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公开(公告)号：US4115369A
公开(公告)日：1978-09-19
申请号：US855905
申请日：1977-11-29
摘要： A process for continuously producing an oxymethylene polymer by continuously polymerizing a starting monomer containing at least 50 mole% of trioxane in bulk in the presence of a catalyst, which comprises feeding the starting monomer into a first-stage polymerization reactor having a self-cleaning action to perform a first-stage polymerization reaction until the conversion reaches 40 to 70%, withdrawing the reaction mixture as a powder from the outlet of the first-stage polymerization reactor, feeding the reaction mixture into a second-stage polymerization reactor having a stirring action to perform a second-stage polymerization reaction until the conversion reaches 95 to 100%, and then withdrawing the polymerization product as a powder from the outlet of the second-stage polymerization reactor.
摘要翻译： 在催化剂存在下，通过连续聚合含有至少50摩尔％的三恶烷的起始单体的方法连续生产甲醛聚合物的方法，其包括将起始单体进料到具有自清洁作用的第一阶段聚合反应器中 进行第一阶段聚合反应，直到转化率达到40〜70％，从第一阶段聚合反应器的出口取出粉末状的反应混合物，将反应混合物进料到具有搅拌作用的第二阶段聚合反应器 进行第二阶段聚合反应，直至转化率达到95〜100％，然后从第二阶段聚合反应器的出口取出作为粉末的聚合产物。
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公开(公告)号：US4301273A
公开(公告)日：1981-11-17
申请号：US153674
申请日：1980-05-27
申请人： Akitoshi Sugio , Akira Amemiya , Tadashi Kunii , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umemura
发明人： Akitoshi Sugio , Akira Amemiya , Tadashi Kunii , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umemura
IPC分类号： B01F7/04 , B01F15/06 , B01J3/00 , B01J19/20 , C08G2/00 , C08G2/18 , C08G2/30 , C08G2/36 , C08G2/28
摘要： In a process for producing a stabilized oxymethylene copolymer which comprises heat-melting an oxymethylene copolymer having unstable, unblocked terminals obtained by the copolymerization of trioxane with a cyclic acetal and/or a cyclic ether to heat decompose it in the presence of available heat stabilizers; the improvement which comprises heating said oxymethylene copolymer having unblocked terminals in a mixer at a temperature between the melting point of said oxymethylene copolymer and a point 100.degree. C. higher than said melting point under a pressure of 0.1 mmHg to a atmospheric pressure for a mean residence time of 5 to 60 minutes, said mixer comprising a casing, a jacket for heating medium fitted over its external wall, and at least two stirring shafts equipped with a plurality of scraping blades disposed in said casing, said stirring shafts being capable of rotating in the same or different directions, and in the meantime, rotating said stirring shafts of said mixer to heat decompose said oxymethylene copolymer while renewing the surface of the molten oxymethylene copolymer.
摘要翻译： 在制备稳定化的甲醛共聚物的方法中，该方法包括将具有不稳定的未封端末端的甲醛共聚物进行加热熔融，其通过三恶烷与环状缩醛和/或环醚的共聚得到，以在可用的热稳定剂存在下将其分解; 改进之处在于，在混合器中将所述具有未封端末端的甲醛共聚物在所述甲醛共聚物的熔点和高于所述熔点的高于所述熔点的100℃的温度下在0.1mmHg的压力下加热至平均气压 停留时间为5至60分钟，所述混合器包括壳体，装配在其外壁上的加热介质的护套，以及至少两个配备有设置在所述壳体中的刮刀的搅拌轴，所述搅拌轴能够旋转 在相同或不同的方向上，并且同时旋转所述混合器的所述搅拌轴以使所述甲醛共聚物分解，同时更新熔融的甲醛共聚物的表面。
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公开(公告)号：US4343929A
公开(公告)日：1982-08-10
申请号：US200065
申请日：1980-10-23
申请人： Akitoshi Sugio , Kazuyoshi Taka , Akira Amemiya , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umemura , Yoshihiro Ono
发明人： Akitoshi Sugio , Kazuyoshi Taka , Akira Amemiya , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umemura , Yoshihiro Ono
CPC分类号： C08G2/00 , B01J19/20 , C08G2/10 , C08G2/18 , B01J2219/00779 , B01J2219/182
摘要： A process for producing a polyacetal homopolymer or copolymer which comprises continuously feeding a liquid starting mixture containing molten trioxane and a catalyst and optionally a comonomer through a feed opening of a reactor, said reactor being a continuously stirring-type mixer having two stirring shafts having a plurality of plate-like paddles fixed thereto the cross-section of each of said paddles taken perpendicularly of the axial direction of the stirring shaft having a shape of a convex lens, an ellipse or a quasipolygon inscribing a phantom circle at each vertex, one of said paddles facing another paddle fixed to the other stirring shaft and said one paddle being positioned such that it rotates while the edges thereof keep a slight clearance from the inner surface of the barrel and the other paddle; polymerizing the starting mixture while moving it toward the discharge opening by the rotation of the paddles, the improvement wherein the profiles of the paddles are changed, or the arrangement of the paddles is changed continuously or stepwise, so that the transportability of the reaction mixture becomes progressively smaller from the feed opening toward the discharge opening of the reactor.
