公开(公告)号：US09062159B2

公开(公告)日：2015-06-23

申请号：US14129111

申请日：2011-11-03

申请人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Bingcai Pan

发明人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Bingcai Pan

IPC分类号： C08G63/87 ,  A61L27/18 ,  A61K47/34 ,  A61L17/00 ,  C08G63/06 ,  C08G63/08 ,  C08G63/82 ,  A61L27/54 ,  A61L17/12

CPC分类号： C08G63/87 ,  A61K47/34 ,  A61L17/00 ,  A61L17/12 ,  A61L27/18 ,  A61L27/54 ,  A61L2300/602 ,  A61L2430/02 ,  C08G63/06 ,  C08G63/08 ,  C08G63/78 ,  C08G63/823 ,  C08L67/04

摘要： A method for synthesizing a medical grade biodegradable material, poly(lactic-co-glycolic acid), copolycondensation of lactic acid and glycolic acid catalyzed by biomass creatinine. The present invention uses commercialized creatinine (a type of biomaterial organic guanidine compounds—the arginine metabolite creatinine (CR) in human body) as the catalyst and industrial lactic acid (LA, mass content 85%, aqueous solution) and glycolic acid (GA, 95%) as the monomer to synthesize the high biosafety of medical poly(lactic-co-glycolic acid) in terms of two steps polycondensation without solvent. The method of the present invention has the following characters: green technology is used, raw materials required are low in costs, operation is simple and convenient, and it is easy for industrialization; the catalyst, creatinine, used in the invention has high biocompatibility and biosafety, and no cytotoxicity; the poly(lactic-co-glycolic acid) synthesized is free of any metal and other toxic residues; Further, the molecular weight distribution for all synthesized products is narrow and the molecular weight is controllable within 1.8-17.7×104; and the poly(lactic-co-glycolic acid) synthesized is suitable for use as implantable material for hard tissue repair, surgical sutures, and the carrier for targeting drugs and controlled release drugs.

摘要翻译： 用于合成医用级生物降解材料的方法，聚（乳酸 - 共 - 乙醇酸），由生物体肌酐催化的乳酸和乙醇酸的共缩聚。 本发明使用商业化肌酐（一种生物材料有机胍化合物 - 人体中的精氨酸代谢物肌酸酐（CR））作为催化剂和工业乳酸（LA，质量含量85％，水溶液）和乙醇酸（GA， 95％）作为单体，以两步缩聚无溶剂的方式合成医用聚（乳酸 - 共 - 乙醇酸）的高生物安全性。 本发明的方法具有以下特征：使用绿色技术，所需原料成本低，操作简单方便，工业化容易; 本发明使用的催化剂，肌酸酐具有高生物相容性和生物安全性，无细胞毒性; 合成的聚（乳酸 - 共 - 乙醇酸）不含任何金属和其他有毒残留物; 此外，所有合成产物的分子量分布窄，分子量可控于1.8-17.7×104; 合成的聚（乳酸 - 共 - 乙醇酸）适用于硬组织修复，手术缝合线和用于靶向药物和控释药物的载体的植入材料。

公开(公告)号：US08846853B2

公开(公告)日：2014-09-30

申请号：US13511311

申请日：2011-11-03

申请人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Wei Huang ,  Bingcai Pan

发明人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Wei Huang ,  Bingcai Pan

IPC分类号： C08G63/08 ,  A61K47/32 ,  C08G63/82

CPC分类号： C08G63/823 ,  A61K47/32 ,  C08G63/08

摘要： A direct polycondensation method for medical biodegradable polylactic acid (PLA). The invention uses commercialized creatinine (a type of biomaterial organic guanidine compounds—the arginine metabolite creatinine in human body) as the catalyst and industrial lactic acid (mass content 85-90%, aqueous solution) as the monomer to synthesize the PLA in terms of second polycondensation without solvent. Instead of tin catalysts having cytotoxicity, the catalyst used in the invention has high biocompatibility and biosafety. The synthesized PLA does not contain any metal and other toxic components; therefore, it can be used as the carrier for targeting drugs and controlled release drugs. The green catalyst and green processing method (no solvent applied and no toxic products produced) are used to synthesize the green biodegradable PLA with high biosafety. The molecular weight distribution for all synthesized products is narrow and the molecular weight is controllable within 1.5-3.0×104.

