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    • 6. 发明申请
    • HERSTELLUNG VON POLYMEREN DURCH KONTROLLIERTE RADIKALISCHE POLYMERISATION
    • 聚合物通过受控的自由基聚合生产
    • WO2013030261A1
    • 2013-03-07
    • PCT/EP2012/066838
    • 2012-08-30
    • BASF SEHESSE, PascalFLEISChmann, SvenBECKER, FlorianMÜHLBACH, KlausHUNGENBERG, Klaus-DieterBRYM, MarkusKLEINER, Matthias
    • HESSE, PascalFLEISChmann, SvenBECKER, FlorianMÜHLBACH, KlausHUNGENBERG, Klaus-DieterBRYM, MarkusKLEINER, Matthias
    • C08F4/10C08F4/40C08F293/00C08F297/00
    • C08F2/01C08F2/38C08F4/40C08F220/14C08F293/005C08F2220/1825C08F2438/01C08F2438/02
    • Verfahren zur Herstellung von Polymeren durch kontrollierte radikalische Polymerisation, wobei die Polymerisation eines oder mehrerer radikalisch polymerisierbarer Momomere der allgemeinen Formel (I) mit R 1 , R 2 , R 3 H, C 1 -C 4 -Alkyl, R 4 C(=0)OR 5 , C(=0)NHR 15 , C(=0)NR 5 R 6 , OC(=0)CH 3 , C(=0)OH, CN, Aryl, Hetaryl, C(=0)OR 5 OH, C(=0)OR 5 Si(OR 5 ) 3 , Halogen, NHC(0)H, P(=0)(OR 7 ) 2 , R 5 C 1 -C 20 -Alkyl, R 15 C 1 -C 20 -Alkyl, R 6 C 1 -C 20 -Alkyl, R 7 H, C 1 -C 20 -Alkyl, in Gegenwart a. eines oder mehrerer Katalysatoren enthaltend Cu in Form von Cu(0), Cu(l), Cu (II) oder Mischungen aus diesen, b. eines oder mehrerer Initiatoren gewählt aus der Gruppe der organischen Halogenide oder Pseudohalogenide, c. eines oder mehrer Liganden, d. optional eines oder mehrer Lösungsmittel, e. optional eines oder mehrerer anorganischer Halogenidsalze, erfolgt, umfassend die Schritte i) Zugabe des Katalysators a., ii) optional Zugabe von Monomeren der allgemeinen Formel (I), iii) optional Zugabe von Lösungsmittel d., iv) Zugabe von Ligand c, v) Zugabe von Initiator b., vi) Zugabe von Monomeren der allgemeinen Formel (I), vii) optional Zugabe anorganischer Halogenidsalze e., unter der Maßgabe, dass die Zugabe zumindest eines Teiles der Monomeren der allgemeinen Formel (I) unmittelbar vor oder kurz nach dem letzten der Schritte i), iv) und v) erfolgt.
    • 一种通过受控的自由基聚合制备的聚合物,其中一个或多个可自由基聚合的Momomere通式(I)的R1,R2的聚合中,R 3是H,C1-C4烷基过程中,R 4为C(= O)OR 5,C(= 0)NHR15,-C(= O)NR 5 R 6,OC(= O)CH 3,C(= O)OH,CN,芳基,杂芳基,C(= O)OR5OH,C(= O)OR5Si(OR 5)3,卤素 ,NHC(O)H,P(= O)(OR 7)2,R 5的C1-C20烷基,R15 C 1 -C 20烷基,R 6 C 1 -C 20烷基,R 7是H,C1-C20烷基,在一个存在 , 含Cu量在Cu的形式的一种或多种催化剂(0),铜(I),铜(II)或它们的混合物,B。 选自有机卤化物或拟卤化物,C中的一种或多种引发剂。 一个或多个配体,D。 任选的一种或多种溶剂,例如 ,是任选的一种或多种无机卤化物盐,其包含i的添加催化剂,步骤a)一个,ii)任选地加入上述通式(I)的单体,iii)任选地加入溶剂天。,IV)另外配位体C的,V )添加引发剂b的。,ⅵ)除了通式(I)的单体的,VII)任选地添加无机卤化物盐即,其条件是在加入通式(I的单体的至少一部分的前立即或不久) 在最后的步骤i发生时),iv)和v)中。
    • 8. 发明申请
    • REVERSE-PHASE POLYMERISATION PROCESS
    • 反相聚合方法
    • WO2015014826A1
    • 2015-02-05
    • PCT/EP2014/066255
    • 2014-07-29
    • BASF SE
    • HASCHICK, RobertJELICIC, AleksandraBARRATT, John, ScottHESSE, PascalSOETJE, OliverFONSECA ZEPEDA, Gabriela, EugeniaKEELAPANDAL RAMAMOORTHY, Shankara NarayananLANGLOTZ, Björn
    • C08F2/32C08F20/56
    • C08F220/56B01J19/123B01J19/24B01J2219/0869B01J2219/1203B01J2219/24C08F2/32C08F220/06C08F220/20C08F226/10C08F2220/382C08F2220/385C08F220/34
    • A reverse-phase suspension polymerisation process for the manufacture of polymer beads comprising forming aqueous monomer beads comprising an aqueous solution of water-soluble ethylenically unsaturated monomer or monomer blend and polymerising the monomer or monomer blend to form polymer beads while suspended in a non-aqueous liquid, and recovering polymer beads, in which the process comprises, providing in a vessel (1) a volume (2) of non-aqueous liquid wherein the volume of non-aqueous liquid extends between at least one polymer bead discharge point (3) and at least one monomer feed point (4), feeding the aqueous monomer or monomer blend through orifices (5) into, or onto, the non-aqueous liquid to form aqueous monomer beads, allowing the aqueous monomer beads to flow towards the polymer bead discharge point subjecting the aqueous monomer beads to polymerisation conditions to initiate polymerisation to form polymerising beads, wherein the polymerising beads have formed polymer beads when they reach the polymer bead discharge point, removing a suspension of the polymer beads in non-aqueous liquid from the vessel at the polymer bead discharge point and recovering water soluble or water swellable polymer beads from the suspension. The invention also relates to the apparatus suitable for carrying out a reverse-phase suspension polymerisation and polymer beads obtainable by the process or employing the apparatus.
