TWI327575B - Method of producing styrene polymers using high speed catalytic dispersion technology - Google Patents
Method of producing styrene polymers using high speed catalytic dispersion technology Download PDFInfo
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Abstract
Description
⑶/575 19721 pj f 九、發明說明: 【發明所屬之技術領域】 本發明是關於製備苯乙烯聚合物 ::本發明是關於製備具有高間規度之笨 【先前技術】 稀取二^而。’ Μ聚合反應使周茂金屬觸媒來製備苯乙 活二茂Ϊ屬觸媒經例如甲基鋁氧烷之烷基銘化合物 屬。匕3與娘烷二烯基或其衍生物鍵結之第4族過渡金 製備具有間練之苯乙騎合物伴隨有凝膠化,且因 :防止蜂如生長成整塊凝膠,其為此項技術中所熟知。 哭於=目的,美國專利第5,〇37,9〇7號揭露包括刮擦反應 為内壁之混合器的垂直槽型反應器以及使用所述反應器f 備苯乙烯聚合物的方法。 、 入根據美國專利第5,037,907號,藉由將反應器用作聚 合媒體’大量聚含顆粒分散於液態單體中以在顆粒表面誘 發聚合’且因此在理論上可防止聚合物塊之快速形成。然 而’貫際上在低轉化區域内無法防止此等大顆粒或塊之形 成。尤其當聚合物未充分混合時,聚合物更可能結塊。 美國專利第5,254,647號揭露用於製備苯乙烯聚合物 之刮表面式反應器。所述刮表面式反應器使用兩對習知螺 旋槳來混合單體以防止低轉化範圍下的凝聚,其中顆粒生 長開始迅速。接著將經攪拌苯乙烯聚合物轉移至粉床型反 1327575 19721pif 應器(powder bed type reactor)。因此可獲得高轉化比。 儘管粉床型反應器展示低混合效率,但可獲得相對均 勻產物。此外,藉由使用刮表面式反應器’防止快速聚人 且因此可能易於控制聚合。然而,根據反應為'圓;I:主體中戶斤 安裝之槳狀物的結構,反應器之旋轉受限。因此對反應、而 言’裝入圓柱體之反應物具有不充足的停留時間。此外, 使用螺旋槳結構導致處理能力降低且製造成本升高。 如其他關於製造苯乙烯聚合物之參考案,存在美國專 利第5,484,862號’其揭露經改良之液相粉床型反應器· 以及美國專利第6,242,542號,其揭露作為串聯或並聯反 應裔中之反應器的反向混合反應器。 ^然而製備具有間規性之苯乙烯聚合物的習知方法伴隨 2勝形成,且具有2毫米或更紅平均純的大顆教以 ㈣式附接至反應㈣内钱_器。絲反應物難以騎 牙夕’且在隨後反應中難以混合。 ^ 因此,跟據上文所描述之此等專利案製備苯乙烯聚合 取八求昂貴的裝置’且因此所製備之苯乙稀聚合物具有低 口生產率。此外,存在由無法防止凝膠 特性劣化的風險。 【發明内容】 且本强明提供藉由防止聚合期間所出現的凝膠化來製備 2高活性、高立體規則性以及均勻分子f分佈之苯乙乂 聚合物的方法。 本發明亦提供使用所述方法製備的苯乙烯聚合物。 1327575 )972lpif(3) / 575 19721 pj f IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to the preparation of a styrene polymer: the present invention relates to the preparation of a stupid [previous technique] with high syndiotacticity . The ruthenium polymerization reaction causes the ruthenium metal catalyst to prepare a benzene bismuth catalyzed by a olefinic compound such as methylaluminoxane. The Group 4 transition metal prepared by the combination of 匕3 with the mother alkadienyl group or a derivative thereof is accompanied by gelation, and because: the bee is prevented from growing into a whole gel, It is well known in the art. For example, U.S. Patent No. 5, No. 37,9,7, discloses a vertical trough type reactor including a mixer for scraping the reaction into an inner wall and a method for preparing a styrene polymer using the reactor. According to U.S. Patent No. 5,037,907, by using a reactor as a polymerization medium, a large amount of poly-containing particles are dispersed in a liquid monomer to induce polymerization on the surface of the particles, and thus it is theoretically possible to prevent rapid formation of polymer blocks. However, it is not possible to prevent the formation of such large particles or blocks in a low conversion region. Especially when the polymer is not sufficiently mixed, the polymer is more likely to agglomerate. A scraped surface reactor for preparing a styrene polymer is disclosed in U.S. Patent No. 5,254,647. The scraped surface reactor uses two pairs of conventional propellers to mix the monomers to prevent agglomeration at low conversion ranges where the particle growth begins to rapidly. The stirred styrene polymer was then transferred to a powder bed type 1327575 19721pif reactor (powder bed type reactor). Therefore, a high conversion ratio can be obtained. Although the powder bed type reactor exhibits low mixing efficiency, a relatively uniform product can be obtained. Furthermore, by using a scraped surface reactor', rapid aggregation is prevented and thus it is possible to easily control the polymerization. However, the rotation of the reactor is limited according to the structure in which the reaction is 'circle; I: the paddle to be installed in the main body. Therefore, there is insufficient residence time for the reaction, and the reactant charged into the cylinder. In addition, the use of the propeller structure results in reduced processing capacity and increased manufacturing costs. No. Reverse mixing reactor. However, a conventional method of preparing a styrene polymer having a syndiotacticity is accompanied by a formation of 2 wins, and a large-sized one having a mean purity of 2 mm or more is attached to the reaction (4) by a method of (iv). It is difficult for the silk reactant to ride on the teeth and it is difficult to mix in the subsequent reaction. ^ Therefore, the preparation of styrene polymerization according to the above-mentioned patents takes eight expensive means' and thus the prepared styrene polymer has a low port productivity. In addition, there is a risk that the deterioration of gel properties cannot be prevented. SUMMARY OF THE INVENTION The present invention provides a method for preparing a phenethyl hydrazine polymer having high activity, high stereoregularity, and uniform molecular f distribution by preventing gelation occurring during polymerization. The invention also provides styrenic polymers prepared using the methods described. 1327575 )972lpif
