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    • 3. 发明授权
    • Deactivation of catalyst in solution process for polymerization of .alpha.-
o
    • 在α-烯烃聚合的溶液中催化剂失活
    • US4430488A
    • 1984-02-07
    • US443060
    • 1982-11-19
    • Vaclav G. Zboril
    • Vaclav G. Zboril
    • C08F2/00C08F2/04C08F2/06C08F6/00C08F6/02C08F6/06C08F10/00C08F10/02C08F2/42
    • C08F6/02
    • The present invention relates to a solution polymerization process for the preparation of high molecular weight polymers of .alpha.-olefins selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 .alpha.-olefins. The process comprises feeding monomer, coordination catalyst containing vanadium and inert hydrocarbon solvent to a reactor, polymerizing the monomer at a temperature in the range of 105.degree.-320.degree. C. and a pressure of less than 25 MPa and deactivating the catalyst in the solution so obtained by admixing therewith a solution of a salt of an alkaline earth metal or zinc and an aliphatic monocarboxylic acid dissolved in hydrocarbon solvent. The hydrocarbon solvent is then separated from the resultant solution and a composition comprising high molecular weight polymer is recovered. Any catalyst residues remain with the polymer. A particular salt is the salt of a C.sub.8 aliphatic acid, especially calcium 2-ethyl hexanoate.
    • 本发明涉及一种用于制备选自乙烯均聚物和乙烯与C 3 -C 12α-烯烃共聚物的α-烯烃的高分子量聚合物的溶液聚合方法。 该方法包括将单体,含有钒和惰性烃溶剂的配位催化剂加入到反应器中,在105℃-320℃的温度和小于25MPa的压力下使单体聚合,并使溶液中的催化剂失活 如此通过将溶解在烃溶剂中的碱土金属或锌的盐和脂族一元羧酸的溶液混合而获得。 然后将烃溶剂与所得溶液分离,并回收包含高分子量聚合物的组合物。 任何催化剂残留在聚合物上。 特定的盐是C8脂族酸的盐,特别是2-乙基己酸钙。
    • 4. 发明授权
    • Control of a solution process for polymerization of ethylene
    • 控制乙烯聚合的溶液方法
    • US5589555A
    • 1996-12-31
    • US499646
    • 1995-07-07
    • Vaclav G. ZborilStephen J. Brown
    • Vaclav G. ZborilStephen J. Brown
    • C08F10/00C08F10/02C08F110/02C08F4/654
    • C08F10/00C08F10/02C08F110/02
    • A solution process for the preparation of high molecular weight polymers of alpha-olefins selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 higher alpha-olefins is disclosed. Ethylene and/or mixtures of ethylene and C.sub.3 -C.sub.12 higher alpha-olefins are polymerized under non-isothermal conditions in a tubular reactor or in a system of reactors which operate under different conditions, in the presence of a catalytic amount of a titanium-containing coordination catalyst in an inert solvent at a temperature in excess of 105.degree. C. The improvement is characterized in that:(a) the catalyst is activated with a solution of a mixture of aluminum alkyl and alkoxy aluminum alkyl in inert solvent; and(b) the process is controlled by adjusting the ratio of aluminum alkyl to alkoxy aluminum alkyl in the mixture of (a). The aluminum alkyl is of the formula AlR.sub.n X.sub.3-n and the alkoxy aluminum alkyl is of the formula AlR'.sub.m OR".sub.3-m, in which each of R, R' and R" is alkyl or aryl of 1-20 carbon atoms, X is halogen, n is 2-3 and m is 0-3.
    • 公开了一种用于制备选自乙烯均聚物和乙烯和C3-C12高级α-烯烃共聚物的α-烯烃的高分子量聚合物的溶液方法。 乙烯和/或乙烯和C 3 -C 12较高级α-烯烃的混合物在非等温条件下在管式反应器或在不同条件下操作的反应器系统中,在催化量的含钛 配位催化剂在惰性溶剂中的温度超过105℃。改进的特征在于:(a)催化剂用烷基铝和烷氧基铝的混合物在惰性溶剂中的混合物的活化; 和(b)通过调节(a)的混合物中烷基铝与烷氧基烷基铝的比例来控制该方法。 烷基铝为式AlRnX3-n,烷氧基烷基为式AlR'mOR'3-m,其中R,R'和R“各自为1-20个碳原子的烷基或芳基 ,X为卤素,n为2-3,m为0-3。
    • 5. 发明授权
    • Reduction of isomerization in solution process for polymerization of
alpha-olefins
    • 在α-烯烃聚合反应的溶液中减少异构化
    • US4777229A
    • 1988-10-11
    • US95689
    • 1987-09-14
    • Vaclav G. ZborilRonald A. Zelonka
    • Vaclav G. ZborilRonald A. Zelonka
    • C08F2/06C08F2/42C08F10/00C08F210/16C08F10/02
    • C08F2/06C08F10/00C08F210/16
    • A solution polymerization process for the preparation of high molecular weight polymers selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and butene-1 is disclosed. The process comprises feeding monomer(s), coordination catalyst and inert hydrocarbon solvent to a reactor, polymerizing the monomers at a temperature of up to 320.degree. C. and a pressure of less than 25 MPa, and deactivating the catalyst in the solution so obtained. The catalyst is deactivated by sequentially admixing therewith a minor amount of dimethyl carbonate followed by a solution of a salt of an alkaline earth metal or zinc and an aliphatic monocarboxylic acid dissolved in hydrocarbon solvent. The hydrocarbon solvent and other volatile matter are then separated from the resultant solution and a composition comprising the high molecular weight polymer is recovered. The amount of dimethyl carbonate is not more than 2.5 moles, per mole of halogen plus alkyl radicals in the coordination catalyst.
