CN114127142A - 在嵌段共聚物的存在下使组合物聚合的方法 - Google Patents
在嵌段共聚物的存在下使组合物聚合的方法 Download PDFInfo
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- CN114127142A CN114127142A CN202080038511.6A CN202080038511A CN114127142A CN 114127142 A CN114127142 A CN 114127142A CN 202080038511 A CN202080038511 A CN 202080038511A CN 114127142 A CN114127142 A CN 114127142A
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- block copolymer
- macroinitiator
- monomer
- polymerization
- alkoxyamine
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
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- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C64/30—Auxiliary operations or equipment
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Abstract
本发明涉及一种在至少一种嵌段共聚物存在下使组合物聚合的方法,还涉及通过该聚合方法获得的产物。本发明还涉及使用作为本发明主题的聚合方法获得的产物的用途。
Description
技术领域
本发明涉及一种在至少一种嵌段共聚物存在下使组合物聚合的方法,还涉及通过该聚合方法获得的产物。本发明还涉及使用作为本发明主题的聚合方法获得的产物的用途。
背景技术
能够获得嵌段共聚物的合成方法是众所周知的,无论它们是自由基法、阴离子法、开环法或缩聚法。
通过这种方法获得的嵌段共聚物表现出与由纳米域形式的结构化产生的形态相关的特殊性质。纳米域的类型与所获得材料的宏观特性之间的关系,无论它们是机械特性、光学特性、流变特性等特性,今天都得到了更好的理解。
嵌段共聚物的结构和相关的形态可以通过相图来预测。例如,已知将纳米结构的类型作为嵌段的化学性质、它们的分子量或它们的数量的函数。
然而,很难指导特性的组合,例如良好的机械特性和良好的光学特性。
因此,例如,在层状形态上,已知大尺寸的薄片有利于良好的机械特性,但由于由此产生的衍射而不利于光学特性。
相反地,小尺寸的薄片有利于光学特性而损害机械特性。事实上,薄片的尺寸由嵌段共聚物的分子量控制。分子量越高,薄片的尺寸越大,这对机械特性有利但对光学特性不利,反之亦然。虽然组合物中软相含量的增加对机械特性有有利影响,随着软相含量越高,层状形态消失,观察到形态变化,光学特性越差。
迄今为止,除了需要额外阶段且仅在某些情况下的方法之外,还不可能绕过这些障碍。
该方法的新特征之一是获得可控的层状形态,各嵌段的质量比(材料中的整体软/硬)为8.5/91.5至20/80,也就是说,比在热力学平衡下用嵌段共聚物或共聚物和均聚物的混合物获得的40/60和60/40之间的常规值低得多。这导致厚度非常不对称的层状物,即不同性质的薄层和厚层的交替。因此,可以通过添加预成型的嵌段共聚物来控制不对称性。该方法的另一个优点和新特征是实施,铸造片材类型,表现出初始制剂的有限粘度。术语“软”与Tg小于0℃的嵌段相关。术语“硬”与Tg大于20℃的嵌段相关。