根據本發明之一態樣,其提供製備笨乙烯聚合物之方 法’所述方法包含:使用高速均質化混合器(high speed homogenizing mixer),均勻混合苯乙烯單體(styie的 monomers)、一輔觸媒混合物(cocatalyst mixture)與—觸媒 混合物(catalyst mixture) ’以獲得充分混合並精細的—均質 化混合物(homogenized mixture),其中辅觸媒混合物包含第 13族金屬(Group 13 metal-containing)之有機金屬化合物輔 觸媒與惰性有機溶劑(inert organic solvent),而該觸媒,、θ人 物包含茂金屬觸媒(metallocene catalyst)與所述惰性有機、六 劑’再提供所述均質化混合物至反應器,以起始聚合作^ (polymerization) ° 根據本發明之另一態樣 苯乙稀聚合物。 【實施方式】 其提供使_财法製備的According to one aspect of the invention, there is provided a method of preparing a stupid ethylene polymer. The method comprises: uniformly mixing styrene monomer (styie monomers), a supplement using a high speed homogenizing mixer A cocatalyst mixture and a catalyst mixture 'to obtain a well mixed and fine-homogenized mixture, wherein the secondary catalyst mixture comprises a Group 13 metal-containing An organometallic compound auxiliary catalyst and an inert organic solvent, and the catalyst, the θ character comprises a metallocene catalyst and the inert organic, six doses, and the homogenized mixture is further provided To the reactor to initiate polymerization. Another aspect of the invention is a styrene polymer. [Embodiment] It is provided by the method of preparation
本發明之發明者發現,為製備間規笨乙烯聚合物’應 基本上防止當轉化比在10-20%之範圍内時出現凝D膠化,I 此防止可如在觸媒活性糾且聚合開始時使輔觸媒 媒之混合物完全均質化而獲得。若初始聚合__, 媒之混合物未完全均質化,則當聚合繼續進行時,單體之 黏度迅速增加。因此,觸媒難以分散且因此局部非均勻八 散之觸媒起始聚合並形成凝膠。最終,整個反應產物凝二 成一大塊凝膠。因此藉由發現凝膠形成之原因,本發明= 發明者提議製備具有高品質以及優良分子量分佈之間規笨 乙烯聚合物(syndiotactic styrene polymer)的方法,其中美才 1327575 19721pif 上防止凝膠化。 出於此目的,根據本發明之一實施例的聚合物聚合系 統包括用於在短時間内形成聚合物之均質化單體、輔觸媒 及觸媒的均質化混合器,以及其中均質化混合物以聚合物 粉末形成之反應器。The inventors of the present invention have found that in order to prepare a syndiotactic ethylene polymer, 'suppression should be substantially prevented from occurring when the conversion ratio is in the range of 10-20%, and this prevention can be corrected as in the catalyst activity. Initially obtained by completely homogenizing the mixture of the auxiliary catalyst medium. If the initial polymerization __, the mixture of the media is not completely homogenized, the viscosity of the monomer increases rapidly as the polymerization proceeds. Therefore, the catalyst is difficult to disperse and thus the locally non-uniform dispersed catalyst initiates polymerization and forms a gel. Eventually, the entire reaction product is condensed into a large gel. Thus, by discovering the cause of gel formation, the present invention = the inventors propose to prepare a method of syndiotactic styrene polymer having high quality and excellent molecular weight distribution, in which the gelation is prevented on the beauty 1327575 19721pif. For this purpose, a polymer polymerization system according to an embodiment of the present invention includes a homogenization mixer for forming a homogenized monomer, a secondary catalyst and a catalyst for forming a polymer in a short time, and a homogenization mixture thereof A reactor formed from a polymer powder.
根據本發明之一實施例,使用T25系列批次高速均質 化混合器(S25KV-25F,IKA)及T50系列批次型高速均 質化混合器(S50KV-50F,IKA)以高速將單體、輔觸媒 與觸媒之混合物均質化。此外,使用T25系列連續型高速 均質化混合器(S25KV-F-IL,IKA)使單體與輔觸媒之混 合物以及觸媒混合物持續均質化。此等高速均質化混合器 為市售的,且其類型以及結構並不限於本發明。 根據本發明之一實施例,使用多個高速均質化混合器 製備苯乙烯聚合物。根據高速均質化混合器之連接類型, 可使用各種方法。舉例而言,使用第一高速均質化混合器 將苯乙烯單體以及輔觸媒混合物均質化,且接著使用第二 高速均質化混合器將所均質化之產物以及觸媒混合物均質 化。或者分別使用一對第一高速均質化混合器將苯乙烯單 體以及輔觸媒混合物均質化以形成第一均質化產物並將苯 乙烯單體以及觸媒混合物均質化以形成第二均質化產物, 且接著使用第二高速均質化混合器將第一以及第二均質化 產物均質化。 高速均質化混合器之旋轉速度可在]0-]00,000轉/分 鐘(rpm)之範圍内,例如100-50,000 rpm。當高速均質化混 以/575 l972|pif ^ ^之旋轉速度低於】Q rpm時,分散及混合物均質化不適 方:只現本!明之效應。另一方面,當高速均質化混合器之 =轉速度同於1〇〇,〇〇〇 rpm時,獲得過度分散及混合物均 貝化’其可影響混合器之機械元件。當高速均質化混合器 之旋轉速度達到100 φηΜ〇〇,〇〇〇 rpm之範圍内時,可能根 據此合的條件及規模選擇混合器的合適速度。尤其當高逮 均貝化混合為之旋轉速度在4000 _5 〇〇 之 參内時,可獲得有效均質化。 ㈤ 、根據本發明之分散及均質化類似於習知之預混合,因 為反應藉由增加單體與觸媒之間的分散程度來促進。然 而’根據本發明之分散及均質化不同於習知之預混合之處 , ,方;使用咼速均質化混合器使觸媒在短時間内均勻分散於 早體中以進行聚合。大體而言,預混合指反應物在適度條 件下ϋ、.二長日守間緩慢混合以製備用於反應之充分混合的混 二物。然而’如對苯乙騎合物而言’若在觸媒起始聚合 Φ 則,觸媒未在短時間内使用高速均質化混合器均勻分散, 貝j角*]媒不月b與單體均勻混合並分散於其中。因此,觸媒具 有非均勻濃度級,且因此聚合物凝膠化迅速開始且更加促 進凝膠顆粒之間的内部聚合。因此,全部反應物凝結成一 塊且聚合無法進行。此外’當分散及裝載緩慢進行時,混 合過程中可進行聚合,且因此均質化混合器及反應物入口 可堵塞。此外’由於初始分散時所使用的單體,媒混合物 與後期分散時所使用的單體_觸媒混合物之聚合反應速率 之差異,自初始所用混合物形成的凝膠充當凝膠種^促^ 1327575 19721pif 凝膠顆粒之内聚。因此,全部反應物亦可凝結成一個凝膠 塊。由於此等問題,單體以及觸媒之快速混合以及分散對 聚合而言為必要的,其為當與習知預混合相比時的差異。 