摘要翻译： 医用可生物降解聚乳酸（PLA）的直接缩聚方法。 本发明使用商业化肌酐（一种生物材料有机胍化合物 - 人体中的精氨酸代谢物肌酸酐）作为催化剂，工业乳酸（质量含量85-90％，水溶液）作为单体合成PLA 第二次缩聚无溶剂。 代替具有细胞毒性的锡催化剂，本发明中使用的催化剂具有高生物相容性和生物安全性。 合成的PLA不含任何金属和其他有毒成分; 因此，它可以用作靶向药物和控释药物的载体。 使用绿色催化剂和绿色加工方法（无溶剂应用，无有毒产物生产）合成具有高生物安全性的绿色生物降解PLA。 所有合成产物的分子量分布窄，分子量可控1.5-3.0×104。

公开(公告)号：US20130116400A1

公开(公告)日：2013-05-09

申请号：US13511311

申请日：2011-11-03

申请人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Wei Huang ,  Bingcai Pan

发明人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Wei Huang ,  Bingcai Pan

IPC分类号： C08G63/06

CPC分类号： C08G63/823 ,  A61K47/32 ,  C08G63/08

摘要： The present invention provides a direct polycondensation method for medical biodegradable polylactic acid (PLA) using creatinine catalyzed lactic acid. The invention uses commercialized creatinine (a type of biomaterial organic guanidine compounds—the arginine metabolite creatinine (CR) in human body) as the catalyst and industrial lactic acid (LA, mass content 85-90%, aqueous solution) as the monomer to synthesize the high biosafety of medical PLA in terms of second polycondensation without solvent (identity). Instead of tin catalysts having cytotoxicity, the catalyst used in the invention has high biocompatibility and biosafety. The synthesized PLA does not contain any metal and other toxic components; therefore, it can be used as the carrier for targeting drugs and controlled release drugs. In addition, the green catalyst and green processing method (no solvent applied and no toxic products produced) are used in the invention to synthesize the green biodegradable PLA with high biosafety. The polymerization reaction is simple and the raw materials required are low in costs, thus it is easy for industrialization. Further, the molecular weight distribution for all synthesized products is narrow and the molecular weight is controllable within 1.5-3.0×104.

摘要翻译： 本发明提供使用肌酸酐催化乳酸的医用可生物降解聚乳酸（PLA）的直接缩聚方法。 本发明使用商业化肌酐（一种生物材料有机胍化合物 - 人体中的精氨酸代谢物肌酸酐（CR））作为催化剂，工业乳酸（LA，质量含量85-90％，水溶液）作为单体合成 医用PLA的高生物安全性在无溶剂（身份）的第二缩聚方面。 代替具有细胞毒性的锡催化剂，本发明中使用的催化剂具有高生物相容性和生物安全性。 合成的PLA不含任何金属和其他有毒成分; 因此，它可以用作靶向药物和控释药物的载体。 此外，本发明中使用绿色催化剂和绿色加工方法（无溶剂施用，无有毒产物）合成具有高生物安全性的绿色可生物降解PLA。 聚合反应简单，所需原料成本低，易于工业化。 此外，所有合成产物的分子量分布窄，分子量可控制在1.5-3.0×104内。

公开(公告)号：US20140121347A1

公开(公告)日：2014-05-01

申请号：US14129323

申请日：2011-11-02

申请人： Hong Li ,  Quanxing Zhang ,  Wei Huang ,  Wei Jiang ,  Xupeng Zong ,  Bingcai Pan

发明人： Hong Li ,  Quanxing Zhang ,  Wei Huang ,  Wei Jiang ,  Xupeng Zong ,  Bingcai Pan

IPC分类号： C08G63/87 ,  C07D233/50

CPC分类号： C07D233/50 ,  A61K47/34 ,  A61L17/12 ,  A61L27/18 ,  A61L31/06 ,  C07D233/32 ,  C07D233/46 ,  C07D233/88 ,  C08G63/06 ,  C08G63/87

