公开(公告)号：US06441099B1

公开(公告)日：2002-08-27

申请号：US09726297

申请日：2000-11-28

申请人： John W. Connell ,  Joseph G. Smith, Jr. ,  Paul M. Hergenrother

发明人： John W. Connell ,  Joseph G. Smith, Jr. ,  Paul M. Hergenrother

IPC分类号： C08J300

CPC分类号： C08G73/101 ,  C08F251/00 ,  C08F281/00 ,  C08F290/14 ,  C08G73/10

摘要： Phenylethynyl containing reactive additives were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynylphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pyrrolidinone to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

公开(公告)号：US06359107B1

公开(公告)日：2002-03-19

申请号：US09575826

申请日：2000-05-18

申请人： John W. Connell ,  Joseph G. Smith ,  Paul M. Hergenrother

发明人： John W. Connell ,  Joseph G. Smith ,  Paul M. Hergenrother

IPC分类号： C08G7310

CPC分类号： C09J179/08 ,  C08G73/101 ,  C08G73/1014 ,  C08G73/1042 ,  C09D179/08 ,  Y10S526/935 ,  Y10T428/2969 ,  Y10T428/31504 ,  Y10T428/31721

摘要： A composition of and method for making high performance imide resins that are processable by resin transfer molding (RTM) and resin infusion (RI) techniques were developed. Materials with a combination of properties, making them particularly useful for the fabrication of composite parts via RTM and/or RI processes, were prepared, characterized and fabricated into moldings and carbon fiber reinforced composites and their mechanical properties were determined. These materials are particularly useful for the fabrication of structural composite components for aerospace applications. The method for making high performance resins for RTM and RI processes is a multi-faceted approach. It involves the preparation of a mixture of products from a combination of aromatic diamines and aromatic dianhydrides at relatively low calculated molecular weights (i.e. high stoichiometric offsets) and endcapping with latent reactive groups. The combination of these monomers results in a mixture of products, in the imide form, that exhibits a stable melt viscosity of less than approximately 60 poise below approximately 300° C.

摘要翻译： 开发了可通过树脂传递模塑（RTM）和树脂浸渍（RI）技术加工的制备高性能酰亚胺树脂的组合物和方法。 制备具有组合性能的材料，使其对于通过RTM和/或RI工艺制造复合材料部分特别有用，其特征和制造成模制品和碳纤维增强复合材料，并确定其机械性能。 这些材料对于制造用于航空航天应用的结构复合材料部件特别有用。 用于制造RTM和RI工艺的高性能树脂的方法是一种多方面的方法。 它涉及以相当低的计算分子量（即高化学计量偏移）和具有潜在反应性基团的封端物从芳族二胺和芳族二酸酐的组合制备产物的混合物。 这些单体的组合产生了酰亚胺形式的产物的混合物，其在约300℃以下显示出小于约60泊的稳定的熔融粘度。

公开(公告)号：US5637670A

公开(公告)日：1997-06-10

申请号：US376170

申请日：1995-01-20

申请人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith, Jr.

发明人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith, Jr.

IPC分类号： C08G73/18 ,  C09J179/04 ,  C08G73/08

CPC分类号： C08G73/18 ,  C09J179/04 ,  Y10S526/935 ,  Y10T428/31504

摘要： Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

摘要翻译： 通过二（羟基苯基苯并咪唑）单体与活性芳族二卤化物或活性芳族二硝基化合物的芳族亲核置换反应制备新型分子量控制和封端的聚苯并咪唑（PBI）。 PBI被单（羟基苯基）苯并咪唑封端。 聚合在极性非质子溶剂如N-甲基-2-吡咯烷酮或N，N-二甲基乙酰胺中，使用碱金属碱如碳酸钾，在氮气下在升高的温度下进行。 通过苯基-4-羟基苯甲酸酯与二苯砜中的芳族（邻二胺）反应合成单（羟基苯基）苯并咪唑。 制备新化学结构的分子量控制和封端的PBI，其表现出物理和机械性质的有利组合。

公开(公告)号：US5554715A

公开(公告)日：1996-09-10

申请号：US375334

申请日：1995-01-17

申请人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith, Jr.

发明人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith, Jr.

