TWI414533B - Solid catalyst component for olefin polymerization, catalyst for polymerization, and method for producing olefin polymer using the same - Google Patents
Solid catalyst component for olefin polymerization, catalyst for polymerization, and method for producing olefin polymer using the same Download PDFInfo
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Description
本發明係關於活性高且對氫活性良好、能夠以高產率獲得高立體規則性聚合物之烯烴類聚合用固體觸媒成分及觸媒。The present invention relates to a solid catalyst component and a catalyst for olefin polymerization which have high activity and good hydrogen activity and are capable of obtaining a high stereoregular polymer in high yield.
習知,於丙烯等烯烴類之聚合時,已知有含有鎂、鈦、電子供應性化合物及鹵素作為必需成分之固體觸媒成分。另外,提出有多個於包含該固體觸媒成分、有機鋁化合物及有機矽化合物之烯烴類聚合用觸媒之存在下,使烯烴類聚合或共聚合之方法。例如,於專利文獻1(日本專利特開昭63-3010號公報)中,提出有包含固體觸媒成分、有機鋁化合物及有機矽化合物之丙烯聚合用觸媒與丙烯之聚合方法,上述固體觸媒成分係藉由於粉末狀態下對使二烷氧基鎂、芳香族二羧酸酸二酯、芳香族烴化合物及鈦鹵化物相接觸所獲得之生成物進行加熱處理而製備。Conventionally, in the polymerization of olefins such as propylene, a solid catalyst component containing magnesium, titanium, an electron-donating compound, and halogen as essential components is known. Further, a method of polymerizing or copolymerizing olefins in the presence of a plurality of catalysts for olefin polymerization containing the solid catalyst component, the organoaluminum compound, and the organic ruthenium compound has been proposed. For example, a method for polymerizing a catalyst for propylene polymerization containing propylene containing a solid catalyst component, an organoaluminum compound, and an organic cerium compound with propylene is disclosed in Patent Document 1 (Japanese Laid-Open Patent Publication No. SHO63-3010). The medium component is prepared by heat-treating a product obtained by bringing a dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon compound, and a titanium halide into contact in a powder state.
進而,作為內部電子供應性化合物,亦開發有使用丙二酸酯化合物代替習知之鄰苯二甲酸酯化合物之烯烴聚合用固體觸媒成分,於專利文獻2(日本專利特表2000-516987號公報)中,揭示有包含支持於鹵化Mg上、至少具有Ti-鹵素鍵之鈦化合物、及2-異丙基丙二酸二乙酯之類之單烷基取代丙二酸二酯的固體觸媒成分。另外,於專利文獻3(WO03/95504號公報)中,揭示有包含含有烷氧基之鎂化合物、及2,2-二甲基丙二酸二乙酯等二烷基 取代丙二酸二酯之固體觸媒成分,上述含有烷氧基之鎂化合物係使含有含鹵素之鈦化合物、金屬鎂、醇及相對於上述金屬鎂1莫耳為0.0001克原子以上的鹵素原子之鹵素及/或含鹵素之化合物反應而獲得。Further, as an internal electron-donating compound, a solid catalyst component for olefin polymerization using a malonate compound in place of a conventional phthalate compound has been developed, and Patent Document 2 (Japanese Patent Laid-Open No. 2000-516987) In the publication, a solid touch comprising a monoalkyl-substituted malonate diester supported on a halogenated Mg, a titanium compound having at least a Ti-halogen bond, and a diethyl 2-isopropylmalonate is disclosed. Media ingredients. Further, Patent Document 3 (WO03/95504) discloses a dialkyl group containing a magnesium compound containing an alkoxy group and diethyl 2,2-dimethylmalonate. In place of the solid catalyst component of the malonic acid diester, the alkoxy-containing magnesium compound contains a halogen-containing titanium compound, metallic magnesium, an alcohol, and a halogen atom of 0.0001 gram or more with respect to the metal magnesium 1 molar. It is obtained by reacting a halogen and/or a halogen-containing compound.
另外,習知,關於丙二酸二酯,欲獲得2個酯殘基相互不同者時,反應起始物質與目的生成物之2個酯殘基不同者之沸點相近,因而有時難以進行分餾。Further, it is conventionally known that, in the case of the malonic acid diester, when the two ester residues are different from each other, the boiling point of the reaction starting material and the two ester residues of the target product are similar, and thus it is sometimes difficult to carry out fractionation. .
然而,使用如上所述之觸媒所獲得之聚合物,除了汽車或者家電製品等成型品以外,亦利用於容器或薄膜等各種用途中。該等係將藉由聚合而生成之聚合物粉末加以熔融,並利用各種成型機而成型,尤其是於利用射出成型等且製造大型之成型品時,有時要求熔融聚合物之流動性(熔融流動速率)高,因此,進行多種研究以提高聚合物之熔融流動速率。However, the polymer obtained by using the catalyst as described above is used in various applications such as containers and films, in addition to molded articles such as automobiles and home electric appliances. These polymer powders which are produced by polymerization are melted and molded by various molding machines, and in particular, when a large-sized molded article is produced by injection molding or the like, the fluidity of the molten polymer is sometimes required to be melted. The flow rate is high, and therefore, various studies have been conducted to increase the melt flow rate of the polymer.
·熔融流動速率係大幅依存於聚合物之分子量。於業界中,於丙烯聚合時,一般添加氫作為生成聚合物之分子量調節劑。此時於製造低分子量之聚合物之情況下,即為了製造高熔融流動速率之聚合物,通常添加大量氫,但考慮到其安全性而於反應器之耐壓方面存在限度,可添加之氫量亦存在限制。因此,為了添加更多氫,必須降低聚合之單體之分壓,於此情況下生產性會下降。另外,就大量使用氫之情況而言,亦存在成本方面之問題。因此,較佳係開發出如下觸媒,該觸媒能夠以更少量之氫來製造高熔融流動速率之聚合物,即所謂之對氫活性高,且能夠以高產 率獲得高立體規則性聚合物,但上述習知技術並未充分解決該課題。• The melt flow rate is greatly dependent on the molecular weight of the polymer. In the industry, in the polymerization of propylene, hydrogen is generally added as a molecular weight modifier for forming a polymer. In this case, in the case of producing a low molecular weight polymer, that is, in order to produce a polymer having a high melt flow rate, a large amount of hydrogen is usually added, but in view of its safety, there is a limit in the withstand voltage of the reactor, and hydrogen can be added. There is also a limit to the amount. Therefore, in order to add more hydrogen, it is necessary to lower the partial pressure of the polymerized monomer, and in this case, the productivity is lowered. In addition, in the case of the large use of hydrogen, there are also problems in terms of cost. Therefore, it is preferred to develop a catalyst capable of producing a polymer having a high melt flow rate with a smaller amount of hydrogen, that is, a so-called high hydrogen activity and capable of high yield. The rate is high stereoregular polymer, but the above-mentioned conventional techniques do not adequately solve the problem.
(專利文獻1)日本專利特開昭63-3010號公報(申請專利範圍)(專利文獻2)日本專利特表2000-516987號公報(申請專利範圍)(專利文獻3)WO03/95504號公報(申請專利範圍)(Patent Document 1) Japanese Laid-Open Patent Publication No. Sho 63-3010 (Patent Document No.) (Patent Document 2) Japanese Patent Laid-Open Publication No. 2000-516987 (Patent Application) (Patent Document 3) WO03/95504 ( Patent application scope)
即,本發明之目的在於解決上述習知技術中殘留之問題點,提供具有更高之對氫活性、能夠以高產率獲得高立體規則性之聚合物之烯烴類聚合用固體觸媒成分、聚合用觸媒及使用其之烯烴類聚合體之製造方法。That is, the object of the present invention is to solve the problem of the above-mentioned problems in the prior art, and to provide a solid catalyst component for olefin polymerization having a higher hydrogen activity and a polymer capable of obtaining high stereoregularity in a high yield, and polymerization. A catalyst and a method for producing an olefin polymer using the same.
於上述實際情況中,本發明者為了解決上述習知技術中所殘留之課題而反覆進行深入研究,結果發現,使用特定之取代丙二酸二酯作為內部供體(inner donor)而製備之固體觸媒成分具有極高之效果,可解決上述問題,從而完成本發明。In order to solve the problems remaining in the above-mentioned prior art, the present inventors have conducted intensive studies in the above-mentioned actual circumstances, and as a result, found that a solid prepared by using a specific substituted malonic acid diester as an inner donor is found. The catalyst component has an extremely high effect and can solve the above problems, thereby completing the present invention.
即,用以達成上述目的之本發明提供烯烴類聚合用固體觸媒成分,其係使鎂化合物(a)、4價之鹵化鈦化合物(b)及以下述通式(1)表示之電子·供應性化合物(c)相接觸而製備:R1 R2 C(COOR3 )(COOR4 )(1)(式中,R1 及R2 為鹵素原子、碳數1至20之直鏈狀或支鏈狀烷基、環烷基、苯基、乙烯基、烯丙基、芳烷基及取代 有1個或2個鹵素原子之碳數1至10之直鏈狀或支鏈狀烷基之任一者,可相同或不同。R3 表示碳數1~3之烷基、環烷基、乙烯基、烯丙基,R4 為碳數2~20之烷基、環烷基、苯基、乙烯基、烯丙基、芳烷基之任一者,R3 與R4 不同)。In other words, the present invention provides a solid catalyst component for olefin polymerization, which is a magnesium compound (a), a tetravalent titanium halide compound (b), and an electron represented by the following formula (1). The compound (c) is prepared by contacting: R 1 R 2 C(COOR 3 )(COOR 4 )(1) (wherein R 1 and R 2 are a halogen atom, a linear chain having a carbon number of 1 to 20 or Branched alkyl, cycloalkyl, phenyl, vinyl, allyl, aralkyl, and linear or branched alkyl having 1 or 10 carbon atoms substituted with 1 or 2 halogen atoms Any one may be the same or different. R 3 represents an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group, a vinyl group, an allyl group, and R 4 is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, or a phenyl group. Any of vinyl, allyl, and aralkyl, R 3 is different from R 4 ).
另外,本發明提供烯烴類聚合用觸媒,其特徵在於係藉由(A)上述固體觸媒成分、(B)以通式(2)表示之有機鋁化合物:R5 p AlQ3-p (2)Further, the present invention provides a catalyst for olefin polymerization, which is characterized by (A) the above solid catalyst component, and (B) an organoaluminum compound represented by the formula (2): R 5 p AlQ 3-p ( 2)
(式中,R5 表示碳數1~4之烷基,Q表示氫原子或者鹵素原子,p為0<p≦3之實數)、以及(C)外部電子供應性化合物所形成。(wherein R 5 represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, p is a real number of 0 < p≦3), and (C) an external electron-donating compound is formed.
另外,本發明提供烯烴類聚合體之製造方法,其特徵在於,於上述烯烴類聚合用觸媒之存在下進行烯烴類之聚合。Further, the present invention provides a process for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the catalyst for olefin polymerization.
作為製備本發明之烯烴類聚合用固體觸媒成分(A)(以下,有時稱為「固體觸媒成分(A)」)時所使用之鎂化合物(a)(以下,有時稱為「成分(a)」),可舉出二鹵化鎂、二烷基鎂、鹵化烷基鎂、二烷氧基鎂、二芳氧基鎂、鹵化烷氧基鎂或者脂肪酸鎂等。該等鎂化合物之中,較佳為二鹵化鎂、二鹵化鎂與二烷氧基鎂之混合物、二烷氧基鎂,特佳為二烷氧基鎂。The magnesium compound (a) used in the preparation of the solid catalyst component (A) for olefin polymerization of the present invention (hereinafter sometimes referred to as "solid catalyst component (A)") (hereinafter referred to as " The component (a)") may, for example, be a magnesium dihalide, a dialkylmagnesium, an alkylmagnesium halide, a dialkoxymagnesium, a diaryloxymagnesium, a halogenated alkoxymagnesium or a fatty acid magnesium. Among these magnesium compounds, a magnesium dihalide, a mixture of a magnesium dihalide and a dialkoxy magnesium, a magnesium dialkoxide, and particularly a dialkoxy magnesium are preferable.
作為二烷氧基鎂,較佳為以通式Mg(OR10 )(OR11 )(式中, R10 及R11 表示碳數1~10之烷基,可分別相同亦可不同)表示之化合物,更具體而言,可舉出二甲氧基鎂、二乙氧基鎂、二丙氧基鎂、二丁氧基鎂、乙氧基甲氧基鎂、乙氧基丙氧基鎂、丁氧基乙氧基鎂等。另外,該等二烷氧基鎂亦可為使金屬鎂於鹵素或者含鹵素之金屬化合物等之存在下與醇反應而獲得者。另外,上述二烷氧基鎂可單獨使用或者併用2種以上。The magnesium dialkoxide is preferably represented by the formula Mg(OR 10 )(OR 11 ) (wherein R 10 and R 11 represent an alkyl group having 1 to 10 carbon atoms, which may be the same or different). Specific examples of the compound include magnesium dimethoxide, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, ethoxymethoxy magnesium, and ethoxypropyl magnesium oxide. Butoxyethoxy magnesium and the like. Further, the above dialkoxymagnesium may be obtained by reacting magnesium metal with an alcohol in the presence of a halogen or a halogen-containing metal compound or the like. Further, the above dialkoxymagnesium may be used singly or in combination of two or more.
