CN101072811A - 高纯多面体低聚硅倍半氧烷单体的制备方法 - Google Patents
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Abstract
多面体低聚硅倍半氧烷的合成方法，其以高收率产生适用在微电子用途中的低树脂含量、无溶剂且无痕量金属的单体。使POSS硅烷醇与硅烷偶联剂在溶剂和超强碱存在下反应。
Description
相关申请和专利的交叉引用
本申请要求2004年12月7日提交的美国临时专利申请序列号60/634,249号的权益。
技术领域
本发明总体上涉及提高丙烯酸和甲基丙烯酸光刻胶组合物性能的方法，更具体地，涉及掺入光刻胶配方和相关微电子和医疗产品中的高纯纳米结构化学品的制备方法。
POSS纳米结构化学品在光刻胶配方中是合意的，因为它们提供改进的透明度、降低的线边缘粗糙度和降低的放气(outgassing)性能。
发明背景
长期公认的是，聚合物的性能可以通过如聚合物序列、结构、添加剂和填料掺入、组成、形态、热力学和动力学加工控制之类的变量高度调整。类似地，已知也可以在聚合物或单体混合物中掺入各种尺寸和形状的填料、和微粒(例如碳酸钙、二氧化硅、炭黑等等)和树脂以提高它们的物理和材料性能。
光刻胶中可用的聚合物配方是高度工程化的体系，并由此采用几乎所有之前已知的性能控制技术。此外，光刻胶聚合物要求高纯度以最佳地发挥其成象和蚀刻功能并确保电子电路可靠性。最近的技术(WO2004/04040371)集中于通过提供填料型增强但呈可溶化学体形式的被称作POSS的纳米结构化学体的掺入来改性光刻胶。只有使用高纯POSS分子才可获得光刻胶的最佳性能。
现有工程学实践以高收率产生POSS分子，但它们还需要进一步精制以使它们适用于光刻胶用途。美国专利申请09/631,892和10/186,318(经此引用并入本文)中论述的现有方法描述了采用质子酸和含氢氧化物的碱来促进用硅烷偶联剂进行的POSS硅烷醇的硅基化(silation)。尽管这些方法已知总体上是有效的，但它们受限于质子酸和氢氧化物碱也可以催化POSS硅烷醇自缩合成低聚的树脂(图1)。这类树脂被称作聚硅倍半氧烷(polysilsesquioxane)或T-树脂，在光刻胶中是不合意的，因为它们的结构在分子上不精确，它们会导致结块和形态不规则性，它们会提高粘度、降低贮存寿命，并导致光刻胶配方过滤中的困难。
纳米结构化学品能够充当1-10纳米增强剂的关键因素是：(1)它们在聚合物链尺度上的独特大小，和(2)它们能够与聚合物体系相容以克服推斥力的能力，推斥力会助长不相容性和聚合物链对纳米增强剂的驱逐。也就是说，可以通过各个纳米结构上的R基团的变化来调整纳米结构化学品以表现出与某些聚合物微结构的优先亲合力/相容性。同时，可以调整纳米结构化学品以与同一聚合物中的其它微结构不相容或相容，由此能够选择性增强特定的聚合物微结构。因此，影响选择性纳米增强的因素包括纳米结构化学品的特定纳米尺寸、纳米尺寸分布、和纳米结构化学品与聚合物体系之间的相容性和不一致性。对于POSS，分子的分散和它们与聚合物片段的相容性是通过混合方程(ΔG＝ΔH-TΔS)的自由能热力学控制的。R基团的性质和POSS笼上的反应性基团与聚合物和表面反应或相互作用的能力极大影响有利的焓(ΔH)项，而POSS的熵项(ΔS)由于单一范围的(monoscopic)笼尺寸和1.0的分布而高度有利。
纳米结构化学品的最佳例子是以低成本的多面体低聚硅倍半氧烷(POSS，Polyhedral Oligomeric Silsesquioxane)和多面体低聚硅酸盐(POS)为基础的那些。POSS体系含有混杂(即，有机-无机)组合物，其中内部笼状骨架主要由无机硅-氧键构成。纳米结构的外部被反应性和非反应性有机官能团(R)覆盖，这些官能团确保纳米结构与有机单体和聚合物的相容性和可调适性。在授予Lichtenhan等人的美国专利No.5,412,053和美国专利No.5,484,867(全文特此引用并入本文)中详细论述了纳米结构化学品的这些和其它性能和特征。
