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    • 6. 发明授权
    • Method for making polycarbonate
    • 制作聚碳酸酯的方法
    • US06569985B2
    • 2003-05-27
    • US09924137
    • 2001-08-08
    • Patrick Joseph McCloskeyAlberto NisoliWarren William Reilly
    • Patrick Joseph McCloskeyAlberto NisoliWarren William Reilly
    • C08G6400
    • C08G64/307
    • Polycarbonates having a high level of endcapping and containing a low level of Fries rearrangement product are prepared from dihydroxy aromatic compounds, such as bisphenol A, and diaryl carbonates such as diphenyl carbonate in a two stage process involving a tetraalkyl phosphonium carboxylate catalyzed oligomerization of the reactants in a first reaction stage followed by the addition of an alkali metal hydroxide co-catalyst in the second stage of the polymerization reaction. The late addition of the co-catalyst provides improved polymerization reaction rates as judged by higher polycarbonate molecular weights. The amount of alkali metal hydroxide co-catalyst is small thus avoiding the formation of excessive amounts of Fries product. The method has been used to provide Fries product levels between 200 and 800 parts per million in polycarbonates having Mn values between 7,500 and 8,500 Daltons.
    • 具有高水平的封端并含有低含量的Fries重排产物的聚碳酸酯由二羟基芳族化合物如双酚A和碳酸二芳基酯如碳酸二苯酯在涉及四烷基鏻羧酸酯催化的反应物低聚的两步法中制备 在第一反应阶段,然后在聚合反应的第二阶段加入碱金属氢氧化物助催化剂。 通过较高的聚碳酸酯分子量判断,辅助催化剂的晚期添加提供了改进的聚合反应速率。 碱金属氢氧化物助催化剂的量很小,从而避免形成过量的油炸产品。 该方法已经被用于在Mn值在7,500和8,500道尔顿之间的聚碳酸酯中提供200至800ppm之间的Fries产品水平。
    • 8. 发明授权
    • Method of polycarbonate preparation
    • 聚碳酸酯制备方法
    • US06797802B2
    • 2004-09-28
    • US10265419
    • 2002-10-07
    • Patrick Joseph McCloskeyWarren William Reilly
    • Patrick Joseph McCloskeyWarren William Reilly
    • C08G6400
    • C08G64/307
    • The present invention provides a method of preparing polycarbonate, said method comprising (A) oligomerising in the presence of a catalyst at least one dihydroxyaromatic compound at a temperature in a range between about 220-280° C. and a pressure in a range between 180 mbar and 20 mbar, said catalyst comprising a tetraarylphosphonium compound and optionally a co-catalyst, to provide an oligomeric polycarbonate having a number average molecular weight, Mn, in a range between about 1000 and about 6000 daltons; and (B) in a second step heating the oligomeric polycarbonate formed in step (A) at a temperature range between about 280 and about 310° C. and a pressure in a range between about 15 mbar and about 0.1 mbar, to provide a polycarbonate having a weight average molecular weight, in a range between about 15,000 and about 50,000 daltons, said product polycarbonate comprising less than 1000 parts per million Fries product.
    • 本发明提供一种制备聚碳酸酯的方法,所述方法包括(A)在催化剂存在下,在至少一种二羟基芳族化合物的存在下,在约220-280℃之间的温度和180℃ 所述催化剂包含四芳基鏻化合物和任选的助催化剂,以提供数均分子量Mn在约1000至约6000道尔顿范围内的低聚聚碳酸酯; 和(B)在步骤(A)中形成的低聚聚碳酸酯在约280℃至约310℃之间的温度范围和约15毫巴至约0.1毫巴范围内的压力下进行加热,以提供聚碳酸酯 重均分子量在约15,000至约50,000道尔顿之间的范围内,所述产品聚碳酸酯包含小于1000份百万份薯条产品。
    • 9. 发明授权
    • Method of polycarbonate preparation
    • 聚碳酸酯制备方法
    • US06723823B2
    • 2004-04-20
    • US10167965
    • 2002-06-12
    • Patrick Joseph McCloskeyWarren William ReillyBrian James Grimmond
    • Patrick Joseph McCloskeyWarren William ReillyBrian James Grimmond
    • C08G600
    • C08G64/307
    • Mixed alkali metal salts of phosphoric acid in combination with a co-catalyst such as tetramethylammonium hydroxide (TMAH) are excellent transesterification catalysts for use in the preparation of polycarbonate from bisphenol A and diphenyl carbonate. The mixed alkali metal phosphate salts were shown by kinetic measurements made on a model system composed of p-tert-octylphenol and bis(p-cumylphenyl) carbonate to be inherently more potent catalysts than salts of phosphoric acid comprising a single alkali metal ion. In addition to providing higher rates of polymerization, the new catalysts were shown to provide polycarbonates containing reduced levels of Fries rearrangement product relative to polymerization reactions catalyzed by conventional catalyst systems such as sodium hydroxide together with TMAH co-catalyst.
    • 磷酸的混合碱金属盐与诸如四甲基氢氧化铵(TMAH)的助催化剂组合是用于从双酚A和碳酸二苯酯制备聚碳酸酯的优异的酯交换催化剂。 混合的碱金属磷酸盐通过在由对叔辛基苯酚和双(对枯基苯基)碳酸酯组成的模型系统上进行的动力学测量显示为比含有单一碱金属离子的磷酸盐更具有效力的催化剂。 除了提供更高的聚合速率之外,新催化剂显示出提供聚碳酸酯,其含有相对于常规催化剂体系如氢氧化钠与TMAH助催化剂催化的聚合反应的降低水平的Fries重排产物。
    • 10. 发明授权
    • Preparation of polycarbonate having a predetermined molecular weight and level of endcapping
    • 具有预定分子量和封端水平的聚碳酸酯的制备
    • US06399739B1
    • 2002-06-04
    • US09934929
    • 2001-08-22
    • Patrick Joseph McCloskeyAlberto NisoliWarren William Reilly
    • Patrick Joseph McCloskeyAlberto NisoliWarren William Reilly
    • C08G6400
    • C08G64/307
    • A melt method of preparing polycarbonate having a predetermined number average molecular weight and percent endcapping is described. A computerized process model is used to determine the reaction parameters to be employed in order to furnish the product polycarbonate possessing the desired Mn and %EC. Reaction parameters of importance include a suitable starting molar ratio of diaryl carbonate to dihydroxy aromatic compound, the most appropriate reaction time, reaction temperature and pressure ranges. The target polycarbonate is then prepared using reaction parameters indicated by the process model in a reactor which forms an element of the process model. Characteristics of the reactor which may be included in the process model include agitation rate and reflux ratio during the distillative removal of hydroxy aromatic compound formed as a by-product during the polymerization.
    • 描述了制备具有预定数均分子量和百分比封端的聚碳酸酯的熔融方法。 使用计算机化过程模型来确定要使用的反应参数,以便提供具有期望的Mn和%EC的产物聚碳酸酯。 重要的反应参数包括碳酸二芳基酯与二羟基芳族化合物的合适起始摩尔比,最合适的反应时间,反应温度和压力范围。 然后使用形成过程模型元素的反应器中由过程模型指示的反应参数制备目标聚碳酸酯。 可以包括在过程模型中的反应器的特征包括在蒸馏除去在聚合期间作为副产物形成的羟基芳族化合物的搅拌速率和回流比。