進而,於本發明中,製備固體觸媒成分(A)時所使用之二烷氧基鎂為顆粒狀或粉末狀,其形狀可使用不定形或者球狀者。例如於使用球狀二烷氧基鎂之情況下,可獲得具有更加良好之粒子形狀與窄粒度分布之聚合體粉末,聚合操作時之生成聚合體粉末之處理操作性提高,可消除生成聚合體粉末中所含有之微粉所引起之堵塞等問題。Further, in the present invention, the magnesium dialkoxide used in the preparation of the solid catalyst component (A) is in the form of granules or powder, and the shape thereof may be amorphous or spherical. For example, in the case of using spheroidal dialkoxymagnesium, a polymer powder having a more favorable particle shape and a narrow particle size distribution can be obtained, and the handling workability for producing a polymer powder during a polymerization operation is improved, and the formation of a polymer can be eliminated. Problems such as clogging caused by the fine powder contained in the powder.
上述球狀二烷氧基鎂並非必須為圓球狀,亦可使用橢圓狀或者馬鈴薯狀者。具體而言,該粒子之形狀,長軸徑1與短軸徑w之比(l/w)為3以下,較佳為1至2,更佳為1至1.5。The globular dialkoxymagnesium is not necessarily spherical, and an elliptical or potato-like shape may also be used. Specifically, the shape of the particles has a ratio (l/w) of the major axis diameter 1 to the minor axis diameter w of 3 or less, preferably 1 to 2, more preferably 1 to 1.5.
另外,上述二烷氧基鎂之平均粒徑可使用1至200 μ m者。較佳為5至150 μ m。於球狀二烷氧基鎂之情況下,其平均粒徑為1至100 μ m,較佳為5至50 μ m,更佳為10至40 μ m。另外,關於其粒度,較佳係使用微粉及粗粉少、粒度分布窄者。具體而言,5 μ m以下之粒子為20%以下,較佳為10%以下。另一方面,100 μ m以上之粒子為10%以下,較佳為5%以下。進而若以In(D90/D10)表示 其粒度分布(此處,D90係以累計粒度為90%時之粒徑,D10係累計粒度為10%時之粒徑),則為3以下,較佳為2以下。Further, the above-mentioned dialkoxymagnesium may have an average particle diameter of from 1 to 200 μm. It is preferably 5 to 150 μm. In the case of spheroidal dialkoxymagnesium, the average particle diameter is from 1 to 100 μm, preferably from 5 to 50 μm, more preferably from 10 to 40 μm. Further, as for the particle size, it is preferred to use a fine powder, a coarse powder, and a narrow particle size distribution. Specifically, the particles of 5 μm or less are 20% or less, preferably 10% or less. On the other hand, the particles of 100 μm or more are 10% or less, preferably 5% or less. Further, if expressed as In (D90/D10) The particle size distribution (herein, D90 is a particle diameter when the cumulative particle size is 90%, and D10 is a particle diameter when the cumulative particle size is 10%) is 3 or less, preferably 2 or less.
如上所述球狀二烷氧基鎂之製造方法,例如揭示於日本專利特開昭58-41832號公報、日本專利特開昭62-51633號公報、日本專利特開平3-74341號公報、日本專利特開平4-368391號公報、日本專利特開平8-73388號公報等。For example, Japanese Laid-Open Patent Publication No. SHO-58-41832, JP-A-62-51633, Japanese Patent Laid-Open No. Hei 3-74341, and Japan Japanese Patent Publication No. Hei 4-368391, Japanese Patent Laid-Open No. Hei 8-73388, and the like.
製備本發明中固體觸媒成分(A)時所使用之4價之鹵化鈦化合物(b)係自以通式Ti(OR12 )n X4-n (式中,R12 表示碳數1~4之烷基,X表示氯、溴、碘等鹵素原子,n為0≦n≦4之整數)表示之鹵化鈦或烷氧基鹵化鈦群組中選擇之化合物的1種或者2種以上。The tetravalent titanium halide compound (b) used in the preparation of the solid catalyst component (A) of the present invention is derived from the general formula Ti(OR 12 ) n X 4-n (wherein R 12 represents a carbon number of 1~) The alkyl group of 4, X represents a halogen atom such as chlorine, bromine or iodine, and n is an integer of 0≦n≦4. One or more compounds selected from the group consisting of titanium halides or alkoxy titanium halides.
具體而言,作為鹵化鈦,可例示四氯化鈦、四溴化鈦、四碘化鈦等四鹵化鈦,作為烷氧基鹵化鈦,可例示甲氧基三氯化鈦、乙氧基三氯化鈦、丙氧基三氯化鈦、正丁氧基三氯化鈦、二甲氧基二氯化鈦、二乙氧基二氯化鈦、二丙氧基二氯化鈦、二正丁氧基二氯化鈦、三甲氧基氯化鈦、三乙氧基氯化鈦、三丙氧基氯化鈦、三正丁氧基氯化鈦等。其中,較佳為四鹵化鈦,特佳為四氯化鈦。該等鈦化合物可單獨使用或者併用2種以上。Specifically, as the titanium halide, titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide or titanium tetraiodide can be exemplified, and as the alkoxy titanium halide, methoxy titanium trichloride or ethoxylated three can be exemplified. Titanium chloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two positive Butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n-butoxytitanium chloride, and the like. Among them, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred. These titanium compounds may be used alone or in combination of two or more.
製備本發明中之固體觸媒成分(A)時所使用之電子供應性化合物(c)係以上述通式(1)表示之化合物。該等化合物為二鹵素取代丙二酸二酯、烷基及鹵素取代丙二酸二酯、二烷基取代丙二酸二酯或鹵化烷基取代丙二酸二酯等(以 下,亦稱為「取代丙二酸二酯」)。上述通式(1)中之R1 及R2 中,作為鹵素原子,為氯原子、溴原子、碘原子、氟原子,較佳為氯原子及溴原子。另外上述通式中,R1 較佳為甲基或異丁基,R1 為甲基及R2 為第三丁基,或者R1 及R2 均為異丁基。另外,R1 及R2 較佳為含有1個以上之二級碳、三級碳或者四級碳之碳數3~10之支鏈狀烷基,特佳為異丁基、第三丁基、異戊基、新戊基。另外,上述通式(1)中,作為羰基之酯殘基之R3 ,較佳為碳數1~3之直鏈狀或者支鏈狀烷基,具體為甲基、乙基、丙基、異丙基,特佳為甲基或乙基。另外,R4 較佳為碳數2~20之烷基,特佳為碳數2~8之直鏈狀或者支鏈狀烷基,具體為乙基、丙基、丁基、戊基、己基、庚基、辛基、異丙基、異丁基、異戊基、新戊基、異己基、異庚基、異辛基。The electron-donating compound (c) used in the preparation of the solid catalyst component (A) in the present invention is a compound represented by the above formula (1). These compounds are dihalogen-substituted malonic acid diesters, alkyl and halogen-substituted malonic acid diesters, dialkyl-substituted malonic acid diesters or halogenated alkyl-substituted malonic acid diesters (hereinafter also referred to as "Substituting malonate diester"). In the above-mentioned general formula (1), R 1 and R 2 are a halogen atom, a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and preferably a chlorine atom or a bromine atom. Further, in the above formula, R 1 is preferably a methyl group or an isobutyl group, R 1 is a methyl group and R 2 is a third butyl group, or both R 1 and R 2 are isobutyl groups. Further, R 1 and R 2 are preferably a branched alkyl group having 3 or more carbon atoms of one or more secondary carbons, tertiary carbons or quaternary carbons, particularly preferably isobutyl or tert-butyl. , isoamyl, neopentyl. Further, in the above formula (1), R 3 which is an ester residue of a carbonyl group is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, specifically methyl group, ethyl group, propyl group, Isopropyl, particularly preferably methyl or ethyl. Further, R 4 is preferably an alkyl group having 2 to 20 carbon atoms, particularly preferably a linear or branched alkyl group having 2 to 8 carbon atoms, specifically ethyl, propyl, butyl, pentyl or hexyl groups. , heptyl, octyl, isopropyl, isobutyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl.
作為二鹵素取代丙二酸二酯之具體例,可舉出二氯丙二酸甲基乙酯、二氯丙二酸甲基丙酯、二氯丙二酸甲基丁酯、二氯丙二酸甲基異丁酯、二氯丙二酸甲基戊酯、二氯丙二酸甲基新戊酯、二氯丙二酸甲基己酯、二氯丙二酸甲基異己酯、二氯丙二酸甲基庚酯、二氯丙二酸甲基異庚酯、二氯丙二酸甲基辛酯、二氯丙二酸甲基異辛酯、二氯丙二酸乙基丙酯、二氯丙二酸乙基丁酯、二氯丙二酸乙基異丁酯、二氯丙二酸乙基戊酯、二氯丙二酸乙基新戊酯、二氯丙二酸乙基己酯、二氯丙二酸乙基異己酯、二氯丙二酸乙基庚酯、二氯丙二酸乙基異庚酯、二氯丙二酸乙基辛酯、二氯丙二酸乙基異辛酯、二溴代丙二酸甲基乙酯、二 溴代丙二酸甲基丙酯、二溴代丙二酸甲基丁酯、二溴代丙二酸甲基異丁酯、二溴代丙二酸甲基戊酯、二溴代丙二酸甲基新戊酯、二溴代丙二酸甲基己酯、二溴代丙二酸甲基異己酯、二溴代丙二酸甲基庚酯、二溴代丙二酸甲基異庚酯、二溴代丙二酸甲基辛酯、二溴代丙二酸甲基異辛酯、二溴代丙二酸乙基丙酯、二溴代丙二酸乙基丁酯、二溴代丙二酸乙基異丁酯、二溴代丙二酸乙基戊酯、二溴代丙二酸乙基新戊酯、二溴代丙二酸乙基己酯、二溴代丙二酸乙基異己酯、二溴代丙二酸乙基庚酯、二溴代丙二酸乙基異庚酯、二溴代丙二酸乙基辛酯、二溴代丙二酸乙基異辛酯等。Specific examples of the dihalogen-substituted malonic acid diester include methyl ethyl dichloromalonate, methyl propyl dipropyl malonate, methyl butyl dichloromalonate, and dichloropropane. Acid methyl isobutyl ester, methyl amyl malonate, methyl neopentyl dichloromalonate, methylhexyl dichloromalonate, methyl isopropionate dichloride, dichloro Methylheptyl malonate, methyl isoheptane dichloromalonate, methyl octyl dichloromalonate, methyl isooctyl dichloromalonate, ethyl propyl dipropyl malonate, Ethyl butyl dichloromalonate, ethyl isobutyl dichloromalonate, ethyl amyl dichloromalonate, ethyl neopentyl dichloromalonate, ethyl dichloromalonate Ester, ethyl isohexyl dichloromalonate, ethyl heptyl dichloromalonate, ethyl isoheptane dichloromalonate, ethyl octyl dichloromalonate, ethyl dichloromalonate Isooctyl ester, methyl ethyl bromide malonate, two Methyl propyl bromomalonate, methyl butyl bromomalonate, methyl isobutyl dibromomalonate, methyl amyl bromomalonate, dibromomalonic acid Methyl neopentyl ester, methylhexyl bromomalonate, methyl isohexyl dibromomalonate, methyl heptyl dibromomalonate, methyl isoheptyl dibromomalonate , methyloctyl malonyl malonate, methyl isooctyl dibromomalonate, ethyl propyl dibromomalonate, ethyl butyl dibromomalonate, dibromopropyl Ethyl isobutyl dicarboxylate, ethyl amyl bromomalonate, ethyl neopentyl dibromomalonate, ethylhexyl dibromomalonate, ethyl dibromomalonate Isohexyl ester, ethyl heptyl dibromomalonate, ethyl isoheptyl dibromomalonate, ethyl octyl dibromomalonate, ethyl isooctyl dibromomalonate, and the like.
作為烷基及鹵素取代丙二酸二酯之具體例,可舉出乙基氯代丙二酸甲基乙酯、乙基氯代丙二酸甲基丙酯、乙基氯代丙二酸甲基丁酯、乙基氯代丙二酸乙基丁酯、乙基氯代丙二酸乙基異辛酯、乙基溴代丙二酸甲基乙酯、乙基溴代丙二酸甲基丙酯、乙基溴代丙二酸甲基丁酯、乙基溴代丙二酸乙基丁酯、乙基溴代丙二酸乙基異辛酯、異丙基氯代丙二酸甲基乙酯、異丙基氯代丙二酸甲基丙酯、異丙基氯代丙二酸甲基丁酯、異丙基氯代丙二酸乙基丁酯、異丙基氯代丙二酸乙基異辛酯、異丙基溴代丙二酸甲基乙酯、異丙基溴代丙二酸甲基丙酯、異丙基溴代丙二酸甲基丁酯、異丙基溴代丙二酸乙基丁酯、異丙基溴代丙二酸乙基異辛酯、丁基氯代丙二酸甲基乙酯、丁基氯代丙二酸甲基丙酯、丁基氯代丙二酸甲基丁酯、丁基氯代丙二酸乙基丁 酯、丁基氯代丙二酸乙基異辛酯、丁基溴代丙二酸甲基乙酯、丁基溴代丙二酸甲基丙酯、丁基溴代丙二酸甲基丁酯、丁基溴代丙二酸乙基丁酯、丁基溴代丙二酸乙基異辛酯、異丁基氯代丙二酸甲基乙酯、異丁基氯代丙二酸甲基丙酯、異丁基氯代丙二酸甲基丁酯、異丁基氯代丙二酸乙基丁酯、異丁基氯代丙二酸乙基異辛酯、異丁基溴代丙二酸甲基乙酯、異丁基溴代丙二酸甲基丙酯、異丁基溴代丙二酸甲基丁酯、異丁基溴代丙二酸乙基丁酯、異丁基溴代丙二酸乙基異辛酯等。Specific examples of the alkyl group and the halogen-substituted malonic acid diester include ethyl chloromalonate methyl ethyl ester, ethyl chloromalonate methyl propyl ester, and ethyl chloromalonate. Butyl ester, ethyl chloropropyl malonate, ethyl isooctyl ethyl chloromalonate, methyl ethyl bromomalonate, methyl bromomalonate Propyl ester, methyl bromomalonate methyl butyl ester, ethyl bromomalonate ethyl butyl ester, ethyl bromomalonate ethyl isooctyl ester, isopropyl chloromalonate methyl Ethyl ester, methyl propyl chloromalonate, methyl butyl isopropyl chloromalonate, ethyl butyl chloropropyl malonate, isopropyl chloromalonic acid Ethyl isooctyl ester, methyl isopropyl bromomalonate, methyl propyl bromomalonate, methyl butyl propyl bromomalonate, isopropyl bromide Ethyl butyl acrylate, ethyl isooctyl isopropyl bromomalonate, methyl ethyl butyl chloromalonate, methyl propyl chloromalonate, butyl chloro Methyl butyl malonate, ethyl butyl chloromalonate Ester, ethyl isooctyl butyl chloromalonate, methyl ethyl butyl bromomalonate, methyl propyl bromomalonate, methyl butyl bromomalonate , ethyl butyl bromomalonate, ethyl isooctyl butyl bromomalonate, methyl ethyl isobutyl chloromalonate, methyl propyl methacrylate Ester, isobutyl chloromalonate methyl butyl ester, isobutyl chloromalonate ethyl butyl ester, isobutyl chloromalonate ethyl isooctyl ester, isobutyl bromomalonic acid Methyl ethyl ester, isobutyl bromomalonate methyl propyl ester, isobutyl bromomalonate methyl butyl ester, isobutyl bromomalonate ethyl butyl ester, isobutyl bromide Ethyl isooctyl diacidate and the like.
