专利快速检索-快速检索全球专利，免费商用专利数据库-IPRDB

1. 发明授权

US07115540B2 Synthesis of aliphatic 1,3-diols utilizing reduced ligand concentration and water extraction 失效
公开(公告)号：US07115540B2
公开(公告)日：2006-10-03
申请号：US10669485
申请日：2003-09-24
申请人： Joseph Broun Powell , Paul Richard Weider , John Frederick Knifton , Kevin Dale Allen , Lynn Henry Slaugh , Juan Pedro Arhancet
发明人： Joseph Broun Powell , Paul Richard Weider , John Frederick Knifton , Kevin Dale Allen , Lynn Henry Slaugh , Juan Pedro Arhancet
IPC分类号： B01J31/20 , B01J31/28 , B01J31/16
CPC分类号： B01J31/2471 , B01J31/1805 , B01J31/1815 , B01J31/183 , B01J31/20 , B01J31/24 , B01J31/28 , B01J2231/321 , B01J2531/025 , B01J2531/16 , B01J2531/80 , B01J2531/82 , B01J2531/821 , B01J2531/824 , B01J2531/828 , B01J2531/845 , C07C29/16 , Y02P20/584 , C07C31/205
摘要： This invention is a process for synthesizing aliphatic 1,3-diols in one step by hydroformylation and hydrogenation of oxirane, carbon monoxide, and hydrogen employing a catalyst comprising a cobalt carbonyl compound and a cocatalyst metal compound ligated with a ligand in a ligand to cocatalyst metal atom molar ratio in the range of 0.2:1.0 to 0.6:1.0, optionally in the presence of a promoter, where recovery of product is preferably accomplished via water extraction of a diol rich phase from the bulk reaction mixture. The process modifications can, particularly in combination, be beneficial with respect to product recovery, catalyst recycle, and overall economics of a one-step process for producing aliphatic 1,3-diols.

2. 发明授权

US5777182A Cobalt-catalyzed process for preparing 1,3-propanidiol 失效
标题翻译：用于制备1,3-丙二醇的钴催化方法
公开(公告)号：US5777182A
公开(公告)日：1998-07-07
申请号：US703295
申请日：1996-08-26
申请人： Joseph Broun Powell , Lynn Henry Slaugh , Thomas Clayton Forschner , Jiang-Jen Lin , Terry Blane Thomason , Paul Richard Weider , Thomas Carl Semple , Juan Pedro Arhancet , Howard Lam-Ho Fong , Stephen Blake Mullin , Kevin Dale Allen , David Cleve Eubanks , David William Johnson
发明人： Joseph Broun Powell , Lynn Henry Slaugh , Thomas Clayton Forschner , Jiang-Jen Lin , Terry Blane Thomason , Paul Richard Weider , Thomas Carl Semple , Juan Pedro Arhancet , Howard Lam-Ho Fong , Stephen Blake Mullin , Kevin Dale Allen , David Cleve Eubanks , David William Johnson
IPC分类号： C07C29/141 , C07C45/58 , C07C45/80 , C07C27/04
CPC分类号： C07C45/58 , C07C29/141 , C07C45/80
摘要： 1,3-propanediol is prepared in a process which involves hydroformylating ethylene oxide: (a) in an essentially non-water-miscible solvent in the presence of a non-ligated cobalt catalyst and a catalyst promoter at a temperature within the range of about 50.degree. to about 100.degree. C. and a pressure within the range of about 500 to about 5000 psig, to produce an intermediate product mixture comprising less than about 15 wt % 3-hydroxypropanal; (b) adding an aqueous liquid and extracting at a temperature less than about 100.degree. C. the 3-hydroxypropanal to provide an aqueous phase comprising 3-hydroxypropanal in greater concentration than the concentration of 3-hydroxypropanal in said intermediate product mixture, and an organic phase comprising the cobalt catalyst; (c) separating the aqueous phase from the organic phase; (d) hydrogenating the 3-hydroxypropanal to provide a hydrogenation product mixture comprising 1,3-propanediol; and (e) recovering 1,3-propanediol from said hydrogenation product mixture. The process enables the production of 1,3-propanediol in high yields and selectivity without the use of a phosphine ligand-modified cobalt catalyst.
摘要翻译： 1,3-丙二醇的制备方法包括在环氧乙烷中加氢甲酰化：（a）在非连接的钴催化剂和催化剂助催化剂存在下，在基本上与水不混溶的溶剂中，温度范围为约 50℃至约100℃，压力范围为约500至约5000psig，以产生包含小于约15重量％的3-羟基丙醛的中间产物混合物; （b）加入水性液体并在低于约100℃的温度下提取3-羟基丙醛，以提供比所述中间产物混合物中3-羟基丙醛浓度更高浓度的3-羟基丙醛的水相，以及包含钴催化剂的有机相; （c）将水相与有机相分离; （d）氢化3-羟基丙醛以提供包含1,3-丙二醇的氢化产物混合物; 和（e）从所述氢化产物混合物中回收1,3-丙二醇。该方法能够以高产率和选择性生产1,3-丙二醇，而不需要使用膦配体改性的钴催化剂。