申请人公司已经发现可以控制由组合物本体聚合引起的嵌段共聚物的(优选层状)形态的形态和尺寸,无论它们的分子量如何。
这可以通过在合成过程中在嵌段的组合物中添加一种或多种其他嵌段共聚物(数种性质和结构的嵌段共聚物)来实现,这些嵌段共聚物可以具有相同或不同的性质。
发明内容
本发明涉及一种组合物的(本体)聚合方法,所述组合物包含至少一种大分子引发剂、至少一种嵌段共聚物和至少一种单体(所述单体与大分子引发剂中存在的单体完全不同或部分不同),所述方法包括以下阶段:
在包含至少一种液态单体的溶液中混合至少一种大分子引发剂和至少一种嵌段共聚物,
使该溶液聚合,
回收由共聚物混合物组成的固体。
具体实施方式
术语“本体聚合”应理解为是指在玻璃板之间进行的过程,称为“铸造片材”过程、悬浮过程、反应性或非反应性挤出过程,以及涉及容纳有待聚合组合物的成分的容器的任何其他过程。
聚合可以以阴离子方式、通过缩聚或以自由基方式,在热或光化学引发下进行。优选地,聚合以自由基方式进行。
术语“大分子引发剂”应理解为是指一种低聚物或聚合物,其重均分子量介于5000和350000克/摩尔之间,优选介于25000和250000克/摩尔之间,携带能够引发由RAFT、ATRP、NMP、RITP或Cu(0),优选由NMP(氮氧化物介导的聚合)控制的自由基聚合的至少一种官能团。
术语“受控的自由基聚合”也应理解为意指IUPAC限定的“可逆的失活自由基聚合”。
本发明方法中使用的大分子引发剂、单体以及嵌段共聚物的组成单体由选自以下列表的单体形成:
乙烯基单体、亚乙烯基单体、二烯单体、烯烃单体、烯丙基单体或(甲基)丙烯酸类单体,更特别是乙烯基芳族单体,例如苯乙烯或取代苯乙烯,特别是α-甲基苯乙烯或甲硅烷基化苯乙烯;丙烯酸类单体,例如丙烯酸或其盐,烷基、环烷基或芳基丙烯酸酯,例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙基己酯或丙烯酸苯酯;丙烯酸羟烷酯,例如丙烯酸-2-羟乙酯;丙烯酸醚烷基酯,例如丙烯酸-2-甲氧基乙酯;烷氧基-或芳氧基聚亚烷基二醇丙烯酸酯,例如甲氧基聚乙二醇丙烯酸酯、乙氧基聚乙二醇丙烯酸酯、甲氧基聚丙二醇丙烯酸酯、甲氧基聚乙二醇-聚丙二醇丙烯酸酯或其混合物;丙烯酸氨基烷基酯,例如丙烯酸-2-(二甲氨基)乙酯(DAMEA);氟代丙烯酸酯,丙烯酸异冰片酯,4-(叔丁基)环己基丙烯酸酯,甲硅烷基化丙烯酸酯;含磷丙烯酸酯,例如亚烷基二醇磷酸酯丙烯酸酯;缩水甘油基或二环戊烯氧基乙基丙烯酸酯;甲基丙烯酸类单体,如甲基丙烯酸或其盐;烷基-、环烷基-、烯基-或芳基-甲基丙烯酸酯,如甲基丙烯酸甲酯(MMA),或月桂基-、环己基-、烯丙基-、苯基-或萘基-甲基丙烯酸酯;甲基丙烯酸羟烷酯,比如2-羟乙基甲基丙烯酸酯或甲基丙烯酸-2-羟丙酯;甲基丙烯酸醚烷基酯,例如甲基丙烯酸-2-乙氧基乙酯;烷氧基-或芳氧基聚亚烷基二醇甲基丙烯酸酯,例如甲氧基聚乙二醇甲基丙烯酸酯、乙氧基聚乙二醇甲基丙烯酸酯、甲氧基聚丙二醇甲基丙烯酸酯、甲氧基聚乙二醇-聚丙二醇甲基丙烯酸酯或其混合物;甲基丙烯酸氨基烷基酯,例如甲基丙烯酸-2-(二甲氨基)乙酯(DAMEMA);氟甲基丙烯酸酯,例如甲基丙烯酸-2,2,2-三氟乙酯;甲硅烷基化甲基丙烯酸酯,例如3-甲基丙烯酰氧基丙基三甲基硅烷;含磷的甲基丙烯酸酯,例如亚烷基二醇磷酸酯甲基丙烯酸酯,羟乙基咪唑酮甲基丙烯酸酯,羟乙基咪唑啉酮甲基丙烯酸酯、2-(2-氧代-1-咪唑烷基)乙基甲基丙烯酸酯;丙烯腈、丙烯酰胺或取代丙烯酰胺;4-丙烯酰氧基吗啉、N-羟甲基丙烯酰胺、甲基丙烯酰胺或取代的甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、甲基丙烯酰胺基丙基三甲基氯化铵(MAPTAC)、甲基丙烯酸缩水甘油酯或甲基丙烯酸二环戊烯氧基乙酯;衣康酸、马来酸或其盐、马来酸酐、烷基-或烷氧基-或芳氧基聚亚烷基二醇马来酸酯或半马来酸酯;乙烯基吡啶、乙烯基吡咯烷酮;(烷氧基)聚(亚烷基二醇)乙烯基醚或二乙烯基醚,例如甲氧基聚(乙二醇)乙烯基醚或聚(乙二醇)二乙烯基醚;烯烃单体,其中可提及乙烯、丁烯、己烯和1-辛烯;二烯单体,包括丁二烯或异戊二烯;以及氟代烯烃单体;和亚乙烯单体,其中可提及偏二氟乙烯;单独或作为至少两种上述单体的混合物。
