
i)将PANI-GMA以预定量(参见表2)装入烧瓶中。
ii)将乙烯基单体(HEMA、MMA、BMA、AA等)以预定量(参见表2)装入烧瓶中。
iii)加入预定量(参见表2)的溶剂(THF)。
iv)加入预定量(参见表2)的AIBN使得相对于各个乙烯基单体AIBN的浓度为2摩尔%。
v)在表2所示反应条件下进行反应。
vi)将沉淀物装入3L甲醇中,并保持其静止3天。
[表2]
PANI-GMA和树脂单体(HEMA、MMA、BMA、AA)的共聚
*1:测定基于当装入甲醇中时是否存在聚合物的沉淀和NMR的测量结果。仅将AA装入正己烷(n-Hex)中。
起始试剂浓度:相对于乙烯基单体2摩尔%
反应浓度:20重量%
通过H-NMR评估沉淀物(检查苯环的C=C键为7ppm左右,检查C=C键为6ppm左右)。另外,通过GPC测量沉淀物的分子量。
不同于AA,在NMR中双键的峰消失,所以推测双键用于加聚。图4-图6(由于加入的量提高而从其中识别GMA的双键)显示PANI-GMA/HEMA、PANI-GMA/MMA和PANI-GMA/BMA的相应NMR。
第三实施例:RANI和树脂单体(2-甲基丙烯酰氧基乙基异氰酸酯)的预聚合
使用以下化学式表示且在其末端具有NCO基团的(甲基)丙烯酸-2-异氰酸酯基乙酯(Karenz MOI(注册商标))代替GMA尝试预聚合。
【化学式5]
Karenz MOI
【甲基丙烯酸-2-异氰酸酯基乙酯】
Mw=155.15
预聚合以以下合成程序进行。
i)将PANI和Karenz MOI以预定量(参见表3)装入烧瓶中。
ii)在表3所示反应条件下进行反应。
iii)将沉淀物装入3L甲醇中,并保持它静止3天(除去多余GMA)。
iv)将沉淀物在50℃的温度下干燥24消失。
【表3]
*1:Karenz MOI(甲基丙烯酸-2-异氰酸酯基乙酯)
*2:测定基于NMR中是否存在GMA的双键。
通过H-NMR评估沉淀物(检查苯环的C=C键为7ppm左右,检查C=C键为6ppm左右)。结果显示如同在GMA的情况下,识别源自PANI的苯环的C=C键和MOI的C=C键。
图7显示PANI-MOI的NMR。图7中7ppm左右的苯环峰表明每个C=C加入约1个苯环(3.46/4=0.865)。用于合成的PANI的重均分子量为5000,PANI(5000)包括约55个苯环(5000/91=54.9)。假如PANI分子在反应期间不分解,则由NMR的结果预期每一个PANI分子键合约63个GMA分子(54.9/0.865=63.45)。推测MO1不仅与各个PANI的两端反应,而且与各个PANI中间的所有亚氨基(-NH-)反应以接枝GMA。
通过将PANI-GMA/HEMA、PANI-GMA/MMA、PANI-GMA/BMA或PANI-MOI掺入油漆树脂和油漆制备方法中,它可以以其中聚苯胺接枝在油漆树脂上的状态或以其中聚苯胺接枝聚合物与油漆树脂交联的状态含在油漆或涂料中。这显著改善了油漆中聚苯胺的稳定性和涂料中聚苯胺的分散性。
第四实施例:通过二异氰酸酯化合物将PANI接枝聚合物交联
通过以上化学式所示交联反应使聚苯胺接枝聚合物被二异氰酸酯化合物交联。所用二异氰酸酯化合物为(1)异氰脲酸酯类型(BURNOCKDN-980;HDI系列,DIC制备),(2)异氰脲酸酯类型(BURNOCK DN-981;HDI系列,DIC制备)和(3)加合物类型(BURNOCK DN-750;TDI系列,DIC制备)。
实际上,通过IR检查HEMA的-OH与二异氰酸酯的-NCO是否反应。图8显示当DN-981用作交联剂时反应以前和以后的IR。结果显示-NCO的吸收消失,HEMA的-OH与二异氰酸酯的-NCO反应。
类似地,图9显示当DN-980用作交联剂时反应以前和以后的IR。结果显示-NCO的吸收消失,HEMA的-OH与二异氰酸酯的-NCO反应。图10显示当DN-750用作交联剂时反应以前和以后的IR。结果显示-NCO的吸收消失,HEMA的-OH与二异氰酸酯的-NCO反应。
尽管已阐述了本发明的一些实施方案,应当理解本发明不限于所述实施方案的详情,而是可包括本领域技术人员可不偏离本发明范围地作出的各种变化、改进和改善,