    • 公开了用于制备选自乙烯均聚物和乙烯和丁烯-1的共聚物的高分子量聚合物的溶液聚合方法。 该方法包括将单体,配位催化剂和惰性烃溶剂进料到反应器中,在高达320℃的温度和小于25MPa的压力下使单体聚合,并使所得溶液中的催化剂失活 。 通过依次与少量的碳酸二甲酯混合,然后将碱土金属或锌的盐和溶解在烃溶剂中的脂肪族单羧酸的溶液依次混合,使催化剂失活。 然后将烃溶剂和其它挥发性物质与所得溶液分离,并回收包含高分子量聚合物的组合物。 在配位催化剂中,每摩尔卤素加上烷基,碳酸二甲酯的量不超过2.5摩尔。
    • 7. 发明授权
    • Monitoring and control of process streams at elevated temperatures
    • 在高温下监测和控制工艺流
    • US5342499A
    • 1994-08-30
    • US53623
    • 1993-03-25
    • Vaclav G. Zboril
    • Vaclav G. Zboril
    • G01N27/416G01N27/26
    • G01N27/4166
    • A method and apparatus for the monitoring and control of concentration of an ion in a solution at an elevated temperature of at least 100.degree. C. are disclosed. The method comprises the steps of contacting a first electrode with a flowing first solution containing said ion at the elevated temperature, and contacting a second electrode with a second flowing solution containing said ion at the elevated temperature. The rate of flow of the second solution is substantially lower than the rate of flow of the first solution. The first and second solutions are then contacted or admixed. The electrodes must be capable of detecting the ion at the elevated temperature and have the same response characteristics to changes in concentration of the ion at the elevated temperature. The concentration of the ion in the second solution is measured at a temperature lower than the elevated temperature under conditions permitting accurate measurement of the concentration of the ion, and the concentration of the ion in the first solution is monitored and controlled by adjusting the concentration of the ion in at least one of the first and second solutions. The method is particularly adapted for the monitoring and control of salt solutions used in the manufacture of polyamides, using palladium hydride electrodes.
    • 公开了一种在至少100℃的升高的温度下监测和控制溶液中的离子浓度的方法和装置。 该方法包括以下步骤:在升高的温度下使第一电极与含有所述离子的流动的第一溶液接触,并且在升高的温度下将第二电极与含有所述离子的第二流动溶液接触。 第二溶液的流速基本上低于第一溶液的流速。 然后将第一和第二溶液接触或混合。 电极必须能够在升高的温度下检测离子,并且具有与高温下离子浓度变化相同的响应特性。 在允许精确测量离子浓度的条件下,在低于升高温度的温度下测量第二溶液中的离子浓度,并且通过调节第一溶液的浓度来监测和控制第一溶液中的离子浓度 在第一和第二溶液中的至少一个中的离子。 该方法特别适用于使用钯氢化物电极监测和控制用于制造聚酰胺的盐溶液。
    • 8. 发明授权
    • Reduction of isomerization in solution process for polymerization of
alpha-olefins
    • 在α-烯烃聚合反应的溶液中减少异构化
    • US4701504A
    • 1987-10-20
    • US824354
    • 1986-01-23
    • David J. MitchellVaclav G. Zboril
    • David J. MitchellVaclav G. Zboril
    • C08F2/42C08F10/00C08F6/06C08F6/10
    • C08F10/00
    • A solution polymerization process for the preparation of high molecular weight polymers of alpha-olefins selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and C.sub.4 -C.sub.12 alpha-olefins is disclosed. The process comprises feeding monomer(s), coordination catalyst and inert hydrocarbon solvent to a reactor, polymerizing the monomers at a temperature of up to 320.degree. C. and a pressure of less than 25 MPa, and deactivating the catalyst in the solution so obtained. The catalyst is deactivated by sequentially admixing therewith a minor amount of a nitrogenous base, especially an aqueous solution of such a base, followed by a solution of a salt of an alkaline earth metal or zinc and an aliphatic monocarboxylic acid dissolved in hydrocarbon solvent. The ratio of water:nitrogenous base should not be greater than 5. The hydrocarbon solvent and other volatile matter are then separated from the resultant solution and a composition comprising said high molecular weight polymer is recovered. The amount of nitrogenous base plus any water is not more than 2.5 moles per mole of halogen plus alkyl radicals in the coordination catalyst.