摘要翻译： 一种制备聚缩醛均聚物或共聚物的方法，其包括通过反应器的进料口连续地供给含有熔融三恶烷和催化剂和任选的共聚单体的液体起始混合物，所述反应器是具有两个搅拌轴的连续搅拌型混合器， 多个板状的叶片固定在其上，垂直于搅拌轴的轴向垂直于每个顶点形成凸透镜，椭圆形或准圆体的形状的每个顶板上的假体圆的横截面， 所述桨叶面向固定到另一个搅拌轴的另一个桨叶，并且所述一个桨叶定位成使得其旋转，同时其边缘保持与筒体和另一个桨叶的内表面的微小间隙; 使起始混合物通过桨叶的旋转而朝向排出口移动而聚合起始混合物，改进了桨叶的轮廓改变，或者桨叶的排列被连续或逐步地改变，使得反应混合物的输送性变为 从进料口向反应器的排出口逐渐变小。
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公开(公告)号：US4189565A
公开(公告)日：1980-02-19
申请号：US971565
申请日：1978-12-20
申请人： Akitoshi Sugio , Akira Amemiya , Tetsuya Abe , Tomotaka Furusawa , Takeo Suzumori , Mutsuhiko Takeda , Masaharu Kimura , Yoshiharu Ohtsuki , Katsumasa Tanaka , Toshikazu Umemura , Kiyokazu Kawaguchi , Michio Ohba
发明人： Akitoshi Sugio , Akira Amemiya , Tetsuya Abe , Tomotaka Furusawa , Takeo Suzumori , Mutsuhiko Takeda , Masaharu Kimura , Yoshiharu Ohtsuki , Katsumasa Tanaka , Toshikazu Umemura , Kiyokazu Kawaguchi , Michio Ohba
IPC分类号： C07D323/06 , C08F2/10 , C08G2/00 , C08G2/10 , C08G2/18
摘要： A process for polymerizing trioxane made from an aqueous solution of methanol-containing formaldehyde by a conventional method or copolymerizing the trioxane with another monomer, characterized bycooling the trioxane to crystallize it,allowing the trioxane in a crystalline state to stand in an open system in an atmosphere of air or an inert gas to remove polyoxymethylene dimethoxide from the trioxane,melting the trioxane, andpolymerizing the trioxane or copolymerizing the trioxane and the another monomer.