优选地,它们是丙烯酸烷基酯和甲基丙烯酸烷基酯、丙烯酸异冰片酯和甲基丙烯酸异冰片酯、丙烯酸-4-(叔丁基)环己酯和/或取代或未取代的苯乙烯,优选丙烯酸丁酯、丙烯酸异冰片酯和甲基丙烯酸酯、丙烯酸-4-(叔丁基)环己酯、甲基丙烯酸甲酯和苯乙烯。
大分子引发剂(或大分子引发剂们)可以是单官能团的或多官能团的。优选地,它是多官能团的。当涉及自由基聚合时,大分子引发剂可以用以下方式表示:
[化学式1]
A是含有杂原子或不含杂原子的烃基,其可以包含至少一种金属物质,并且具有聚合物或低聚物性质,
R1是含有杂原子或不含杂原子的烃基,其可以包含至少一种金属物质,
R2是含有杂原子或不含杂原子的烃基,其可含有至少一种金属物质,
Z是1和10之间的整数,包括端值,优选2至4的整数,包括端值,更优选2至3的整数,包括端值。
它使用任何类型的烷氧基胺和上述单体制备,但优选使用以下烷氧基胺:
关于用于合成大分子引发剂的单烷氧基胺,在本发明的上下文中可以使用任何类型的单烷氧基胺;然而,优选下式的单烷氧基胺:
[化学式2]
[化学式3]
[化学式4]
更特别地,将选择以下单烷氧基胺:
[化学式5]
关于用于合成大分子引发剂的二烷氧基胺,在本发明的上下文中可以使用任何类型的二烷氧基胺;然而,优选下式的二烷氧基胺:
[化学式6]
[化学式7]
更特别地,以下结构将是优选的:
[化学式8]
更优选地,将选择以下二烷氧基胺:
[化学式9]
它可以通过将N-(2-甲基丙基)-N-(1-二乙基膦酰基-2,2-二甲基丙基)-O-(2-羧丙-2-基)羟胺加成到丁二醇二丙烯酸酯中来制备。
关于用于合成大分子引发剂的三烷氧基胺,在本发明的上下文中可以使用任何类型的三烷氧基胺;然而,优选下式的三烷氧基胺,N-(2-甲基丙基)-N-(1-二乙基膦酰基-2,2-二甲基丙基)-O-(2-羧丙-2-基)羟胺加成到季戊四醇三丙烯酸酯中的产物:
[化学式10]
本发明方法中使用的嵌段共聚物可以是线性或星形分支的多嵌段共聚物。优选地,本发明方法中使用的嵌段共聚物是二嵌段或三嵌段共聚物,优选三嵌段共聚物,更优选线性三嵌段共聚物。本发明方法中使用的嵌段共聚物具有玻璃化转变温度Tg小于0℃,优选小于-10℃,更优选小于-30℃的至少一种嵌段,以及具有大于20℃且优选大于30℃的玻璃化转变温度Tg的至少一种嵌段。本发明方法中使用的嵌段共聚物的含量为0重量%至90重量%,不包括0重量%,优选为2.5重量%至30重量%。
使用本发明的方法获得的共聚物的形态可以类似于线性和星形分支嵌段共聚物的理论相图(在热力学平衡时)允许或不允许的任何类型的形态;例如层状、球形、圆柱形、螺旋形、多面体或多边形,优选层状形态。
结构域的尺寸和形态可以根据与大分子引发剂的特性结合使用的嵌段共聚物进行调整。
因此,可以根据嵌段共聚物的分子量和它们的量,每个嵌段的分子量、嵌段的性质以及它们的数量,和/或大分子引发剂的分子量,单体的官能度和/或类型,确定形态和结构域尺寸。
本发明还涉及使用本发明方法获得的聚合物。由本发明方法得到的这些聚合物可以以物体的形式直接提供。例如,这些是通过“铸造片材”方法获得的板。因此,本发明还涉及这些对象,尤其涉及这些铸造片材,无论它们的厚度和尺寸如何。
本发明还涉及这些铸造片材在一般玻璃(vitrage)领域,更特别是城市和运动玻璃、汽车、摩托车、弹道学或电子学领域中的用途。
