公开(公告)号：US07173098B2

公开(公告)日：2007-02-06

申请号：US10495225

申请日：2002-11-01

申请人： Mitsuo Tsukamoto ,  Kenji Otoi ,  Hideki Nakaya ,  Yoshiyuki Hiraga ,  Tomohisa Noda

发明人： Mitsuo Tsukamoto ,  Kenji Otoi ,  Hideki Nakaya ,  Yoshiyuki Hiraga ,  Tomohisa Noda

IPC分类号： C08F4/28

CPC分类号： C08F14/18 ,  Y02P20/544

摘要： The present invention has for its object to provide a method of producing fluoropolymers with high productivity under comparatively low temperature and low pressure conditions which are conducive to reduced cost of commercial-scale production equipment. The present invention is directed to a method of producing a fluoropolymer which comprises polymerizing a radical polymerizable monomer in a defined reaction-field, said radical polymerizable monomer comprising a fluorine-containing ethylenic monomer and said defined reaction-field being in supercriticality-expression state with a monomer density [ρm]-monomer critical density [ρ0] ratio of [ρm/ρ0] not less than 1.1.

摘要翻译： 本发明的目的是提供一种在相对较低的温度和低压条件下以高生产率生产含氟聚合物的方法，这有利于降低商业规模生产设备的成本。 本发明涉及含氟聚合物的制造方法，该方法包括在规定的反应场中聚合自由基聚合性单体，所述自由基聚合性单体含有含氟乙烯性单体，所述规定的反应场为超临界表达状态， 单体密度[rhom] m - 单体密度[rhom] /单体密度[r / m] >]不小于1.1。

公开(公告)号：US20050043498A1

公开(公告)日：2005-02-24

申请号：US10495225

申请日：2002-11-01

申请人： Mitsuo Tsukamoto ,  Kenji Otoi ,  Hideki Nakaya ,  Yoshiyuki Hiraga ,  Tomohisa Noda

发明人： Mitsuo Tsukamoto ,  Kenji Otoi ,  Hideki Nakaya ,  Yoshiyuki Hiraga ,  Tomohisa Noda

IPC分类号： C08F2/00 ,  C08F14/18 ,  C08F4/28

CPC分类号： C08F14/18 ,  Y02P20/544

摘要： The present invention has for its object to provide a method of producing fluoropolymers with high productivity under comparatively low temperature and low pressure conditions which are conducive to reduced cost of commercial-scale production equipment. The present invention is directed to a method of producing a fluoropolymer which comprises polymerizing a radical polymerizable monomer in a defined reaction-field, said radical polymerizable monomer comprising a fluorine-containing ethylenic monomer and said defined reaction-field being in supercriticality-expression state with a monomer density [ρm]−monomer critical density [ρ0] ratio of [ρm/ρ0] not less than 1.1.

摘要翻译： 本发明的目的是提供一种在相对较低的温度和低压条件下以高生产率生产含氟聚合物的方法，这有利于降低商业规模生产设备的成本。 本发明涉及含氟聚合物的制造方法，该方法包括在规定的反应场中聚合自由基聚合性单体，所述自由基聚合性单体含有含氟乙烯性单体，所述规定的反应场为超临界表达状态， [rhom / rho0]的单体密度[rhom] - 单体临界密度[rho0]比不小于1.1。

公开(公告)号：US07151141B2

公开(公告)日：2006-12-19

申请号：US10880537

申请日：2004-07-01

申请人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Masayuki Namimatsu ,  Hiroyuki Imanishi

发明人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Masayuki Namimatsu ,  Hiroyuki Imanishi

IPC分类号： C08F8/42

CPC分类号： C08F8/44 ,  C08F2800/10 ,  C08F2810/40 ,  C08F214/26 ,  C08F8/00

摘要： To a fluorine-containing polymer, 0.1 to 10% of a compound having an alkali metal or an alkaline earth metal in terms of the number of atoms of the alkali metal or the alkaline earth metal based on the total number of the above terminal groups, 0.1 to 10% of ammonia in terms of the number of ammonia molecules based on the total number of the above terminal groups, or 0.1 to 10% of a compound having an ammonium group in terms of the number of the ammonium groups based on the total number of the above terminal groups is added, and heated at a temperature of at least 200° C. in an atmosphere containing moisture. By this process, unstable terminal groups such as terminal carboxylic acid groups and coloration caused by such terminal groups are effectively removed from the fluorine-containing polymer, and furthermore unstable bonds in the backbones can be removed. The obtained fluorine-containing polymer contains 1.0×1013 spins/g or less of unpaired electrons on the carbon atoms in terms of a spin density measured with electron spin resonance at a temperature of 10K.

