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    • 1. 发明申请
    • PROCESS FOR THE PURIFICATION OF POLYOL PFPE DERIVATIVE
    • 多元醇PFPE衍生物的纯化方法
    • WO2009112578A1
    • 2009-09-17
    • PCT/EP2009/052999
    • 2009-03-13
    • SOLVAY SOLEXIS S.p.A.TONELLI, ClaudioVEZZULLI, Graziano, GiuseppePICOZZI, RosaldoGAVEZOTTI, Piero
    • TONELLI, ClaudioVEZZULLI, Graziano, GiuseppePICOZZI, RosaldoGAVEZOTTI, Piero
    • C08G65/30
    • C08G65/30C08G65/007C08G65/22C08G65/24
    • The invention pertains to a process for the purification of a tetraol PFPE derivative [tetraol (T)] of formula (I): HO-CH 2 -CH(OH)-CH 2 -O-CH 2 -CF 2 -O-R f -CF 2 -CH 2 O-CH 2 -CH(OH)-CH 2 OH (I), wherein R f represents a fluoropolyoxyalkene chain (chain R f ), i.e. a fluorocarbon segment comprising ether linkages in main chain, from a mixture of hydroxyl (per)fluoropolyether derivatives [mixture (M)], said mixture comprising said tetraol (T) and at least one hydroxyl (per)fluoropolyether [PFPE (OH)] comprising a chain R f terminated with at least one end group of formula: -CF 2 CH 2 OH) -CF 2 CH 2 O-CH(OH)-CH 2 -O-CH 2 -CH(OH)-CH 2 OH; 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 [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 [mixture (P f )]; step 3: fractional distillation of the mixture (P f ) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); step 4. hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T).
    • 本发明涉及纯化式(I)的四醇PFPE衍生物[四醇(T))的方法:HO-CH2-CH(OH)-CH2-O-CH2-CF2-O-Rf-CF2-CH2O -CH 2 -CH(OH)-CH 2 OH(I),其中R f表示氟代聚氧亚烷基链(链Rf),即包含主链中的醚键的氟烃链段,由羟基(全)氟聚醚衍生物的混合物[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末端基团终止的链Rf:-CF 2 CH 2 OH)-CF 2 CH 2 O-CH(OH) CH2-O-CH2-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[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,使得能够进行实质的挥发性改性,以获得官能化的保护的混合物[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; 步骤4.水解四醇(T)的缩醛/缩酮衍生物,以回收纯四醇(T)。
    • 2. 发明申请
    • PROCESS FOR THE MANUFACTURE OF POLYOL PERFLUOROPOLYETHER DERIVATIVE
    • 聚氟乙烯衍生物的制备方法
    • WO2009043928A1
    • 2009-04-09
    • PCT/EP2008/063278
    • 2008-10-03
    • SOLVAY SOLEXIS S.P.A.TONELLI, ClaudioVEZZULLI, Graziano, GiuseppePICOZZI, RosaldoGAVEZOTTI, PieroDI MEO, Antonella
    • TONELLI, ClaudioVEZZULLI, Graziano, GiuseppePICOZZI, RosaldoGAVEZOTTI, PieroDI MEO, Antonella
    • C08G65/00C08G65/48
    • C07C41/26C07C43/126C08G65/007C08G65/22C08G65/2639C08G65/3312C10M2211/063
    • The invention pertains to a process for the manufacture of a polyol (per)fluoropolyether derivative [polyol PFPE (PFPE-OH)], said process comprising: 1. reacting at least one triol having two protected hydroxyl functions and a free hydroxyl group [protected triol (PT)] with an activating agent, to yield an activated protected triol [activated protected triol (APT)]; 2. reacting said activated protected triol with a functional (per)fluoropolyether derivative of formula (Ia) [functional PFPE (E)], wherein: R f represents a fluoropolyoxyalkene chain (chain R f ), i.e. a fluorocarbon segment comprising ether linkages in main chain; T 1 and T 2 , equal to or different from each other, are independently selected from - non-functional groups of formula: -CF 3 , -CF 2 -CF 3 , -CF 2 CI, -CF 2 CF 2 CI, -CF 2 -COF, -COF : and - functional hydroxyl groups comprising at least one hydroxyl group, with the provisio that at least one of T 1 and T 2 is a functional hydroxyl group as above detailed; to yield a protected polyol (per)fluoropolyether derivative [protected polyol PFPE (p-PFPE-OH)]; 3. deprotecting said protected polyol PFPE (p-PFPE-OH) to yield the polyol PFPE (PFPE-OH).
    • 本发明涉及制备多元醇(全)氟聚醚衍生物[多元醇PFPE(PFPE-OH)]的方法,所述方法包括:使至少一种具有两个保护的羟基官能团和游离羟基的三醇[保护的 三醇(PT)]与活化剂反应,得到活化的保护三醇[活性保护三醇(APT)]; 2.使所述活化的被保护的三醇与式(Ia)的功能性(全)氟聚醚衍生物[功能性PFPE(E)]反应,其中:Rf表示氟聚氧亚烷基链(链Rf),即在主链中包含醚键的氟烃链段 ; T1和T2彼此相同或不同,独立地选自以下的非官能团:-CF 3,-CF 2 -CF 3,-CF 2 Cl,-CF 2 CF 2 Cl,-CF 2 -COF,-COF:和 - 官能羟基 包含至少一个羟基的基团,条件是T1和T2中的至少一个是如上详述的官能羟基; 得到受保护的多元醇(全)氟聚醚衍生物[保护的多元醇PFPE(p-PFPE-OH)]; 3.将保护的多元醇PFPE(p-PFPE-OH)脱保护,得到多元醇PFPE(PFPE-OH)。
    • 6. 发明授权
    • PROCESS FOR THE PURIFICATION OF POLYOL PFPE DERIVATIVE
    • 程序对清洁PFPE多元醇衍生物
    • EP2254931B1
    • 2011-08-31
    • EP09721134.6
    • 2009-03-13
    • Solvay Solexis S.p.A.
    • TONELLI, ClaudioVEZZULLI, Graziano, GiuseppePICOZZI, RosaldoGAVEZOTTI, Piero
    • C08G65/30
    • C08G65/30C08G65/007C08G65/22C08G65/24
    • The invention pertains to a process for the purification of a tetraol PFPE derivative [tetraol (T)] of formula (I): HO-CH
      2 -CH(OH)-CH
      2 -O-CH
      2 -CF
      2 -O-R
      f -CF
      2 -CH
      2 O-CH
      2 -CH(OH)-CH
      2 OH (I), wherein R
      f represents a fluoropolyoxyalkene chain (chain R
      f ), i.e. a fluorocarbon segment comprising ether linkages in main chain, from a mixture of hydroxyl (per)fluoropolyether derivatives [mixture (M)], said mixture comprising said tetraol (T) and at least one hydroxyl (per)fluoropolyether [PFPE (OH)] comprising a chain R
      f terminated with at least one end group of formula: -CF
      2 CH
      2 OH) -CF
      2 CH
      2 O-CH(OH)-CH
      2 -O-CH
      2 -CH(OH)-CH
      2 OH; 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 [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 [mixture (P
      f )]; step 3: fractional distillation of the mixture (P
      f ) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); step 4. hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T).