現將麥考所附圖式描述根據本發明之貧施例的均質化 方法。According to an embodiment of the present invention, the T25 series batch high-speed homogenizing mixer (S25KV-25F, IKA) and the T50 series batch type high-speed homogenizing mixer (S50KV-50F, IKA) are used to transfer the monomer and the auxiliary at a high speed. The mixture of catalyst and catalyst is homogenized. In addition, the T25 series continuous high-speed homogenization mixer (S25KV-F-IL, IKA) was used to continuously homogenize the mixture of monomer and auxiliary catalyst and the catalyst mixture. These high speed homogenizing mixers are commercially available, and their types and structures are not limited to the present invention. According to one embodiment of the invention, a styrene polymer is prepared using a plurality of high speed homogenization mixers. Various methods can be used depending on the type of connection of the high speed homogenizing mixer. For example, the styrene monomer and the auxiliary catalyst mixture are homogenized using a first high speed homogenization mixer, and then the homogenized product and the catalyst mixture are homogenized using a second high speed homogenization mixer. Alternatively, the styrene monomer and the auxiliary catalyst mixture are homogenized using a pair of first high speed homogenization mixers to form a first homogenized product and homogenize the styrene monomer and the catalyst mixture to form a second homogenized product. And then homogenizing the first and second homogenized products using a second high speed homogenization mixer. The rotational speed of the high speed homogenizing mixer can be in the range of 0-]00,000 revolutions per minute (rpm), for example 100-50,000 rpm. When high-speed homogenization is mixed with /575 l972|pif ^ ^, the rotation speed is lower than 】Q rpm, the dispersion and mixture homogenization are not suitable: only present! The effect of the Ming. On the other hand, when the high speed homogenization mixer has a rotation speed equal to 1 Torr, 〇〇〇 rpm, excessive dispersion and homogenization of the mixture are obtained, which can affect the mechanical components of the mixer. When the rotational speed of the high-speed homogenization mixer reaches 100 φηΜ〇〇, 〇〇〇 rpm, the appropriate speed of the mixer may be selected according to the conditions and scale of the combination. Effective homogenization is achieved especially when the high-speed baton mixing is performed at a rotational speed of 4000 _5 〇〇. (V) Dispersion and homogenization according to the present invention are similar to conventional premixing because the reaction is promoted by increasing the degree of dispersion between the monomer and the catalyst. However, the dispersion and homogenization according to the present invention are different from the conventional premixing, and the catalyst is uniformly dispersed in the early body for polymerization in a short time using an idling homogenization mixer. In general, premixing means that the reactants are mixed under moderate conditions and slowly mixed for two long days to prepare a mixture for thorough mixing of the reaction. However, as in the case of styrene-butadiene conjugates, if the catalyst starts to polymerize Φ, the catalyst is not uniformly dispersed in a short time using a high-speed homogenizer, and the shell j-angle*] Mix evenly and disperse in it. Therefore, the catalyst has a non-uniform concentration level, and thus gelation of the polymer starts rapidly and further promotes internal polymerization between the gel particles. Therefore, all of the reactants condense into one piece and polymerization cannot proceed. Furthermore, when the dispersion and loading are carried out slowly, the polymerization can be carried out during the mixing, and thus the homogenization mixer and the reactant inlet can be clogged. In addition, the gel formed from the initial mixture used as a gel species due to the difference in the polymerization rate of the monomer used in the initial dispersion, the monomer mixture and the monomer-catalyst mixture used in the later dispersion, 1327575 Cohesion of 19721pif gel particles. Therefore, all of the reactants can also coagulate into a gel block. Due to these problems, rapid mixing and dispersion of the monomer and the catalyst are necessary for the polymerization, which is the difference when compared with the conventional premixing. The McCorm's drawing will now describe a homogenization process for a poor embodiment according to the present invention.
