• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Ethylene and at least one other 1-monoolefin monomer, alone or in admixture with a non-conjugated hydrocarbon diene monomer, are copolymerized in the presence of organic chlorine compound-activated Ziegler-Natta catalyst, wherein the organic chlorine compound is a hydrocarbon or a halohydrocarbon ester of up to 15 carbon atoms of 2,3,4,4-tetrachloro-3-butenoic acid.
    公开号:SU839440A3
    申请号:SU792733998
    申请日:1979-03-05
    公开日:1981-06-15
    发明作者:Маас Гюнтер；Ромбуш Конрад；Цаар Вольфганг
    申请人:Хемише Верке Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

    54) METHOD FOR OBTAINING TROPICAL COPOLYMER
    权利要求:
    Claims (3)
    [1]
    This invention relates to polymer chemistry, in particular to the process for the preparation of an ethylene terpolymer. A method of producing copolymers of ethylene and propylene by copolymerizing monomers in a hydrocarbon solvent in the presence of a mixed catalyst, for example a mixture of a halogen-containing aluminum compound with vanadium chloroxide, and an activator, such as a trihaloacetic acid ester l. The disadvantage of this method is the unsatisfactory yield of the target product. A method is known for producing ethylene and propylene copolymers by copolymerizing monomers in a carbon solvent environment in the presence of a mixed catalyst, for example, a mixture of halogen-containing aluminum compound and vanadium oxychloride, and an activator, hexachlorocyclopentadiene. The disadvantage of this method is the poor yield of the solid product. The closest to the invention in its technical essence and the achieved result is the method of obtaining the terpolymer copolymer of ethylene, propylene and ethylidenneorbornene E in a hydrocarbon solvent in the presence of a catalyst consisting of an aluminum halide and vanadium oxychloride, and an organochlorine ester 2, 3,4,4,4 pentachlor-2-butenoic acid 3. The disadvantage of this method is that the yield of the target product and its physicomechanical properties, in particular elongation, are not satisfactory. The aim of the invention is to increase the yield and improve the physical and mechanical properties of the final product. This goal is achieved by the fact that according to the method of producing a ternary copolymer of ethylene, propylene and ethylidenenorbornene in a hydrocarbon solvent medium in the presence of a catalyst, 5-250 mol per 1 organochlorine activator used as the organochlorine compound of aluminum and oxychloride oxychloride 1 mole of rakadi oxychloride. complex i 2, J, 4, 4-tetrachloro-3-fiy TCHOIJOH ki / s oC ::; oit of the formula CC Ej-CC t-CHC & COO where is ispma.ch 11 or branched C, -Cg-aJiivUJi or chloralkyl, or tol CiJoP.ctDa TjiOHHbJX soiol: msrO13,; pHije, in the table, 5G1;.) one: 1 s.1: edduy1ts; 1m oGpaj udsi; na: -1 viscosity (i, l% -Horc Paragraph E of para-xylene g. ri ne1:) ASTs) kollszymeny in tolu ol at 90 ° C, otorazhoiio; (otory; the whole copolymer; .5ac. hv (sp; dc, After oh,): hardening components, kg, are deposited every time and up to; 1);;; the weight of the sample /. to l;: ches-of double c Bnaevi on YuO atom ;, yrj; c: pozui - inf1 zakras:; oh with p e to 1 p o c k i p I: e u, npfj4i ocT;) with growth /; ui and elongation - according to the standard ФР1 53504, iltjKoci-b Muii ML, 4 - standard rotor 1; р; -; K) C-C in teyuny 4 min,; ic; cj; c:; re; a warmer warmed up in the case of an MRI; . PRI me R 1. Reak1Or. : ioj; y4e dkg of triple ethylene propylene and ethylidene norbornene npor-cviMT in cTeidKHHOM® e: ostia 2l, i which is injected with 1.5 l sous; -: o1o rsKCdiHa. Stekly;: 1: - And the reactor is equipped with mea and coy and thunder graduated drip. First drip: 1 crown ooj cpsnT О, 1 g 1 mol CO С С-), in 1 liter of hexane, which is added at 0.02: MMOJH; per hour and for 4 hours. The average composition in the reactor is 7 liters of solution:; g; h ;; 1 is 0.14 :: mol VOCt ;; on 1 l. The second; orange voren; a s; c; earl 7 50 mmol seksvn; Lori, aa; Tii /: and the nomines KOTfjOoui instill in but 2, j t..K; j ;;, i-. 1 hour, which is 7.143 m; / olu, and 1 l to recalculated for; ruz1 y. third to a g; spruce on the funnel contains,: -: and t 8, 4 84 mol per mmol VOCCr THJxjBoro ether {; a 2, 3, 4, 4-hectares, -button acid: and Y, MMJJ: de1 Norbornen in 2.5 l ge (..: ana velocity dropping; I) 1 2.5 and 1. 