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：US20120252968A1

公开(公告)日：2012-10-04

申请号：US13286715

申请日：2011-11-01

申请人： Christopher J. Wohl ,  John W. Connell ,  Emilie J. Siochi ,  Joseph G. Smith

发明人： Christopher J. Wohl ,  John W. Connell ,  Emilie J. Siochi ,  Joseph G. Smith

IPC分类号： C09D167/00 ,  B05D3/00 ,  C07D305/08 ,  B05D7/24 ,  C08G63/682 ,  C08L67/00

CPC分类号： C07D305/08 ,  C08G65/18 ,  C08G65/322 ,  C08G65/33389 ,  C08G73/1042 ,  C08G73/105 ,  C09D179/08

摘要： Copoly(imide oxetane) materials are disclosed that can exhibit a low surface energy while possessing the mechanical, thermal, chemical and optical properties associated with polyimides. The copoly(imide oxetane)s are prepared using a minor amount of fluorinated oxetane-derived oligomer with sufficient fluorine-containing segments of the copoly(imide oxetane)s that migrate to the exterior surface of the polymeric material to yield low surface energies. Thus the coatings and articles of manufacture made with the copoly(imide oxetane)s of this invention are characterized as having an anisotropic fluorine composition. The low surface energies can be achieved with very low content of fluorinated oxetane-derived oligomer. The copolymers of this invention can enhance the viability of polyimides for many applications and may be acceptable where homopolyimide materials have been unacceptable.

摘要翻译： 公开了共聚（酰亚胺氧杂环丁烷）材料，其具有低表面能，同时具有与聚酰亚胺相关的机械，热学，化学和光学性能。 使用少量的具有足够的共聚（酰亚胺氧杂环丁烷）的含氟链段的氟化氧杂环丁烷衍生的低聚物制备共聚（酰亚胺氧杂环丁烷），其迁移到聚合物材料的外表面以产生低的表面能。 因此，用本发明的共聚（酰亚胺氧杂环丁烷）制备的涂料和制品被表征为具有各向异性氟组合物。 低表面能可以用非常低含量的氟化氧乙烷衍生的低聚物来实现。 本发明的共聚物可以增强聚酰亚胺在许多应用中的存活力，并且在均聚酰亚胺材料已经不可接受的情况下可以是可接受的。

公开(公告)号：US5689004A

公开(公告)日：1997-11-18

申请号：US747472

申请日：1996-11-12

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： C08J5/18 ,  B32B27/34 ,  C07C217/90 ,  C07C225/22 ,  C08G73/10 ,  C09J179/08 ,  C07C317/36

CPC分类号： C07C217/90 ,  C07C225/22 ,  C08G73/101 ,  C08G73/1042 ,  C08G73/1078 ,  C09J179/08 ,  Y10S526/935 ,  Y10T428/31504 ,  Y10T428/31721

摘要： Controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPIs) and endcapped with nonreactive or phenylethynyl groups have been prepared by the cyclodehydration of the precursor amide acid oligomers or co-oligomers containing pendent phenylethynyl groups and endcapped with nonreactive or phenylethynyl groups. The amine terminated amide acid oligomers or co-oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and diamine containing pendent phenylethynyl groups and subsequently endcapped with a phenylethynyl phthalic anhydride or monofunctional anhydride. The anhydride terminated amide acid oligomers and co-oligomers are prepared from the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and subsequently endcapped with a phenylethynyl amine or monofunctional amine. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide under nitrogen at room temperature. The amide acid oligomers or co-oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. The polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties that includes higher glass transition temperatures after curing and higher retention of neat resin, adhesive and carbon fiber reinforced mechanical properties at temperatures up to 204.degree. C. under wet conditions without sacrificing melt flow behavior and processability as compared to similar materials. These materials are useful as adhesives, coatings, films, moldings and composite matrices.

摘要翻译： 已经通过将含有侧链苯基乙炔基的前体酰胺酸低聚物或共低聚物环状脱水并用非反应性或苯基乙炔基封端而制备了含有侧链苯基乙炔基（PEPI）和封端有非反应性或苯基乙炔基的受控分子量酰亚胺低聚物和共低聚物 。 胺封端的酰胺酸低聚物或共低聚物由二酐与过量的二胺和含有侧基苯基乙炔基的二胺的反应制备，随后用苯基乙炔基邻苯二甲酸酐或单官能酐封端。 酸酐封端的酰胺酸低聚物和共低聚物由二胺和含有侧基苯乙炔基的二胺与过量的二酐的反应制备，随后用苯乙炔胺或单官能胺封端。 聚合在极性非质子溶剂如N-甲基-2-吡咯烷酮和N，N-二甲基乙酰胺中，在室温下在氮气下进行。 酰胺酸低聚物或共低聚物随后热或化学地与相应的酰亚胺低聚物环化脱水。 由这些材料制备的聚合物和共聚物表现出独特和意想不到的性能组合，其包括固化后较高的玻璃化转变温度和更高的纯树脂保留率，粘合剂和碳纤维增强的机械性能在高达204℃的温度下在潮湿条件下没有 与类似材料相比，牺牲熔体流动行为和加工性能。 这些材料可用作粘合剂，涂料，薄膜，模制品和复合基质。

公开(公告)号：US5410012A

公开(公告)日：1995-04-25

申请号：US45339

申请日：1993-03-05

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

CPC分类号： C08G73/18

摘要： Novel poly(N-arylenebenzimidazole)s (PNABIs) 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(hydroxyphenyl-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取代反应制备新型聚（N-亚芳基苯并咪唑）（PNABI）。 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地制备PNABI的方法。