圖1為根據本發明之一實施例製備間規苯乙烯聚合物 的方法,其中將單體1與輔觸媒混合物2以及觸媒混合物 4之混合物裝入安裝有高速均質化混合器 (S25KV-25F-IL,IKA)之反應器ό以快速均質化,並將 所均質化產物裝入與反應器&串聯連接的反應器c。 圖2為根據本發明之另一實施例製備間規苯乙烯聚合 物的方法,其中使用第一高速均質化混合器W將單體1 以及輔觸媒混合物2均質化,使用第二高速均質化混合器 W將所得均質化混合物流體3以及觸媒混合物4均質化, 並將最終均質化混合物流體5裝入串聯之反應器c。 圖3為說明根據本發明之另一實施例製備間規苯乙烯 聚合物之方法的視圖,其中使用均質化混合器6將使用反 應器製備的單體]與輔觸媒混合物2之混合物以及使用 反應器β製備的單體1與觸媒混合物4之混合物均質化, 並將所得均質化混合流體5裝入反應器c。 圖4為說明根據本發明之另一實施例製備間規苯乙烯 聚合物之方法的視圖,其中使用多個並聯以及串聯連接之 高速均質混混合器6 以及替代反應器α。 根據本發明之一實施例,建構反應器使得高剪切特性BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a process for preparing a syndiotactic styrene polymer according to an embodiment of the present invention, wherein a mixture of monomer 1 and auxiliary catalyst mixture 2 and catalyst mixture 4 is loaded with a high-speed homogenization mixer (S25KV- The reactor of 25F-IL, IKA) was rapidly homogenized and the homogenized product was charged to reactor c connected in series with the reactor & 2 is a process for preparing a syndiotactic styrene polymer according to another embodiment of the present invention, wherein the monomer 1 and the auxiliary catalyst mixture 2 are homogenized using a first high-speed homogenization mixer W, using a second high-speed homogenization The mixer W homogenizes the resulting homogenized mixture fluid 3 and the catalyst mixture 4, and loads the final homogenization mixture fluid 5 into the reactor c in series. 3 is a view illustrating a method of preparing a syndiotactic styrene polymer according to another embodiment of the present invention, in which a mixture of a monomer prepared using a reactor and a secondary catalyst mixture 2 is used and used using a homogenization mixer 6. The mixture of monomer 1 and catalyst mixture 4 prepared in reactor β was homogenized, and the resulting homogenized mixed fluid 5 was charged into reactor c. Figure 4 is a view illustrating a method of preparing a syndiotactic styrene polymer in accordance with another embodiment of the present invention, in which a plurality of high-speed homomixers 6 connected in parallel and in series are used, and a reactor α is replaced. According to an embodiment of the invention, the reactor is constructed such that high shear properties
10 1327575 19721ρίΓ 保留以在均質化單體生長為聚合物時防止顆粒内聚。 反應器包括:具有内部空間之主體,其包括均質化混 合物投入之入口;以及反應產物自其取出之出口;安裝在 主體内用纽合所料質化混合物的混合器㈣⑽.);以及 與主體相連藉由循環加熱或冷卻油加咖QHefrjge]耐 0_j反應溫度之溫度控制單元。混合器:有一個錨盥混 合器連接,並聽與反應器內奴間的間隔降至最小,且 使加熱或冷卻油沿錨循環。混合器為垂直槽型反應哭 (vertical tank type reactor) - t ^ (anch〇r blade)^ii 接’且將其中心軸移除以防止由於混合時線速度降低,聚 合物附著至混合器上。此外,將混合“(mixingbia半 反應器内壁之間的距離盡可能降至最小附 環從而可另外防止聚合^^==油沿混合葉片循 現將參看圖1詳細描述本發明。 一使用高速均質化混合器均勻混合精製笨 含弟]3族金屬之有機金屬化合物輔觸媒 機— 劑之輔觸媒混合物以及茂金屬觸媒與非活性有機』= 媒混合物,並將所述經均勻混合的產物裝入哮二θ同 苯乙烯單體由PhCH=CH2表示,其中二匕 -個取代基的苯基,所述取絲具有4、 歧 選自c、0、p、s以及sn之原子。 ”次至夕们 苯^稀單體之實例包括烧基笨乙稀(叫y吻t ene)、齒 化本乙烯(halogemzed styrene)、經鹵素取代的烷基笨乙烯 1327575 I972lpif (halogen-substituted alkyJslylene)、烧氧基苯乙歸 (a丨koxystyrene)、乙稀基聯苯(vinylbiphenyl)、乙稀基苯基 萘(vinylphenyl naphthalene)、乙烯基苯基芘(vinylpheny丨 pyrene)、乙稀基苯基蒽(vinylphenylanthracene)、三:):完基石夕 坑基乙烯基聯苯(trialkylsilylvinylbiphenyl)、;):完基石夕貌基笨 乙稀(alkylsilylstyrene)、炫基酯苯乙烯(alkylesterstyrene)、10 1327575 19721ρίΓ is reserved to prevent particle cohesion when the homogenized monomer is grown into a polymer. The reactor includes: a body having an internal space including an inlet for the homogenization mixture input; and an outlet from which the reaction product is taken out; a mixer (4) (10).) installed in the main body to neutralize the mixture with the mixture; and Connected to the temperature control unit with a 0_j reaction temperature by circulating heating or cooling oil plus QHefrjge]. Mixer: There is an anchor mixer connection and the spacing between the slaves in the reactor is minimized and the heating or cooling oil is circulated along the anchor. The mixer is a vertical tank type reactor - t ^ (anch〇r blade) ^ii and removes its central axis to prevent the polymer from adhering to the mixer due to a decrease in line speed during mixing. . In addition, the mixing "(the distance between the inner walls of the mixing semi-reactor is reduced as much as possible to the minimum appendage so that the polymerization can be additionally prevented). The oil will be described along the mixing blade. The invention will be described in detail with reference to Figure 1. The chemical mixer uniformly mixes and refines the organometallic compound of the Group 3 metal, the auxiliary catalyst mixture of the agent and the metallocene catalyst and the inert organic medium, and the homogeneous mixture The product is charged with a rhodium sigma styrene monomer represented by PhCH=CH2, wherein the quinone-substituted phenyl group has 4 atoms which are selected from the group consisting of c, 0, p, s and sn. Examples of benzoic monomers include succinyl ether (called y kiss t ene), halogemzed styrene, halogen-substituted alkyl stupid ethylene 1327575 I972lpif (halogen-substituted alkyJslylene) ), a丨koxystyrene, vinylbiphenyl, vinylphenyl naphthalene, vinylphenypyrene, ethylene phenyl蒽(vinylphenylanthracene), three: ): Teralkylsilylvinylbiphenyl, ;): alkylsilylstyrene, alkylesterstyrene,