3. 发明授权

US06660892B2 Synthesis of aliphatic 1,3-diols utilizing reduced ligand concentration and water extraction 失效
标题翻译：利用配体浓度降低和水提取合成脂肪族1,3-二醇
公开(公告)号：US06660892B2
公开(公告)日：2003-12-09
申请号：US10360302
申请日：2003-02-07
申请人： Joseph Broun Powell , Paul Richard Weider , John Frederick Knifton , Kevin Dale Allen , Lynn Henry Slaugh , Juan Pedro Arhancet
发明人： Joseph Broun Powell , Paul Richard Weider , John Frederick Knifton , Kevin Dale Allen , Lynn Henry Slaugh , Juan Pedro Arhancet
IPC分类号： C07C2700
CPC分类号： B01J31/2471 , B01J31/1805 , B01J31/1815 , B01J31/183 , B01J31/20 , B01J31/24 , B01J31/28 , B01J2231/321 , B01J2531/025 , B01J2531/16 , B01J2531/80 , B01J2531/82 , B01J2531/821 , B01J2531/824 , B01J2531/828 , B01J2531/845 , C07C29/16 , Y02P20/584 , C07C31/205
摘要： This invention is a process for synthesizing aliphatic 1,3-diols in one step by hydroformylation and hydrogenation of oxirane, carbon monoxide, and hydrogen employing a catalyst comprising a cobalt carbonyl compound and a cocatalyst metal compound ligated with a ligand in a ligand to cocatalyst metal atom molar ratio in the range of 0.2:1.0 to 0.6:1.0, optionally in the presence of a promoter, where recovery of product is preferably accomplished via water extraction of a diol rich phase from the bulk reaction mixture. The process modifications can, particularly in combination, be beneficial with respect to product recovery, catalyst recycle, and overall economics of a one-step process for producing aliphatic 1,3-diols.
摘要翻译：本发明是通过使用包含羰基钴化合物的催化剂和与配位体中的配体连接的助催化剂金属化合物进行助催化剂的环氧乙烷，一氧化碳和氢气的加氢甲酰化和氢化来合成脂肪族1,3-二醇的方法金属原子摩尔比在0.2:1.0至0.6:1.0的范围内，任选地在助催化剂存在下，其中产物的回收优选通过从本体反应混合物中萃取富含二醇的相来完成。关于产物回收，催化剂再循环以及用于生产脂族1,3-二醇的一步法的总体经济性，方法修饰尤其可以组合地是有益的。