作為二烷基取代丙二酸二酯之具體例,可舉出二異丙基丙二酸甲基乙酯、二異丙基丙二酸甲基丙酯、二異丙基丙二酸甲基丁酯、二異丙基丙二酸甲基異丁酯、二異丙基丙二酸甲基戊酯、二異丙基丙二酸甲基新戊酯、二異丙基丙二酸甲基己酯、二異丙基丙二酸甲基異己酯、二異丙基丙二酸甲基庚酯、二異丙基丙二酸甲基異庚酯、二異丙基丙二酸甲基辛酯、二異丙基丙二酸甲基異辛酯、二異丙基丙二酸乙基丙酯、二異丙基丙二酸乙基丁酯、二異丙基丙二酸乙基異丁酯、二異丙基丙二酸乙基戊酯、二異丙基丙二酸乙基己酯、二異丙基丙二酸乙基異己酯、二異丙基丙二酸乙基庚酯、二異丙基丙二酸乙基異庚酯、二異丙基丙二酸乙基辛酯、二異丙基丙二酸乙基異辛酯、二異丁基丙二酸甲基乙酯、二異丁基丙二酸甲基丙酯、二異丁基丙二酸甲基丁酯、二異丁基丙二酸甲基異丁酯、二異丁基丙二酸甲基戊酯、二異丁基丙二酸甲基新戊酯、二異丁基丙二酸 甲基己酯、二異丁基丙二酸甲基異己酯、二異丁基丙二酸甲基庚酯、二異丁基丙二酸甲基異庚酯、二異丁基丙二酸甲基辛酯、二異丁基丙二酸甲基異辛酯、二異丁基丙二酸乙基丙酯、二異丁基丙二酸乙基丁酯、二異丁基丙二酸乙基異丁酯、二異丁基丙二酸乙基戊酯、二異丁基丙二酸乙基新戊酯、二異丁基丙二酸乙基己酯、二異丁基丙二酸乙基異己酯、二異丁基丙二酸乙基庚酯、二異丁基丙二酸乙基異庚酯、二異丁基丙二酸乙基辛酯、二異丁基丙二酸乙基異辛酯、第三丁基甲基丙二酸甲基乙酯、第三丁基甲基丙二酸甲基丙酯、第三丁基甲基丙二酸甲基丁酯、第三丁基甲基丙二酸甲基異丁酯、第三丁基甲基丙二酸甲基戊酯、第三丁基甲基丙二酸甲基新戊酯、第三丁基甲基丙二酸甲基己酯、第三丁基甲基丙二酸甲基異己酯、第三丁基甲基丙二酸甲基庚酯、第三丁基甲基丙二酸甲基異庚酯、第三丁基甲基丙二酸甲基辛酯、第三丁基甲基丙二酸甲基異辛酯、第三丁基甲基丙二酸乙基丙酯、第三丁基甲基丙二酸乙基丁酯、第三丁基甲基丙二酸乙基異丁酯、第三丁基甲基丙二酸乙基戊酯、第三丁基甲基丙二酸乙基新戊酯、第三丁基甲基丙二酸乙基己酯、第三丁基甲基丙二酸乙基異己酯、第三丁基甲基丙二酸乙基庚酯、第三丁基甲基丙二酸乙基異庚酯、第三丁基甲基丙二酸乙基辛酯、第三丁基甲基丙二酸乙基異辛酯、第三丁基乙基丙二酸甲基乙酯、第三丁基乙基丙二酸甲基丙酯、第三丁基乙基丙二酸甲基丁酯、第三丁基乙基丙二酸甲基異丁酯、第三丁基 乙基丙二酸甲基戊酯、第三丁基乙基丙二酸甲基新戊酯、第三丁基乙基丙二酸甲基己酯、第三丁基乙基丙二酸甲基異己酯、第三丁基乙基丙二酸甲基庚酯、第三丁基乙基丙二酸甲基異庚酯、第三丁基乙基丙二酸甲基辛酯、第三丁基乙基丙二酸甲基異辛酯、第三丁基乙基丙二酸乙基丙酯、第三丁基乙基丙二酸乙基丁酯、第三丁基乙基丙二酸乙基異丁酯、第三丁基乙基丙二酸乙基戊酯、第三丁基乙基丙二酸乙基新戊酯、第三丁基乙基丙二酸乙基己酯、第三丁基乙基丙二酸乙基異己酯、第三丁基乙基丙二酸乙基庚酯、第三丁基乙基丙二酸乙基異庚酯、第三丁基乙基丙二酸乙基辛酯、第三丁基乙基丙二酸乙基異辛酯、第三丁基正丙基丙二酸甲基乙酯、第三丁基正丙基丙二酸甲基丙酯、第三丁基正丙基丙二酸甲基丁酯、第三丁基正丙基丙二酸甲基異丁酯、第三丁基正丙基丙二酸甲基戊酯、第三丁基正丙基丙二酸甲基新戊酯、第三丁基正丙基丙二酸甲基己酯、第三丁基正丙基丙二酸甲基異己酯、第三丁基正丙基丙二酸甲基庚酯、第三丁基正丙基丙二酸甲基異庚酯、第三丁基正丙基丙二酸甲基辛酯、第三丁基正丙基丙二酸甲基異辛酯、第三丁基正丙基丙二酸乙基丙酯、第三丁基正丙基丙二酸乙基丁酯、第三丁基正丙基丙二酸乙基異丁酯、第三丁基正丙基丙二酸乙基戊酯、第三丁基正丙基丙二酸乙基新戊酯、第三丁基正丙基丙二酸乙基己酯、第三丁基正丙基丙二酸乙基異己酯、第三丁基正丙基丙二酸乙基庚酯、第三丁基正丙基丙二酸乙基異庚酯、第三丁 基正丙基丙二酸乙基辛酯、第三丁基正丙基丙二酸乙基異辛酯、第三丁基異丙基丙二酸甲基乙酯、第三丁基異丙基丙二酸甲基丙酯、第三丁基異丙基丙二酸甲基丁酯、第三丁基異丙基丙二酸甲基異丁酯、第三丁基異丙基丙二酸甲基戊酯、第三丁基異丙基丙二酸甲基新戊酯、第三丁基異丙基丙二酸甲基己酯、第三丁基異丙基丙二酸甲基異己酯、第三丁基異丙基丙二酸甲基庚酯、第三丁基異丙基丙二酸甲基異庚酯、第三丁基異丙基丙二酸甲基辛酯、第三丁基異丙基丙二酸甲基異辛酯、第三丁基異丙基丙二酸乙基丙酯、第三丁基異丙基丙二酸乙基丁酯、第三丁基異丙基丙二酸乙基異丁酯、第三丁基異丙基丙二酸乙基戊酯、第三丁基異丙基丙二酸乙基新戊酯、第三丁基異丙基丙二酸乙基己酯、第三丁基異丙基丙二酸乙基異己酯、第三丁基異丙基丙二酸乙基庚酯、第三丁基異丙基丙二酸乙基異庚酯、第三丁基異丙基丙二酸乙基辛酯、第三丁基異丙基丙二酸乙基異辛酯、二異戊基丙二酸甲基乙酯、二異戊基丙二酸甲基丙酯、二異戊基丙二酸甲基丁酯、二異戊基丙二酸甲基異丁酯、二異戊基丙二酸甲基戊酯、二異戊基丙二酸甲基新戊酯、二異戊基丙二酸甲基己酯、二異戊基丙二酸甲基異己酯、二異戊基丙二酸甲基庚酯、二異戊基丙二酸甲基異庚酯、二異戊基丙二酸甲基辛酯、二異戊基丙二酸甲基異辛酯、二異戊基丙二酸乙基丙酯、二異戊基丙二酸乙基丁酯、二異戊基丙二酸乙基異丁酯、二異戊基丙二酸乙基戊酯、二異戊基丙二酸乙基新戊酯、二異戊基丙 二酸乙基己酯、二異戊基丙二酸乙基異己酯、二異戊基丙二酸乙基庚酯、二異戊基丙二酸乙基異庚酯、二異戊基丙二酸乙基辛酯、二異戊基丙二酸乙基異辛酯、異丙基異丁基丙二酸甲基乙酯、異丙基異丁基丙二酸甲基丙酯、異丙基異丁基丙二酸甲基丁酯、異丙基異丁基丙二酸甲基異丁酯、異丙基異丁基丙二酸甲基戊酯、異丙基異丁基丙二酸甲基新戊酯、異丙基異丁基丙二酸甲基己酯、異丙基異丁基丙二酸甲基異己酯、異丙基異丁基丙二酸甲基庚酯、異丙基異丁基丙二酸甲基異庚酯、異丙基異丁基丙二酸甲基辛酯、異丙基異丁基丙二酸甲基異辛酯、異丙基異丁基丙二酸乙基丙酯、異丙基異丁基丙二酸乙基丁酯、異丙基異丁基丙二酸乙基異丁酯、異丙基異丁基丙二酸乙基戊酯、異丙基異丁基丙二酸乙基新戊酯、異丙基異丁基丙二酸乙基己酯、異丙基異丁基丙二酸乙基異己酯、異丙基異丁基丙二酸乙基庚酯、異丙基異丁基丙二酸乙基異庚酯、異丙基異丁基丙二酸乙基辛酯、異丙基異丁基丙二酸乙基異辛酯、異丙基異戊基丙二酸甲基乙酯、異丙基異戊基丙二酸甲基丙酯、異丙基異戊基丙二酸甲基丁酯、異丙基異戊基丙二酸甲基異丁酯、異丙基異戊基丙二酸甲基戊酯、異丙基異戊基丙二酸甲基新戊酯、異丙基異戊基丙二酸甲基己酯、異丙基異戊基丙二酸甲基異己酯、異丙基異戊基丙二酸甲基庚酯、異丙基異戊基丙二酸甲基異庚酯、異丙基異戊基丙二酸甲基辛酯、異丙基異戊基丙二酸甲基異辛酯、異丙基異戊基丙二酸乙基丙酯、異丙基異戊基丙二酸乙基 丁酯、異丙基異戊基丙二酸乙基異丁酯、異丙基異戊基丙二酸乙基戊酯、異丙基異戊基丙二酸乙基新戊酯、異丙基異戊基丙二酸乙基己酯、異丙基異戊基丙二酸乙基異己酯、異丙基異戊基丙二酸乙基庚酯、異丙基異戊基丙二酸乙基異庚酯、異丙基異戊基丙二酸乙基辛酯、異丙基異戊基丙二酸乙基異辛酯等。Specific examples of the dialkyl-substituted malonic acid diester include methyl ethyl diisopropyl malonate, methyl propyl diisopropyl malonate, and methyl diisopropyl malonate. Butyl ester, methyl isobutyl malonyl malonate, methyl amyl diisopropyl malonate, methyl neopentyl diisopropylmalonate, methyl diisopropylmalonate Hexyl ester, methyl isopropionate diisopropylmalonate, methyl heptyl diisopropylmalonate, methyl isoheptyl diisopropylmalonate, methyl octyl diisopropylmalonate Ester, methyl isooctyl malonate, ethyl propyl diisopropyl malonate, ethyl butyl diisopropyl malonate, ethyl isobutyl diisopropyl malonate Ester, ethyl amyl diisopropylmalonate, ethylhexyl diisopropylmalonate, ethyl isopropanyl diisopropylmalonate, ethyl heptyl diisopropylmalonate, Ethyl isoheptyl diisopropylmalonate, ethyl octyl diisopropylmalonate, ethyl isooctyl diisopropylmalonate, methyl ethyl diisobutylmalonate, Methyl propyl diisopropionate, methyl butyl diisobutylmalonate, diisobutyl Acid, methyl isobutyl, diisobutyl malonate methylpentyl, diisobutyl malonate methyl neopentyl, diisobutyl malonate Methylhexyl ester, diisobutylmalonate methyl isohexyl ester, diisobutylmalonate methylheptyl ester, diisobutylmalonate methylisoheptyl ester, diisobutylmalonate Kesin ester, diisobutylmalonate methyl isooctyl ester, diisobutylmalonate ethyl propyl ester, diisobutylmalonate ethyl butylate, diisobutylmalonate ethyl Isobutyl ester, diisobutylmalonate ethyl amyl ester, diisobutylmalonate ethyl neopentyl ester, diisobutylmalonate ethylhexyl, diisobutylmalonate ethyl Isohexyl ester, diisobutylmalonate ethylheptyl ester, diisobutylmalonate ethyl isoheptyl ester, diisobutylmalonate ethyloctyl ester, diisobutylmalonate ethyl Octyl ester, methyl ethyl butyl trimethyl malonate, methyl propyl tributyl methyl malonate, methyl butyl tributyl methyl malonate, methyl isobutyl tributyl methyl malonate Ester, methyl pentyl methyl malonate, methyl neopentyl tributylmethyl malonate, methyl hexyl butyl methyl malonate, methyl isobutyl methacrylate Tributylmethylmalonate methylheptyl ester Methyl iso-heptyl methyl malonate, methyl octyl t-butyl methyl malonate, methyl isooctyl t-butyl methyl malonate, ethyl propyl propyl trimethyl malonate, Ethyl butyl butyl methacrylate, ethyl isobutyl tributyl methacrylate, ethyl amyl butyl methacrylate, ethyl neopentyl butyl methacrylate Third butyl methylmalonate ethylhexyl ester, tert-butylmethylmalonate ethyl isohexyl ester, tert-butylmethylmalonate ethylheptyl ester, tert-butylmethylmalonate ethylisoheptyl ester, Trioctylmethylmalonate ethyloctyl ester, tert-butylmethylmalonate ethyl isooctyl ester, tert-butylethylmalonate methylethyl ester, tert-butylethylmalonate methylpropyl Ester, tert-butylethylmalonate methyl butyl ester, tert-butylethylmalonate methyl isobutyl ester, tert-butyl Ethylmalonate methyl amyl ester, tert-butylethylmalonate methyl neopentyl ester, tert-butylethylmalonate methylhexyl ester, tert-butylethylmalonate methyl Isohexyl ester, tributylethylmalonate methylheptyl ester, tert-butylethylmalonate methylisoheptyl ester, tert-butylethylmalonate methyloctyl ester, tert-butyl Ethylmalonate methyl isooctyl ester, tert-butylethylmalonate ethyl propyl ester, tert-butylethylmalonate ethyl butylate, tert-butylethylmalonate ethyl Isobutyl ester, ethyl pentyl ethanoethyl malonate, ethyl neopentyl tributate, butyl ethyl malonate, third butyl ethyl malonate Ethyl ethyl malonate ethyl isohexyl ester, tert-butyl ethyl malonate ethyl heptyl ester, tert-butyl ethyl malonate ethyl isoheptyl ester, tert-butyl ethyl malonate Lithyl octyl ester, ethyl octyl octyl propyl malonate, methyl ethyl butyl propyl propyl malonate, methyl propyl propyl propyl propyl malonate, Tributyl n-propyl malonate methyl butyl ester, t-butyl n-propyl malonate methyl isobutyl ester, Butyl-n-propylmalonate methyl amyl ester, t-butyl-n-propylmalonate methyl-pivalate, tert-butyl-n-propylmalonate methylhexyl ester, tert-butyl-n-propyl Methyl isopropionate malonate, methyl butyl hectyl tributyl n-propyl malonate, methyl isoheptyl t-butyl-n-propylmalonate, t-butyl-n-propylmalonate Methyl octyl ester, t-butyl-n-propylmalonate methyl isooctyl ester, tert-butyl-n-propylmalonate ethyl propyl ester, t-butyl-n-propylmalonate ethyl butyl ester , t-butyl n-propylmalonate ethyl isobutyl ester, t-butyl-n-propylmalonate ethyl amyl ester, t-butyl-n-propylmalonate ethyl neopentyl ester, third Butyl-n-propylmalonate ethylhexyl ester, tert-butyl-n-propylmalonate ethyl isohexyl