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    • 1. 发明授权
    • Manufacture of medical implants
    • 医疗植入物的制造
    • US09345806B2
    • 2016-05-24
    • US12303348
    • 2007-06-07
    • Claudio TonelliPiero GavezottiRitalba Lamendola
    • Claudio TonelliPiero GavezottiRitalba Lamendola
    • A61L27/14A61L28/00A61L29/04A61L31/04
    • A61L27/14A61L28/0026A61L29/049A61L31/04
    • The invention pertains to a process for the manufacture cola medical implant, said process comprising: reacting a mixture of non functional, monofunctional, and bifunctional perfluoropolyethers comprising hydroxyl terminal groups, wherein the average functionality is of at least 1.97 [mixture (M)] with suitable reactants for producing a thermoplastic elastomer; moulding the so-obtained thermoplastic elastomer for yielding at least a part of the medical implant. It has been surprisingly found that by using a mixture of perfluoropolyethers having high functionality, it is advantageously possible to manufacture, by moulding thermoplastic elastomers therefrom, medical implants which exhibit improved biocompatibility and which are submitted to reduced chemicals extraction by biological fluids.
    • 本发明涉及制造可乐医用植入物的方法,所述方法包括:使包含羟基端基的非官能,单官能和双功能全氟聚醚的混合物反应,其中平均官能度为至少1.97 [混合物(M)]与 用于生产热塑性弹性体的合适的反应物; 模制如此获得的热塑性弹性体以产生医用植入物的至少一部分。 已经令人惊奇地发现,通过使用具有高官能度的全氟聚醚的混合物,有利地可以通过从其中模制热塑性弹性体来制造具有改善的生物相容性并且被降低的生物流体的化学品提取的医用植入物。
    • 2. 发明授权
    • Process for the purification of polyol PFPE derivative
    • 多元醇PFPE衍生物的纯化方法
    • US08304515B2
    • 2012-11-06
    • US12921844
    • 2009-03-13
    • Claudio TonelliGraziano Giuseppe VezzulliRosaldo PicozziPiero Gavezotti
    • Claudio TonelliGraziano Giuseppe VezzulliRosaldo PicozziPiero Gavezotti
    • C08F6/00
    • C08G65/30C08G65/007C08G65/22C08G65/24
    • A process for the purification of a tetraol PFPE derivative [tetraol (T)] of formula (I): HO—CH2—CH(OH)—CH2—O—CH2—CF2—O—Rf—CF2—CH2O—CH2—CH(OH)—CH2OH, wherein Rf represents a fluoropolyoxyalkene chain (chain Rf), from a mixture (M) of hydroxyl (per)fluoropolyether derivatives, said mixture comprising said tetraol (T) and at least one hydroxyl (per)fluoropolyether [PFPE (OH)] comprising a chain Rf terminated with at least one end group of formula: —CF2CH2OH; —CF2CH2O—CH(OH)—CH2—O—CH2—CH(OH)—CH2OH; said process comprising: step 1: reacting the mixture (M) with ketones and/or aldehydes so as to selectively protect couples of hydroxyl groups on vicinal carbon atoms by forming corresponding cyclic ketal/acetal derivatives, so as to yield a protected mixture (P); step 2: reacting residual hydroxyl groups of the mixture (P) with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture (Pf); step 3: fractional distillation of the mixture (Pf) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); and step 4: hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T).
    • 一种用于纯化式(I)的四醇PFPE衍生物[四醇(T))的方法:HO-CH 2 -CH(OH)-CH 2 -O-CH 2 -CF 2 -O-Rf-CF 2 -CH 2 O-CH 2 -CH (OH)-CH 2 OH,其中Rf表示氟代聚氧亚烷基链(链Rf),由羟基(全)含氟聚醚衍生物的混合物(M),所述混合物包含所述四醇(T)和至少一种羟基(全)氟聚醚[PFPE (OH)],其包含用至少一个具有下列结构的端基终止的链Rf:-CF 2 CH 2 OH; -CF 2 CH 2 O-CH(OH)-CH 2 -O-CH 2 -CH(OH)-CH 2 OH; 所述方法包括:步骤1:使混合物(M)与酮和/或醛反应,以便通过形成相应的环缩酮/缩醛衍生物来选择性保护连位碳原子上的羟基,从而产生受保护的混合物(P ); 步骤2:使混合物(P)的残余羟基与合适的官能化试剂反应,从而获得功能化的保护的混合物(Pf); 步骤3:分馏混合物(Pf),以分离四醇(T)的环状缩醛/缩酮衍生物; 和步骤4:水解四醇(T)的缩醛/缩酮衍生物以回收纯四醇(T)。
    • 3. 发明申请
    • Process for the purification of polyol PFPE derivative
    • 多元醇PFPE衍生物的纯化方法
    • US20110003968A1
    • 2011-01-06
    • US12921844
    • 2009-03-13
    • Claudio TonelliGraziano Giuseppe VezzulliRosaldo PicozziPiero Gavezotti
    • Claudio TonelliGraziano Giuseppe VezzulliRosaldo PicozziPiero Gavezotti
    • C08F6/28
    • C08G65/30C08G65/007C08G65/22C08G65/24
    • A process for the purification of a tetraol PFPE derivative [tetraol (T)] of formula (I): HO—CH2—CH(OH)—CH2—O—CH2—CF2—O—Rf—CF2—CH2O—CH2—CH(OH)—CH2OH, wherein Rf represents a fluoropolyoxyalkene chain (chain Rf), from a mixture (M) of hydroxyl (per)fluoropolyether derivatives, said mixture comprising said tetraol (T) and at least one hydroxyl (per)fluoropolyether [PFPE (OH)] comprising a chain Rf terminated with at least one end group of formula: —CF2CH2OH; —CF2CH2O—CH(OH)—CH2—O—CH2—CH(OH)—CH2OH; said process comprising: step 1: reacting the mixture (M) with ketones and/or aldehydes so as to selectively protect couples of hydroxyl groups on vicinal carbon atoms by forming corresponding cyclic ketal/acetal derivatives, so as to yield a protected mixture (P); step 2: reacting residual hydroxyl groups of the mixture (P) with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture (Pf); step 3: fractional distillation of the mixture (Pf) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); and step 4: hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T).