    • 一种用于制备聚合物珠粒的反相悬浮聚合方法,包括形成包含水溶性烯属不饱和单体或单体共混物的水溶液的含水单体珠粒,并将单体或单体共混物聚合以形成聚合物珠粒,同时悬浮在非水性 液体和回收的聚合物珠,其中该方法包括在容器(1)中提供非水性液体的体积(2),其中非水性液体的体积在至少一个聚合物珠粒排出点(3) 和至少一个单体进料点(4),通过孔(5)将含水单体或单体共混物进料到非水性液体中或其上,以形成含水单体珠,使单体水单体流向聚合物珠粒 放电点使含水单体珠粒聚合条件以引发聚合以形成聚合珠粒,其中聚合珠粒已形成聚合物珠粒 当它们到达聚合物珠粒排放点时,在聚合物珠粒排出点处从容器中除去非水液体中的聚合物珠子的悬浮液并从悬浮液中回收水溶性或水可溶胀的聚合物珠粒。 本发明还涉及适用于进行反相悬浮聚合的装置和可通过该方法获得的聚合物珠粒,或采用该装置。
    • 9. 发明申请
    • REVERSE-PHASE POLYMERISATION PROCESS
    • 反相聚合方法
    • WO2015014824A1
    • 2015-02-05
    • PCT/EP2014/066251
    • 2014-07-29
    • BASF SE
    • BARRATT, John, ScottJELICIC, AleksandraHESSE, PascalSOETJE, OliverHASCHICK, RobertFONSECA ZEPEDA, Gabriela, EugeniaKEELAPANDAL RAMAMOORTHY, Shankara, NarayananJECK, SandraKUHN, Jelan
    • C08F2/32B01D29/00C08F20/56C08J11/02
    • C08F265/04B01D29/00B01J19/24B01J2219/24C08F2/32C08F220/06C08F220/20C08F220/56C08F226/10C08F2220/382C08F2220/385C08J3/12C08J11/02C08J2351/00C08F220/34
    • A reverse-phase suspension polymerisation process for the manufacture of polymer beads comprising forming aqueous monomer beads of an aqueous solution comprising water-soluble ethylenically unsaturated monomer or monomer blend and polymerising the monomer or monomer blend to form polymer beads while suspended in a non-aqueous liquid, recovering polymer beads, and then cleaning the non-aqueous liquid in which the process comprises providing the non-aqueous liquid in a vessel (1), forming a suspension of monomer beads from the aqueous monomer or monomer blend in the non-aqueous liquid, initiating polymerisation to form polymerising beads, removing a suspension of the polymer beads in non-aqueous liquid from the vessel and recovering, water soluble or water swellable polymer beads from the suspension, in which the non-aqueous liquid contains impurities which comprise particles, and then transferring the non-aqueous liquid from the suspension to a cleaning stage, in which the cleaning stage provides a cleaned non-aqueous liquid suitable for use in a reverse-phase suspension polymerisation process, which cleaning stage comprises removing particles from the non-aqueous liquid in at least one filtration step. The invention also relates to the apparatus suitable for carrying out a reverse-phase suspension polymerisation and polymer beads obtainable by the process or employing the apparatus. The invention further relates to a cleaned non-aqueous liquid obtainable by the process.