4. 发明授权

US5723389A Process for preparing alkanediols 失效
标题翻译：制备烷二醇的方法
公开(公告)号：US5723389A
公开(公告)日：1998-03-03
申请号：US729932
申请日：1996-10-15
申请人： Lynn Henry Slaugh , Paul Richard Weider , Joseph Broun Powell , Juan Pedro Arhancet
发明人： Lynn Henry Slaugh , Paul Richard Weider , Joseph Broun Powell , Juan Pedro Arhancet
IPC分类号： C07C29/141 , C07C45/58 , C07C47/02 , C07C27/00 , C07C27/04 , C07C45/00
CPC分类号： C07C29/141 , C07C45/58
摘要： An alkanediol such as 1,3-propanediol is prepared in a process which involves reacting an alkylene oxide with carbon monoxide and hydrogen in an essentially non-water-miscible solvent in the presence of a non-phosphine-ligated cobalt or rhodium catalyst and a cobalt or rhodium porphyrin promoter to produce an intermediate product mixture containing a hydroxyalkanal in an amount less than 15 wt %; extracting the hydroxyalkanal from the intermediate product mixture into an aqueous liquid at a temperature less than about 100.degree. C. and separating the aqueous phase containing hydroxyalkanal from the organic phase containing cobalt catalyst; hydrogenating the hydroxyalkanal in the aqueous phase to an alkanediol; and recovering the alkanediol. The process enables the production of an alkanediol such as 1,3-propanediol in high yields and selectivity without the use of a phosphine ligand with the cobalt or rhodium catalyst.
摘要翻译：在一种方法中制备链烷二醇，例如在非磷化氢连接的钴或铑催化剂存在下使环氧烷与一氧化碳和氢气在基本上不与水相混溶的溶剂中反应，钴或铑卟啉促进剂，以产生含有小于15重量％的羟基卡那定的中间产物混合物; 在低于约100℃的温度下将羟基卡那酸从中间产物混合物中提取成含水液体，并将含羟基卡那酸的水相与含钴催化剂的有机相分离; 将水相中的羟基卡那酸氢化成链烷二醇; 并回收链烷二醇。该方法能够以高产率和选择性生产链烷二醇如1,3-丙二醇，而不需要使用与钴或铑催化剂的膦配体。

5. 发明授权

US5731478A Process for preparing alkanediols 失效
标题翻译：制备烷二醇的方法
公开(公告)号：US5731478A
公开(公告)日：1998-03-24
申请号：US729971
申请日：1996-10-15
申请人： Lynn Henry Slaugh , Paul Richard Weider , Joseph Broun Powell , Juan Pedro Arhancet
发明人： Lynn Henry Slaugh , Paul Richard Weider , Joseph Broun Powell , Juan Pedro Arhancet
IPC分类号： C07C29/141 , C07C45/58 , C07C47/62 , C07C27/00 , C07C27/04 , C07C45/00
CPC分类号： C07C29/141 , C07C45/58
摘要： An alkanediol such as 1,3-propanediol is prepared in a process which involves reacting an alkylene oxide with carbon monoxide and hydrogen in an essentially non-water-miscible solvent in the presence of a non-phosphine-ligated cobalt or rhodium catalyst and a manganese porphyrine promoter to produce an intermediate product mixture containing a hydroxyalkanal in an amount less than 15 wt %; extracting the hydroxyalkanal from the intermediate product mixture into an aqueous liquid at a temperature less than about 100.degree. C. and separating the aqueous phase containing hydroxyalkanal from the organic phase containing cobalt catalyst; hydrogenating the hydroxyalkanal in the aqueous phase to an alkanediol; and recovering the alkanediol. The process enables the production of an alkanediol such as 1,3-propanediol in high yields and selectivity without the use of a phosphine ligand with the cobalt or rhodium catalyst.
摘要翻译：在一种方法中制备链烷二醇，例如在非磷化氢连接的钴或铑催化剂存在下使环氧烷与一氧化碳和氢气在基本上不与水相混溶的溶剂中反应，锰卟吩促进剂，以产生含有小于15重量％的量的羟基卡那定的中间产物混合物; 在低于约100℃的温度下将羟基卡那酸从中间产物混合物中提取成水性液体，并将含有羟基卡那的水相与含钴催化剂的有机相分离; 将水相中的羟基卡那酸氢化成链烷二醇; 并回收链烷二醇。该方法能够以高产率和选择性生产链烷二醇如1,3-丙二醇，而不需要使用与钴或铑催化剂的膦配体。