缓曱基苯乙稀(carboxymethylstyrene)、乙缔基苯石黃酸g旨 (vinylbenzene sulfonic acid ester)、乙烯基苄基二;):完氧基石粦 酸酯(vinylbenzyl dialkoxyphosphate)、諸如對二乙稀基苯以 及間二乙稀基苯之二乙烯基苯(divinylbenzene)、三乙稀基 苯(trivinylbenzene)以及芳基苯乙稀(ary】 styrene)及其類似 物。 貌基苯乙烯之實例包括苯乙稀(stylene)、甲基苯乙稀 (methylstylene)、乙基苯乙烯(ethylstylene) ' 丁基苯乙婦 (butylstylene)、對甲基苯乙稀(p-methylstylene)、對第三丁 基苯乙烯(p-tertiary-butylstylene)、二曱基苯乙稀(dimethyl stylene)、環己基苯乙稀(cyclohexylstylene)及其類似物。鹵 化苯乙稀之實例包括氟苯乙稀(fluorostylene)、氯苯乙焊 (chlorostylene)、';臭苯乙烯(bromostylene)及其類似物。經鹵 素取代之烷基苯乙烯的實例包括氣曱基苯乙烯 (chloromethyl stylene)、溴乙基苯乙烯(bromoethylstyjene) 及其類似物。烷氧基苯乙烯之實例包括曱氧基苯乙烯 (methoxystylene)、乙氧基苯乙烯(etoxystylene)、丁氧基苯 乙烯(butoxystylene)及其類似物。乙烯基聯苯之實例包括 12 1327575 1972 ] pif 4-乙稀基聯笨(4_vinyibi phenyl)、3-乙稀基聯笨 (3-vinylbiphenyl)及其類似物。乙烯基苯基萘之實例包括 ]_(4-乙稀基聯苯萘)(1-(4-vinylbiphenyl naphthalene))、2-(4-乙稀基聯笨萘)(2-(4-vinylbiplienyl naphthalene))、1 -(3-乙稀 基聯苯萘)(]-(3-vinylbiphenyl naphthalene))、1-(2-乙稀基聯 本奈)(l-(2-vinylbiphenyl naphthalene)及其類似物。乙烯基 笨基芘之實例包括 1-(4-乙烯基苯基)芘 參 (l-(4-vinylphenyl)pyrene) 、2-(4-乙烯基苯基)芘 (2-(4-vinylpheny])pyrene)及其類似物。乙烯基苯基蒽之實 例包括 1-(4-乙稀基苯基)蒽(]-(4-vinylpheny丨)anthracene)、 2-(4-乙稀基苯基)蒽(2-(4-vinylphenyl)anthracene)及其類似 物。三烷基矽烷基乙烯基聯苯之實例包括4-乙烯基-4-三曱 • 基石夕烧基聯苯(4-vinyl-4-trimethylsiIy丨biphenyl)及其類似 . 物。烷基矽烷基笨乙烯之實例包括鄰-三曱基矽烷基苯乙烯 (o-tri methylsilylstylene)、間三乙基石夕;):完基苯乙烯 (m-triethyl silylstylene) >對三乙基石夕;):完基苯乙炼 ’(p-t〗,iethy】silylstylene)及其類似物。 茂金屬觸媒用於製備具有高間規度之苯乙烯聚合物, 且可為此項技術中所熟知的任何茂金屬觸媒。 大體而言,茂金屬觸媒為第4族過渡金屬化合物與選 自一或兩種環炫基二稀基(cycloalkyldienyl group)以及其 衍生物之配位基的鍵結產物(bonding product)。週期表中所 示的第4族過渡金屬化合物可為Ti、Zr、Hf、V、Nb或 丁a之化合物,例如Ti化合物。在本發明之一實施例中使Carboxymethylstyrene, vinylbenzene sulfonic acid ester, vinylbenzyl dichloride;): vinylbenzyl dialkoxyphosphate, such as p-diethylene Diphenylbenzene, trivinylbenzene, and styrene, and the like, and bis-phenylene benzene. Examples of the styrene styrene include stylene, methylstylene, ethylstylene 'butylstylene', and p-methylstylene. ), p-tertiary-butylstylene, dimethyl stylene, cyclohexylstylene and the like. Examples of the halogenated styrene include fluorostylene, chlorostylene, 'bromostylene, and the like. Examples of the halogenated substituted alkylstyrene include chloromethyl stylene, bromoethylstyjene, and the like. Examples of the alkoxystyrene include methoxystylene, etoxystylene, butoxystylene, and the like. Examples of the vinylbiphenyl include 12 1327575 1972 ] pif 4-vinyl diphenyl, 3-vinylbiphenyl, and the like. Examples of the vinyl phenylnaphthalene include: 1-(4-vinylbiphenyl naphthalene), 2-(4-ethylenebiphenylnaphthalene) (2-(4-vinylbiplienyl) (2-(4-vinylbiplienyl)) Naphthalene)), 1-(3-vinylbiphenyl naphthalene), 1-(2-vinylbiphenyl naphthalene) and its Examples of the vinyl stupid base include 1-(4-vinylphenyl) fluorene (1-(4-vinylphenyl)pyrene), 2-(4-vinylphenyl)fluorene (2-(4) -vinylpheny])pyrene) and its analogs. Examples of vinylphenyl hydrazine include 1-(4-ethlylphenyl)anthracene (]-(4-vinylpheny丨)anthracene), 2-(4-ethylene 2-(4-vinylphenyl)anthracene and its analogs. Examples of trialkylsulfonylalkylbiphenyl include 4-vinyl-4-triterpene • sulphur-based biphenyl (4) -vinyl-4-trimethylsiIy丨biphenyl) and the like. Examples of alkyl fluorenyl alkyl styrene include o-tri methylsilylstylene, m-triethyl sulphate; Styrene (m-triethyl silylstylene) > triethyl stellate;): complete benzene acetonitrile p-t〗, iethy] silylstylene) and the like. Metallocene catalysts are used to prepare styrene polymers having a high degree of syndiotacticity and can be any metallocene catalyst well known in the art. In general, the metallocene catalyst is a bonding product of a Group 4 transition metal compound with a ligand selected from one or two cycloalkyldienyl groups and derivatives thereof. The Group 4 transition metal compound shown in the periodic table may be a compound of Ti, Zr, Hf, V, Nb or D, such as a Ti compound. In an embodiment of the invention
13 1327575 I9721pif 用的茂金屬觸媒可為五曱基環戊二烯基鈦三曱氧化物 (penta methylcyclopentadienyltitaniumtrimethoxide)、五甲美 環戊一稀基鈦三 氯化物 (pentamethylcyclopentadienyll;itanhimtrichloi.ide)或其類似 物。13 1327575 The metallocene catalyst for I9721pif may be pentamethylcyclopentadienyltitanium trimethoxide or pentamethylcyclopentadiadiyll (itanhimtrichloi.ide) or analog.