本发明还涉及通过除铸造片材方法之外的方法获得的聚合物和物体,无论它们是例如通过悬浮方法(粉末)还是挤出方法(颗粒或挤出棒、线)获得的聚合物和物体。
在悬浮方法的情况下,获得的粉末可用于许多领域,例如通过激光烧结进行3D印刷,或使用添加剂可以改善其他聚合物,特别是丙烯酸聚合物或含氟聚合物的机械特性和/或加工特性。因此,本发明还涉及这些粉末在这两个领域中的用途。
关于3D印刷,本发明的方法也可用于立体光刻,聚合被至少一种光引发剂启动。
在挤出方法的情况下,获得的颗粒或挤出的棒状物、线状物可用于许多领域作为添加剂,从而可以改善其他聚合物,特别是丙烯酸聚合物或含氟聚合物的机械特性和/或加工特性,但还可用于3D印刷(激光烧结或长丝沉积)。因此,本发明还涉及这些粉末在这两个领域中的用途。
实施例
实施例1:大分子引发剂的合成
大分子引发剂的合成根据EP 1526138在实施例1中描述的方案进行,不同的是,在本案中,仅丙烯酸丁酯用作单体。本实施例中使用的官能化合物是1,4-丁二醇二丙烯酸酯,使得能够合成双官能大分子引发剂,但是,为了制备官能度>2的大分子引发剂,本领域技术人员将能够选择适当的官能团化合物(例如季戊四醇三丙烯酸酯以获得官能度为3的大分子引发剂)。
实施例2:聚合物的合成
聚合物的合成通过将反应混合物倒入模具中,然后进行聚合来进行。随后指出的数量对应于获得样品3所需的数量,其数据见表1。该方法分四个阶段进行。第一阶段包括将14.6g大分子引发剂溶解在180.4g MMA(甲基丙烯酸甲酯)中,并在锥形烧瓶中磁力搅拌约15分钟。在第二阶段,在磁力搅拌下将5g预成型的嵌段共聚物添加至大分子引发剂/MMA混合物中直至预成型的共聚物完全溶解,即2小时。第三阶段包括将反应溶液在氮气下脱气30分钟。第四阶段是在玻璃模具中浇铸,尺寸为25厘米×25厘米,PVC密封厚度为4毫米;然后转移到烘箱进行聚合。所采用的聚合循环如下:在50分钟内从25℃到75℃的第一温度梯度,然后在520分钟内达到85℃的第二梯度。在430分钟内达到125℃的最终梯度,然后在相同温度下达到60分钟的平台期,可以确保MMA的完全聚合。随后打开模具以回收板材。
在下文中,最终样品中总聚丙烯酸丁酯的重量百分比被认为是软相的含量。这考虑了由大分子引发剂贡献的聚丙烯酸丁酯的量以及由添加的预成型的共聚物贡献的量。下面的实施例详细描述了100g样品3的计算:
一方面:
预成型的共聚物的量=2.5%,即2.5g
预成型的嵌段共聚物中聚丙烯酸丁酯(PnBA)的含量=47%
共聚物贡献的PnBA的总量=2.5×0.47=1.2g
另一方面:
大分子引发剂/MMA溶液的量=97.5%,即97.5g
大分子引发剂/MMA溶液中PnBA的含量=7.5%
大分子引发剂/MMA溶液贡献的PnBA总量=97.5×0.075=7.3g
软相的总含量:
最终样品中PnBA的总量=1.2g+7.3g=8.5g,即8.5重量%。
实施例3:形态学
表1:在AFM中观察到的样品
原子力显微镜(AFM)测试使研究表面结构成为可能。为了进行这些分析,使用Leica EM UC7超薄切片机在环境温度下通过超薄切片术预先切割样品。所用的金刚石刀具是用于预切割的Diatome Diamond Knife Cryotrim45和用于最终切割的Diatome DiamondKnife Ultra 45。用于产生图像的AFM装置是处于峰值力QNM(定量纳米力学)模式的布鲁克多模式8原子力显微镜,其氮化硅尖端的标称曲率半径为2nm(ScanAssist-AIR)。图中使用和呈现的图像是5×5微米的表面形貌图像(高度图像),其空间分辨率为512×512像素。用于测量和图像处理操作的软件是Bruker NanoScope Analysis Version 1.5。图8所示的层间尺寸是至少12次测量的平均值;根据标准偏差计算误差线。