6. 发明授权

US5770776A Process for preparing 1,3-propanediol 失效
标题翻译： 1,3-丙二醇制备方法
公开(公告)号：US5770776A
公开(公告)日：1998-06-23
申请号：US615544
申请日：1996-03-11
申请人： Joseph Broun Powell , Stephen Blake Mullin , Paul Richard Weider , David Cleve Eubanks , Juan Pedro Arhancet
发明人： Joseph Broun Powell , Stephen Blake Mullin , Paul Richard Weider , David Cleve Eubanks , Juan Pedro Arhancet
IPC分类号： B01J31/20 , C07C29/141 , C07C29/16 , C07C45/58 , C07C45/80 , C07C29/36
CPC分类号： C07C29/16 , B01J31/0268 , B01J31/04 , B01J31/20 , B01J31/2234 , B01J31/26 , B01J31/4046 , C07C29/141 , C07C45/58 , C07C45/80 , B01J2231/48 , B01J2531/822 , Y02P20/52 , Y02P20/584
摘要： 1,3-propanediol is prepared in a process in which ethylene oxide is reacted with carbon monoxide and hydrogen in an essentially non-water-miscible solvent in the presence of an effective amount of a non-phosphine-ligated cobalt catalyst and an effective amount of a catalyst promoter under reaction conditions effective to produce an intermediate product mixture comprising less than about 15 wt % 3-hydroxypropanal. The 3-hydroxypropanal is extracted in water from the product mixture in more concentrated form, with the majority of the cobalt catalyst remaining in the solvent phase for recycle to the hydroformylation reaction. At least a portion of any residual catalyst in the water phase following extraction is removed by re-extraction with non-water-miscible solvent and recycled to hydroformylation. The 3-hydroxypropanal is then hydrogenated in aqueous solution to the desired 1,3-propanediol.
摘要翻译：在有效量的非磷化氢连接的钴催化剂和有效量的存在下，使环氧乙烷与一氧化碳和氢气在基本上不与水相混溶的溶剂中反应的方法制备1,3-丙二醇的催化剂促进剂在有效产生包含小于约15重量％3-羟基丙醛的中间产物混合物的反应条件下进行。 3-羟基丙醛在水中以更浓缩的形式从产物混合物中提取，大部分钴催化剂保留在溶剂相中循环进行加氢甲酰化反应。提取后的水相中的任何残留催化剂的至少一部分通过用非水混溶性溶剂重新萃取除去并再循环至加氢甲酰化反应。然后将3-羟基丙醛水溶液加氢至所需的1,3-丙二醇。

7. 发明授权

US5786524A Process for preparation of 1,3-propanediol via hydrogenation of 3-hydroxypropanal 失效
标题翻译： 3-羟基丙醛氢化制备1,3-丙二醇的方法
公开(公告)号：US5786524A
公开(公告)日：1998-07-28
申请号：US655639
申请日：1996-05-30
申请人： Joseph Broun Powell , William Ridley Pledger , Andreas Nikolaos Matzakos , Paul Richard Weider , Juan Pedro Arhancet
发明人： Joseph Broun Powell , William Ridley Pledger , Andreas Nikolaos Matzakos , Paul Richard Weider , Juan Pedro Arhancet
IPC分类号： C07C29/141 , C07C45/58 , C07C31/18 , C07C27/04
CPC分类号： C07C29/141 , C07C45/58
摘要： 1,3-propanediol is prepared from 3-hydroxypropanal in a process comprising the steps of: (a) contacting, at a temperature within the range of about 50.degree. to about 100.degree. C. and a pressure within the range of about 500 to about 5000 psig, ethylene oxide with carbon monoxide and hydrogen in an essentially non-water-miscible solvent in the presence of an effective amount of a non-phosphine-ligated cobalt or rhodium catalyst and an effective amount of a catalyst promoter under reaction conditions effective to produce an intermediate product mixture comprising less than 15 wt % 3-hydroxypropanal; (b) adding an aqueous liquid to said intermediate product mixture and extracting into said aqueous liquid a major portion of the 3-hydroxypropanal at a temperature less than about 100.degree. C. so as to provide an aqueous phase comprising 3-hydroxypropanal in a concentration of at least about 20 wt %, and an organic phase comprising at least a portion of the cobalt or rhodium catalyst or a cobalt- or rhodium-containing derivative thereof; (c) separating the aqueous phase from the organic phase; (d) diluting the aqueous phase comprising 3-hydroxy-propanal with an aqueous liquid to form a 3-hydroxypropanal solution having a 3-hydroxypropanal concentration within the range of about 0.2 to about 15 weight percent; (e) passing said aqueous 3-hydroxypropanal solution to a hydrogenation zone and in contact with a fixed-bed hydrogenation catalyst under hydrogenation conditions for a time effective to form an aqueous solution comprising 1,3-propanediol; and (f) recovering said 1,3-propanediol.
摘要翻译： 1,3-丙二醇由3-羟基丙醛制备，其方法包括以下步骤：（a）在约50℃至约100℃的温度和约500至约100℃的压力范围内接触，在有效量的非磷化氢连接的钴或铑催化剂和有效量的催化剂助催化剂的存在下，在反应条件下有效量的催化剂助催化剂，在大约5000psig的环氧乙烷与一氧化碳和氢气基本上是非水混溶性溶剂中以产生包含小于15重量％的3-羟基丙醛的中间产物混合物; （b）向所述中间产物混合物中加入水性液体，并在低于约100℃的温度下将大部分3-羟基丙醛提取到所述含水液体中，以提供浓度为3-羟基丙醛的水相至少约20重量％，以及包含至少一部分钴或铑催化剂或其含钴或铑的衍生物的有机相; （c）将水相与有机相分离; （d）用水性液体稀释含有3-羟基 - 丙醛的水相，形成3-羟基丙醛浓度在约0.2-约15重量％范围内的3-羟基丙醛溶液; （e）在氢化条件下将所述3-羟基丙醛水溶液通入氢化区并与固定床氢化催化剂接触，有效形成包含1,3-丙二醇的水溶液; 和（f）回收所述1,3-丙二醇。