對於茂金屬觸媒以及苯乙烯單體之總量而言,茂金屬 觸媒之量可在0.00005-0.02莫耳%的範圍内。當茂金屬觸 媒之量低於0.00005莫耳%時,聚合活性實質上降低,且 因此純化產物成本昂貴。另一方面,當茂金屬觸媒之量低 於0.02莫耳%時,聚合物之分子量降低,且由於聚合期間 所產生的大量熱,難以控制聚合。 茂金屬觸媒可連同作為包含至少一種選自烷基鋁氧烷 (alkylaluminoxane)、烧基在呂化合物(alky[alumirmm compound)以及叾朋酸鹽化合物(borate compound)之化合物 的有機化合物之輔觸媒一起使用。 烷基鋁氧烷可為具有高穩定性包含甲基鋁氧烷 (methylaluminoxane,MAO )以及烧基I呂化合物之改良曱 基铭氧烧(modified MAO,MMAO )。院基銘化合物之實 例包括三曱基|呂(1;1,丨11161:11)^111111丨111_1111)'三乙基|呂(1;士(:】1}/1 aluminum)、二曱基紹氯化物(dimethylaluminiumchloride)、 二乙基铭氯化物(diethyl aluminiumchloride)、三異丁基在呂 (tri isobutylahiminum,TIBAL)、三(正 丁基)紹(ti,j (n-butyl) aluminium)、三(正丙基)|呂(tri (n-pmpyl) ahiminium)以及三 異丙基铭(triisopropylaluminium)及其類似物。舉例而言, 14 1327575 19721pif 烷基鋁化合物為T]BAL。硼酸鹽化合物之實例包括棚烧 (borane)、二苯基金炭四(五氟笨基)硼酸鹽(trjphenyl carboniumtetra(pentafluoiOphenyl)borate)、鄰-氰基-N_ 曱基 口比。定鑌四(五氟苯基)石朋酸鹽(〇-Cyano_N_methylpyi•丨diumtetra (pentafk丨〇r〇Phenyl)b〇rate)、三(五氟苯基)石朋(td(pentaf丨·〇 phenyDboron)、1,1-二甲基二茂鐵·四(五氟苯基)硼酸鹽 (],1 - d i m e th y 1 fer r 〇 c e nui m -1 etr a(p e nt afl u ο ιό p h εη y 丨)b or ate)以 及 > 基一曱基一戊鐵四(五氟苯基)石朋酸鹽(benzyldimethyl ierrocenium tetra(pentafluorophenyl)borate)及其類似物。 對於茂金屬觸媒中所包含之〗莫耳金屬而言,以輔觸 媒中所包含之金屬的量計,輔觸媒的量可在12,〇〇〇莫耳 範圍内,較佳lO-LOOO莫耳。當輔觸媒的量低於丨莫耳 . 日夸’輔觸媒的絕對量太低且因此難以活化觸媒。另一方面, • 當輔觸媒之量大於2,000莫耳時,甚至在輔觸媒參與觸媒 活化後仍存在過量輔觸媒,且因而難以控制聚合物製備過 程中的聚合速度,且聚合物之平均分子量下降。 蒙 以具有转性有驗歉混合_紐Μ金屬觸媒 ,輔觸媒。非活性有機溶劑之實例包括狀、己烧、環己 院、庚炫、辛烧、壬垸、癸烧、苯、五氟苯、甲苯以及類 似溶劑。 =媒混合物之濃度可在Q莫耳々升之範圍 ,車又佳0‘〇〇〇]_〇」莫耳/公升。 ^蜀媒混合物之濃度低於0 0001莫耳/公升時,所用 '有機溶劑的相對量增加,且因此聚合效應下降。另 I327575 19721 pir —方面’客觸媒混合物之濃度局於0.]莫耳/公升時,所用 觸媒混合物量與單體之量相比太小,且不太可能纟^ 輪入比率。 ' 聚合反應可在0-120°C之溫度下進行,較佳3〇_1〇〇它。 當反應溫度低於〇°C時,反應性降低或轉化比低。另—方 面,當反應溫度尚於120 C時’觸媒活性下降且更多單骨边 熱改質。For the total amount of metallocene catalyst and styrene monomer, the amount of metallocene catalyst can range from 0.00005 to 0.02 mole percent. When the amount of the metallocene catalyst is less than 0.00005 mol%, the polymerization activity is substantially lowered, and thus the purified product is expensive. On the other hand, when the amount of the metallocene catalyst is less than 0.02 mol%, the molecular weight of the polymer is lowered, and it is difficult to control the polymerization due to a large amount of heat generated during the polymerization. The metallocene catalyst may be used in conjunction with an organic compound comprising at least one compound selected from the group consisting of alkylaluminoxane, alky[alumirmm compound, and borate compound. Use together with the media. The alkyl aluminoxane can be a modified MAO (MMAO) having a high stability comprising methylaluminoxane (MAO) and an alkyl iluene compound. Examples of the compound of the compound of the hospital include triterpene | Lu (1; 1, 丨 11161: 11) ^ 111111 丨 111_1111) 'Triethyl | Lu (1; Shi (:) 1} / 1 aluminum), diterpene Dimethylaluminium chloride, diethyl aluminium chloride, triisobutylahiminum (TIBAL), ti,j (n-butyl) aluminium, Tri(n-pmpyl) ahiminium and triisopropylaluminium and the like. For example, 14 1327575 19721pif alkyl aluminum compound is T]BAL. Borate compound Examples include borane, trjphenyl carboniumtetra(pentafluoiOphenyl)borate, ortho-cyano-N_ oxime ratio, and tetrakis(pentafluorophenyl)石-Cyano_N_methylpyi•丨diumtetra (pentafk丨〇r〇Phenyl) b〇rate), tris(pentafluorophenyl) shipen (td(pentaf丨·〇phenyDboron), 1,1-dimethyl Diferrocene·tetrakis(pentafluorophenyl)borate (], 1 - dime th y 1 fer r 〇ce nui m -1 etr a(pe nt afl u ο ό ph εη y 丨)b or ate) and > benzyldimethyl ierrocenium tetra(pentafluorophenyl)borate and its analogs. The amount of the auxiliary catalyst in the amount of the metal contained in the auxiliary catalyst may be in the range of 12, 〇〇〇mol, preferably lO-LOOO. The amount of auxiliary catalyst is lower than that of 丨莫耳. The absolute amount of the auxiliary catalyst is too low and therefore it is difficult to activate the catalyst. On the other hand, • when the amount of the auxiliary catalyst is more than 2,000 moles, even in the auxiliary touch Excessive auxiliary catalyst still exists after the catalyst participates in the activation of the catalyst, and thus it is difficult to control the polymerization rate in the preparation process of the polymer, and the average molecular weight of the polymer decreases. The transition has an apologetic mixture _ Μ Μ metal catalyst, Auxiliary catalysts. Examples of inactive organic solvents include hexahydrate, hexazone, cyclohexyl, heptyl, octyl, oxime, oxime, benzene, pentafluorobenzene, toluene, and the like. = The concentration of the media mixture can be in the range of Q Moss, and the car is good 0 '〇〇〇】_〇" Moer / liter. When the concentration of the oxime mixture is less than 0 0001 mol/liter, the relative amount of 'organic solvent used' increases, and thus the polymerization effect decreases. In addition, I327575 19721 pir - the concentration of the guest catalyst mixture is 0.] Moere / liter, the amount of catalyst mixture used is too small compared to the amount of monomer, and is unlikely to be a rounding ratio. The polymerization can be carried out at a temperature of 0 to 120 ° C, preferably 3 〇 1 〇〇. When the reaction temperature is lower than 〇 ° C, the reactivity is lowered or the conversion ratio is low. On the other hand, when the reaction temperature is still at 120 C, the activity of the catalyst decreases and more single-edge thermal reform.