摘要翻译： 对于含氟聚合物，基于上述末端基团的总数，以碱金属或碱土金属的原子数计，具有碱金属或碱土金属的化合物为0.1〜10％ 基于上述末端基团的氨基分子数为0.1〜10％的氨，或以氨基数为基准的具有铵基的化合物的0.1〜10％ 加入上述末端基团的数量，并在含有水分的气氛中在至少200℃的温度下加热。 通过该方法，可以从含氟聚合物中有效地除去末端羧酸基等不稳定末端基团和由这些末端基团引起的着色，从而可以除去骨架中的不稳定键。 以10K的电子自旋共振测定的自旋密度，所得到的含氟聚合物含有1.0×10 13个/克或更少的不成对电子。

公开(公告)号：US06777501B1

公开(公告)日：2004-08-17

申请号：US09623756

申请日：2000-09-08

申请人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Masayuki Namimatsu ,  Hiroyuki Imanishi

发明人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Masayuki Namimatsu ,  Hiroyuki Imanishi

IPC分类号： C08F800

CPC分类号： C08F8/44 ,  C08F2800/10 ,  C08F2810/40 ,  C08F214/26 ,  C08F8/00

摘要： To a fluorine-containing polymer, 0.1 to 10% of a compound comprising an alkali metal or an alkaline earth metal in terms of the number of atoms of the alkali metal or the alkaline earth metal based on the total number of the above terminal groups, 0.1 to 10% of ammonia in terms of the number of ammonia molecules based on the total number of the above terminal groups, or 0.1 to 10% of a compound having an ammonium group in terms of the number of the ammonium groups based on the total number of the above terminal groups is added, and heated at a temperature of at least 2000C in an atmosphere containing moisture. By this process, unstable terminal groups such as terminal carboxylic acid groups and coloration caused by such terminal groups are effectively removed from the fluorine-containing polymer, and furthermore unstable bonds in the backbones can be removed. The obtained fluorine-containing polymer contains 1.0×1013 spins/g or less of unpaired electrons on the carbon atoms in terms of a spin density measured with spin resonance at a temperature of 10K.

摘要翻译： 对于含氟聚合物，以碱金属或碱土金属的原子数为基准，含有碱金属或碱土类金属的化合物的0.1〜10％以上述末端基的总数计， 基于上述末端基团的氨基分子数为0.1〜10％的氨，或以氨基数为基准的具有铵基的化合物的0.1〜10％ 加入上述末端基团的数量，并在含有水分的气氛中在至少200℃的温度下加热。 通过该方法，可以从含氟聚合物中有效地除去末端羧酸基等不稳定末端基团和由这些末端基团引起的着色，从而可以除去骨架中的不稳定键。 所获得的含氟聚合物在10K的温度下以自旋共振测定的自旋密度，在碳原子上含有1.0×10 13个/ g以下的不成对电子。

公开(公告)号：US06664337B2

公开(公告)日：2003-12-16

申请号：US10061203

申请日：2002-02-04

申请人： Yoshiyuki Hiraga ,  Tomohisa Noda ,  Hiroyuki Imanishi ,  Satoshi Komatsu

发明人： Yoshiyuki Hiraga ,  Tomohisa Noda ,  Hiroyuki Imanishi ,  Satoshi Komatsu

IPC分类号： C08F822

CPC分类号： B29B7/002 ,  B29K2027/12 ,  C08F8/00 ,  C08F2800/20 ,  C08F2810/40 ,  Y02P70/26 ,  C08F214/26

摘要： A melt-processable fluorine-containing polymer is melt kneaded with a kneader which has a residence time of at least 10 minutes, a usable volume ratio (usable space in a container/space in a container) of larger than 0.3, and a power factor K of less than 8000, the power factor K being represented by the formula: K=Pv/&mgr;/n2 in which Pv is a power requirement per unit volume (W/m3), &mgr; is a melt viscosity (Pa.s), and n is a rotation speed (rps), to effectively remove terminal groups and bonds in the backbones, which are unstable during melt kneading, from the melt-processable fluorine-containing polymer, and obtain a colorless fluorine-containing polymer.