摘要翻译： 聚合由甲醇含甲醛的水溶液通过常规方法或将三恶烷与另一种单体共聚的三恶烷的方法，其特征在于冷却三恶烷以使其结晶，使得结晶状态的三恶烷以开放体系 空气或惰性气体气氛，从三恶烷中除去聚甲醛二甲氧基化物，熔融三恶烷，聚合三恶烷或共聚三恶烷和另一种单体。
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公开(公告)号：US4339569A
公开(公告)日：1982-07-13
申请号：US150986
申请日：1980-05-19
申请人： Akitoshi Sugio , Akira Amemiya , Tadashi Kunii , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umemura
发明人： Akitoshi Sugio , Akira Amemiya , Tadashi Kunii , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umemura
摘要： In a process for producing an oxymethylene homopolymer or copolymer having improved stability which comprises polymerizing trioxane or a mixture of trioxane and a cyclic ether and/or a cyclic acetal in bulk in the presence of a catalyst which is at least one compound selected from the group consisting of boron trifluoride, boron trifluoride hydrate and coordination compounds of boron trifluoride with organic compounds containing an oxygen or sulfur atom, the improvement which comprises performing the bulk polymerization without destroying the bulk polymerization system, or which comprises adding a tertiary phosphine compound to the polymerization system to deactivate the catalyst, before the polymerization system formed by the bulk polymerization is destroyed.
摘要翻译： 在制备具有改进的稳定性的甲醛均聚物或共聚物的方法中，该方法包括在催化剂存在下，本体上聚合三恶烷或三恶烷和环醚和/或环状缩醛的混合物，所述催化剂是至少一种选自 由三氟化硼，三氟化硼水合物和三氟化硼与含有氧或硫原子的有机化合物的配位化合物组成，其改进包括进行本体聚合而不破坏本体聚合体系，或包括向聚合物中加入叔膦化合物 在通过本体聚合形成的聚合体系被破坏之前使催化剂失活的系统。
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公开(公告)号：US4224435A
公开(公告)日：1980-09-23
申请号：US48178
申请日：1979-06-13
申请人： Akitoshi Sugio , Akira Amamiya , Tadashi Kunii , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umenura , Kiyokazu Kawaguchi
发明人： Akitoshi Sugio , Akira Amamiya , Tadashi Kunii , Tomotaka Furusawa , Mutsuhiko Takeda , Katsumasa Tanaka , Toshikazu Umenura , Kiyokazu Kawaguchi
摘要： In a method for mixing a trioxane, a polymerization catalyst and a comonomer for producing of oxymethylene copolymers by continuously copolymerizing trioxane with a cyclic ether or a cyclic acetal as a comonomer, the improved method comprises following steps:spouting a comonomer and a polymerization catalyst from nozzle openings which are set adjacent to each other,while washing both openings at the tip end of the nozzles with a flow of trioxane,whereby mixing said comonomer, said polymerization catalyst and said trioxane,and then feeding the mixture to a polymerization reactor to effect copolymerization.The raw materials are mixed together before they are fed to the polymerization reactor, and no clogging trouble at the tip end of the nozzle for feeding a polymerization catalyst occurs. Further the resulting copolymer has a much superior heat stability. In addition, since each of the reaction raw materials is quantititively fed, the molecular weight and conversion of the copolymer extended from the polymerization reactor is so constant that a stabilized operation of the polymerization reactor can be secured.
摘要翻译： 在通过将三恶烷与环醚或环状缩醛连续共聚作为共聚单体的三恶烷，聚合催化剂和用于制备甲醛共聚物的共聚单体的方法中，改进的方法包括以下步骤：将共聚单体和聚合催化剂从 喷嘴开口彼此相邻设置，同时用三恶烷流洗涤喷嘴前端的两个开口，由此混合所述共聚单体，所述聚合催化剂和所述三恶烷，然后将混合物进料到聚合反应器中以实现 共聚。 在将原料进料到聚合反应器中之前将原料混合在一起，并且不会在用于进料聚合催化剂的喷嘴的前端发生堵塞问题。 此外，所得共聚物具有非常优异的热稳定性。 此外，由于每个反应原料都是定量供料的，从聚合反应器中延伸的共聚物的分子量和转化率是恒定的，从而可以确保聚合反应器的稳定运行。
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公开(公告)号：US4201849A
公开(公告)日：1980-05-06
申请号：US964445
申请日：1978-11-28
摘要： An acetal resin composition comprising an admixture of 100 parts by weight of an acetal resin and 0.01 to 15 parts by weight of a petroleum resin, said petroleum resin being prepared by polymerizing a cracked petroleum fraction boiling between -15.degree. C. and 200.degree. C. and containing unsaturated hydrocarbons, and having a molecular weight in the range of 400 to 2500 and a second order transition temperature in the range of 35.degree. to 90.degree. C.