因此，仍然需要对形成纳米结构单体的POSS硅基化反应的现有技术方法进行改进。以下描述了产生更高纯度且在分子上精确的硅基化POSS体系的改进方法。
发明概述
本发明描述了制备具有低树脂含量、且不含溶剂和痕量金属的[(R1SiO1.5)8(R2R3R4SiO1)∑9、[((R1SiO1.5)8)2(R2R3SiO2)]∑17、[((R1SiO1.5)8)3(R2SiO3)]∑25、[(R1SiO1.5)6(R1SiO1)2(R2R3R4SiO)2]∑10、[(R1SiO1.5)6(R1SiO1)2(R2R3SiO2)]∑9、[(R1SiO1.5)6(R1HOSiO1)1(R2R3SiO)]∑8、[(R1SiO1.5)6(R1(R2R3R4SiO)SiO1)(R2R3SiO)]∑9、[(R1SiO1.5)4(R1(R2R3R4SiO)SiO1)3]∑10、[(R1SiO1.5)7(R2SiO1.5)1]∑8型POSS组合物的改进的合成方法。这些式本身为人所关注，尤其优选用在微电子用途中。
优选方法包括式[(R1SiO1.5)7(HOSiO1.5)1]∑8、[(R1SiO1.5)6(R1HOSiO1)2]∑8、[(R1SiO1.5)4(R1HOSiO1)3]∑7的POSS硅烷醇与式R2R3R4SiX、R2R3SiX2、R2SiX3的硅烷偶联剂在溶剂和超强碱存在下的反应。
附图简述
图1显示了现有技术与改进的硅基化反应方法的比较。
具体实施方式
纳米结构的代表式的定义
为了理解本发明的化学组成，对多面体低聚硅倍半氧烷(POSS)和多面体低聚硅酸盐(POS)纳米结构的代表式作出下列定义。
聚硅倍半氧烷是式[RSiO1.5]∞所示的材料，其中∞代表聚合的摩尔程度，R代表有机取代基(H、甲硅烷氧基、环状或直链脂族或芳族基团，它们还可以含有反应性官能团，例如醇、酯、胺、酮、烯烃、醚或卤化物，或可以含有氟化基团)。聚硅倍半氧烷可以是均片段的(homoleptic)或杂片段(heteroleptic)的。均片段体系只含一种R基团，而杂片段体系含有一种以上的R基团。
POSS和POS纳米结构组合物由下式表示：
对于均片段组合物：[(RSiO1.5)n]∑#，
对于杂片段组合物：[(RSiO1.5)n(R’SiO1.5)m]∑#，(其中R≠R′)
对于官能化杂片段组合物：[(RSiO1.5)n(RXSiO1.0)m]∑#，(其中R基团可以相同或不相同)。
在所有上式中，R定义如上，X包括但不限于OH、Cl、Br、I、烷氧化物(OR)、乙酸盐(OCOR)、酸(OCOH、酯(OCOR)、过氧化物(OOR)、胺(NR2)、异氰酸酯(NCO)、和R。符号m和n是指该组合物的化学计量比。符号∑是指该组合物形成纳米结构，符号#是指纳米结构中所含的硅原子数。#的值通常为m+n的总和，其中n通常为1至24，m通常为1至12。应该指出，∑#不能被混淆为决定化学计量比的乘数，因为其仅仅描述该体系的总体纳米结构特征(aka笼尺寸)。
优选实施方案详述
本发明教导了用于POSS纳米结构化学品的硅基化反应的改进的合成方法，与此前的描述相比，既获得更高的纯度，又获得成本更低的生产方法。
POSS硅烷醇(例如，式[(R1SiO1.5)7(HOSiO1.5)1]Σ8、[(R1SiO1.5)6(R1HOSiO1)2]∑8、[(R1SiO1.5)4(R1HOSiO1)3]∑7)可以与硅烷偶联剂(例如，式R2R3R4SiX、R2R3SiX2、R2SiX3)在溶剂和超强碱存在下反应。发生HX的消除，并分别产生下式的单官能POSS单体：[(R1SiO1.5)8(R2R3R4SiO1)∑9、[((R1SiO1.5)8)2(R2R3SiO2)]∑17、[((R1SiO1.5)8)3(R2SiO3)]∑25、[(R1SiO1.5)6(R1SiO1)2(R2R3R4SiO)2]∑10、[(R1SiO1.5)6(R1SiO1)2(R2R3SiO2)]∑9、[(R1SiO1.5)6(R1HOSiO1)1(R2R3SiO)]∑8、[(R1SiO1.5)6(R1(R2R3R4SiO)SiO1)(R2R3SiO)]∑9、