摘要翻译： 可熔融加工的含氟聚合物与停留时间为至少10分钟，可用体积比（容器中容器中的可用空间/容器中的空间）大于0.3的捏合机和功率因数 K小于8000，功率因数K由以下公式表示：K = Pv / mu / n <2>其中Pv是每单位体积的功率要求（W / m 3），μ是熔体粘度 （Pa.s），n为转速（rps），从熔融混炼时有效地除去在熔融混炼过程中不稳定的骨架中的端基和键合，得到无色的含氟聚合物， 含聚合物。

公开(公告)号：US06794487B2

公开(公告)日：2004-09-21

申请号：US10417158

申请日：2003-04-17

申请人： Yoshiyuki Hiraga ,  Tomohisa Noda ,  Hiroyuki Imanishi ,  Satoshi Komatsu

发明人： Yoshiyuki Hiraga ,  Tomohisa Noda ,  Hiroyuki Imanishi ,  Satoshi Komatsu

IPC分类号： C08F626

CPC分类号： B29B7/002 ,  B29K2027/12 ,  C08F8/00 ,  C08F2800/20 ,  C08F2810/40 ,  Y02P70/26 ,  C08F214/26

摘要： A melt-processable fluorine-containing polymer is melt kneaded with a kneader which has a residence time of at least 10 minutes, a usable volume ratio (usable space in a container/space in a container) of larger than 0.3, and a power factor K of less than 8000, the power factor K being represented by the formula: K=Pv/&mgr;/n2 in which Pv is a power requirement per unit volume (W/m3), &mgr; is a melt viscosity (Pa.s), and n is a rotation speed (rps), to effectively remove terminal groups and bonds in the backbones, which are unstable during melt kneading, from the melt-processable fluorine-containing polymer, and obtain a colorless fluorine-containing polymer.

摘要翻译： 可熔融加工的含氟聚合物与停留时间为至少10分钟，可用体积比（容器中容器中的可用空间/容器中的空间）大于0.3的捏合机和功率因数 K小于8000，功率因数K由以下公式表示：K = Pv / mu / n <2>其中Pv是每单位体积的功率要求（W / m 3），μ是熔体粘度 （Pa.s），n为转速（rps），从熔融混炼时有效地除去在熔融混炼过程中不稳定的骨架中的端基和键合，得到无色的含氟聚合物， 含聚合物。

公开(公告)号：US06451962B1

公开(公告)日：2002-09-17

申请号：US09830969

申请日：2001-05-03

申请人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Yasuhiro Utsumi

发明人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Yasuhiro Utsumi

IPC分类号： C08F600

CPC分类号： C08J3/00 ,  C08F8/00 ,  C08F2800/10 ,  C08J2327/12 ,  C08F214/26

摘要： To provide the stabilization method, in which unstable groups of melt-processable fluorine-containing polymer having unstable groups can be stabilized rapidly and effectively, and even if the obtained stabilized polymer is melt-molded, an obtained molded article is free from bubbles and cavity and no coloration arises. The method of stabilizing a fluorine-containing polymer by melt-kneading a melt-processable fluorine-containing polymer having unstable groups in a kneader having a stabilization treatment zone which satisfies the following conditions: (1) an oxygen-containing gas is present in the stabilization treatment zone, (2) water is present in the stabilization treatment zone, and (3) an absolute pressure in the stabilization treatment zone is adjusted to a pressure of 0.2 MPa or more or (a) an oxygen-containing gas is present in the stabilization treatment zone in a sufficient amount that the fluorine-containing polymer after the stabilization treatment has the number of carbon radical spins measured by an electron spin resonance absorption analysis at a temperature of 77 K of not more than 5×1013 spin/g, and (b) water is present in the stabilization treatment zone.