IPC分类号： C08G73/18

CPC分类号： C08G73/18

摘要： Novel poly(N-arylenebenzimidazole)s (PNABls) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl-N-arylenebenzimidazole) monomers are synthesized by reacting phenyl-4-hydroxybenzoate with bis(2-aminoanilino)arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyI-N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

摘要翻译： 通过新型二（羟基苯基-N-亚芳基苯并咪唑）单体与活性芳族二卤化物或活性芳族二硝基化合物的芳族亲核置换反应制备新型聚（N-亚芳基苯并咪唑）（PNABls）。 聚合在极性非质子溶剂如N-甲基-2-吡咯烷酮或N，N-二甲基乙酰胺中，使用碱金属碱如碳酸钾，在氮气下在升高的温度下进行。 二（羟基苯基-N-亚芳基苯并咪唑）单体通过苯基-4-羟基苯甲酸酯与二（2-氨基苯胺基）亚芳基在二苯基砜中反应合成。 制备中等分子量的新化学结构的PNABI，其表现出物理和机械性能的有利组合。 新型二（羟基苯基）-N-亚芳基苯并咪唑的使用允许比以前的路线更经济和更容易的制备PNABI的方法。

公开(公告)号：US5182356A

公开(公告)日：1993-01-26

申请号：US650336

申请日：1991-01-24

申请人： John W. Connell ,  Paul M. Hergenrother ,  Peter Wolf

发明人： John W. Connell ,  Paul M. Hergenrother ,  Peter Wolf

IPC分类号： C08G73/08

CPC分类号： C08G73/08

摘要： Poly(1,2,4-triazoles)(PT) have been prepared by involving the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)-1,2,4-triazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl)-1,2,4-triazole monomers are first synthesized by reacting bis(4-hydroxyphenyl) hydrazide with aniline hydrochloride at 250.degree. C. in the melt and also by reacting 1,3 or 1,4-bis-(4-hydroxyphenyl)phenylenedihydrazide with 2 moles of aniline hydrochloride in the melt. Purification of the di(hydroxyphenyl)-1,2,4-triazole monomers is accomplished by recrystallization. This synthetic route has provided high molecular weight PT of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides.

摘要翻译： 通过涉及二（羟基苯基）-1,2,4-三唑单体与活性芳族二卤化物或活性芳族二硝基化合物的芳族亲核取代反应制备了聚（1,2,4-三唑）（PT）。 反应在极性非质子溶剂如环丁砜或二苯基砜中，使用碱金属碱如碳酸钾在氮气下在升高的温度下进行。 二（羟基苯基）-1,2,4-三唑单体首先通过双（4-羟基苯基）酰肼与苯胺盐酸盐在250℃下在熔体中反应，并通过使1,3或1,4-双 - （4-羟基苯基）亚苯基二酰肼与2摩尔苯胺盐酸盐在熔体中反应。 二（羟基苯基）-1,2,4-三唑单体的纯化是通过重结晶实现的。 这种合成路线提供了新的化学结构的高分子量PT，在经济上和综合性上比其他途径更有利，并且由于大量活性芳族二卤化物的可用性而允许容易的化学结构变化。

公开(公告)号：US06958192B2

公开(公告)日：2005-10-25

申请号：US10414562

申请日：2003-04-07

申请人： Paul M. Hergenrother ,  Joseph G. Smith, Jr. ,  John W. Connell ,  Kent A. Watson

发明人： Paul M. Hergenrother ,  Joseph G. Smith, Jr. ,  John W. Connell ,  Kent A. Watson

IPC分类号： C08G73/10 ,  B32B27/00

CPC分类号： C08G73/1057 ,  C08G73/1039 ,  C08G73/105 ,  Y10T428/31721

摘要： The present invention relates generally to polyimides. It relates particularly to novel polyimides prepared from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and aromatic diamines. These novel polyimides have low color, good solubility, high thermal emissivity, low solar absorptivity and high tensile strength.

摘要翻译： 本发明一般涉及聚酰亚胺。 特别涉及由2,3,3'，4'-联苯四羧酸二酐和芳族二胺制备的新型聚酰亚胺。 这些新型聚酰亚胺具有颜色低，溶解性好，热发射率高，太阳吸收率低，拉伸强度高。

公开(公告)号：US5412059A

公开(公告)日：1995-05-02

申请号：US45335

申请日：1993-04-05

申请人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith, Jr.

发明人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith, Jr.