摘要： Disclosed is a high molecular weight polylactic acid synthesized by using a method for synthesizing and catalytically-polycondensing bionic creatinine-guanidinium chloride. Creatinine is used as the material in a reaction with aqueous hydrochloric acid to synthesize a bionic creatinine-guanidinium salt catalyst, creatinine-guanidinium chloride (CR.Cl). The creatinine-guanidinium chloride synthesized is used as a catalyst, an industrial grade lactic acid (LA, 85% to 90%, aqueous solution) is used as a monomer, a solvent-free two-step polycondensation method is used to synthesize and afford metal-free and toxic residue-free polylactic acid featuring high biological safety and high molecular weight.

摘要翻译： 本发明公开了一种通过使用合成和催化缩聚仿生肌酐 - 氯化胍的方法合成的高分子量聚乳酸。 使用肌酸酐作为与盐酸水溶液反应的材料，以合成肌酸酐 - 胍盐催化剂，肌酸酐 - 氯化胍（CR.Cl）。 使用合成的肌酸胍 - 氯化胍作为催化剂，使用工业级乳酸（LA，85％〜90％，水溶液）作为单体，使用无溶剂的两步缩聚法合成并提供 无金属和无毒无残留的聚乳酸，具有高生物安全性和高分子量。

公开(公告)号：US09062006B2

公开(公告)日：2015-06-23

申请号：US14129323

申请日：2011-11-02

申请人： Hong Li ,  Quanxing Zhang ,  Wei Huang ,  Wei Jiang ,  Xupeng Zong ,  Bingcai Pan

发明人： Hong Li ,  Quanxing Zhang ,  Wei Huang ,  Wei Jiang ,  Xupeng Zong ,  Bingcai Pan

IPC分类号： C08G63/87 ,  C07D233/50 ,  A61L27/18 ,  A61L31/06 ,  A61K47/34 ,  A61L17/12 ,  C07D233/32 ,  C08G63/06

CPC分类号： C07D233/50 ,  A61K47/34 ,  A61L17/12 ,  A61L27/18 ,  A61L31/06 ,  C07D233/32 ,  C07D233/46 ,  C07D233/88 ,  C08G63/06 ,  C08G63/87

摘要： Disclosed is a high molecular weight polylactic acid synthesized by using a method for synthesizing and catalytically-polycondensing bionic creatinine-guanidinium chloride. Creatinine is used as the material in a reaction with aqueous hydrochloric acid to synthesize a bionic creatinine-guanidinium salt catalyst, creatinine-guanidinium chloride (CR.Cl). The creatinine-guanidinium chloride synthesized is used as a catalyst, an industrial grade lactic acid (LA, 85% to 90%, aqueous solution) is used as a monomer, a solvent-free two-step polycondensation method is used to synthesize and afford metal-free and toxic residue-free polylactic acid featuring high biological safety and high molecular weight.

摘要翻译： 本发明公开了一种通过使用合成和催化缩聚仿生肌酐 - 氯化胍的方法合成的高分子量聚乳酸。 使用肌酸酐作为与盐酸水溶液反应的材料，以合成肌酸酐 - 胍盐催化剂，肌酸酐 - 氯化胍（CR.Cl）。 使用合成的肌酸胍 - 氯化胍作为催化剂，使用工业级乳酸（LA，85％〜90％，水溶液）作为单体，使用无溶剂的两步缩聚法合成并提供 无金属和无毒无残留的聚乳酸，具有高生物安全性和高分子量。

公开(公告)号：US20140142275A1

公开(公告)日：2014-05-22

申请号：US14129111

申请日：2011-11-03

申请人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Bingcai Pan

发明人： Hong Li ,  Quanxing Zhang ,  Wei Jiang ,  Bingcai Pan

IPC分类号： C08G63/87

CPC分类号： C08G63/87 ,  A61K47/34 ,  A61L17/00 ,  A61L17/12 ,  A61L27/18 ,  A61L27/54 ,  A61L2300/602 ,  A61L2430/02 ,  C08G63/06 ,  C08G63/08 ,  C08G63/78 ,  C08G63/823 ,  C08L67/04