[(R1SiO1.5)4(R1(R2R3R4SiO)SiO1)3]∑10、[(R1SiO1.5)7(R2SiO1.5)1]∑8。所得单体基本不含杂质并具有可通过组成、R基团和纳米结构尺寸和拓扑的选择控制的性能。高纯纳米结构POSS单体是合意的，因为它们与不纯体系相比表现出改进的过滤能力、降低了的污染和粘度、更可靠的聚合、更低的成本和减少的废物。
本发明关键是能够使用膦腈超强碱催化POSS硅烷醇的硅基化反应。可使用一系列膦腈并包括分子量和组成不同的聚膦腈。优选使用膦腈低聚物和分子，特别是P1型P(NtBu)(NH2)3、P2型(H2N)3P＝N-P(NH2)4、P3型(H2N)3P＝N-P(NH2)-N＝P(NH2)3、P4型(H2N)3P＝N-P(NH2)3＝N-P(NH2)3-N＝P(NH2)3。膦腈超强碱的碱性随磷原子数的增加而增加，这提供了这种试剂应用中有价值的工具。超强碱相对于三硅烷醇的优选浓度为2摩尔％，但可用范围包括0.1摩尔％至10摩尔％。
适用于所有工艺的通用工艺变量
如化学工艺中常见的那样，存在许多可用于控制任何工艺的纯度、选择性、速率和机理的变量。影响该工艺的变量包括纳米结构化学品的尺寸、多分散性和组成；溶剂、分离和离析方法；和催化剂或助催化剂的使用。此外，动力学和热力学控制方式、合成机理、速率和产品分布也是可以影响产品质量和经济性的已知行业手段。
实施例
[(EtSiO1.5)7(甲基丙烯酰基丙基SiO1.0)1]∑8：
将[(EtSiO1.5)4(Et(OH)SiO1.0)3]∑7(476克，0.8摩尔)溶于甲醇(1405毫升)，然后添加甲基丙烯酰基丙基三甲氧基硅烷(198.68克，0.8摩尔)，并将溶液冷却至0℃。然后加入膦腈超强碱(FW234.32，15.72毫摩尔)，并将混合物在0℃搅拌3天。然后将溶液用乙酸(1.5克)终止反应，搅拌并过滤。用甲醇(1400毫升)洗涤固体并干燥，以69％收率产生415克纯净白色产物。
Claims (15)
1.制备POSS单体的方法，包括使POSS硅烷醇与硅烷偶联剂在溶剂和超强碱存在下反应。
2.权利要求1的方法，其中使含有多种POSS硅烷醇的混合物反应。
3.权利要求1的方法，其中使用多种超强碱。
4.权利要求1的方法，其中使用多种溶剂。
5.权利要求1的方法，采用连续硅基化反应法，以超强碱作为多相催化剂或辅助试剂(coreagent)。
6.权利要求1的方法，其中POSS单体选自[(R1SiO1.5)7(HOSiO1.5)1]Σ8、[(R1SiO1.5)6(R1HOSiO1)2]Σ8和[(R1SiO1.5)4(R1HOSiO1)3]Σ7。
7.权利要求1的方法，其中硅烷偶联剂选自R2R3R4SiX、R2R3SiX2和R2SiX3。
8.权利要求1的方法，其中超强碱是膦腈。
9.权利要求8的方法，其中膦腈选自P1型、P2型、P3型和P4型。
10.权利要求8的方法，采用连续硅基化反应法，以超强碱作为多相催化剂或辅助试剂。
11.权利要求8的方法，其中硅烷偶联剂选自R2R3R4SiX、R2R3SiX2和R2SiX3。
12.权利要求8的方法，其中POSS单体选自[(R1SiO1.5)7(HOSiO1.5)1]Σ8、[(R1SiO1.5)6(R1HOSiO1)2]Σ8和[(R1SiO1.5)4(R1HOSiO1)3]Σ7。
13.权利要求11的方法，其中POSS单体选自[(R1SiO1.5)7(HOSiO1.5)1]Σ8、[(R1SiO1.5)6(R1HOSiO1)2]Σ8和[(R1SiO1.5)4(R1HOSiO1)3]Σ7。
14.权利要求9的方法，其中硅烷偶联剂选自R2R3R4SiX、R2R3SiX2和R2SiX3。
15.权利要求9的方法，其中POSS单体选自[(R1SiO1.5)7(HOSiO1.5)1]Σ8、[(R1SiO1.5)6(R1HOSiO1)2]Σ8和[(R1SiO1.5)4(R1HOSiO1)3]Σ7。权利要求14的方法，其中POSS单体选自[(R1SiO1.5)7(HOSiO1.5)1]Σ8、[(R1SiO1.5)6(R1HOSiO1)2]Σ8和[(R1SiO1.5)4(R1HOSiO1)3]Σ7。
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