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公开(公告)号：GB1023002A
公开(公告)日：1966-03-16
申请号：GB2276562
申请日：1962-06-13
Applicant: STAMICARBON
Inventor： SOETERBROEK JOHANNES CORNELIS , ADEMA EDUARD HILBRAND
IPC: C08F10/00
Abstract: a -Alkenes preferably containing at least 3 carbon atoms are homo- or copolymerized using a catalyst system comprising violet titanium trichloride, a monoalkyl-aluminium dihalide and an alkoxytitanium compound. Two or more monoalkylaluminium dihalides and/or two or more alkoxytitanium compounds may be used. The monoalkylaluminium dihalide is preferably the chloride, bromide or iodide and the alkyl group preferably has 1 to 12 carbon atoms and the alkoxytitanium compound is preferably a tetra-alkoxytitanium, e.g. tetrabutoxytitanium, but may be an alkoxytitanium halide. The polymerization may be carried out in a solvent and the catalyst components may be separately added to the reactor or two of the components in the solvent may be reacted together and then the monomer and then the third catalyst component added. Preferably the catalyst is preformed by reacting the three catalyst components in the presence of an alkene, such as the a -alkene to be polymerized.
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公开(公告)号：DE1177346B
公开(公告)日：1964-09-03
申请号：DEST014727
申请日：1959-02-02
Applicant: STAMICARBON
Abstract: 909,063. Titanium trichloride. STANICARBON N.V. Feb. 4, 1959 [Feb. 6, 1958; Oct. 20, 1958], No. 3986/59. Class 1(3) [Also in Group IV(a)] The titanium trichloride component of a catalyst employed for polymerization of alpha olefinic hydrocarbons containing at least 3 carbon atoms, is prepared by reducing titanium tetrachloride with a hydride or organo metallic compound of a metal of Group I to III of the Periodic system, at 15‹ to 20‹C. and thereafter heating the resulting titanium trichloride containing mass, during or after at least partial removal of the chlorinated reducing agent, to a temperature from 200‹-350‹C. The stereospecificity of the catalyt is thereby improved. The polymerization catalyst consists of the titanium trichloride compound as above prepared, together with a tri-alkyl aluminium compound such as tri-ethyl, tri-propyl, dimethyl ethyl, diethyl isobutyl, tri-hexyl aluminium or an alkyl aluminium hydride such as diethyl aluminium hydride or di-isobutyl aluminium hydride. The two catalyst components may be brought together before the polymerization or separately and continuously added, preferably in ratios such that the Al :Ti ratio is greater than 1. The reduction of the titanium tetrachloride may be effected in an inert diluent such as saturated hydrocarbons, for example, hexane, heptane or cyclohexane, or gasoline, kerosene, benzene, toluene or haologenated hydrocarbons such as chlorobenzene. The reduction may be promoted by the addition of ethanol or butanol. Particularly suitable Group I to III metal reducing agents are diethyl aluminium hydride di-isobutyl aluminium chloride, triethyl-, trimethyl-, triphenyl-aluminium, diethyl aluminium chloride, methyl aluminium dichloride, diphenyl aluminium chloride, ditolyl aluminium bromide and ethyl aluminium sesquichloride or sesquibromide. Other reducing compounds may be sodium hydrides, cesium hydrides, dimethyl magnesium, diethyl cadmium, dipropyl zinc, dihexyl zinc, methyl sodium and diphenyl cadmium. The bi-products of the reaction are preferably removed from the titanium tetrachloride by distillation in the presence of a liquid with an atmospheric boiling point above 180‹C. Such liquid may be present initially or may be added after reductionbut prior to distillation. Distillation may be effected in vacuuo and the required heating at 200‹-350‹C. effected as a subsequent step, or the heating and distillation may be simultaneous. Alternatively the titanium trichloride may be separated from the chlorinated reducing compound and exposed to dry heating in the absence of moisture and oxidizing gases. According to Examples (1) a solution of titanium tetrachloride in heptane was mixed at room temperature with a solution of tri-isobutyl aluminium in heptane and after the resulting precipitate had settled the liquid was removed by decantation. The precipitated titanium trichloride was washed in heptane and heated at 250‹C. for 30 minutes, in an argon atmosphere, and kept for 30 minutes, in an argon atmosphere, and kept in this atmosphere or suspended in heptane until required for polymerization. Propylene polymerization was effected in a rocking autoclave to which titanium trichloride prepared as above, triethyl aluminium and dry heptane were added simultaneously after which oxygen-free propylene was fed whilst the temperature was maintained at 70‹C. and at pressure at 2À5 atmosphere. The resulting polymer suspension was diluted with heptane and the catalyst decomposed by adding butanol and stirring at 80‹-90‹C. The polymer was then washed with a mixture of methanol and water, filtered and dried thereby obtaining polypropylene containing 95 % crystalline polymer. The amorphous polypropylene was extracted by diethyl ether at 30‹-35‹C. and hexane at 65‹C. (4) A solution of titanium tetrachloride in heptane and a separate solution of di-isobutyl aluminium hydride in heptane was continuously fed as separate streams to a stirring vessel whilst maintaining the Al/Ti ratio at unity. The reaction vessel was maintained at 15‹-20‹C. and the titanium trichloride suspension was withdrawn and separated in a nitrogen atmosphere and heated at 300‹C. (5) A solution of triethyl aluminium in a hydrocarbon fraction (B.P. 175 to 50‹C.) was slowly added to a solution of titanium chloride in the same solvent at room temperature. After 3 hours the temperature was raised 200‹-225‹C. whereupon the byproducts and part of the hydrocarbon fraction distilled off. The polymerization catalyst is thereafter prepared by adding di-isobutyl aluminium hydride to the titanium trichloride suspension thus treated.