    • 公开了用于制备选自乙烯均聚物和乙烯与C 4 -C 12α-烯烃共聚物的α-烯烃的高分子量聚合物的溶液聚合方法。 该方法包括将单体,配位催化剂和惰性烃溶剂进料到反应器中,在高达320℃的温度和小于25MPa的压力下使单体聚合,并使所得溶液中的催化剂失活 。 通过依次混合少量的含氮碱,特别是这种碱的水溶液,然后将碱土金属或锌的盐和溶解在烃溶剂中的脂族一元羧酸的溶液顺序混合,使催化剂失活。 水:含氮碱的比例不应大于5.然后从所得溶液中分离烃溶剂和其它挥发物,并回收包含所述高分子量聚合物的组合物。 在配位催化剂中,氮碱加上任何水的量不超过2.5摩尔每摩尔卤素加烷基。
    • 9. 发明授权
    • Solution process for the preparation of polymers of .alpha.-olefins
    • 用于制备α-烯烃聚合物的溶液方法
    • US5492876A
    • 1996-02-20
    • US190750
    • 1994-02-01
    • Daniel J. GillisVaclav G. ZborilMillard C. Hughson
    • Daniel J. GillisVaclav G. ZborilMillard C. Hughson
    • C08F10/00B01J31/36B01J31/38
    • C08F10/00
    • A solution process, and a catalyst therefor, for the preparation of high molecular weight polymers of alpha-olefins viz. homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 alpha-olefins, is disclosed. The process is operated under solution polymerization conditions at 105.degree.-320.degree. C. The catalyst is obtained from titanium tetrahalides, vanadium oxytrihalides and organoaluminum compounds, in which an admixture of catalyst components is heat-treated at 180.degree.-250.degree. C. and subsequently cooled to a temperature of less than 150.degree. C. Additional vanadium oxytrihalide is then added. The resultant catalyst solution is activated with an aluminum compound. The catalyst has good activity, showing superior activity to catalysts in which additional vanadium oxytrihalide is not added or added at temperatures above 150.degree. C.
    • 用于制备α-烯烃的高分子量聚合物的溶液方法及其催化剂, 公开了乙烯的均聚物和乙烯和C 3 -C 12α-烯烃的共聚物。 该方法在105℃-320℃的溶液聚合条件下进行。催化剂由四卤化钛,三氧化三钒和有机铝化合物得到,其中催化剂组分的混合物在180-250℃下热处理, 随后冷却至小于150℃的温度。然后加入另外的三氧化二铁。 所得催化剂溶液用铝化合物活化。 该催化剂具有良好的活性,对催化剂具有优异的活性,其中在高于150℃的温度下不加入或加入额外的三氧化二钒
    • 10. 发明授权
    • Monitoring and control of process streams at elevated temperatures
    • 在高温下监测和控制工艺流
    • US5213668A
    • 1993-05-25
    • US829845
    • 1992-01-31
    • Vaclav G. Zboril
    • Vaclav G. Zboril
    • G01N27/416
    • G01N27/4166
    • A method and apparatus for the monitoring and control of concentration of an ion in a solution at an elevated temperature of at least 100.degree. C. are disclosed. The method comprises the steps of contacting a first electrode with a flowing first solution containing said ion at the elevated temperature, and contacting a second electrode with a second flowing solution containing said ion at the elevated temperature. The rate of flow of the second solution is substantially lower than the rate of flow of the first solution. The first and second solutions are then contacted or admixed. The electrodes must be capable of detecting the ion at the elevated temperature and have the same response characteristics to changes in concentration of the ion at the elevated temperature. The concentration of the ion in the second solution is measured at a temperature lower than the elevated temperature under conditions permitting accurate measurement of the concentration of the ion, and the concentration of the ion in the first solution is monitored and controlled by adjusting the concentration of the ion in at least one of the first and second solutions. The method is particularly adapted for the monitoring and control of salt solutions used in the manufacture of polyamides, using palladium hydride electrodes.
    • 公开了一种在至少100℃的升高的温度下监测和控制溶液中的离子浓度的方法和装置。 该方法包括以下步骤:在升高的温度下使第一电极与含有所述离子的流动的第一溶液接触,并且在升高的温度下使第二电极与含有所述离子的第二流动溶液接触。 第二溶液的流速基本上低于第一溶液的流速。 然后将第一和第二溶液接触或混合。 电极必须能够在升高的温度下检测离子,并且具有与高温下离子浓度变化相同的响应特性。 在允许精确测量离子浓度的条件下,在低于升高温度的温度下测量第二溶液中的离子浓度,并且通过调节第一溶液的浓度来监测和控制第一溶液中的离子浓度 在第一和第二溶液中的至少一个中的离子。 该方法特别适用于使用钯氢化物电极监测和控制用于制造聚酰胺的盐溶液。