ester, tert-butyl-n-propylmalonate ethylheptyl ester, tert-butyl-n-propyl Ethyl isoheptyl malonate, third Ethyl octyl malonate, ethyl isooctyl propyl propyl malonate, methyl ethyl butyl propyl malonate, tert-butyl isopropyl Methyl propyl malonate, methyl butyl tributyl isopropyl malonate, methyl isobutyl tributyl isopropyl malonate, tert-butyl isopropyl malonate Methyl amyl ester, methyl neopentyl butyl isopropyl malonate, methyl hexyl butyl isopropyl malonate, methyl isobutyl hexapropyl isopropyl malonate, Tert-butylisopropylmalonate methylheptyl ester, tert-butylisopropylmalonate methylisoheptyl ester, tert-butylisopropylmalonate methyloctyl ester, tert-butyl Isopropyl malonate methyl isooctyl ester, tert-butyl isopropyl malonate ethyl propyl ester, tert-butyl isopropyl malonate ethyl butyl ester, tert-butyl isopropyl propyl Ethyl isobutyl dicarboxylate, ethyl amyl tributate tributyl isopropyl malonate, ethyl neopentyl tributate tributyl isopropyl malonate, and third butyl isopropyl malonate Hexyl hexyl ester, ethyl hexyl isopropyl isopropyl malonate, ethyl butyl butyl isopropyl acrylate Ester, tert-butyl isopropyl malonate ethyl isoheptyl ester, tributyl isopropyl malonate ethyl octyl ester, tert-butyl isopropyl malonate ethyl isooctyl ester, two Isoamylmalonate methyl ethyl ester, diisoamylmalonate methyl propyl ester, diisoamylmalonate methyl butyl ester, diisoamylmalonate methyl isobutyl ester, diiso) Methyl amyl pentyl malonate, methyl neopentyl diisoamylmalonate, methyl hexyl diisoamylmalonate, methyl isohexyl diisoamylmalonate, diisoamyl Methylheptyl malonate, methyl isoheptyl diisoamylmalonate, methyloctyl diisoamylmalonate, methyl isooctyl diisoamylmalonate, diisoamyl Ethyl propyl primary malonate, ethyl butyl diisoamylmalonate, ethyl isobutyl diisoamylmalonate, ethyl amyl diisoamylmalonate, diisoamyl Ethyl neopentyl malonate, diisoamyl propyl Ethylhexyl diacrylate, ethyl isohexyl diisoamylmalonate, ethyl heptyl diisoamylmalonate, ethyl isoheptyl diisoamylmalonate, diisoamylpropane Ethyl ethyl octylate, ethyl isooctyl diisoamylmalonate, methyl ethyl isopropyl isobutyl malonate, methyl propyl isobutyl malonate, isopropyl Isobutyl malonate methyl butyl ester, isopropyl isobutyl malonate methyl isobutyl ester, isopropyl isobutyl malonate methyl amyl ester, isopropyl isobutyl malonate Neopentyl ester, isopropyl isobutyl malonate methyl hexyl ester, isopropyl isobutyl malonate methyl isohexyl ester, isopropyl isobutyl malonate methyl heptyl ester, isopropyl Isobutylammonium malonate, methyl octyl isopropionate, methyl isooctyl isopropyl isobutyl malonate, isopropyl isobutyl malonate Ethyl propyl ester, ethyl butyl isobutyl malonate, ethyl isobutyl isopropyl isobutyl malonate, ethyl amyl isopropyl isobutyl malonate, isopropyl Ethyl neopentyl malonate, ethyl isopropyl isobutyl malonate, isopropyl iso Ethyl isopropionate, ethyl heptyl isopropyl isobutylmalonate, ethyl isoheptyl isopropyl isobutyl malonate, ethyl octyl isopropyl isobutyl malonate Ester, ethyl isooctyl isopropyl isobutyl malonate, methyl ethyl isopropyl isoamylmalonate, methyl propyl isoamylmalonate, isopropyl isoprene Methyl butyl acrylate, methyl isobutyl isopropyl isoamylmalonate, methyl amyl isopropyl isoamylmalonate, methyl isopropyl isoamylmalonate Amyl Ester, Methyl Hexyl Isoamylmalonate, Methyl Isohexyl Isoamylmalonate, Methylheptyl Isoamylmalonate, Isopropylidene Methyl isoheptyl malonate, methyl octyl isopropyl isoamylmalonate, methyl isooctyl isopropyl isoamylmalonate, ethyl isopropyl isoamylmalonate Propyl ester, isopropylisoamylmalonate ethyl Butyl ester, isopropyl isoamylmalonate ethyl isobutyl ester, isopropyl isoamylmalonate ethyl amyl ester, isopropylisoamylmalonate ethyl neopentyl ester, isopropyl Isoamylmalonate ethylhexyl ester, isopropylisoamylmalonate ethyl isohexyl ester, isopropylisoamylmalonate ethylheptyl ester, isopropylisoamylmalonate ethyl Isoheptyl ester, ethyl octyl isoamylmalonate, ethyl isooctyl isopropyl isoamylmalonate, and the like.
作為鹵化烷基取代丙二酸二酯之具體例,可舉出雙(氯甲基)丙二酸甲基丁酯、雙(溴甲基)丙二酸甲基丁酯、雙(氯乙基)丙二酸甲基丁酯、雙(溴乙基)丙二酸甲基丁酯、雙(3-氯-正丙基)丙二酸甲基丁酯、雙(3-溴-正丙基)丙二酸甲基丁酯。Specific examples of the halogenated alkyl-substituted malonic acid diester include bis(chloromethyl)malonate methylbutyl ester, bis(bromomethyl)malonate methylbutyl ester, and bis(chloroethyl). ) methyl butyl malonate, methyl butyl bis(bromoethyl)malonate, methyl butyl bis(3-chloro-n-propyl)malonate, bis(3-bromo-n-propyl) ) methyl butyl acrylate.
上述取代丙二酸二酯之中,特佳為異丙基溴代丙二酸甲基丁酯、丁基溴代丙二酸甲基丁酯、丁基溴代丙二酸乙基丁酯、異丁基溴代丙二酸甲基丁酯、二異丙基丙二酸甲基丁酯、二丁基丙二酸甲基丁酯、二異丁基丙二酸乙基丁酯、二異丁基丙二酸甲基乙酯、二異丁基丙二酸乙基異辛酯、二異丁基丙二酸甲基丁酯、二異戊基丙二酸甲基丁酯、異丙基異丁基丙二酸甲基丁酯、異丙基異戊基丙二酸甲基丁酯、第三丁基甲基丙二酸甲基丁酯、雙(3-氯-正丙基)丙二酸甲基丁酯、雙(3-溴-正丙基)丙二酸甲基丁基。上述電子供應性化合物(c)可單獨使用1種或者組合使用2種以上。再者,上述化合物中,酯殘基之「丁基」為正丁基或異丁基。Among the above substituted malonic acid diesters, particularly preferred are methyl butyl bromomalonate, methyl butyl bromomalonate, ethyl butyl bromomalonate, Isobutyl bromide malonate, methyl butyl diisopropyl malonate, methyl butyl dibutyl malonate, ethyl butyl butyl diisopropionate, diisobutyl Methyl ethyl butyl malonate, ethyl isooctyl diisobutylmalonate, methyl butyl diisobutylmalonate, methyl butyl diisoamylmalonate, isopropyl Isobutyl malonate methyl butyl ester, isopropyl isoamylmalonate methyl butyl ester, tert-butyl methyl malonate methyl butyl ester, bis (3-chloro-n-propyl) malonic acid Methyl butyl ester, bis(3-bromo-n-propyl)malonate methyl butyl. The above-mentioned electron-donating compound (c) may be used alone or in combination of two or more. Further, in the above compound, the "butyl group" of the ester residue is n-butyl or isobutyl.
另外,製備本發明之固體觸媒成分(A)時,鎂化合物(a) 使用二乙氧基鎂,作為電子供應性化合物(c),於R3 與R4 之酯殘基之烷基使用乙基以外之不同酯殘基之烷基之情況下,於使各成分相接觸而製備固體觸媒成分之過程中,二乙氧基鎂之乙氧基與1種電子供應性化合物(c)之酯殘基會產生交換,最終包含固體觸媒成分中所含有之電子供應性化合物(c),丙二酸二酯化合物成為3種以上。例如,使用二乙氧基鎂作為鎂化合物(a)、使用二異丁基丙二酸甲基正丁酯作為電子供應性化合物(c)之情況下,固體觸媒成分中所含有之酯類為二異丁基丙二酸二甲酯、二異丁基丙二酸甲基乙酯、二異丁基丙二酸甲基正丁酯、二異丁基丙二酸乙基正丁酯及二異丁基丙二酸二正丁酯之5種。如此,使用R3 與R4 之酯殘基之烷基相互不同之種類之電子供應性化合物,故最終於固體觸媒成分中生成多種酯,藉此亦可獲得高對氫活性之固體觸媒成分。Further, in the preparation of the solid catalyst component (A) of the present invention, the magnesium compound (a) uses diethoxymagnesium as the electron-donating compound (c), and the alkyl group of the ester residue of R 3 and R 4 is used. In the case of an alkyl group having a different ester residue other than an ethyl group, an ethoxy group of diethoxymagnesium and an electron-donating compound (c) in the process of preparing a solid catalyst component by bringing the components into contact The ester residue is exchanged, and finally contains the electron-donating compound (c) contained in the solid catalyst component, and the malonic acid diester compound is three or more types. For example, when diethoxy magnesium is used as the magnesium compound (a) and diisobutylmalonate methyl n-butyl ester is used as the electron-donating compound (c), the ester contained in the solid catalyst component is used. It is dimethyl diisobutylmalonate, methyl ethyl diisobutylmalonate, methyl n-butyl diisobutylmalonate, ethyl n-butyl diisobutylmalonate and Five kinds of di-n-butyl malonate. Thus, by using an electron-donating compound of a type in which the alkyl groups of the ester residues of R 3 and R 4 are different from each other, a plurality of esters are finally formed in the solid catalyst component, whereby a solid catalyst having high hydrogen activity can be obtained. ingredient.