IPC分类号： C08G73/18 ,  C09J179/04 ,  C08G63/00 ,  C08G8/02

CPC分类号： C08G73/18 ,  C09J179/04 ,  Y10S526/935 ,  Y10T428/31504

摘要： Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

摘要翻译： 通过二（羟基苯基苯并咪唑）单体与活性芳族二卤化物或活性芳族二硝基化合物的芳族亲核置换反应制备新型分子量控制和封端的聚苯并咪唑（PBI）。 PBI被单（羟基苯基）苯并咪唑封端。 聚合在极性非质子溶剂如N-甲基-2-吡咯烷酮或N，N-二甲基乙酰胺中，使用碱金属碱如碳酸钾，在氮气下在升高的温度下进行。 通过苯基-4-羟基苯甲酸酯与二苯砜中的芳族（邻二胺）反应合成单（羟基苯基）苯并咪唑。 制备新化学结构的分子量控制和封端的PBI，其表现出物理和机械性质的有利组合。

公开(公告)号：US5317078A

公开(公告)日：1994-05-31

申请号：US790730

申请日：1991-10-30

申请人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith

发明人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith

IPC分类号： C07D235/18 ,  C08G73/18

CPC分类号： C08G73/18 ,  C07D235/18

摘要： Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-4-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

摘要翻译： 由苯基-4-羟基苯甲酸酯和芳族双（邻二胺）制备二（羟基苯基）苯并咪唑单体。 这些单体用于合成可溶性聚苯并咪唑。 该反应涉及各种二（羟基苯基）苯并咪唑单体与活性芳族二卤化物或活性芳族二硝基化合物在碱金属碱存在下的芳族亲核取代。 这些聚合物显示出比其商业对应物更低的玻璃化转变温度，改善的溶解性和更好的压模成型性。

公开(公告)号：US5245044A

公开(公告)日：1993-09-14

申请号：US941816

申请日：1992-09-08

申请人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith

发明人： John W. Connell ,  Paul M. Hergenrother ,  Joseph G. Smith

IPC分类号： C07D235/18 ,  C08G73/18

CPC分类号： C07D235/18 ,  C08G73/18

摘要： Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-4-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

摘要翻译： 由苯基-4-羟基苯甲酸酯和芳族双（邻二胺）制备二（羟基苯基）苯并咪唑单体。 这些单体用于合成可溶性聚苯并咪唑。 该反应涉及各种二（羟基苯基）苯并咪唑单体与活性芳族二卤化物或活性芳族二硝基化合物在碱金属碱存在下的芳族亲核取代。 这些聚合物显示出比其商业对应物更低的玻璃化转变温度，改善的溶解性和更好的压模成型性。

公开(公告)号：US5116934A

公开(公告)日：1992-05-26

申请号：US732884

申请日：1991-07-19

申请人： John W. Connell ,  Paul M. Hergenrother

发明人： John W. Connell ,  Paul M. Hergenrother

IPC分类号： C07D233/54 ,  C07F9/6506 ,  C08G65/40 ,  C08G73/06 ,  C08G73/18

CPC分类号： C07D233/64 ,  C07F9/65062 ,  C08G65/4037 ,  C08G73/0616 ,  C08G73/18

摘要： Polyimidazoles (Pl) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethylacetamide, sulfolane, N-methylpyrrolidinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl)imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl)imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxyphenyl)imidazole monomer. This synthetic route has provided high molecular weight Pl of new chemical structure, is economically and sythetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

摘要翻译： 通过二（羟基苯基）咪唑单体与活性芳族二卤化物或活性芳族二硝基化合物的芳族亲核取代反应制备聚咪唑（P1）。 反应在极性非质子溶剂如N，N-二甲基乙酰胺，环丁砜，N-甲基吡咯烷酮，二甲基亚砜或二苯基砜中，使用碱金属碱如碳酸钾，在氮气下在升高的温度下进行。 二（羟基苯基）咪唑单体是通过使芳族醛与二甲氧基苯甲醚反应或在乙酸铵存在下使芳族二醛与甲氧基苯甲醚反应来制备的。 随后用氢溴酸水溶液处理二（甲氧基苯基）咪唑，得到二（羟基苯基）咪唑单体。 这种合成路线提供了新的化学结构的高分子量P1，在经济上和应用上比其他途径更有利，并且由于大量活性芳族二卤化物和二硝基化合物的可用性而允许容易的化学结构变化。