反應時間可在〗〇分鐘-600分鐘之範圍内,較佳分 鐘-300分鐘。 如上所述製備之具有間規構型之苯乙烯聚合物具有 10-100%之聚合轉化比(polymerization conversion rati0),較 佳30-90%,且具有1,000-2,000,000之重量平均分子量, 較佳10,000-l,000,00〇aC13NMR分析之結果為:笨乙烯聚 合物具有75%或更南之間規立體規則性 stereoregularity),較佳 90%或更高。 將參考下列實例進一步詳細描述本發明。此等實例僅 為說明性目的’且並不希望限制本發明之範圍。 實例 實例1 串聯連接安裝有高速均質化混合器(S25 KV-25F, IKA)之5公升垂直槽型反應器以及安裝有錨混合器之2〇 公升垂直槽型反應器,此等反應器之内部溫度設定為75°c 並將此等反應器抽真空隔夜。接著使用高純氬氣將反應器 淨化3次。將37·5毫升1.0莫耳/公升之三異丁基鋁曱苯溶 >972ΐρίΓ 液(Alddch)以及49.2毫升含有4 68重量%之鋁的曱基鋁 氧烷曱笨溶液(Albemmrl)與4,〇〇〇毫升精製苯乙烯單體 順序混合。使用高速均質化混合器以24,〇〇〇 將37 5 毫升0.005莫耳/公升之五甲基環戊二烯基鈦三曱氧化物 (Cp*Ti(0ME)3)曱苯溶液與所述混合產物混合】分鐘。 _接著,打開高速均質化混合器之下端闕,並將所得混 :物迅速裝入20公升反應器=接著,在混合葉片之旋轉速 X保持在80 rpm時起始反應。 *反應進行1小時’且排空反應器以完全收集未反應單 體。接著打開反應器之閥以獲得聚合物粉末。未收集以及 附著至反應器與混合器之内壁之聚合物的量可忽略不計。 使用含有少量HC1之過量ψ醇充分洗騎獲聚合產物 :在,空爐f乾燥。定量所得產物。結果,粉末型聚合產 =為2]80公克(產率:6〇 4%)。聚合產物具有398,〇〇〇 Ϊ:平均分子量且分子量分佈為2.81,NMr分析的結果 ,、,、·聚合產物展*93%或更大的間規立體規則性。 實例2 除南速均質化混合為之旋轉速度為n,刪—外,實 人二件與貫例1相同。貫驗完錢,紐、乾燥並定量聚 物。結果所知聚合產物之量為21〇2公克(產率: 板认/〇)。未收集以及附著至反應器與混合器之内壁之聚合 息里可忽略不計。聚合產物具有4Q5,_之重量平均分 里’分子置分佈為2.74,且間規立體規則性為93%或更 1327575 19721pif 實例3The reaction time can be in the range of from 〇 minute to 600 minutes, preferably from minute to minute. The styrene polymer having a syndiotactic configuration prepared as described above has a polymerization conversion ratio of 10 to 100%, preferably 30 to 90%, and has a weight average molecular weight of 1,000 to 2,000,000, preferably 10,000. The result of the -l, 000, 00 〇 a C13 NMR analysis is that the stupid ethylene polymer has a stereoregularity of 75% or more, preferably 90% or more. The invention will be described in further detail with reference to the following examples. These examples are for illustrative purposes only and are not intended to limit the scope of the invention. EXAMPLES Example 1 A 5 liter vertical tank type reactor equipped with a high-speed homogenization mixer (S25 KV-25F, IKA) and a 2 liter liter vertical tank type reactor equipped with an anchor mixer were connected in series, and the inside of such reactors The temperature was set to 75 ° C and the reactors were evacuated overnight. The reactor was then purged 3 times with high purity argon. 37. 5 ml of 1.0 mol/liter of triisobutylaluminum bismuth benzene <972 ΐρίΓ solution (Alddch) and 49.2 ml of cerium-based aluminoxane solution (Albemmrl) containing 4 68 wt% of aluminum and 4 , 〇〇〇ml refined styrene monomer is mixed in sequence. 37 5 ml of 0.005 mol/L of pentamethylcyclopentadienyltitanium trioxide (Cp*Ti(0ME)3) ruthenium benzene solution with 24 liters using a high speed homogenization mixer Mix the mixture for a minute. Then, the lower end of the high-speed homogenization mixer was turned on, and the resulting mixture was quickly charged into a 20-liter reactor = then, the reaction was started while the rotational speed X of the mixing blade was maintained at 80 rpm. * The reaction was carried out for 1 hour' and the reactor was evacuated to completely collect unreacted monomers. The valve of the reactor was then opened to obtain a polymer powder. The amount of polymer that was not collected and attached to the inner walls of the reactor and mixer was negligible. The polymerized product was thoroughly washed with an excess of sterol containing a small amount of HCl: dried in an empty furnace f. The resulting product was quantified. As a result, the powder type polymerization yield was 2] 80 g (yield: 6 〇 4%). The polymerization product had a molecular weight distribution of 398, 〇〇〇 Ϊ: average molecular weight and a molecular weight distribution of 2.81, and the results of NMr analysis, and the polymerization product exhibited *93% or more. Example 2 Except for the south speed homogenization mixing, the rotation speed is n, and the second one is the same as the first example. Complete the test, add, dry and quantify the polymer. As a result, the amount of the polymerization product was found to be 21 〇 2 g (yield: plate recognition / enthalpy). The aggregates that are not collected and attached to the inner wall of the reactor and mixer are negligible. The polymerization product has a weight average of '4', a molecular distribution of 2.74, and a syndiotactic stereoregularity of 93% or 1327575, 19721 pif.