8. 发明授权

US06903044B2 One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a N-heterocyclic ligand 失效
标题翻译：从环氧乙烷和合成气一步生产1,3-丙二醇与催化剂与N-杂环配体
公开(公告)号：US06903044B2
公开(公告)日：2005-06-07
申请号：US10298866
申请日：2002-11-18
申请人： John Frederick Knifton , Talmadge Gail James , Kevin Dale Allen , Paul Richard Weider , Joseph Broun Powell , Lynn Henry Slaugh , Timothy Williams
发明人： John Frederick Knifton , Talmadge Gail James , Kevin Dale Allen , Paul Richard Weider , Joseph Broun Powell , Lynn Henry Slaugh , Timothy Williams
IPC分类号： B01J31/28 , B01J31/18 , B01J31/20 , C07B61/00 , C07C29/16 , C07C29/44 , C07C31/20 , B01J31/00
CPC分类号： C07C29/16 , B01J31/181 , B01J31/1815 , B01J31/183 , B01J31/20 , B01J31/28 , B01J2231/48 , B01J2531/0208 , B01J2531/025 , B01J2531/821 , B01J2531/845 , Y02P20/52 , C07C31/205
摘要： Disclosed is a new catalyst composition comprising a bimetallic Co—Ru catalyst complexed with a N-heterocylcic ligand that is effective, economical, and provides improvements in oxidative stability in the one step synthesis of 1,3-propanediol (1,3-PDO) from ethylene oxide and synthesis gas. For example, cobalt-ruthenium-2,2′-bipyrimidine, 2,2′-dipyridyl, or 2,4,6-tripridyl-s-triazine catalyst precursors in cyclic ether solvents, such as 1,3-dioxolane, 1,4-dioxolane, 1,4-dioxane, and 2-ethyl-2-methyl-1,3-dioxolane, provide good yields of 1,3-PDO in a one step synthesis.
摘要翻译：公开了一种新的催化剂组合物，其包含与N-杂环配体络合的双金属Co-Ru催化剂，该双金属Co-Ru催化剂有效，经济，并且在一步合成1,3-丙二醇（1,3-PDO）中提供氧化稳定性的改善，来自环氧乙烷和合成气。例如，在环醚溶剂中的钴 - 钌-2,2'-联嘧啶，2,2'-二吡啶基或2,4,6-三苯基-s-三嗪催化剂前体，如1,3-二氧戊环， 4-二氧戊环，1,4-二恶烷和2-乙基-2-甲基-1,3-二氧戊环，在一步合成中可提供1,3-PDO的良好产率。

