公开(公告)号：EP4190769A1

公开(公告)日：2023-06-07

申请号：EP22750655.7

申请日：2022-06-21

申请人： Zhejiang University ,  Zhejiang NHU Company Ltd. ,  Zhejiang NHU Special Materials Co., Ltd. ,  ZHEJIANG NHU NYLON MATERIALS CO., LTD.

发明人： CHEN, Zhirong ,  WU, Wenbin ,  YIN, Hong ,  ZHA, Zengshi ,  WANG, Keyan ,  MA, Li ,  HUANG, Guodong ,  ZHOU, Guiyang ,  XU, Yong

IPC分类号： C07C255/04 ,  C07C253/10 ,  B01J31/24 ,  C07F9/6571

摘要： The present disclosure relates to a use of a multidentate phosphite ligand in the catalytic synthesis of adiponitrile. The ligand is represented by the following general formula (I). The method of catalytic synthesis of adiponitrile comprises primary hydrocyanation, isomerization, and secondary hydrocyanation reactions, wherein the catalyst adopted each comprises a phosphite ligand-nickel complex composed of a nickel precursor and a multidentate phosphite ligand. The ligand molecule has a higher electron cloud density, and the phosphorus content capable of participating in coordination in the ligand molecule per unit mass is higher, so that the catalytic activity of the catalyst is improved, and the amount of the catalyst is reduced. Meanwhile, the steric and spatial configuration of the phosphite ligand-nickel complex may be adjusted by designing and optimizing the framework structure of the ligand, and the chemical environment and the steric effect around a metal center may be changed by the designing and optimizing mentioned above combine with flexibly regulating the electronic effect and the steric hindrance effect of a substituent on the molecular structure of the ligand, so that the selectivity of a linear product adiponitrile is improved.

公开(公告)号：EP4289855A1

公开(公告)日：2023-12-13

申请号：EP22755062.1

申请日：2022-06-29

申请人： Zhejiang NHU Company Ltd. ,  Zhejiang University ,  Zhejiang NHU Special Materials Co., Ltd. ,  ZHEJIANG NHU NYLON MATERIALS CO., LTD.

发明人： ZHA, Zengshi ,  CHEN, Zhirong ,  WU, Wenbin ,  ZHANG, Tinglan ,  YIN, Hong ,  WANG, Keyan ,  ZHOU, Litao ,  LI, Haoran ,  HUANG, Guodong ,  XU, Yong

IPC分类号： C07F9/141 ,  C07F9/145 ,  C07F9/572 ,  C07F9/6506 ,  C07F9/6584 ,  B01J31/02 ,  B01J31/06 ,  B01J35/08

摘要： A method for preparing a phosphorus-containing ligand is provided, which includes: mixing a phosphorus chloride compound, polypyridine ionic liquid-loaded porous microspheres with a first organic solvent to obtain a first mixture, and mixing a compound in Formula (2) with a second organic solvent to obtain a second mixture,

wherein Z is a multivalent aliphatic hydrocarbon group or a multivalent aromatic hydrocarbon group comprising at least one substituent group, wherein the substituent group is selected from hydrogen atom, halogen atom, C 1 -C 10 alkyl group, C 1 -C 10 alkoxy group, C 1 -C 10 alkanoyl group, aryl group, heteroaryl group, cyano group, or nitro group, and n is an integer from 1 to 8; and mixing the first mixture with the second mixture to make the first mixture react with the second mixture to obtain a reaction mixture, removing generated HCl, filtrating to obtain a filter liquor, and treating the filter liquor to obtain the phosphorus-containing ligand.

公开(公告)号：EP3677617A1

公开(公告)日：2020-07-08

申请号：EP18894563.8

申请日：2018-07-12

申请人： Zhejiang NHU Company Ltd. ,  Zhejiang University ,  Zhejiang NHU Special Materials Co., Ltd.

发明人： LI, Woyuan ,  YIN, Hong ,  CHEN, Zhirong ,  HU, Baishan ,  ZHOU, Guiyang ,  DENG, Hangjun ,  LIAN, Ming ,  ZHANG, Xiongwei ,  LI, Qichuan ,  ZHAO, Jiang

IPC分类号： C08G75/029 ,  C08G75/0254 ,  C08L81/02

摘要： The disclosure relates to a preparation method of a polyphenylene sulfide resin, and a polyphenylene sulfide resin prepared by the method. The disclosure uses a sulfur-containing compound, an alkaline substance and p-dichlorobenzene as raw materials, a fatty acid as a polycondensation aid to carry out a polycondensation reaction. After purification treatment, a primary polyphenylene sulfide is obtained, which then reacts with a terminal-group adjusting agent at a high temperature to generate the polyphenylene sulfide resin. The preparation method of the disclosure has high yield and low cost, and the prepared polyphenylene sulfide resin has high reactivity, high melting crystallization temperature and excellent thermal stability. The polyphenylene sulfide resin of the disclosure can be directly used for extrusion and injection molding, and is especially applicable to fields such as automobile parts, electronic / electrical equipment, chemical industry, and machinery industry.

公开(公告)号：EP4242242A1

公开(公告)日：2023-09-13

申请号：EP21913231.3

申请日：2021-09-16

申请人： Zhejiang University ,  Zhejiang NHU Company Ltd. ,  Shandong Nhu Amino Acid Co., Ltd. ,  Zhejiang NHU Special Materials Co., Ltd.