1 h. average content {.) a.and c: Tojpe is 1.2 or 7.143. n; 1 l. Polymerization. Hexane:; s; shak; t itnlen and propyleneg in a molar ratio; x: eiii 1.8: 0.3 for 1/2 h n; oi KCiMiiari OH 1 temperature and non-ligation. Then they heat up to 30-35 ° C and r; o; i keep this on to the temneretu;.; U on those;:.; Booster bath for 4 hours. Ii during this time put the ratios of individual components; gogo1 catalyst and ethylene and propyl / commemorate hourly in molar co: t;: O1:; en.ik Lererabotkg. Solution hl-; the copolymer was withdrawn at the Sasmsle crane with a wide, wide view: -; vto.ro; the apparatus with meialko, the content of 10 completely desalted and 5 g ks M of the 3 rchea stabilizer, layer: .-; octadecyl ether j) -2,4-di-tert (Zutil-3-okoif; shl-propionly KJICJIOt. Reaction of preEr yes; from d, about 350 ml of isopropanol; then 5; hexane water: m steam is removed from the solution-a. After this operation, from Tol -; sea contains KiiTfv-BO% by weight of water, which is removed g by a vacuum drying cabinet at. C .;); the process of ternary copolymerization is equal to 265 g. The properties of the copolymer in this material are pl. Examples 2-8 and a comparative example are carried out according to the procedure of Example 1. The difference lies in naming other activators and / or their concentration. Thus, the proposed method allows to increase the physicomechanical indicators and the yield of the final product. Formula of the Invention A method for producing a ternary copolymer by copolymerizing ethylene, propylene and ethylidene norbornene in a hydrocarbon solvent in the presence of a catalyst consisting of The organic organic compound of aluminum and vanadium oxychloride, and the organochlorine activator, is necessary in order to increase the yield and improve the physicomechanical 1 of their properties of the final product, 5-250 mmol per 1 mole of 2,3,4,4-tetrachloro-3-butenoic acid vanadium oxyde of the general formula CCFg CCt-CHCECOOR, where R is normal or branched, is used as organochlorine activator. C, -C0-alkyl or chloralkyl, or tolyl. Sources of information taken into account in the examination 1.Patent of France 1417195, cl. From 08 f, pub. 1965.
    [2]
    2. The patent of France No. 1370358, cl. From 08- f, pub. 1964.
    [3]
    3. The patent of Germany No. 1595442, cl. From 08 f 15/04, publ. 1973 (prototype).
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    同族专利:
    公开号 | 公开日
    DE2810396A1|1979-09-27|
    IT7948269D0|1979-03-08|
    JPS54125288A|1979-09-28|
    FR2419300A1|1979-10-05|
    GB2018790A|1979-10-24|
    NL7901913A|1979-09-12|
    US4181790A|1980-01-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3645993A|1967-03-14|1972-02-29|Copolymer Rubber & Chem Corp|Interpolymerization of a mixture of monoolefins and a polyene in the presence of a base and a halogenated compound|DE2933885C3|1979-08-22|1982-05-06|Chemische Werke Hüls AG, 4370 Marl|Process for the preparation of copolymers of ethylene with at least one other 1-monoolefin and optionally a non-conjugated diene|
    US5013801A|1983-06-15|1991-05-07|Charles Cozewith|Molecular weight distribution modification in a tubular reactor|
    US4789714A|1983-06-15|1988-12-06|Exxon Research & Engineering Co.|Molecular weight distribution modification in tubular reactor|
    JPH0452285B2|1983-08-10|1992-08-21|Japan Synthetic Rubber Co Ltd|
    US5011891A|1985-12-27|1991-04-30|Exxon Research & Engineering Company|Elastomer polymer blends|
    US5177147A|1986-03-03|1993-01-05|Advanced Elastomer Systems, Lp|Elastomer-plastic blends|
    US4843129A|1985-12-27|1989-06-27|Exxon Research & Engineering Company|Elastomer-plastic blends|
    US5502127A|1994-03-31|1996-03-26|Union Carbide Chemicals & Plastics Technology Corporation|Process for production of homogeneous polyethylene|
    US6833417B2|2002-12-31|2004-12-21|Univation Technologies, Llc|Processes for transitioning between chrome-based and mixed polymerization catalysts|
    EA014355B1|2006-03-30|2010-10-29|Тотал Петрокемикалс Рисерч Фелюй|Slurry polymerisation process of ethylene in the presence of low amount of scavenger|
    US9035000B2|2011-03-01|2015-05-19|Mehrdad Seifali Abbas-Abadi|Polyolefin production using an improved catalyst system|
    EP3344667B1|2015-08-31|2020-12-30|Bridgestone Corporation|Copolymerization of polyenes and alkenes|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19782810396|DE2810396A1|1978-03-10|1978-03-10|PROCESS FOR THE PRODUCTION OF COPOLYMERIZED MATERIALS FROM ETHYLENE, AT LEAST ONE OTHER 1-MONOOLEFIN AND, IF NON-CONJUGATED|
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