摘要翻译： 一种缩醛树脂组合物，其包含100重量份的缩醛树脂和0.01至15重量份的石油树脂的混合物，所述石油树脂通过使沸点在-15℃和200℃之间的裂化石油馏分 并含有不饱和烃，分子量为400〜2500，二级转变温度为35〜90℃。
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公开(公告)号：US4087411A
公开(公告)日：1978-05-02
申请号：US722671
申请日：1976-09-13
摘要： A process for preparing oxymethylene polymers which comprises polymerizing trioxane or both trioxane and a specific cyclic ether in the presence of a catalytic amount of a boron fluoride-type catalyst, stopping the polymerization, and then subjecting the resulting polymer to a terminal stabilizing treatment, wherein the polymerization is stopped by adding a specific trivalent organic phosphorus compound and then the terminal stabilizing treatment is performed without removing the catalyst from the polymer.
摘要翻译： 一种制备甲醛聚合物的方法，其包括在催化量的硼氟化物型催化剂存在下聚合三恶烷或三恶烷和特定环醚，停止聚合，然后使所得聚合物进行末端稳定化处理，其中 通过加入特定的三价有机磷化合物停止聚合，然后在不从聚合物中除去催化剂的情况下进行末端稳定化处理。
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9.发明授权
公开(公告)号：US4058504A
公开(公告)日：1977-11-15
申请号：US677843
申请日：1976-04-16
摘要： In the production of polyphenylene ethers by oxidative polycondensation of phenols in the presence of a complex catalyst, an aminocarboxylic acid derivative and a reducing agent are simultaneously added to the reaction mixture when the resulting polyphenylene ether has attained the desired degree of polymerization, thereby to terminate the polymerization and simultaneously purify the reaction mixture. Hence, a stable purified polymer can be obtained.
摘要翻译： 在通过在络合物催化剂存在下通过酚的氧化缩聚生产聚苯醚时，当所得聚苯醚达到所需聚合度时，向反应混合物中同时加入氨基羧酸衍生物和还原剂，从而终止 聚合并同时净化反应混合物。 因此，可以获得稳定的纯化聚合物。
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公开(公告)号：US4246398A
公开(公告)日：1981-01-20
申请号：US35503
申请日：1979-05-02
申请人： Akitoshi Sugio , Atsuo Kuramoto , Takao Kawaki , Hiroyuki Urabe , Tatsuhiko Kurihara , Isamu Masumoto , Akio Hasebe
发明人： Akitoshi Sugio , Atsuo Kuramoto , Takao Kawaki , Hiroyuki Urabe , Tatsuhiko Kurihara , Isamu Masumoto , Akio Hasebe
CPC分类号： C08G65/46
摘要： A method for recovering polyphenylene oxide having a high bulk density and a reduced content of fine particles from a solution of a polyphenylene oxide, which comprises adding a non-solvent composed of a lower alkyl alcohol and water to an aromatic solvent solution of a polyphenylene oxide substantially free from impurities to precipitate the polyphenylene oxide, the weight ratio of the aromatic solvent to the lower alkyl alcohol being from 1:1 to 1:2 and the weight ratio of the lower alkyl alcohol to water being from 1:0.005 to 1:0.1 in the precipitation system, and the addition of the non-solvent being controlled such that a liquid composition of the aromatic solvent, the lower alkyl alcohol and water forms a single phase; and recovering the precipitated polyphenylene oxide.
摘要翻译： 从聚苯醚溶液中回收具有高堆积密度和微粒含量降低的聚苯醚的方法，其包括将由低级烷基醇和水组成的非溶剂加入到聚苯醚的芳族溶剂溶液中 基本上不含杂质以沉淀聚苯醚，芳族溶剂与低级烷基醇的重量比为1:1至1:2，低级烷基醇与水的重量比为1:0.005至1:1。 0.1，并且将非溶剂的添加控制为使得芳族溶剂，低级烷基醇和水的液体组合物形成单相; 并回收沉淀的聚苯醚。
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