    • 一种用于纯化式(I)的四醇PFPE衍生物[四醇(T))的方法:HO-CH 2 -CH(OH)-CH 2 -O-CH 2 -CF 2 -O-Rf-CF 2 -CH 2 O-CH 2 -CH (OH)-CH 2 OH,其中Rf表示氟代聚氧亚烷基链(链Rf),由羟基(全)氟代聚醚衍生物的混合物(M),所述混合物包含所述四醇(T)和至少一种羟基(全)氟聚醚[PFPE (OH)],其包含用至少一个具有下列结构的端基终止的链Rf:-CF 2 CH 2 OH; -CF 2 CH 2 O-CH(OH)-CH 2 -O-CH 2 -CH(OH)-CH 2 OH; 所述方法包括:步骤1:使混合物(M)与酮和/或醛反应,以便通过形成相应的环缩酮/缩醛衍生物来选择性保护连位碳原子上的羟基,从而产生受保护的混合物(P ); 步骤2:使混合物(P)的残余羟基与合适的官能化试剂反应,从而获得功能化的保护的混合物(Pf); 步骤3:分馏混合物(Pf),以分离四醇(T)的环状缩醛/缩酮衍生物; 和步骤4:水解四醇(T)的缩醛/缩酮衍生物以回收纯四醇(T)。
    • 8. 发明授权
    • Process for the preparation of perfluoropolyoxyalkylenes with hydroxyl end groups
    • 用羟基端基制备全氟聚氧化烯的方法
    • US06509509B2
    • 2003-01-21
    • US09750101
    • 2000-12-29
    • Claudio TonelliAntonio RussoEzio Strepparola
    • Claudio TonelliAntonio RussoEzio Strepparola
    • C07C4311
    • C08G65/324C08G65/007
    • A process for preparing perfluoropolyoxyalkylenes with hydroxyl end groups having structure: T1—CFW1—O—Rf—CFW2—T2  (I) wherein: T1, T2, are selected from —CH2OH, —F, —CF3, —CF2CF3 with the proviso that at least one of T1 and T2 is —CH2OH; W1 and W2 are selected from F, CF3; Rf is a perfluoropolyoxyalkylene chain having a number average molecular weight 500-10,000 comprising one or more units of the type —CF2CF2O—, —CF2O—, —C3F6O—, —CF2(CF2)zCF2O— (z=1,2); —CR4R5CF2CF2O— with R4 and R5 selected from H, Cl, perfluoroalkyl group; said process comprising the following steps: a) adding an ester precursor having structure (I) and T1, T2 end groups selected from —F, —CF3, —CF2CF3, —COOR (R=linear or branched alkyl group having a number of C atoms from 1 to 5), with the proviso that at least one of T1 and T2 is —COOR, in a reaction mixture formed by: an inert or protic reaction solvent; a reducing agent selected from metal hydrides; an unreactive organic base with respect to the ester; b) hydrolysis of the product obtained in step a) for obtaining the compounds of structure (I) with at least a —CH2OH end group.