9. 发明授权

US06180838B2 Process for preparing alkanediols 失效
标题翻译：制备烷二醇的方法
公开(公告)号：US06180838B2
公开(公告)日：2001-01-30
申请号：US08618734
申请日：1996-03-20
申请人： Lynn Henry Slaugh , Paul Richard Weider , Joseph Broun Powell
发明人： Lynn Henry Slaugh , Paul Richard Weider , Joseph Broun Powell
IPC分类号： C07C2704
CPC分类号： B01J31/04 , B01J31/0268 , B01J31/20 , B01J31/2234 , B01J31/26 , B01J31/4046 , B01J2231/48 , B01J2531/822 , C07C29/141 , C07C29/16 , C07C45/58 , C07C45/80 , Y02P20/584 , C07C47/19 , C07C31/205 , C07C31/207
摘要： An alkanediol such as 1,3-propanediol is prepared in a process which involves reacting an alkylene oxide with carbon monoxide and hydrogen in an essentially non-water-miscible solvent in the presence of a non-phosphine-ligated rhodium catalyst and a catalyst promoter to produce an intermediate product mixture containing a hydroxyalkanal in an amount less than 15 wt %; extracting the hydroxyalkanal from the intermediate product mixture into an aqueous liquid at a temperature less than about 100° C. and separating the aqueous phase containing hydroxyalkanal from the organic phase containing rhodium catalyst; hydrogenating the hydroxyalkanal in the aqueous phase to an alkanediol; and recovering the alkanediol. The process enables the production of an alkanediol such as 1,3-propanediol in high yields and selectivity without the use of a phosphine ligand-modified rhodium catalyst.
摘要翻译：在包含非磷化氢连接的铑催化剂和催化剂促进剂的存在下，使烯化氧与一氧化碳和氢气在基本上不与水混合的溶剂中进行反应的方法制备了1,3-二醇，以产生含有小于15重量％的量的羟基卡那尔的中间产物混合物; 在低于约100℃的温度下将羟基卡那酸从中间产物混合物中提取成含水液体，并将含有羟基卡那酸的水相与含铑催化剂的有机相分离; 将水相中的羟基卡那酸氢化成链烷二醇; 并回收链烷二醇。该方法能够以高产率和选择性生产链烷二醇如1,3-丙二醇，而不需要使用膦配体改性的铑催化剂。

10. 发明授权

US5981808A Cobalt-catalyzed process for preparing 1, 3-propanediol from etylene oxide 失效
标题翻译：用于由乙烯氧化物制备1,3-丙二醇的钴催化方法
公开(公告)号：US5981808A
公开(公告)日：1999-11-09
申请号：US892831
申请日：1997-07-15
申请人： Joseph Broun Powell , Lynn Henry Slaugh , David Cleve Eubanks , Stephan Blake Mullin , Terry Blain Thomason , Paul Richard Weider , Thomas Carl Semple
发明人： Joseph Broun Powell , Lynn Henry Slaugh , David Cleve Eubanks , Stephan Blake Mullin , Terry Blain Thomason , Paul Richard Weider , Thomas Carl Semple
IPC分类号： C07C29/141 , C07C45/58 , C07C27/00
CPC分类号： C07C29/141 , C07C45/58
摘要： 1,3-Propanediol is prepared in a process which involves reacting ethylene oxide with carbon monoxide and hydrogen in an essentially non-water-miscible solvent in the presence of a non-phosphine-ligated cobalt catalyst and a catalyst promoter to produce an intermediate product mixture containing 3-hydroxypropanal in an amount less than 15 wt %; extracting the 3-hydroxypropanal from the intermediate product mixture into an aqueous liquid at a temperature less than about 100.degree. C. and separating the aqueous phase containing 3-hydroxypropanal from the organic phase containing cobalt catalyst; hydrogenating the 3-hydroxypropanal in the aqueous phase to 1,3-propanediol; and recovering the 1,3-propanediol.The process enables the production of 1,3-propanediol in high yield and selectivity without the use of a phosphine ligand-modified cobalt catalyst.
摘要翻译：在一种方法中制备1,3-丙二醇，该方法包括在非磷化氢连接的钴催化剂和催化剂促进剂的存在下，将环氧乙烷与一氧化碳和氢气在基本上不与水相混溶的溶剂中反应以产生中间产物含有小于15重量％的3-羟基丙醛的混合物; 在低于约100℃的温度下将中间产物混合物中的3-羟基丙醛萃取到含水液体中，并从含钴催化剂的有机相中分离出含有3-羟基丙醛的水相; 将水相中的3-羟基丙醛氢化为1,3-丙二醇; 并回收1,3-丙二醇。该方法能够以高产率和选择性生产1,3-丙二醇，而不需要使用膦配位体改性的钴催化剂。

你已经成功收藏专利！

检索式保存成功!

IPRDB

热门服务

关于我们

友情链接

联系方式