摘要翻译： 为了提供稳定化方法，其中不稳定基团的可熔融加工的含氟聚合物的不稳定基团可以快速有效地稳定，并且即使所获得的稳定的聚合物被熔融模塑，所得到的模塑制品没有气泡和空腔 没有着色。 通过在具有稳定化处理区域的捏合机中熔融捏合具有不稳定基团的可熔融加工的含氟聚合物来稳定含氟聚合物的方法，所述捏合机满足以下条件：（1）含氧气体存在于 稳定化处理区域，（2）稳定化处理区域中存在水，（3）将稳定化处理区域的绝对压力调整为0.2MPa以上的压力或（a）含氧气体存在于 稳定化处理区域的稳定化处理区域，其中稳定化处理后的含氟聚合物在77K温度下通过电子自旋共振吸收分析测得的碳自由基数不大于5×1013 spin / g，（ b）稳定化处理区域中存在水。

公开(公告)号：US06268469B1

公开(公告)日：2001-07-31

申请号：US09292855

申请日：1999-04-16

申请人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Hiroyuki Imanishi

发明人： Yoshiyuki Hiraga ,  Satoshi Komatsu ,  Tomohisa Noda ,  Hiroyuki Imanishi

IPC分类号： C08F622

CPC分类号： C08F6/008 ,  C08F6/22 ,  C08L27/12

摘要： Coagulated particles having a low water content are separated and recovered from an emulsified dispersion of fluorine-containing polymer particles. A solid-liquid separation method comprising: a step for adding a coagulant in an emulsified dispersion of fluorine-containing polymer particles to coagulate the fluorine-containing polymer particles with stirring and obtain a slurry of coagulated particles, a step for filtrating the slurry, and a step for pressing the obtained cake. It is preferable to continuously carry out the filtration step and pressing step with a filter press or a belt press. Also a washing step may be provided after the filtration step.

摘要翻译： 从含氟聚合物颗粒的乳化分散体中分离并回收具有低含水量的凝聚颗粒。 一种固液分离方法，其特征在于，包括：在含氟聚合物粒子的乳化分散液中添加凝结剂的工序，在搅拌下使含氟聚合物粒子凝结，得到凝固粒子的浆料，过滤浆料的工序， 按压所得到的饼的步骤。 优选通过压滤机或带式压榨机连续地进行过滤步骤和压制步骤。 也可以在过滤步骤之后提供洗涤步骤。

公开(公告)号：US06388033B2

公开(公告)日：2002-05-14

申请号：US09794104

申请日：2001-02-28

申请人： Tomohisa Noda ,  Satoshi Komatsu

发明人： Tomohisa Noda ,  Satoshi Komatsu

IPC分类号： C08F222

CPC分类号： C08F214/28 ,  C08F14/26 ,  C08F2/38

摘要： A process for preparing a fluoropolymer by the batchwise polymerization of a monomer mixture containing tetrafluoroethylene, in which, after the initiation of a reaction, the monomers are reacted under conditions such that the monomer mixture is supplemented to a polymerization system in an amount more than the amount of the monomers consumed and simultaneously the excessive unreacted monomers are discharged from the polymerization system to maintain the monomer composition in the polymerization system substantially the same as that of the composition of the monomer mixture initially charged, and the monomer mixture supplemented to the polymerization system contains a compound suppressing the autoexplosion of the monomers.

摘要翻译： 通过间歇聚合含有四氟乙烯的单体混合物制备含氟聚合物的方法，其中在反应开始之后，单体在使单体混合物补充到聚合体系上的条件下反应，其量大于 消耗的单体的量和同时过量的未反应单体从聚合体系中排出，以保持聚合体系中的单体组成基本上与最初加入的单体混合物的组成基本相同，并且补充到聚合体系中的单体混合物 含有抑制单体自身爆炸的化合物。

公开(公告)号：US5399643A

公开(公告)日：1995-03-21

申请号：US211022

申请日：1994-03-17

申请人： Tomohisa Noda ,  Hiroyuki Honda ,  Chuzo Okuno

发明人： Tomohisa Noda ,  Hiroyuki Honda ,  Chuzo Okuno

IPC分类号： C08F2/44 ,  C08F2/16 ,  C08F4/28 ,  C08F4/34 ,  C08F214/18 ,  C08F214/26 ,  C08F4/32

CPC分类号： C08F214/26 ,  C08F214/18

摘要： A method for preparing a tetrafluoroethylene/hexafluoropropylene copolymer by polymerizing tetrafluoroethylene and hexafluoropropylene in an aqueous medium using a di(fluoroacyl) peroxide as a polymerization initiator characterized in that a fluoroalkylcarboxylic acid is added gives a stable molecular weight of the tetrafluoroethylene/hexafluoropropylene copolymer and an increased utilization efficiency of the polymerization initiator.