    • 制备具有以下结构的羟基端基的全氟聚氧化烯的方法:其中:T1,T2选自-CH2OH,-F,-CF3,-CF2CF3,条件是T1和T2中的至少一个为-CH2OH; W1和W2 选自F,CF 3; Rf是数均分子量为500-10,000的全氟聚氧亚烷基链,其包含一种或多种-CF 2 CF 2 O-,-CF 2 O-,-C 3 F 6 O-,-CF 2(CF 2)z CF 2 O-(z = 1,2); -CR4R5CF2CF2O-,其中R4和R5选自H,Cl,全氟烷基; 所述方法包括以下步骤:a)加入具有结构(I)和T1的酯前体,T2端基选自-F,-CF 3,-CF 2 CF 3,-COOR(R =直链或支链烷基,其数目为C 原子从1至5),条件是至少一个T1和T2是-COOR,在由惰性或质子反应溶剂形成的反应混合物中;还原剂选自金属氢化物;非反应性有机碱,相对于 酯化; b)在步骤a)中获得的产物的水解,得到至少具有-CH 2 OH端基的结构(I)化合物。
    • 9. 发明授权
    • Coatings based on fluoropolyethers
    • 基于含氟聚醚的涂料
    • US5959058A
    • 1999-09-28
    • US613518
    • 1996-03-11
    • Claudio TonelliMassimo ScicchitanoStefano Turri
    • Claudio TonelliMassimo ScicchitanoStefano Turri
    • C08G18/50C08G18/71C08G18/80C08G59/30C08G65/00C09D171/00C09D171/02C07C43/12
    • C08G65/007C08G18/5015C08G18/71C08G18/718C08G18/8025C08G59/30C09D171/02
    • Use of fluorinated polymers based on fluoropolyethers for the preparation of crosslinkable high dry formulations comprising a fluorinated part R.sub.F and optionally an hydrogenated part R.sub.H, not containing groups capable of linking by means of hydrogen bonds to basic acceptors, an hydrogenated part Rh.sub.1 and Rh.sub.2, wherein Rh.sub.1 is equal to or different from Rh.sub.2, and Rh.sub.1 and/or Rh.sub.2 being linking bonds containing at least a functional group capable of linking by means of hydrogen bonds with basic acceptors, the bonds joining the fluorinated part to the hydrogenated part being of ether C--O simple type, the terminals T'.sub.a and T" being such as to render the structure mono-, bi- or polyfunctional, and subsequent crosslinking of the fluorinated polymer, the monofunctional products being always in admixture with a resin having even a higher functionality than the described type; the preferred fluorinated products have the formula:T"--(Rh.sub.2).sub.y (R.sub.H).sub.x --R.sub.F --(R.sub.H).sub.x --(Rh.sub.1).sub.y' T'.sub.a
    • 使用基于氟聚醚的氟化聚合物制备可交联的高干制剂,其包含氟化部分RF和任选的氢化部分RH,不含能够通过氢键与碱性受体连接的基团,氢化部分Rh1和Rh2,其中 Rh1等于或不同于Rh2,并且Rh1和/或Rh2是至少含有能够通过氢键与碱性受体连接的官能团的连接键,将氟化部分连接到氢化部分上的键为醚CO 简单型,终端T'a和T“使得结构单,双或多官能并随后交联氟化聚合物,单官能产品总是与甚至具有更高官能度的树脂混合 比所描述的类型; 优选的氟化产物具有下式:T“ - (Rh 2)y(RH)x-RF-(RH)x-(Rh1)y'T'a
    • 10. 发明授权
    • Process for preparing perfluoropolyethers
    • 制备全氟聚醚的方法
    • US5910614A
    • 1999-06-08
    • US903060
    • 1997-07-30
    • Stefano TurriClaudio TonelliCarlo Pogliani
    • Stefano TurriClaudio TonelliCarlo Pogliani
    • C08G65/32C08G65/00C08G65/30C07C43/11B01D16/08
    • C08G65/30C08G65/007
    • Separation process of bifunctional macromolecules having hydroxylic termination from non functional and/or monofunctional macromolecules having hydroxylic termination contained in admixture in perfluoropolyoxyalkylenes (I) comprising the following phases:addition of the macromer (I) to a suspension of stationary phase in polar solvent, said stationary phase being formed by a compound containing sites and/or active groups, capable of establishing bonds or interactions of polar type, or hydrogen bonds, with the hydroxylic terminals of the perfluoropolyoxyalkylenes contained in the mixture of formula (I), the macromer/stationary phase ratio ranging from 2/3 to 1/1 w/w; solvent/(stationary phase+macromer) ratio ranging from 0.8/1 to 1.5/1 v/w; evaporation of the solvent, until obtainment of an incoherent and dry powder;first extraction with low polarity fluorinated solvent and separation of the phases by filtering;second extraction of the stationary phase with polar hydrogenated solvent, and separation of the phases by filtering;the macromer fraction having high bifunctionality degree being obtained by concentration of the liquid phase after second extraction, i.e. after removal of the solvent.
    • 具有羟基终止的具有羟基终止的羟基终止的双官能大分子的分离过程包含在包含以下相的全氟聚氧化烯(I)中的混合物中:将大分子单体(I)加入极性溶剂中的固定相的悬浮液,所述 固定相由含有位点和/或活性基团的化合物形成,其能够与式(I)的混合物中所含的全氟聚氧化烯的羟基末端,大分子单体/固定体形成极性型或氢键的键或相互作用 相位比范围为2/3至1/1 w / w; 溶剂/(固定相+大分子单体)比率范围为0.8 / 1至1.5 / 1v / w; 蒸发溶剂,直到得到非相干和干粉; 首先用低极性氟化溶剂萃取并通过过滤分离相; 用极性氢化溶剂二次萃取固定相,通过过滤分离相; 通过第二次萃取后的液相浓缩,即除去溶剂后,获得具有高双官能度的大分子单体馏分。