发明人： CHEN, Zhirong ,  WU, Wenbin ,  YIN, Hong ,  LIU, Yaqing ,  ZHA, Zengshi ,  FENG, Zhichao ,  ZHANG, Tinglan ,  HUANG, Guodong

IPC分类号： C08F230/02 ,  C08J9/00 ,  B01J31/22 ,  B01J31/18 ,  C07C253/10 ,  C07C255/07 ,  C07C255/04 ,  B01J35/10 ,  C08L43/02

摘要： The present disclosure relates to a porous polymer and a method for preparing the same, a catalyst, and a method for preparing adiponitrile. The porous polymer according to the present disclosure has a pore volume of 0.3 to 2.5cm 3 /g; the porous polymer comprises a pore having a first pore diameter and a pore having a second pore diameter, and a ratio of a pore volume of the pore having a first pore diameter to a pore volume of the pore having a second pore diameter is 1 to 10:1, preferably 2 to 8:1, the porous polymer is obtained by self-polymerization or copolymerization of at least one of the phosphorus ligands, and a phosphorous content of the porous polymer is 1 to 5 mmol/g. The porous polymer-nickel catalyst made of the porous polymer according to the present disclosure has a significant increase in water resistance, which may reduce the consumption of phosphorus ligands, eliminating the steps of removing water from raw materials and reaction system water control, which greatly saves process equipment investment. Moreover, when it is used in the preparation of adiponitrile from butadiene, it has high catalytic activity, high reaction selectivity, and high linearity and is easy to recover and recycle.

公开(公告)号：EP3366716A1

公开(公告)日：2018-08-29

申请号：EP17854184.3

申请日：2017-06-29

申请人： Zhejiang NHU Special Materials Co., Ltd. ,  Zhejiang University ,  Zhejiang NHU Company Ltd.

发明人： CHEN, Zhirong ,  YIN, Hong ,  ZHANG, Qin ,  WU, Xiaoxiao ,  HONG, Wengang ,  DENG, Hangjun ,  ZHOU, Guiyang ,  WANG, Changze

IPC分类号： C08G69/26 ,  C08G69/28

CPC分类号： C08G69/28 ,  C08G69/265

摘要： The present disclosure provides a production method of a semi-aromatic polyamide, and a semi-aromatic polyamide. Said production method of a semi-aromatic polyamide includes: step 1 of subjecting an initial charge of a diamine and a binary acid in an amine/acid molar ratio of less than 1.0 to form a slurry together with water and a catalyst, and subjecting the slurry to heating and dissolution to form a saline solution; step 2 of dehydrating said saline solution after detecting the composition thereof, detecting the content of diamine in a steam condensate from a dehydration unit, adjusting the amine/acid molar ratio to be larger than 1.0 by a molten diamine and a monoacid as a molecular weight regulator, and performing pre-polymerization; and step 3 of subjecting a pre-polymerization solution to post-polycondensation after vacuum flashing. The semi-aromatic polyamide of the present disclosure has a low gel content, excellent performance and extensive scope of application.

公开(公告)号：EP2940061A1

公开(公告)日：2015-11-04

申请号：EP13867285.2

申请日：2013-10-29

申请人： Zhejiang Nhu Special Materials Co., Ltd. ,  Zhejiang University ,  Shangyu Nhu Biological Chemical Co., Ltd. ,  Zhejiang Nhu Company Ltd

发明人： CHEN, Zhirong ,  LI, Woyuan ,  LI, Haoran ,  LIAN, Ming ,  YIN, Hong ,  ZHOU, Guiyang ,  ZHENG, Xinfeng

IPC分类号： C08G75/02

CPC分类号： C08G75/16 ,  C08G75/02

摘要： The present invention discloses a fiber-grade polyphenylene sulfide resin synthesis method, taking sodium bisulfide and p-dichlorobenzene as raw materials, N-methyl pyrrolidone as the solvent and C5-C6 fatty acid salt formed through dehydration to C5-C6 fatty acid and sodium hydroxide as the polymerization additive for synthesis through polymerization. White polyphenylene sulfide resin is obtained through acidification and washing of reaction slurry. In view of the fact that MFR is below 125 g/10min, weight-average molecular weight as measured by GPC is over 4.2×10 4 , and whiteness is over 90, it can satisfy requirements for fiber polyphenylene sulfide resin. C5-C6 fatty acid salt according to the method of the present invention has a higher solubility in NMP, which can better promote polymerization. It is to be fully diverted into the filtrate after filter prior to conversion into free fatty acid again through acidification with hydrochloric acid. C5-C6 fatty acid is available for azeotropy with water, which has a limited solubility in water. Therefore, it is applicable to recycle C5-C6 fatty acid from the filtrate through azeotropy with water, and thereby solve the problem with separation of additive and sodium chloride that are soluble in water.

摘要翻译： 本发明公开了以二硫化二钠和对二氯苯为原料的纤维级聚苯硫醚树脂的合成方法，以N-甲基吡咯烷酮为溶剂，通过脱水形成C5-C6脂肪酸和 氢氧化物作为通过聚合合成的聚合添加剂。 白色聚苯硫醚树脂通过反应浆液的酸化和洗涤得到。 考虑到MFR低于125g / 10min，通过GPC测定的重均分子量超过4.2×10 4，白度超过90，可以满足纤维聚苯硫醚树脂的要求。 根据本发明方法的C5-C6脂肪酸盐在NMP中的溶解度较高，这可以更好地促进聚合。 过滤后将其全部转入滤液，然后再用盐酸酸化再转化成游离脂肪酸。 C5-C6脂肪酸可与水共沸，其在水中的溶解度有限。 因此，适用于通过与水共沸从滤液中回收C5-C6脂肪酸，从而解决了可溶于水的添加剂和氯化钠的分离问题。