摘要： A method for synthesizing a medical grade biodegradable material, poly(lactic-co-glycolic acid), copolycondensation of lactic acid and glycolic acid catalyzed by biomass creatinine. The present invention uses commercialized creatinine (a type of biomaterial organic guanidine compounds—the arginine metabolite creatinine (CR) in human body) as the catalyst and industrial lactic acid (LA, mass content 85%, aqueous solution) and glycolic acid (GA, 95%) as the monomer to synthesize the high biosafety of medical poly(lactic-co-glycolic acid) in terms of two steps polycondensation without solvent. The method of the present invention has the following characters: green technology is used, raw materials required are low in costs, operation is simple and convenient, and it is easy for industrialization; the catalyst, creatinine, used in the invention has high biocompatibility and biosafety, and no cytotoxicity; the poly(lactic-co-glycolic acid) synthesized is free of any metal and other toxic residues; Further, the molecular weight distribution for all synthesized products is narrow and the molecular weight is controllable within 1.8-17.7×104; and the poly(lactic-co-glycolic acid) synthesized is suitable for use as implantable material for hard tissue repair, surgical sutures, and the carrier for targeting drugs and controlled release drugs.

摘要翻译： 用于合成医用级生物降解材料的方法，聚（乳酸 - 共 - 乙醇酸），由生物体肌酐催化的乳酸和乙醇酸的共缩聚。 本发明使用商业化肌酐（一种生物材料有机胍化合物 - 人体中的精氨酸代谢物肌酸酐（CR））作为催化剂和工业乳酸（LA，质量含量85％，水溶液）和乙醇酸（GA， 95％）作为单体，以两步缩聚无溶剂的方式合成医用聚（乳酸 - 共 - 乙醇酸）的高生物安全性。 本发明的方法具有以下特征：使用绿色技术，所需原料成本低，操作简单方便，工业化容易; 本发明使用的催化剂，肌酸酐具有高生物相容性和生物安全性，无细胞毒性; 合成的聚（乳酸 - 共 - 乙醇酸）不含任何金属和其他有毒残留物; 此外，所有合成产物的分子量分布窄，分子量可控于1.8-17.7×104; 合成的聚（乳酸 - 共 - 乙醇酸）适用于硬组织修复，手术缝合线和用于靶向药物和控释药物的载体的植入材料。

公开(公告)号：US09138737B2

公开(公告)日：2015-09-22

申请号：US13818773

申请日：2011-05-03

申请人： Bingcai Pan ,  Zhenmao Jiang ,  Weiming Zhang ,  Lu Lv ,  Yingmei Xie ,  Quanxing Zhang

发明人： Bingcai Pan ,  Zhenmao Jiang ,  Weiming Zhang ,  Lu Lv ,  Yingmei Xie ,  Quanxing Zhang

IPC分类号： B01J37/30 ,  B01J35/00 ,  B01J37/16 ,  C23C18/12 ,  C23C18/16 ,  B01J31/08 ,  B01J45/00 ,  B01J41/14 ,  B01J47/00

CPC分类号： B01J37/30 ,  B01J31/08 ,  B01J35/004 ,  B01J37/16 ,  B01J41/14 ,  B01J45/00 ,  B01J47/016 ,  C23C18/1216 ,  C23C18/1233 ,  C23C18/1287 ,  C23C18/1644 ,  C23C18/1658 ,  C23C18/1666

摘要： A method for regulating the distribution of metallic nanoparticles within the resin support is provided. This method uses the ion exchange or absorption resin bearing basic functional groups as the support; firstly introducing the metal in the form of anionic complexes onto the resin support through the ion exchange process, then realizing the purpose of regulating the distribution of the metal and its compound within the resin support by means of changing the concentration of the reductive or deposition agent in water solution and the reaction time. The regulated distribution of metallic nanoparticles within the resin support is in the form of rings with different depths and densities. The different distribution patterns result in improvements upon properties of the inorganic-organic composite material, such as reaction activity, reaction selectivity and metallic stability, and has significant referential value for preparation and structural regulation of other inorganic-organic composite materials of the same kind.