本發明之固體觸媒成分(A)中,作為製備該固體觸媒成分時所使用之電子供應性化合物,若使用以通式(1)表示之取代丙二酸二酯,則能夠以高產率獲得活性高且對氫活性良好之高立體規則性聚合物。In the solid catalyst component (A) of the present invention, as the electron-donating compound used in the preparation of the solid catalyst component, high-yield can be obtained by using the substituted malonic acid diester represented by the general formula (1). A highly stereoregular polymer having high activity and good hydrogen activity is obtained.
於本發明中,固體觸媒成分(A)之製備較佳為於沸點為50~150℃之烴溶劑(d)中懸浮接觸而進行。作為沸點為50~150℃之烴溶劑,較佳為使用甲苯、二甲苯、乙基苯、己烷、庚烷、辛烷、環己烷等。另外,該等可單獨使用亦可混合使用2種以上。若使用沸點為50~150℃之烴溶劑,則於反應或清洗時,雜質之溶解度增大,結果所獲得 之固體觸媒成分之觸媒活性或所獲得之聚合物之立體規則性提高,於此方面並非較佳。In the present invention, the preparation of the solid catalyst component (A) is preferably carried out by suspension contact in a hydrocarbon solvent (d) having a boiling point of 50 to 150 °C. As the hydrocarbon solvent having a boiling point of 50 to 150 ° C, toluene, xylene, ethylbenzene, hexane, heptane, octane, cyclohexane or the like is preferably used. Further, these may be used alone or in combination of two or more. If a hydrocarbon solvent having a boiling point of 50 to 150 ° C is used, the solubility of the impurities increases during the reaction or washing, and the result is obtained. The catalytic activity of the solid catalyst component or the stereoregularity of the polymer obtained is not preferred in this respect.
以下,就各成分之接觸方法加以敍述。本發明之固體觸媒成分(A)可藉由使上述鎂化合物(a)、4價之鹵化鈦化合物(b)、電子供應性化合物(c)相接觸而製備。更具體而言,可舉出以下方法:使鎂化合物(a)懸浮於4價之鹵化鈦化合物(b)或烴溶劑(d)中,進而接觸電子供應性化合物(c)及/或4價之鹵化鈦化合物(b),而獲得固體觸媒成分。該方法中,藉由使用球狀鎂化合物,可獲得球狀且粒度分布窄(sharp)之固體觸媒成分,另外即使不使用球狀鎂化合物,例如藉由使用噴霧裝置而使溶液或者懸浮液噴霧、乾燥(即所謂之噴霧乾燥法)而形成粒子,藉此同樣可獲得球狀且粒度分布窄之固體觸媒成分。Hereinafter, the contact method of each component will be described. The solid catalyst component (A) of the present invention can be produced by bringing the above-mentioned magnesium compound (a), a tetravalent titanium halide compound (b), and an electron-donating compound (c) into contact. More specifically, a method of suspending the magnesium compound (a) in the tetravalent titanium halide compound (b) or the hydrocarbon solvent (d) to contact the electron-donating compound (c) and/or the tetravalent amount may be mentioned. The titanium halide compound (b) is obtained to obtain a solid catalyst component. In this method, by using a spherical magnesium compound, a spherical catalyst having a sharp particle size distribution can be obtained, and a solution or suspension can be obtained, for example, by using a spray device without using a spherical magnesium compound. The particles are formed by spraying and drying (so-called spray drying method), whereby a solid catalyst component having a spherical shape and a narrow particle size distribution can be obtained in the same manner.
各成分之接觸,係於惰性氣體環境下,於除去水分等之狀況下,於具備攪拌機之容器中,一邊攪拌一邊進行。於僅使之接觸並攪拌混合之情況下、或者使之分散或懸浮而進行改質處理之情況下,接觸溫度亦可為室溫附近之相對低溫區域,於接觸後使之反應而獲得生成物之情況下,較佳為40~130℃之溫度區域。反應時之溫度未滿40℃時,無法充分進行反應,結果所製備之固體觸媒成分之性能不充分,超過130℃時,所使用之溶劑之蒸發變得顯著等,而難以控制反應。再者,反應時間為1分鐘以上,較佳為10分鐘以上,更佳為30分鐘以上。The contact of each component is carried out in a container equipped with a stirrer in an inert gas atmosphere while removing water or the like. In the case where it is only contacted, stirred and mixed, or is dispersed or suspended for reforming, the contact temperature may be a relatively low temperature region near room temperature, and reacted after contact to obtain a product. In the case of this, it is preferably a temperature range of 40 to 130 °C. When the temperature at the time of the reaction is less than 40 ° C, the reaction cannot be sufficiently carried out, and as a result, the performance of the prepared solid catalyst component is insufficient. When the temperature exceeds 130 ° C, the evaporation of the solvent to be used becomes remarkable, and it is difficult to control the reaction. Further, the reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
以下,更具體地例示製備本發明之固體觸媒成分(A)時 之接觸順序。Hereinafter, the preparation of the solid catalyst component (A) of the present invention is more specifically exemplified. The order of contact.
(l)(a)→(d)→(b)→(c)→《中間清洗→(d)→(b)》→最終清洗→固體觸媒成分(A)(2)(a)→(d)→(c)→(b)→《中間清洗→(d)→(b)》→最終清洗→固體觸媒成分(A)(3)(a)→(d)→(b)→(c)→《中間清洗→(d)→(b)→(c)》→最終清洗→固體觸媒成分(A)(4)(a)→(d)→(b)→(c)→《中間清洗→(d)→(c)→(b)》→最終清洗→固體觸媒成分(A)(5)(a)→(d)→(c)→(b)→《中間清洗→(d)→(b)→(c)》→最終清洗→固體觸媒成分(A)(6)(a)→(d)→(c)→(b)→《中間清洗→(d)→(c)→(b)》→最終清洗→固體觸媒成分(A)(l) (a) → (d) → (b) → (c) → "intermediate cleaning → (d) → (b)" → final cleaning → solid catalyst component (A) (2) (a) → ( d)→(c)→(b)→“Intermediate cleaning→(d)→(b)”→Final cleaning→Solid catalyst component (A)(3)(a)→(d)→(b)→( c)→“Intermediate cleaning→(d)→(b)→(c)”→Final cleaning→Solid catalyst component (A)(4)(a)→(d)→(b)→(c)→ Intermediate cleaning → (d) → (c) → (b) → → final cleaning → solid catalyst component (A) (5) (a) → (d) → (c) → (b) → "intermediate cleaning → ( d)→(b)→(c)》→Final cleaning→Solid catalyst component (A)(6)(a)→(d)→(c)→(b)→“Intermediate cleaning→(d)→( c)→(b)》→Final cleaning→solid catalyst component (A)
再者,於上述各接觸方法中,關於雙括號(《》)內之步驟,藉由視需要重複進行數次,可進一步提高活性。且《》內之步驟中所使用之成分(b)或者成分(d)可為新加入者,亦可為前步驟之殘留分。另外,除了上述(1)~(6)中所示之清洗步驟以外,亦可於常溫下利用液體之烴化合物對各接觸階段中所生成之生成物進行清洗。Further, in each of the above contact methods, the steps in the double brackets ("") can be further increased by repeating the steps as needed. And the component (b) or component (d) used in the steps in the "" may be a new addition, or may be a residue of the previous step. Further, in addition to the washing step shown in the above (1) to (6), the product formed in each contact stage may be washed with a hydrocarbon compound of a liquid at normal temperature.
基於以上情況,本申請案中之固體觸媒成分(A)之特佳製備方法,係使作為鎂化合物(a)之二烷氧基鎂懸浮於沸點50~150℃之作為烴溶劑(d)之甲苯中,接著使作為4價之鹵化鈦化合物(b)之四氯化鈦接觸該懸浮液後,進行反應處理。此時,使4價之鹵化鈦化合物(b)接觸該懸浮 液之前或接觸之後,於-20~130℃下使之接觸作為電子供應性化合物(c)之二烷基取代丙二酸二酯之1種或者2種以上,獲得固體反應生成物(1)。此時,較佳係於接觸電子供應性化合物(c)之前或之後,於低溫下進行熟成反應。將該固體反應生成物(1)於常溫下以液體之烴化合物加以清洗(中間清洗)後,再次於芳香族烴化合物之存在下,於-20~100℃下使之接觸4價之鹵化鈦化合物(b),進行反應處理,獲得固體反應生成物(2)。再者,視需要亦可進一步反覆進行數次中間清洗及反應處理。接著,於常溫下利用液體之烴化合物對固體反應生成物(2)加以清洗(最終清洗),獲得固體觸媒成分(A)。Based on the above, the solid catalyst component (A) in the present application is preferably prepared by suspending the dialkoxymagnesium as the magnesium compound (a) at a boiling point of 50 to 150 ° C as a hydrocarbon solvent (d). In the toluene, the titanium tetrachloride which is a tetravalent titanium halide compound (b) is brought into contact with the suspension, and then subjected to a reaction treatment. At this time, the tetravalent titanium halide compound (b) is brought into contact with the suspension. The liquid reaction product (1) is obtained by contacting one or two or more kinds of dialkyl-substituted malonic acid diesters as the electron-donating compound (c) at -20 to 130 ° C before or after the contact. . At this time, it is preferred to carry out the ripening reaction at a low temperature before or after contacting the electron-donating compound (c). The solid reaction product (1) is washed with a liquid hydrocarbon compound at normal temperature (intermediate cleaning), and then contacted with a tetravalent titanium halide at -20 to 100 ° C in the presence of an aromatic hydrocarbon compound. The compound (b) is subjected to a reaction treatment to obtain a solid reaction product (2). Further, the intermediate washing and the reaction treatment may be further repeated as needed. Next, the solid reaction product (2) is washed (final cleaning) with a liquid hydrocarbon compound at normal temperature to obtain a solid catalyst component (A).
上述處理或者清洗之較佳條件如下所述。The preferred conditions for the above treatment or cleaning are as follows.
‧低溫熟成反應:-20~70℃,較佳為-10~60℃,更佳為0~30℃,1分鐘~6小時,較佳為5分鐘~4小時,特佳為10分鐘~3小時。‧ low temperature ripening reaction: -20 ~ 70 ° C, preferably -10 ~ 60 ° C, more preferably 0 ~ 30 ° C, 1 minute ~ 6 hours, preferably 5 minutes ~ 4 hours, especially good 10 minutes ~ 3 hour.
‧反應處理:0~130℃,較佳為40~120℃,特佳為50~115℃,0.5~6小時,較佳為0.5~5小時,特佳為1~4小、時。‧Reaction treatment: 0~130°C, preferably 40~120°C, especially preferably 50~115°C, 0.5~6 hours, preferably 0.5~5 hours, especially preferably 1~4 hours.
·清洗:0~110℃,較佳為30~100℃,特佳為30~90℃ 1~20次,較佳為1~15次,特佳為1~10次。再者,清洗時所使用之烴化合物較佳為於常溫下為液體之芳香族化合物或者飽和烴化合物,具體而言,芳香族烴化合物可舉出甲苯、二甲苯、乙基苯等,飽和烴化合物可舉出己烷、庚烷、環己烷等。較佳為中間清洗使用芳香族烴化合物, 最終清洗使用飽和烴化合物。· Cleaning: 0~110 °C, preferably 30~100 °C, especially preferably 30~90 °C 1~20 times, preferably 1~15 times, especially preferably 1~10 times. In addition, the hydrocarbon compound used for the cleaning is preferably an aromatic compound or a saturated hydrocarbon compound which is liquid at a normal temperature. Specifically, the aromatic hydrocarbon compound may, for example, be toluene, xylene or ethylbenzene, or a saturated hydrocarbon. The compound may, for example, be hexane, heptane or cyclohexane. Preferably, the intermediate cleaning uses an aromatic hydrocarbon compound, The final cleaning uses a saturated hydrocarbon compound.
製備固體觸媒成分(A)時之各成分之使用量比根據製備法而有所不同,故不能一概而論,例如相對於每1莫耳鎂化合物(a),4價之鹵化鈦化合物(b)為0.5~100莫耳,較佳為0.5~50莫耳,更佳為1~10莫耳,電子供應性化合物(c)為0.01~10莫耳,較佳為0.01~1莫耳,更佳為0.02~0.6莫耳,烴溶劑(d)為0.001~500莫耳,較佳為0.001~100莫耳,更佳為0.005~10莫耳。The amount of each component used in the preparation of the solid catalyst component (A) is different depending on the preparation method, and therefore cannot be generalized, for example, a tetravalent titanium halide compound (b) per 1 mole of the magnesium compound (a). It is 0.5 to 100 moles, preferably 0.5 to 50 moles, more preferably 1 to 10 moles, and the electron supply compound (c) is 0.01 to 10 moles, preferably 0.01 to 1 mole, more preferably The hydrocarbon solvent (d) is from 0.001 to 0.6 mol, preferably from 0.001 to 500 mol, more preferably from 0.001 to 100 mol, more preferably from 0.005 to 10 mol.