公开(公告)号：US09822088B2

公开(公告)日：2017-11-21

申请号：US13286715

申请日：2011-11-01

申请人： Christopher J. Wohl ,  John W. Connell ,  Emilie J. Siochi ,  Joseph G. Smith

发明人： Christopher J. Wohl ,  John W. Connell ,  Emilie J. Siochi ,  Joseph G. Smith

IPC分类号： C08G73/10 ,  C07D305/08 ,  C09D179/08 ,  C08G65/18 ,  C08G65/322 ,  C08G65/333

CPC分类号： C07D305/08 ,  C08G65/18 ,  C08G65/322 ,  C08G65/33389 ,  C08G73/1042 ,  C08G73/105 ,  C09D179/08

摘要： Copoly(imide oxetane) materials are disclosed that can exhibit a low surface energy while possessing the mechanical, thermal, chemical and optical properties associated with polyimides. The copoly(imide oxetane)s are prepared using a minor amount of fluorinated oxetane-derived oligomer with sufficient fluorine-containing segments of the copoly(imide oxetane)s that migrate to the exterior surface of the polymeric material to yield low surface energies. Thus the coatings and articles of manufacture made with the copoly(imide oxetane)s of this invention are characterized as having an anisotropic fluorine composition. The low surface energies can be achieved with very low content of fluorinated oxetane-derived oligomer. The copolymers of this invention can enhance the viability of polyimides for many applications and may be acceptable where homopolyimide materials have been unacceptable.

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：US6124035A

公开(公告)日：2000-09-26

申请号：US310686

申请日：1999-04-13

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： C07D209/48 ,  C08G73/12 ,  C08G8/02 ,  C08G73/10

CPC分类号： C07D209/48 ,  C08G73/122 ,  Y10T428/31504 ,  Y10T428/31721 ,  Y10T428/31942

摘要： High temperature resins containing phenylethynyl groups that are processable by transfer molding have been prepared. These phenylethynyl containing oligomers were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynlphthalic anhydride in glacial acetic acid to form a mixture of imide compounds in one step. This synthetic approach is advantageous since the products are a mixture of compounds and consequently exhibit a relatively low melting temperature. In addition, these materials exhibit low melt viscosities which are stable for several hours at 210-275.degree. C., and since the thermal reaction of the phenylethynyl group does not occur to any appreciable extent at temperatures below 300.degree. C., these materials have a broad processing window. Upon thermal cure at .about.300-350.degree. C., the phenylethynyl groups react to provide a crosslinked resin system. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

摘要翻译： 已经制备了可通过传递模塑加工的含苯基乙炔基的高温树脂。 这些含苯基乙炔基的低聚物由含苯基乙炔基的芳族二胺和各种比例的邻苯二甲酸酐和4-苯基邻苯二甲酸酐在冰醋酸中制备，从而在一个步骤中形成酰亚胺化合物的混合物。 这种合成方法是有利的，因为产物是化合物的混合物，因此表现出相对较低的熔融温度。 此外，这些材料表现出低熔融粘度，其在210-275℃下稳定数小时，并且由于苯乙炔基的热反应在低于300℃的温度下不会发生任何可察觉的程度，所以这些材料具有 一个广泛的处理窗口。 在300-350℃的温度下热固化时，苯基乙炔基反应以提供交联的树脂体系。 这些新材料表现出优异的性能，并且可能用作粘合剂，涂料，薄膜，模制品和复合基质。

公开(公告)号：US5606014A

公开(公告)日：1997-02-25

申请号：US511422

申请日：1995-08-04

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： C08J5/18 ,  B32B27/34 ,  C07C217/90 ,  C07C225/22 ,  C08G73/10 ,  C09J179/08 ,  C08G69/26

CPC分类号： C07C217/90 ,  C07C225/22 ,  C08G73/101 ,  C08G73/1042 ,  C08G73/1078 ,  C09J179/08 ,  Y10S526/935 ,  Y10T428/31504 ,  Y10T428/31721

摘要： Controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPIs) and endcapped with nonreactive or phenylethynyl groups have been prepared by the cyclodehydration of the precursor amide acid oligomers or co-oligomers containing pendent phenylethynyl groups and endcapped with nonreactive or phenylethynyl groups. The amine terminated amide acid oligomers or co-oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and diamine containing pendent phenylethynyl groups and subsequently endcapped with a phenylethynyl phthalic anhydride or monofunctional anhydride. The anhydride terminated amide acid oligomers and co-oligomers are prepared from the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and subsequently endcapped with a phenylethynyl amine or monofunctional amine. The polymerizations are carried out in polar aprotic solvents such as under nitrogen at room temperature. The amide acid oligomers or co-oligomers are subsequently cyclodehydrated to the corresponding imide oligomers. The polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties.

摘要翻译： 已经通过将含有侧链苯基乙炔基的前体酰胺酸低聚物或共低聚物环状脱水并用非反应性或苯基乙炔基封端而制备了含有侧链苯基乙炔基（PEPI）和封端有非反应性或苯基乙炔基的受控分子量酰亚胺低聚物和共低聚物 。 胺封端的酰胺酸低聚物或共低聚物由二酐与过量的二胺和含有侧基苯基乙炔基的二胺的反应制备，随后用苯基乙炔基邻苯二甲酸酐或单官能酐封端。 酸酐封端的酰胺酸低聚物和共低聚物由二胺和含有侧基苯乙炔基的二胺与过量的二酐的反应制备，随后用苯乙炔胺或单官能胺封端。 聚合在极性非质子溶剂如氮气下在室温下进行。 酰胺酸低聚物或共低聚物随后环化成相应的酰亚胺低聚物。 由这些材料制备的聚合物和共聚物表现出独特且意想不到的性能组合。