摘要翻译： 提供了一种用于调节树脂载体内金属纳米粒子分布的方法。 该方法采用离子交换或吸附树脂作为载体的基础官能团; 首先通过离子交换法将阴离子配合物形式的金属引入到树脂载体上，然后通过改变还原或沉积剂的浓度来实现调节金属及其化合物在树脂载体内的分布的目的 在水溶液中和反应时间。 金属纳米粒子在树脂载体内的调节分布呈不同深度和密度的环形。 不同的分布模式导致无机 - 有机复合材料的性能的改善，如反应活性，反应选择性和金属稳定性，并且具有相同类型的其他无机 - 有机复合材料的制备和结构调节的重要参考价值。

公开(公告)号：US20110155669A1

公开(公告)日：2011-06-30

申请号：US13061521

申请日：2009-08-10

申请人： Bingcai Pan ,  Bingjun Pan ,  Qingjian Zhang ,  Hui Qiu ,  Weiming Zhang ,  Qing Su ,  Xinqing Chen ,  Quanxing Zhang

发明人： Bingcai Pan ,  Bingjun Pan ,  Qingjian Zhang ,  Hui Qiu ,  Weiming Zhang ,  Qing Su ,  Xinqing Chen ,  Quanxing Zhang

IPC分类号： C02F1/42 ,  C02F1/66

CPC分类号： C02F1/288 ,  C02F2101/105 ,  C02F2303/16

摘要： The invention discloses a novel method for trace phosphate removal from water by using a composite resin. Firstly, adjusting the pH value of the raw water to 5.0˜9.0 and prefiltering the water, then leading the filtrate through an absorption tower packed with the composite resin, the trace phosphate in the water is therefore absorbed onto the composite resin; stopping the absorption run when it reaches the leakage point, using a binary NaOH-NaCl solution as the regenerant of the exhausted sorbent, followed by rinsing the composite resin-filled absorption tower with saturated carbon dioxide solution to regenerate the resin. In this invention, a composite resin with nanosized hydrated ferric oxide (HFO) or hydrous manganese dioxide (HMO) particles loaded on its surface is adopted as the absorbent for enhanced phosphate removal from water. A significant decrease of phosphate content in the effluent from this treatment system is found from 0.05-20 ppm to less than 20 ppb (calculated in P), despite of the coexisting competing anions as sulfate, chloride, and hydrocarbonate at much higher molar concentrations than phosphate. This invention is characteristic of large treatment capacity and efficient regeneration for repeated use of the absorbent.

摘要翻译： 本发明公开了一种利用复合树脂从水中去除痕量磷酸的新方法。 首先，将原水的pH值调整至5.0〜9.0，并对水进行预过滤，然后使滤液通过填充复合树脂的吸收塔，水中的微量磷酸盐被吸收到复合树脂上; 使用二元NaOH-NaCl溶液作为排出的吸附剂的再生剂停止吸收运行，然后用饱和二氧化碳溶液冲洗复合树脂填充的吸收塔以再生树脂。 在本发明中，采用纳米级水合氧化铁（HFO）或含水二氧化锰（HMO）颗粒装载在其表面上的复合树脂作为增强磷酸盐从水中除去的吸收剂。 发现来自该处理系统的流出物中的磷酸盐含量显着降低，从0.05-20ppm至小于20ppb（以P计算），尽管以高于摩尔浓度的硫酸盐，氯化物和碳酸氢盐共存阴离子， 磷酸盐。 本发明的特征在于反复使用吸收剂的大的处理能力和有效的再生。

公开(公告)号：US20130310243A1

公开(公告)日：2013-11-21

申请号：US13818773

申请日：2011-05-03

申请人： Bingcai Pan ,  Zhenmao Jiang ,  Weiming Zhang ,  Lu Lv ,  Yingmei Xie ,  Quanxing Zhang

发明人： Bingcai Pan ,  Zhenmao Jiang ,  Weiming Zhang ,  Lu Lv ,  Yingmei Xie ,  Quanxing Zhang