另外,本發明中之固體觸媒成分(A)中之鈦、鎂、鹵素原子、電子供應性化合物之含有量並無特別規定,較佳為鈦為1.8~8.0重量%,較佳為2.0~8.0重量%,更佳為2.0~6.0重量%,鎂為10~70重量%,更佳為10~50重量%,特佳為15~40重量%,更佳為15~25重量%,鹵素原子為20~90重量%,更佳為30~85重量%,特佳為40~80重量%,更佳為45~75重量%,另外電子供應性化合物為合計0.5~30重量%,更佳為合計1~25重量%,特佳為合計2~20重量%。為了更加平衡地發揮本發明之使用電子供應性化合物與其他成分而成之固體觸媒成分(A)之綜合性能,而較佳係鈦含有量為3~8重量%,鎂含有量為15~25重量%,鹵素原子之含有量為45~75重量%,電子供應性化合物之含有量為2~20重量%。Further, the content of titanium, magnesium, a halogen atom, and an electron-donating compound in the solid catalyst component (A) in the present invention is not particularly limited, and is preferably 1.8 to 8.0% by weight of titanium, preferably 2.0 to 2. 8.0% by weight, more preferably 2.0 to 6.0% by weight, magnesium is 10 to 70% by weight, more preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight, more preferably 15 to 25% by weight, halogen atom It is 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, more preferably 45 to 75% by weight, and the electron-donating compound is 0.5 to 30% by weight in total, more preferably The total amount is 1 to 25% by weight, and particularly preferably 2 to 20% by weight. In order to more balance the overall performance of the solid catalyst component (A) using the electron-donating compound and other components of the present invention, the titanium content is preferably 3 to 8% by weight, and the magnesium content is 15%. 25 wt%, the content of the halogen atom is 45 to 75% by weight, and the content of the electron-donating compound is 2 to 20% by weight.
作為形成本發明之烯烴類聚合用觸媒時所使用之有機鋁化合物(B),可使用以通式R5 p AlQ3-p (式中,R5 表示碳數1~4之烷基,Q表示氫原子或者鹵素原子,p為0<p≦3 之實數)表示之化合物。作為此種有機鋁化合物(B)之具體例,可舉出三乙基鋁、二乙基氯化鋁、三異丁基鋁、二乙基溴化鋁、二乙基氫化鋁,可使用1種或者2種以上。較佳為三乙基鋁、三異丁基鋁。As the organoaluminum compound (B) used in forming the catalyst for olefin polymerization of the present invention, a compound of the formula R 5 p AlQ 3-p (wherein R 5 represents an alkyl group having 1 to 4 carbon atoms) can be used. Q represents a hydrogen atom or a halogen atom, and p is a compound represented by a real number of 0 < p≦3. Specific examples of such an organoaluminum compound (B) include triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminum, diethyl aluminum bromide, and diethyl aluminum hydride. Kind or more than two. Preferred is triethyl aluminum or triisobutyl aluminum.
作為形成本發明之烯烴類聚合用觸媒時所使用之外部電子供應性化合物(C)(以下,有時稱為「成分(C)」),可舉出自以通式(3)表示之有機矽化合物以及聚醚中選擇之1種或2種以上:R6 q Si(NR7 R8 )r (OR9 )4- (q十r )(3)(式中,q為0或1~4之整數,r為0或1~4之整數,其中,q十r為0~4之整數,R6 、R7 或R8 為氫原子、碳數1~12之直鏈或支鏈狀烷基、經取代或未經取代之環烷基、苯基、乙烯基、烯丙基、芳烷基之任一者,可含有雜原子,可相同或不同。R9 表示碳數1~4之烷基、環烷基、苯基、乙烯基、烯丙基、芳烷基,可含有雜原子,可相同或不同,R7 與R8 亦可鍵結而形成環狀)。The external electron-donating compound (C) (hereinafter sometimes referred to as "component (C)") used when forming the catalyst for olefin polymerization of the present invention is represented by the formula (3). One or more selected from the group consisting of an organic ruthenium compound and a polyether: R 6 q Si(NR 7 R 8 ) r (OR 9 ) 4- ( q 十r ) (3) (wherein q is 0 or 1 An integer of ~4, r is an integer of 0 or 1 to 4, wherein q is the integer of 0 to 4, and R 6 , R 7 or R 8 is a hydrogen atom or a linear or branched carbon number of 1 to 12. Any of an alkyl group, a substituted or unsubstituted cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group may contain a hetero atom, which may be the same or different. R 9 represents a carbon number of 1~ The alkyl group, the cycloalkyl group, the phenyl group, the vinyl group, the allyl group or the aralkyl group of 4 may contain a hetero atom, which may be the same or different, and R 7 and R 8 may be bonded to each other to form a cyclic group.
通式(3)中,R6 較佳為碳數1~10之直鏈或支鏈狀烷基、碳數5~8之環烷基,特佳為碳數1~8之直鏈或支鏈狀烷基、碳數5~8之環烷基。另外,R7 或R8 較佳為碳數1~10之直鏈或支鏈狀烷基、碳數5~8之環烷基,特佳為碳數1~8之直鏈或支鏈狀烷基、碳數5~8之環烷基。另外,R7 與R8 鍵結而形成環狀之(NR7 R8 )較佳為全氫喹啉基、全氫異喹啉基。另外,R9 較佳為碳數1~6之直鏈或支鏈狀烷基,特佳為碳數1~4之直鏈或支鏈狀烷基。In the formula (3), R 6 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and particularly preferably a linear or branched carbon number of 1 to 8. A chain alkyl group or a cycloalkyl group having 5 to 8 carbon atoms. Further, R 7 or R 8 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and particularly preferably a linear or branched chain having 1 to 8 carbon atoms. An alkyl group or a cycloalkyl group having 5 to 8 carbon atoms. Further, R 7 and R 8 are bonded to form a cyclic (NR 7 R 8 ) group, preferably a perhydroquinolyl group or a perhydroisoquinolyl group. Further, R 9 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
作為此種有機矽化合物,可舉出苯基烷氧基矽烷、烷基烷氧基矽烷、苯基烷基烷氧基矽烷、環烷基烷氧基矽烷、環烷基烷基烷氧基矽烷、(烷基胺基)烷氧基矽烷、烷基(烷基胺基)烷氧基矽烷、烷基(烷基胺基)矽烷、烷基胺基矽烷等。Examples of such an organic ruthenium compound include a phenyl alkoxy decane, an alkyl alkoxy decane, a phenylalkyl alkoxy decane, a cycloalkyl alkoxy decane, and a cycloalkyl alkyl alkoxy decane. And (alkylamino) alkoxydecane, alkyl (alkylamino) alkoxydecane, alkyl (alkylamino) decane, alkyl amino decane, and the like.
通式(3)中,於r為0之情況下,q較佳為1~3,R6 較佳為碳數1~8之直鏈或支鏈狀烷基、碳數5~7之環烷基,R9 較佳為碳數1~4之直鏈或支鏈狀烷基。另外,尤其是於r為0之情況下,q較佳為1~3,R6 較佳為碳數1~8之直鏈或支鏈狀烷基、碳數5~7之環烷基,R9 較佳為碳數1~2之直鏈之烷基。In the general formula (3), when r is 0, q is preferably 1 to 3, and R 6 is preferably a linear or branched alkyl group having 1 to 8 carbon atoms and a ring having 5 to 7 carbon atoms. The alkyl group, R 9 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, especially when r is 0, q is preferably 1 to 3, and R 6 is preferably a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms. R 9 is preferably a linear alkyl group having 1 to 2 carbon atoms.
通式(3)中,於r為0之情況下,特佳之化合物為二正丙基二甲氧基矽烷、二異丙基二甲氧基矽烷、二正丁基二甲氧基矽烷、二異丁基二甲氧基矽烷、二第三丁基二甲氧基矽烷、二正丁基二乙氧基矽烷、第三丁基三甲氧基矽烷、二環己基二甲氧基矽烷、二環己基二乙氧基矽烷、環己基甲基二甲氧基矽烷、環己基甲基二乙氧基矽烷、環己基乙基二甲氧基矽烷、環己基乙基二乙氧基矽烷、二環戊基二甲氧基矽烷、二環戊基二乙氧基矽烷、環戊基甲基二甲氧基矽烷、環戊基甲基二乙氧基矽烷、環戊基乙基二乙氧基矽烷、環己基環戊基二甲氧基矽烷、環己基環戊基二乙氧基矽烷、3-甲基環己基環戊基二甲氧基矽烷、4-甲基環己基環戊基二甲氧基矽烷、3,5-二甲基環己基環戊基二甲氧基矽烷。In the general formula (3), when r is 0, a particularly preferred compound is di-n-propyldimethoxydecane, diisopropyldimethoxydecane, di-n-butyldimethoxydecane, and Isobutyl dimethoxy decane, di-tert-butyl dimethoxy decane, di-n-butyl diethoxy decane, tert-butyl trimethoxy decane, dicyclohexyl dimethoxy decane, bicyclo Hexyldiethoxydecane, cyclohexylmethyldimethoxydecane, cyclohexylmethyldiethoxydecane, cyclohexylethyldimethoxydecane, cyclohexylethyldiethoxydecane, dicyclopentane Dimethoxy decane, dicyclopentyl diethoxy decane, cyclopentyl methyl dimethoxy decane, cyclopentyl methyl diethoxy decane, cyclopentyl ethyl diethoxy decane, Cyclohexylcyclopentyldimethoxydecane, cyclohexylcyclopentyldiethoxydecane, 3-methylcyclohexylcyclopentyldimethoxydecane, 4-methylcyclohexylcyclopentyldimethoxy Decane, 3,5-dimethylcyclohexylcyclopentyl dimethoxydecane.
通式(3)中,式中,作為r為1~4之有機矽化合物,可舉出(烷基胺基)三烷基矽烷、(烷基胺基)二烷基環烷基矽烷、(烷基胺基)烷基二環烷基矽烷、(烷基胺基)三環烷基矽烷、(烷基胺基)(二烷基胺基)二烷基矽烷、(烷基胺基)(二烷基胺基)二環烷基矽烷、雙(烷基胺基)二烷基矽烷、雙(烷基胺基)烷基環烷基矽烷、雙(烷基胺基)二環烷基矽烷、雙(烷基胺基)(二烷基胺基)烷基矽烷、雙(烷基胺基)(二烷基胺基)環烷基矽烷、二(烷基胺基)二烷基矽烷、二(烷基胺基)烷基環烷基矽烷、二(烷基胺基)二環烷基矽烷、二(環烷基胺基)二烷基矽烷、二(環烷基胺基)烷基環烷基矽烷、二(環烷基胺基)二環烷基矽烷、三(烷基胺基)烷基矽烷、三(烷基胺基)環烷基矽烷、三(烷基胺基)烷基矽烷、三(烷基胺基)環烷基矽烷、三(環烷基胺基)烷基矽烷、三(環烷基胺基)環烷基矽烷、四(烷基胺基)矽烷、三(烷基胺基)二烷基胺基矽烷、三(環烷基胺基)二烷基胺基矽烷、雙(二烷基胺基)雙(烷基胺基)矽烷、二烷基胺基三(烷基胺基)矽烷、雙(全氫異喹啉基)雙(烷基胺基)矽烷、雙(全氫喹啉基)雙(烷基胺基)矽烷、雙(環烷基胺基)雙(烷基胺基)矽烷、四(烷基胺基)矽烷、三(烷基胺基)二烷基胺基矽烷、三(環烷基胺基)二烷基胺基矽烷、二(二烷基胺基)二(烷基胺基)矽烷、二烷基胺基三(烷基胺基)矽烷、二(烷基取代全氫異喹啉基)二(烷基胺基)矽烷、二(烷基取代全氫喹啉基)二(烷基胺基)矽烷、二(環烷基胺基)二(烷基胺基)矽烷、烷基(二烷基胺基)(烷基胺 基)烷氧基矽烷、環烷基(二烷基胺基)(烷基胺基)烷氧基矽烷、乙烯基(二烷基胺基)(烷基胺基)烷氧基矽烷、烯丙基(二烷基胺基)(烷基胺基)烷氧基矽烷、芳烷基(二烷基胺基)(烷基胺基)烷氧基矽烷、二烷基(烷基胺基)烷氧基矽烷(二烷基胺基)三烷氧基矽烷、烷基(二烷基胺基)烷氧基矽烷、雙(全氫異喹啉基)二烷氧基矽烷等。該有機矽化合物(C)可使用1種或者組合使用2種以上。聚醚之中,較佳為1,3-二醚,更佳為9,9-雙(甲氧基甲基)茀、2-異丙基-2-異戊基-1,3-二甲氧基丙烷。該等外部電子供應性化合物可使用1種或者組合使用2種以上。In the formula (3), examples of the organofluorene compound having r of 1 to 4 include (alkylamino)trialkylnonane and (alkylamino)dialkylcycloalkylnonane, ( Alkylamino)alkylbicycloalkylnonane, (alkylamino)tricycloalkylnonane, (alkylamino)(dialkylamino)dialkylnonane, (alkylamino) ( Dialkylamino)bicycloalkylnonane, bis(alkylamino)dialkylnonane, bis(alkylamino)alkylcycloalkylnonane, bis(alkylamino)bicycloalkylnonane , bis(alkylamino)(dialkylamino)alkylnonane, bis(alkylamino)(dialkylamino)cycloalkylnonane, di(alkylamino)dialkylnonane, Di(alkylamino)alkylcycloalkylnonane, bis(alkylamino)bicycloalkylnonane, bis(cycloalkylamino)dialkylnonane, bis(cycloalkylamino)alkyl Cycloalkyl decane, bis(cycloalkylamino)bicycloalkylnonane, tris(alkylamino)alkylnonane, tris(alkylamino)cycloalkylnonane, tris(alkylamino)alkane Basear, tris(alkylamino)cycloalkylnonane, tris(cycloalkylamino)alkylnonane, tris(cycloalkylamino)cycloalkylnonane, tetrakis(alkylamino)anthracene , tris(alkylamino)dialkylamino decane, tris(cycloalkylamino)dialkylamino decane, bis(dialkylamino)bis(alkylamino)decane, dialkyl Aminotris(alkylamino)decane, bis(perhydroisoquinolinyl)bis(alkylamino)decane, bis(perhydroquinolinyl)bis(alkylamino)decane, bis(cycloalkane) Amino) bis(alkylamino)decane, tetrakis(alkylamino)decane, tris(alkylamino)dialkylaminodecane, tris(cycloalkylamino)dialkylaminodecane , bis(dialkylamino)bis(alkylamino)decane, dialkylaminotri(alkylamino)decane, di(alkyl-substituted perhydroisoquinolinyl)di(alkylamino) a decane, a di(alkyl-substituted perhydroquinolinyl) bis(alkylamino)decane, a bis(cycloalkylamino)bis(alkylamino)decane, an alkyl (dialkylamino) group ( Alkylamine Alkoxydecane, cycloalkyl (dialkylamino) (alkylamino) alkoxydecane, vinyl (dialkylamino) (alkylamino) alkoxydecane, allyl (dialkylamino)(alkylamino)alkoxydecane, aralkyl (dialkylamino)(alkylamino)alkoxydecane, dialkyl(alkylamino)alkane Oxydecane (dialkylamino) trialkoxydecane, alkyl (dialkylamino) alkoxydecane, bis(perhydroisoquinolinyl) dialkoxydecane, and the like. These organic hydrazine compounds (C) may be used alone or in combination of two or more. Among the polyethers, preferred is 1,3-diether, more preferably 9,9-bis(methoxymethyl)anthracene, 2-isopropyl-2-isopentyl-1,3-dimethylene. Oxypropane. These external electron-donating compounds may be used alone or in combination of two or more.