通过聚苯胺加成预聚物加聚得到的根据本发明方面的聚苯胺接枝聚合物可特别地适用作防腐漆的涂料组分。另外,含聚苯胺接枝聚合物的涂料或膜通过掺杂显示出高导电率,所以涂料或膜可适用于电子材料、传导材料等。
Claims (10)
1.一种聚苯胺接枝聚合物,其特征在于包含:
(a)聚苯胺加成预聚物,其特征在于包含含缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯并在第一步骤中向其中加入聚苯胺,使得(甲基)丙烯酸酯分别经由“缩水甘油基”或脲结构部分化学键合在聚苯胺上;和
(b)含不饱和基团且与根据(a)的聚苯胺加成预聚物进行加成共聚合的另一种单体,所述另一种单体选自(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯和丙烯酸,其中:
(c)在第二步骤中,加成共聚合在根据(a)和(b)的分子的双键之间进行。
2.根据权利要求1的聚苯胺接枝聚合物,其中所述含缩水甘油基的(甲基)丙烯酸酯为(甲基)丙烯酸缩水甘油酯。
3.根据权利要求1的聚苯胺接枝聚合物,其中所述含异氰酸酯基团的(甲基)丙烯酸酯为(甲基)丙烯酸-2-异氰酸酯基乙酯。
4.根据权利要求1-3中任一项的聚苯胺接枝聚合物,其中所述聚苯胺接枝聚合物的重均分子量为1,000-100,000。
5.一种油漆,其特征在于包含含根据权利要求1-4中任一项的聚苯胺接枝聚合物的涂料形成组分。
6.一种制备聚苯胺接枝聚合物的方法,其特征在于包括:
(a)在第一步骤中,通过将聚苯胺加入含有缩水甘油基或异氰酸酯基团的(甲基)丙烯酸酯中使得(甲基)丙烯酸酯分别经由“缩水甘油基”或脲结构部分化学键合在聚苯胺上而合成聚苯胺加成预聚物;和
(b)合成的聚苯胺加成预聚物与含不饱和基团的另一种单体进行加成共聚合,所述另一种单体选自(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯和丙烯酸,其中:
(c)在第二步骤中,加成共聚合在(b)下所述分子的双键之间进行。
7.根据权利要求6的方法,其中所述含缩水甘油基的(甲基)丙烯酸酯为(甲基)丙烯酸缩水甘油酯。
8.根据权利要求6的方法,其中所述含异氰酸酯基团的(甲基)丙烯酸酯为(甲基)丙烯酸-2-异氰酸酯基乙酯。
9.根据权利要求6-8中任一项的方法,其特征在于根据权利要求1-4中任一项的聚苯胺接枝聚合物通过二异氰酸酯化合物交联。
10.一种油漆,其特征在于包含含根据权利要求9的方法制备的交联的聚苯胺接枝聚合物的涂料形成组分。
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CN113416477B (zh) * | 2021-07-02 | 2022-12-20 | 江南大学 | 一种光敏植酸掺杂聚苯胺基紫外光固化防腐涂料及其制备方法 |
CN115537092B (zh) * | 2022-10-26 | 2023-06-30 | 广东省漆色彩新型材料有限公司 | 一种水性长效防腐涂料及其制备方法 |
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- 2010-01-27 CN CN201080005982.3A patent/CN102300907B/zh not_active Expired - Fee Related
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CN102300907A (zh) | 2011-12-28 |
US20110281997A1 (en) | 2011-11-17 |
JP2010174147A (ja) | 2010-08-12 |
WO2010086707A1 (en) | 2010-08-05 |
JP5443009B2 (ja) | 2014-03-19 |
DE112010000765T5 (de) | 2012-10-11 |
US8546495B2 (en) | 2013-10-01 |
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