IPC分类号： B01J37/30 ,  B01J31/08

CPC分类号： B01J37/30 ,  B01J31/08 ,  B01J35/004 ,  B01J37/16 ,  B01J41/14 ,  B01J45/00 ,  B01J47/016 ,  C23C18/1216 ,  C23C18/1233 ,  C23C18/1287 ,  C23C18/1644 ,  C23C18/1658 ,  C23C18/1666

摘要： A method for regulating the distribution of metallic nanoparticles within the resin support is provided. This method uses the ion exchange or absorption resin bearing basic functional groups as the support; firstly introducing the metal in the form of anionic complexes onto the resin support through the ion exchange process, then realizing the purpose of regulating the distribution of the metal and its compound within the resin support by means of changing the concentration of the reductive or deposition agent in water solution and the reaction time. The regulated distribution of metallic nanoparticles within the resin support is in the form of rings with different depths and densities. The different distribution patterns result in improvements upon properties of the inorganic-organic composite material, such as reaction activity, reaction selectivity and metallic stability, and has significant referential value for preparation and structural regulation of other inorganic-organic composite materials of the same kind.

摘要翻译： 提供了一种用于调节树脂载体内金属纳米粒子分布的方法。 该方法采用离子交换或吸附树脂作为载体的基础官能团; 首先通过离子交换法将阴离子配合物形式的金属引入到树脂载体上，然后通过改变还原或沉积剂的浓度来实现调节金属及其化合物在树脂载体内的分布的目的 在水溶液中和反应时间。 金属纳米粒子在树脂载体内的调节分布呈不同深度和密度的环形。 不同的分布模式导致无机 - 有机复合材料的性能的改善，如反应活性，反应选择性和金属稳定性，并且具有相同类型的其他无机 - 有机复合材料的制备和结构调节的重要参考价值。

公开(公告)号：US09387458B2

公开(公告)日：2016-07-12

申请号：US13818834

申请日：2011-11-04

申请人： Bingcai Pan ,  Jing Wang ,  Shujuan Zhang ,  Lu Lv ,  Weiming Zhang

发明人： Bingcai Pan ,  Jing Wang ,  Shujuan Zhang ,  Lu Lv ,  Weiming Zhang

IPC分类号： B01J20/32 ,  C02F1/28 ,  B01J20/06 ,  B01J20/26 ,  C02F101/10 ,  C02F101/20

CPC分类号： B01J20/3295 ,  B01J20/06 ,  B01J20/267 ,  B01J20/321 ,  B01J20/3236 ,  C02F1/288 ,  C02F2101/103 ,  C02F2101/20 ,  C02F2305/08

摘要： A method for regulating the structure and properties of the composite nanoabsorbent is provided. This method uses nanoporous chloromethylated polystyrene-divinylbenzene beads as the support material and adopts in situ precipitation method to load dissociative functional nanoparticles thereon; the composite nanoabsorbent of different absorption capacity and absorption speed can be prepared through regulating the pore structure, which is realized herein by means of starting crosslinking reactions through heating chloromethylated beads under existence of the swelling agent and the catalyst; through changing the proportions of different components in the reaction system, modes of heating and time of reaction, the polymer support with different pore structures can be prepared. This invention can successfully regulate the distribution and size of inorganic nanoparticles; the composite nanomaterials prepared by the resin of different degrees of crosslinking present different structures and properties, and the specific structure and properties can be selected in order to meet practical requirements.

摘要翻译： 提供了一种用于调节复合纳米吸收剂的结构和性能的方法。 该方法采用纳米多氯甲基化聚苯乙烯 - 二乙烯基苯珠作支撑材料，采用原位沉淀法在其上负载解离功能纳米粒子; 可以通过调节孔结构来制备不同吸收容量和吸收速度的复合纳米吸收剂，这通过在溶胀剂和催化剂存在下加热氯甲基化珠来开始交联反应而实现; 通过改变反应体系中不同组分的比例，加热方式和反应时间，可制备不同孔结构的聚合物载体。 本发明可以成功调节无机纳米颗粒的分布和尺寸; 由不同交联度的树脂制备的复合纳米材料具有不同的结构和性能，可以选择具体的结构和性能，以满足实际需要。