其次,本發明之烯烴類聚合用觸媒含有上述烯烴類聚合用固體觸媒成分(A)、成分(B)及成分(C),於該觸媒之存在下進行烯烴類之聚合或共聚合。作為烯烴類,為乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、乙烯基環己烷等,該等烯烴類可使用1種或者併用2種以上。尤其是可較佳地使用乙烯、丙烯及1-丁烯。特佳為丙烯。於丙烯聚合時,亦可與其他烯烴類進行共聚合。作為共聚合之烯烴類,為乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、乙烯基環己烷等,該等烯烴類可使用1種或者併用2種以上。尤其是可較佳地使用乙烯及1-丁烯。Next, the catalyst for olefin polymerization of the present invention contains the above-mentioned olefin polymerization solid catalyst component (A), component (B) and component (C), and the olefin polymerization or copolymerization is carried out in the presence of the catalyst. . Examples of the olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins may be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene can be preferably used. Particularly good for propylene. When propylene is polymerized, it can also be copolymerized with other olefins. The olefin to be copolymerized may be ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene or vinylcyclohexane. These olefins may be used alone or in combination of two or more. . In particular, ethylene and 1-butene can be preferably used.
各成分之使用量比於不影響本發明之效果之範圍內為任意,並無特別限定,有機鋁化合物(B)通常於相對於每1莫耳固體觸媒成分(A)中之鈦原子為1~2000莫耳、較佳為50~1000莫耳之範圍內加以使用。有機矽化合物(C) 於相對於每1莫耳(B)成分為0.002~10莫耳、較佳為0.01~2莫耳、特佳為0.01~0.5莫耳之範圍內加以使用。The amount of each component used is not particularly limited as long as it does not affect the effects of the present invention, and the organoaluminum compound (B) is usually a titanium atom per 1 mol of the solid catalyst component (A). It is used in the range of 1 to 2000 moles, preferably 50 to 1000 moles. Organic germanium compound (C) It is used in the range of 0.002 to 10 mol, preferably 0.01 to 2 mol, and particularly preferably 0.01 to 0.5 mol per 1 mol of the component (B).
各成分之接觸順序為任意,較佳係首先向聚合系內裝入有機鋁化合物(B),其次使之接觸有機矽化合物(C),進而使之接觸烯烴類聚合用固體觸媒成分(A)。The order of contact of each component is arbitrary, and it is preferred to first introduce the organoaluminum compound (B) into the polymerization system, and then contact the organic ruthenium compound (C), and then contact the solid catalyst component for olefin polymerization (A). ).
本發明中之聚合方法可於有機溶劑之存在下進行,亦可於不存在下進行,另外丙烯等烯烴單量體可於氣體及液體之任一狀態下使用。聚合溫度為200℃以下,較佳為100℃以下,聚合壓力為10 MPa以下,較佳為5 MPa以下。另外,可為連續聚合法、批次式聚合法之任一種。進而可以1階段進行聚合反應,亦可以2階段以上進行聚合反應。The polymerization method in the present invention can be carried out in the presence of an organic solvent or in the absence of it, and an olefin monomer such as propylene can be used in any of a gas and a liquid. The polymerization temperature is 200 ° C or lower, preferably 100 ° C or lower, and the polymerization pressure is 10 MPa or less, preferably 5 MPa or less. Further, it may be either a continuous polymerization method or a batch polymerization method. Further, the polymerization reaction may be carried out in one step, or the polymerization may be carried out in two or more stages.
進而,於本發明中,使用含有烯烴類聚合用固體觸媒成分(A)、成分(B)及成分(C)之觸媒使烯烴聚合時(亦稱為正式聚合),為了進一步改善觸媒活性、立體規則性及生成之聚合體之粒子性狀等,而較佳係於正式聚合之前進行預聚合。預聚合時,可使用與正式聚合同樣之烯烴類或者苯乙烯等單體。Further, in the present invention, when a olefin is polymerized by using a catalyst containing a solid catalyst component (A) for olefin polymerization, a component (B) and a component (C) (also referred to as a formal polymerization), in order to further improve the catalyst The activity, the stereoregularity, and the particle properties of the resulting polymer are preferably pre-polymerized prior to the formal polymerization. In the prepolymerization, a monomer such as an olefin or a styrene similar to the formal polymerization can be used.
進行預聚合時,各成分及單體之接觸順序為任意,較佳為首先向設定為惰性氣體環境或者烯烴氣體環境之預聚合系內裝入成分(B),其次使之接觸烯烴類聚合用固體觸媒成分(A),其後使之接觸丙烯等烯烴及/或1種或者2種以上之其他烯烴類。於組合成分(C)進行預聚合之情況下,較佳係為如下方法:首先向設定為惰性氣體環境或者烯烴氣體環境之預聚合系內裝入成分(B),其次使之接觸 成分(C),進而使之接觸烯烴類聚合用固體觸媒成分(A),其後使之接觸丙烯等烯烴及/或1種或者其他2種以上之烯烴類。In the prepolymerization, the order of contact between each component and the monomer is arbitrary, and it is preferred to first charge the component (B) into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and secondly, to contact the olefin polymerization. The solid catalyst component (A) is then contacted with an olefin such as propylene and/or one or more other olefins. In the case where the component (C) is prepolymerized, it is preferably a method of first charging the component (B) into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then bringing it into contact. The component (C) is further contacted with the solid catalyst component (A) for olefin polymerization, and then contacted with an olefin such as propylene and/or one or two or more other olefins.
於藉由本發明所形成之烯烴類聚合用觸媒之存在下,進行烯烴類之聚合之情況下,與使用習知之觸媒之情況相比,具有更高之對氫活性,進而能夠以高產率獲得高立體規則性之聚合物。When the olefin is polymerized in the presence of a catalyst for olefin polymerization formed by the present invention, it has a higher hydrogen activity and can be produced in a higher yield than in the case of using a conventional catalyst. A highly stereoregular polymer is obtained.
以下,將本發明之實施例與比較例加以對比而具體説明,但並不限制本發明。Hereinafter, the examples of the present invention will be specifically described in comparison with comparative examples, but the present invention is not limited thereto.
[固體觸媒成分(A)之製備] 於以氮氣加以充分置換、具備攪拌機之容量500 ml之圓底燒瓶中,裝入20 g二乙氧基鎂及160 ml甲苯,形成懸浮狀態。其次向該懸浮溶液中添加40 ml四氯化鈦,並進行升溫,於達到60℃時添加4.5 ml二異丁基丙二酸乙基正丁酯,進一步升溫使之達到90℃。其後於保持90℃之溫度之狀態下,一邊攪拌2小時一邊使之反應。反應結束後,將所獲得之反應生成物以200 ml之90℃之甲苯清洗4次,重新添加40 ml四氯化鈦及80 ml甲苯,升溫至110℃,一邊攪拌1小時一邊使之反應。反應結束後,以200 ml之40℃之正庚烷清洗7次,獲得固體觸媒成分。再者,分離該固體觸媒成分中之固液,測定固體分中之鈦含有率,結果為4.5重量%。另外,根據使用氣相層析法 之分析,觸媒中含有0.31重量%之二異丁基丙二酸二乙酯、13.34重量%之二異丁基丙二酸乙基正丁酯、0.11重量%之二異丁基丙二酸二正丁酯。[Preparation of solid catalyst component (A)] In a round bottom flask which was sufficiently substituted with nitrogen and equipped with a stirrer having a capacity of 500 ml, 20 g of diethoxymagnesium and 160 ml of toluene were charged to form a suspension state. Next, 40 ml of titanium tetrachloride was added to the suspension solution, and the temperature was raised. When 60 ° C was reached, 4.5 ml of ethyl n-butyl diisobutylmalonate was added, and the temperature was further raised to 90 ° C. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 90 ° C to cause a reaction. After completion of the reaction, the obtained reaction product was washed 4 times with 200 ml of 90 ° C toluene, 40 ml of titanium tetrachloride and 80 ml of toluene were further added, and the mixture was heated to 110 ° C, and stirred for 1 hour to cause a reaction. After completion of the reaction, the mixture was washed 7 times with 200 ml of 40 ° C n-heptane to obtain a solid catalyst component. Further, the solid solution in the solid catalyst component was separated, and the titanium content in the solid fraction was measured and found to be 4.5% by weight. In addition, according to the use of gas chromatography In the analysis, the catalyst contained 0.31% by weight of diethyl diisobutylmalonate, 13.34% by weight of ethyl isobutyl butyl diisopropionate, and 0.11% by weight of diisobutylmalonic acid. Di-n-butyl ester.
[聚合觸媒之形成及聚合] 向以氮氣加以完全置換之內容積2.0公升之附有攪拌機之高壓釜中,裝入1.32 mmol三乙基鋁、0.13 mmol環己基甲基二甲氧基矽烷及以鈦原子計為0.0026 mmol之上述固體觸媒成分,形成聚合用觸媒。其後,裝入2.0公升氫氣、1.4公升液化丙烯,於20℃進行5分鐘預聚合後升溫,於70℃進行1小時聚合反應。此時之每1g固體觸媒成分之聚合活性、生成聚合體中之沸騰正庚烷不溶分之比例(HI)、生成聚合體(a)之熔融流動速率之值(MFR;表示為「MI」)示於表1。[Formation and Polymerization of Polymerization Catalyst] To a 2.0 liter autoclave equipped with a stirrer, which was completely replaced with nitrogen, was charged with 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxydecane and 0.0026 mmol of titanium atom as described above. The solid catalyst component forms a catalyst for polymerization. Thereafter, 2.0 liters of hydrogen and 1.4 liters of liquefied propylene were charged, and the mixture was heated at 20 ° C for 5 minutes, and then heated at 70 ° C for 1 hour. At this time, the polymerization activity per 1 g of the solid catalyst component, the ratio of the boiling n-heptane insoluble fraction in the polymer (HI), and the melt flow rate of the polymer (a) (MFR; expressed as "MI" ) is shown in Table 1.
再者,每單位之此處使用之固體觸媒成分之聚合活性根據下式算出。聚合活性=生成聚合體(g)/固體觸媒成分(g)Further, the polymerization activity of the solid catalyst component used per unit here was calculated according to the following formula. Polymerization activity = polymer formation (g) / solid catalyst component (g)
另外,生成聚合體中之沸騰正庚烷不溶分之比例(HI),設為將該生成聚合體以沸騰正庚烷萃取6小時時的不溶解於正庚烷之聚合體之比例(重量%)。Further, a ratio (HI) of boiling n-heptane insoluble in the polymer was produced, and the proportion of the polymer insoluble in n-heptane when the resulting polymer was extracted by boiling n-heptane for 6 hours (% by weight) ).
除了使用5.4 ml二異丁基丙二酸乙基異辛酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果,所獲得之固體觸媒成分中之鈦含有量為4.6重量%。 聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 5.4 ml of ethyl isooctyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the obtained solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
除了使用3.9 ml二異丁基丙二酸甲基乙酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果,所獲得之固體觸媒成分中之鈦含有量為4.3重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 3.9 ml of methyl ethyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate to further form a polymerization catalyst. And polymerization. As a result, the titanium content in the obtained solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 1.