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公开(公告)号：DE1079620B
公开(公告)日：1960-04-14
申请号：DEST014542
申请日：1958-12-08
Applicant: STAMICARBON
Abstract: Adipic acid is crystallized from solution by first cooling the solution to at least 30 DEG C. by direct heat exchange and then further cooling by indirect heat exchange, the direct heat exchange being effected in one or more stages by admixing the solution with a recycled portion of the suspension resulting from the second cooling and/or with a portion of the mother liquor Z remaining after removal of crystal product from non-recycled suspension resulting from the second cooling. When the direct heat exchange is effected in more than one stage, the solution is preferably cooled to 35 DEG -70 DEG C. in the first stage. The adipic acid may be formed by the oxidation of cyclohexanol in an excess of nitric acid. The invention may be applied to crystallization of the adipic acid from the nitric acid or to recrystallization of the adipic acid from water. In one embodiment (Fig. 1, not shown) a solution of adipic acid in nitric acid at 90 DEG C. is mixed with a recycled crystal suspension at 15 DEG C. in a first crystallizer to produce a crystal suspension at 45 DEG C. which is mixed with further recycled crystal suspension at 15 DEG C. in a second crystallizer to produce a crystal suspension at 20 DEG C. which is cooled to 15 DEG C. in an indirect heat exchanger and then passed in part to a centrifugal separator and in part to the first and second recrystallizers as recycle. Part of the suspension from the second crystallizer may pass directly to the centrifuge. In a second embodiment (Fig. 2, not shown) a solution of adipic acid in water at 90 DEG C. is mixed with recycled mother liquor at 12,5 DEG C. in a first crystallizer to produce a crystal suspension at 65 DEG C. which is mixed with recycled crystal suspension at 12,5 DEG C. to produce a crystal suspension at 15 DEG C. which is cooled to 12,5 DEG C. in an indirect heat exchanger and then passed in part to a centrifugal separator, and in part to the second recrystallizer as recycle, mother liquor from the centrifugal separator being passed to the first recrystallizer as recycle. Specification 745,063 is referred to.ALSO:Adipic acid is crystallized from solution by first cooling the solution to at least 30 DEG C. by direct heat exchange and then further cooling by indirect heat exchange, the direct heat exchange being effected in one or more stages by admixing the solution with a recycled portion of the suspension resulting from the second cooling and/or with a portion of the mother liquor remaining after removal of crystal product from nonrecycled suspension resulting from the second cooling. When the direct heat exchange is effected in more than one stage, the solution is preferably cooled to 35 DEG C.-70 DEG C. in the first stage. The adipic acid may be formed by the oxidation of cyclohexanol in an excess of nitric acid. The invention may be applied to crystallization of the adipic acid from the nitric acid or recrystallation of the adipic acid from water. In one embodiment (Fig. 1, not shown) a solution of adipic acid in nitric acid at 90 DEG C. is mixed with a recycled crystal suspension at 15 DEG C. in a first crystallizer to produce a crystal suspension at 45 DEG C. which is mixed with further recycled crystal suspension at 15 DEG C. in a second crystallizer to produce a crystal suspension at 20 DEG C. which is cooled to 15 DEG C. in an indirect heat exchanger and then passed in part to a centrifugal separator and in part to the first and second recrystallizers as recycle. Part of the suspension from the second crystallizer may pass directly to the centrifuge. In a second embodiment (Fig. 2, not shown) a solution of adipic acid in water at 90 DEG C. is mixed with recycled mother liquor at 12.5 DEG C. in a first crystallizer to produce a crystal suspension at 65 DEG C. which is mixed with recycled crystal suspension at 12.5 DEG C. to produce a crystal suspension at 15 DEG C. which is cooled to 12.5 DEG C. in an indirect heat exchanger and then passed in part to a centrifugal separator, and in part to the second recrystallizer as recycle, mother liquor from the centrifugal separator being passed to the first recrystallizer as recycle. Specification 745,063 is referred to.
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