观察到的样品总结在表1中。如果存在,开始时引入的嵌段共聚物是表2的样品C。
[表1]
在AFM中观察在不存在嵌段共聚物的情况下制备的对照样品的两种组合物,分别含有7.5重量%和15重量%的软相(大分子引发剂的P(BuA-co-Sty));图1和图2。
观察到样品中软相从7.5%变化到15%的事实导致形态从层状变为多边形。
在图3、4、5、6和7的AFM中观察到分别在2.5重量%、5重量%、10重量%、16重量%和30重量%的嵌段共聚物存在下制备的作为本发明主题的样品。
在所有情况下,观察到层状形态的保留,即使是在30%的嵌段共聚物存在下制备的30%样品上,这是软相含量为19.7%的情况。
在合成前存在嵌段共聚物的情况下,观察到层状形态的保留,随着嵌段共聚物比例的增加,层间距离减小(图8)。
随着软相含量的增加,抗冲强度将随着软相含量的增加而提高,同时减小薄片尺寸的情况也是如此。
因此,这是一个重大进步,因为这些软相含量高的产物将表现出良好的机械特性和良好的光学特性(无光散射,由于层间距离小,因此透明度高)。
研究了嵌段共聚物类型的影响。在相同的比例和相同的样品软相含量下,比较星形分支和线性嵌段共聚物。测试的各种共聚物的特性总结在表2中。
[表2]
摩尔质量通过尺寸排阻色谱法使用PS校准确定。
使用各种预成型的嵌段共聚物进行的测试总结在表3中。
[表3]
分子量通过SEC、聚苯乙烯样品测量。
据观察,嵌段共聚物的类型决定了形态(图9、图10和图11),其分子量决定了形态以及层间距离,这为精细调整形态和相关特性提供了额外的杠杆。
Claims (17)
1.一种组合物的本体聚合的方法,所述组合物包含至少一种大分子引发剂、至少一种嵌段共聚物和至少一种单体,所述单体与所述大分子引发剂中存在的单体完全不同或部分不同,所述方法包括以下阶段:
在包含至少一种单体的溶液中混合至少一种大分子引发剂和至少一种嵌段共聚物,
使所述溶液聚合,
回收获得的聚合物。
2.根据权利要求1所述的方法,其中,所述聚合是自由基类型的,通过ATRP、RAFT、RITP或NMP途径控制。
4.根据权利要求3所述的方法,其中,进行热引发。
5.根据权利要求3所述的方法,其中,进行光化学引发。
6.根据权利要求3所述的方法,其中,烷氧基胺的官能度为3。
7.根据权利要求6所述的方法,其中,所述烷氧基胺包括丙烯酸类单体和/或苯乙烯单体。
8.根据权利要求7所述的方法,其中,所述烷氧基胺包括苯乙烯和丙烯酸丁酯单体。
9.根据权利要求7所述的方法,其中,大分子引发的烷氧基胺的重均分子量为5000-350000g/mol。
10.根据权利要求7所述的方法,其中,所述组合物的单体包括甲基丙烯酸甲酯。
11.根据权利要求1所述的方法,其中,所述嵌段共聚物是线性或星形分支的三嵌段共聚物并且展示出至少一种嵌段具有小于0℃的玻璃化转变温度Tg和至少一种嵌段具有大于20℃的玻璃化转变温度Tg。
12.根据权利要求11所述的方法,其中,所述嵌段共聚物以0%至90%的重量比存在,不包括0%。
13.根据权利要求5所述的方法在通过立体光刻的3D印刷中的用途,该立体光刻涉及使用至少一种光引发剂的光聚合反应。
14.一种使用权利要求1至11中一项所述的方法获得的制品,该制品能够是铸造片材、粉末、颗粒或棒。
15.权利要求14所述的铸造片材在一般玻璃,更特别地城市和运动玻璃;汽车;摩托车或弹道学领域中的用途。
16.权利要求14所述的粉末在诸如通过激光烧结的3D印刷,或者能够改进其他聚合物的机械特性的添加剂的领域中的用途。
17.权利要求14所述的棒或颗粒作为添加剂的用途,所述添加剂能够改善其他聚合物的机械特性,或者在3D印刷,例如激光烧结或长丝沉积中的用途。
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