    • 一种用于制造聚合物珠粒的反相悬浮聚合方法,包括形成包含水溶性烯键式不饱和单体或单体共混物的水溶液的含水单体珠粒,并将单体或单体共混物聚合以形成聚合物珠粒,同时悬浮于非水性 液体,回收聚合物珠粒,然后清洗非水液体,其中该方法包括在容器(1)中提供非水性液体,从非水性单体或单体共混物形成单体珠粒悬浮液 液体,引发聚合以形成聚合珠,从容器中除去聚合物小珠在非水液体中的悬浮液,并从悬浮液中回收水溶性或水可溶胀的聚合物珠,其中非水性液体含有包含颗粒的杂质 ,然后将非水性液体从悬浮液转移到清洁阶段,其中清洗步骤 e提供适用于反相悬浮聚合方法的清洁的非水性液体,该清洗阶段包括在至少一个过滤步骤中从非水性液体中除去颗粒。 本发明还涉及适用于进行反相悬浮聚合的装置和可通过该方法获得的聚合物珠粒,或采用该装置。 本发明还涉及通过该方法可获得的清洁的非水性液体。
    • 10. 发明申请
    • REVERSE-PHASE POLYMERISATION PROCESS
    • 反相聚合方法
    • WO2015014825A1
    • 2015-02-05
    • PCT/EP2014/066252
    • 2014-07-29
    • BASF SE
    • HESSE, PascalJELICIC, AleksandraFONSECA ZEPEDA, Gabriela EugeniaHASCHICK, RobertKEELAPANDAL RAMAMOORTHY, Shankara NarayananNAYLOR, Gareth IanBARRATT, John ScottSOETJE, OliverLIEVRE, MarcelRAINAU, FlorianLEBKÜCHER, Mark
    • C08F2/32C08F20/56
    • C08F2/32B01J19/10B01J2219/0888B01J2219/24C08F2/01C08F220/06C08F220/20C08F220/56C08F226/10C08F2220/382C08F2220/385C08F220/34
    • A reverse-phase suspension polymerisation process for the manufacture of polymer beads comprising forming aqueous monomer beads comprising an aqueous solution of water-soluble ethylenically unsaturated monomer or monomer blend and polymerising the monomer or monomer blend, to form polymer beads while suspended in a non-aqueous liquid, and recovering polymer beads, in which the process comprises providing in a vessel (1) a volume (2) of non-aqueous liquid wherein the volume of non-aqueous liquid extends between at least one polymer bead discharge point (3) and at least one monomer feed point (4), feeding the aqueous monomer or monomer blend through orifices (5) into, or onto, the non-aqueous liquid to form aqueous monomer beads, allowing the aqueous monomer beads to flow towards the polymer bead discharge point initiating polymerisation of the aqueous monomer beads to form polymerising beads, wherein the polymerising beads form polymer beads when they reach the polymer bead discharge point, removing a suspension of the polymer beads in non-aqueous liquid from the vessel at the polymer bead discharge point and recovering, water soluble or water swellable polymer beads from the suspension, in which the aqueous monomer or monomer blend and/or the orifices is/are vibrated such that the frequency multiplied by the weight average droplet diameter is between 150 and 800 mm/s. The invention also relates to the apparatus suitable for carrying out a reverse-phase suspension polymerisation and polymer beads obtainable by the process or employing the apparatus. Furthermore, the invention also relates to polymer beads having a weight mean particle size in the range of 0.05 to 5 mm which are held in a container in an amount of at least 300 kg having a standard deviation of particle size less than 20%. In addition, the invention also provides polymer beads having a weight mean particle size in the range 0.05 to 5 mm having a standard deviation of particle size less than 20% and having an amount of residual acrylamide of less than 500 ppm.
    • 一种用于制造聚合物珠粒的反相悬浮聚合方法,包括形成包含水溶性烯键式不饱和单体或单体共混物的水溶液的含水单体珠,并聚合单体或单体共混物,以形成聚合物珠粒, 水性液体和回收的聚合物珠粒,其中该方法包括在容器(1)中提供非水性液体的体积(2),其中非水性液体的体积在至少一个聚合物珠粒排出点(3) 和至少一个单体进料点(4),通过孔(5)将含水单体或单体共混物进料到非水性液体中或其上,以形成含水单体珠,使单体水单体流向聚合物珠粒 引发单体珠水聚合形成聚合珠,其中聚合珠形成聚合物珠,当它们到达聚合物珠粒放电po 在聚合物珠粒排出点处从容器中除去聚合物小珠在非水性液体中的悬浮液,并从悬浮液中回收水溶性或水可溶胀的聚合物珠,其中单体或单体混合物和/或孔 被振动,使得乘以重量平均液滴直径的频率在150和800mm / s之间。 本发明还涉及适用于进行反相悬浮聚合的装置和可通过该方法获得的聚合物珠粒,或采用该装置。 此外,本发明还涉及重量平均粒径在0.05至5mm范围内的聚合物珠,其以至少300kg的量保持在容器中,其具有小于20%的粒度的标准偏差。 此外,本发明还提供了重均粒径在0.05-5mm范围内的聚合物珠,其粒径的标准偏差小于20%,残留丙烯酰胺的量小于500ppm。