除了使用4.3 ml二異丁基丙二酸甲基正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果,所獲得之固體觸媒成分中之鈦含有量為4.3重量%。另外,根據使用氣相層析法之分析,觸媒中,含有0.19重量%之二異丁基丙二酸二甲酯、0.19重量%之二異丁基丙二酸甲基乙酯、15.27重量%酯二異丁基丙二酸甲基正丁酯、0.61重量%之二異丁基丙二酸乙基正丁酯、0.48重量%之二異丁基丙二酸二正丁酯。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of methyl n-butyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the obtained solid catalyst component was 4.3% by weight. Further, according to the analysis by gas chromatography, the catalyst contains 0.19% by weight of dimethyl diisobutylmalonate, 0.19% by weight of methyl ethyl diisobutylmalonate, and 15.27 by weight. % ester diisobutylmalonate methyl n-butyl ester, 0.61% by weight of di-n-butylmalonate ethyl n-butyl ester, 0.48% by weight of di-n-butylmalonate di-n-butyl ester. The polymerization results are shown in Table 1.
除了使用4.9 ml雙(3-氯-正丙基)丙二酸甲基正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果,所獲得之固體觸媒成分中之鈦含有量為3.9重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.9 ml of bis(3-chloro-n-propyl)malonate methyl n-butyl ester was used instead of 4.5 ml of ethyl n-butyl bis-isobutylmalonate. Further, formation and polymerization of a polymerization catalyst are carried out. As a result, the titanium content in the obtained solid catalyst component was 3.9% by weight. The polymerization results are shown in Table 1.
除了使用3.7 ml丁基溴代丙二酸甲基正丁基代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為3.4重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 3.7 ml of methyl n-butyl butyl bromomalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 3.4% by weight. The polymerization results are shown in Table 1.
除了使用4.3 ml丁基溴代丙二酸乙基正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為3.3重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of ethyl n-butyl butyl bromomalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 3.3% by weight. The polymerization results are shown in Table 1.
除了使用4.3 ml第三丁基甲基丙二酸甲基正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為3.3重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of methyl n-butyl methyl butyl methacrylate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 3.3% by weight. The polymerization results are shown in Table 1.
除了使用4.5 ml二異丁基丙二酸乙基異丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.6重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.5 ml of ethyl isobutyl butyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
除了使用4.3 ml二異丁基丙二酸甲基異丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.4重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of methyl isobutyl butyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 4.4% by weight. The polymerization results are shown in Table 1.
除了使用5.4 ml第三丁基甲基丙二酸甲基異丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.6重量%。聚合結果示於表1。A solid catalyst component was prepared in the same manner as in Example 1 except that 5.4 ml of methyl isobutyl methyl butyl methacrylate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
除了使用4.0 ml鄰苯二甲酸二正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為3.5重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.0 ml of di-n-butyl phthalate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate, and further, formation and polymerization of a polymerization catalyst were carried out. As a result, the titanium content in the solid catalyst component was 3.5% by weight. The polymerization results are shown in Table 2.
除了使用4.1 ml二異丁基丙二酸二乙酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.5重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of diethyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate, and the formation of a polymerization catalyst was further carried out. polymerization. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
【固體觸媒成分(A)之製備】 於以氮氣加以充分置換、具備攪拌機之容量500 ml之 圓底燒瓶中,裝入20 g無水氯化鎂(東邦鈦製)、106 ml癸烷及102 ml之2-乙基己基醇,一邊攪拌一邊升溫至130℃,處理2小時而使之溶解無水氯化鎂,製成均勻溶液。其後添加4.4 g鄰苯二甲酸酐,進而於130℃一邊攪拌1小時一邊使之反應。另外於以氮氣加以充分置換、具備攪拌機之容量11之圓底燒瓶中,裝入170 ml四氯化鈦,冷卻至-20℃,向其中滴加上述均勻溶液。其後升溫至110℃,添加4.0 ml二異丁基丙二酸甲基正丁酯。其後於110℃處理2小時。除去上清液後,重新導入170 ml四氯化鈦,於110℃一邊攪拌2小時一邊使之反應。反應結束後,以200 ml之40℃之正庚烷清洗7次,獲得固體觸媒成分。再者,分離該固體觸媒成分中之固液,測定固體分中之鈦含有率,結果為3.0重量%。[Preparation of solid catalyst component (A)] Fully replaced with nitrogen, with a capacity of 500 ml of a blender In a round bottom flask, 20 g of anhydrous magnesium chloride (manufactured by Toho Titanium), 106 ml of decane and 102 ml of 2-ethylhexyl alcohol were charged, and the mixture was heated to 130 ° C while stirring, and treated to dissolve anhydrous magnesium chloride for 2 hours. Make a homogeneous solution. Thereafter, 4.4 g of phthalic anhydride was added, and the mixture was further stirred at 130 ° C for 1 hour to cause a reaction. Further, in a round bottom flask which was sufficiently substituted with nitrogen and equipped with a capacity of a stirrer 11, 170 ml of titanium tetrachloride was placed, and the mixture was cooled to -20 ° C, and the above homogeneous solution was added dropwise thereto. Thereafter, the temperature was raised to 110 ° C, and 4.0 ml of methyl n-butyl malonate was added. Thereafter, it was treated at 110 ° C for 2 hours. After removing the supernatant, 170 ml of titanium tetrachloride was introduced again, and the mixture was stirred at 110 ° C for 2 hours to cause a reaction. After completion of the reaction, the mixture was washed 7 times with 200 ml of 40 ° C n-heptane to obtain a solid catalyst component. Further, the solid liquid in the solid catalyst component was separated, and the titanium content in the solid fraction was measured and found to be 3.0% by weight.
[聚合觸媒之形成及聚合] 除了使用上述固體觸媒成分以外,與實施例1同樣進行聚合觸媒之形成及聚合。所得結果示於表1。[Formation and Polymerization of Polymerization Catalyst] The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 1 except that the above solid catalyst component was used. The results obtained are shown in Table 1.
[固體觸媒成分(A)之製備] 於以氮氣加以充分置換、具備攪拌機之容量500 ml之圓底燒瓶中,裝入20 g二乙氧基鎂、4.0 ml二異丁基丙二酸甲基正丁酯及100 ml二氯甲烷,製成懸浮狀態,其後升溫,於回流狀態下一邊攪拌1小時一邊使之反應。另外於以氮氣加以充分置換、具備攪拌機之容量2000 ml之圓底燒瓶中,裝入800 ml室溫之四氯化鈦,向其中滴加 上述懸浮液。其後升溫至110℃,一邊攪拌2小時一邊使之反應。除去上清液後,以800 ml癸烷清洗3次,重新導入800 ml四氯化鈦,於120℃一邊攪拌2小時一邊使之反應。反應結束後,以800 ml之40℃之正庚烷清洗7次,獲得固體觸媒成分。再者,分離固體觸媒成分中之固液,測定固體分中之鈦含有率,結果為3.3重量%。[Preparation of solid catalyst component (A)] 20 g of diethoxymagnesium, 4.0 ml of methyl n-butyl malonate and 100 ml of dichloromethane were placed in a round bottom flask with a capacity of 500 ml which was sufficiently substituted with nitrogen and equipped with a stirrer. The suspension was placed in a state of suspension, and then the temperature was raised, and the mixture was stirred while being refluxed for 1 hour to cause a reaction. In addition, in a round bottom flask with a capacity of 2000 ml which is sufficiently substituted with nitrogen and equipped with a stirrer, 800 ml of titanium tetrachloride at room temperature is charged and added thereto. The above suspension. Thereafter, the temperature was raised to 110 ° C, and the mixture was stirred for 2 hours to cause a reaction. After the supernatant was removed, it was washed three times with 800 ml of decane, and 800 ml of titanium tetrachloride was introduced again, and the mixture was stirred at 120 ° C for 2 hours to cause a reaction. After completion of the reaction, it was washed 7 times with 800 ml of 40 ° C n-heptane to obtain a solid catalyst component. Further, the solid solution in the solid catalyst component was separated, and the titanium content in the solid fraction was measured and found to be 3.3% by weight.
[聚合觸媒之形成及聚合] 除了使用上述固體觸媒成分以外,與實施例1同樣進行聚合觸媒之形成及聚合。所得結果示於表1。[Formation and Polymerization of Polymerization Catalyst] The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 1 except that the above solid catalyst component was used. The results obtained are shown in Table 1.
除了使用0.13 mmol之9,9-雙(甲氧基甲基)茀代替0.13 mmol環己基甲基二甲氧基矽烷以外,與實施例4同樣進行聚合觸媒之形成及聚合。聚合結果示於表1。The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 4 except that 0.13 mmol of 9,9-bis(methoxymethyl)anthracene was used instead of 0.13 mmol of cyclohexylmethyldimethoxydecane. The polymerization results are shown in Table 1.
除了使用0.13 mmol二環戊基雙(乙基胺基)矽烷代替0.13 mmol環己基甲基二甲氧基矽烷以外,與實施例4同樣進行聚合觸媒之形成及聚合。聚合結果示於表1。The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 4 except that 0.13 mmol of dicyclopentyl bis(ethylamino) decane was used instead of 0.13 mmol of cyclohexylmethyldimethoxydecane. The polymerization results are shown in Table 1.
除了使用4.1 ml之2-異丙基丙二酸乙基異丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.5重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of ethyl isobutyl acrylate 2-isopropylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. The formation and aggregation of media. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
除了使用4.1 ml之2-異丙基丙二酸乙基新戊酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.5重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of ethyl isoamyl 2-isopropylpropionate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. The formation and aggregation of media. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
[固體觸媒成分(A)之製備] 除了使用4.0 ml鄰苯二甲酸二正丁酯代替4.0 ml二異丁基丙二酸甲基正丁酯以外,與實施例12同樣製備固體觸媒成分。其結果固體觸媒成分中之鈦含有量為2.7重量%。[Preparation of solid catalyst component (A)] A solid catalyst component was prepared in the same manner as in Example 12 except that 4.0 ml of di-n-butyl phthalate was used instead of 4.0 ml of methyl n-butyl malonate. As a result, the titanium content in the solid catalyst component was 2.7% by weight.
[聚合觸媒之形成及聚合] 除了使用上述固體觸媒成分以外,與實施例1同樣進行聚合觸媒之形成及聚合。所得結果示於表2。[Formation and Polymerization of Polymerization Catalyst] The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 1 except that the above solid catalyst component was used. The results obtained are shown in Table 2.
[固體觸媒成分(A)之製備] 除了使用4.0 ml鄰苯二甲酸二正丁酯代替4.0 ml二異丁基丙二酸甲基正丁酯以外,與實施例13同樣製備固體觸媒成分。其結果固體觸媒成分中之鈦含有量為2.9重量%。[Preparation of solid catalyst component (A)] A solid catalyst component was prepared in the same manner as in Example 13 except that 4.0 ml of di-n-butyl phthalate was used instead of 4.0 ml of methyl n-butyl malonate. As a result, the titanium content in the solid catalyst component was 2.9% by weight.
[聚合觸媒之形成及聚合] 除了使用上述固體觸媒成分以外,與實施例1同樣進行聚合觸媒之形成及聚合。所得結果示於表2。[Formation and Polymerization of Polymerization Catalyst] The formation and polymerization of a polymerization catalyst were carried out in the same manner as in Example 1 except that the above solid catalyst component was used. The results obtained are shown in Table 2.
除了使用4.5 ml二異丁基丙二酸二正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.6重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.5 ml of di-n-butyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. And polymerization. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 2.
除了使用4.1 ml之2-異丙基丙二酸乙基正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.3重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of ethyl 2-n-butylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. The formation and aggregation of media. As a result, the titanium content in the solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 2.
除了使用5.4 ml二異丁基丙二酸二辛酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.8重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 5.4 ml of dioctyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate, and further, polymerization catalyst formation was carried out. polymerization. As a result, the titanium content in the solid catalyst component was 4.8% by weight. The polymerization results are shown in Table 2.
除了使用4.1 ml之2-異丙基丙二酸乙基異辛酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.5重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of ethyl isopropenyl 2-isopropylmalonate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. The formation and aggregation of media. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
除了使用4.5 ml二異丁基丙二酸二甲酯代替4.5 ml二 異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.3重量%。聚合結果示於表2。In addition to using 4.5 ml of dimethyl diisobutylmalonate instead of 4.5 ml A solid catalyst component was prepared in the same manner as in Example 1 except for ethyl n-butylmalonate, and the formation and polymerization of a polymerization catalyst were further carried out. As a result, the titanium content in the solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 2.
除了使用4.1 ml之2-異丙基丙二酸甲基乙酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.6重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of methyl 2-isopropylpropionate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 2.
除了使用4.1 ml之2-異丙基丙二酸甲基正丁酯代替4.5 ml二異丁基丙二酸乙基正丁酯以外,與實施例1同樣製備固體觸媒成分,進而進行聚合觸媒之形成及聚合。其結果固體觸媒成分中之鈦含有量為4.5重量%。聚合結果示於表2。A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of methyl n-butyl 2-isopropylpropionate was used instead of 4.5 ml of ethyl n-butyl acrylate of diisobutylmalonate. The formation and aggregation of media. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
由表1及表2之結果可知,藉由使用本發明之固體觸媒成分及觸媒進行丙烯之聚合,可顯示更高之對氫活性,進而能夠以高產率獲得高立體規則性之烯烴類聚合體。From the results of Tables 1 and 2, it is understood that the polymerization of propylene by using the solid catalyst component and the catalyst of the present invention can exhibit higher hydrogen activity and further obtain high stereoregular olefins in high yield. Polymer.
使用本發明之烯烴類聚合用觸媒使烯烴類聚合時,活性高且對氫活性良好,能夠以高產率獲得高立體規則性聚合物。When the olefin is polymerized by the catalyst for olefin polymerization of the present invention, the activity is high and the hydrogen activity is good, and a highly stereoregular polymer can be obtained in a high yield.
圖1為表示製備本發明之聚合觸媒之步驟之流程圖。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing the steps of preparing the polymerization catalyst of the present invention.
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