除使用具有比S25 KV-25F更大規模之高速均質化混 合器(S50KV-50F)而非使用S25KV-25F,且高速均質化 混合器之旋轉速度為每分鐘11,000轉外,實驗條件與實例 1相同。反應完成後,洗條、乾燥並定量聚合產物。結果 所得聚合產物之量為2230公克(產率:61.7%)。在反應 器以及混合器之内壁上未發現聚合物。聚合產物具有 379,000之重量平均分子量,分子量分佈為2.83,且間規 立體規則性為93%或更大。 實例4Except using a high-speed homogenization mixer (S50KV-50F) with a larger scale than S25 KV-25F instead of S25KV-25F, and the rotation speed of the high-speed homogenization mixer is 11,000 rpm, the experimental conditions and example 1 the same. After the reaction is completed, the strips are washed, dried and the polymerized product is quantified. As a result, the amount of the obtained polymerization product was 2230 g (yield: 61.7%). No polymer was found on the reactor and on the inner wall of the mixer. The polymerization product had a weight average molecular weight of 379,000, a molecular weight distribution of 2.83, and a syndiotactic stereoregularity of 93% or more. Example 4
在與實例3相同之實驗條件下將高速均質化混合器之 旋轉速度保持在每分鐘4,000轉歷時】分鐘,且其他條件 與實例1相同。反應完成後,洗滌、乾燥並定量聚合產物。 結果所得聚合產物之量為2213公克(產率:61.3%)。在 反應器以及混合器之内壁上未發現聚合物。聚合產物具有 381,000之重量平均分子量,分子量分佈為2.57,且間規 立體規則性為93%或更大。 實例5 將連續運作之高速均質化混合器S25 KV-F-IL安裝於 20公升反應器而非5公升反應器之前端上。將37.5毫升 1.0莫耳/公升之三異丁基鋁甲苯溶液(Aldrich)以及49.2 毫升含有4.68重量%之鋁的曱基鋁氧烷曱苯溶液 (Albermarl)順序添力口至4,000毫升精製苯乙烯單體,且 接著充分混合以製備單體/輔觸媒混合物。接著,使用泵以 1327575 I972lpif 817.0毫升/分鐘以及7·5毫升/分鐘之流速分別 媒混合物以及37.5毫升0.005莫耳/公升之五 a稍响 τ丞ί衣戌-松 基鈦三曱氧化物(Cp*Ti(OME)3)曱苯溶液連續裝邮 均質化混合器。此時,高速均質化混合器之^向速 24,000丨.pm。此外’由於反應物連續裝入並、、ώ度為 "丨〔、‘、工兩速均皙 化混合器’因此混合時間極短。在本實驗中,反 、貝 入/愚物以备The rotational speed of the high-speed homogenization mixer was maintained at 4,000 revolutions per minute for the same experimental conditions as in Example 3, and the other conditions were the same as in Example 1. After the reaction is completed, the product is washed, dried and quantified. As a result, the amount of the obtained polymerization product was 2213 g (yield: 61.3%). No polymer was found on the reactor and on the inner wall of the mixer. The polymerization product had a weight average molecular weight of 381,000, a molecular weight distribution of 2.57, and a syndiotactic stereoregularity of 93% or more. Example 5 A continuously operating high speed homogenization mixer S25 KV-F-IL was installed on the front end of a 20 liter reactor instead of a 5 liter reactor. 37.5 ml of 1.0 mol/L of triisobutylaluminum toluene solution (Aldrich) and 49.2 ml of a solution of 4.68 wt% of aluminum in a solution of cerium-based aluminoxane benzene (Albermarl) were sequentially added to 4,000 ml of refined styrene. The monomers are then thoroughly mixed to prepare a monomer/auxiliary catalyst mixture. Next, a pump was used to separate the mixture with a flow rate of 1327575 I972lpif 817.0 ml/min and a flow rate of 7·5 ml/min, and 37.5 ml of 0.005 mol/liter of a slightly τ丞ί-戌-titanium triterpene oxide ( Cp*Ti(OME)3) Benzene solution continuous loading homogenization mixer. At this time, the high speed homogenization mixer has a speed of 24,000 丨.pm. In addition, the mixing time is extremely short because the reactants are continuously charged and the enthalpy is "丨[, ‘, two speeds of the mixer”. In this experiment, reverse, in/out
分鐘5公升-10公升之速率流經高速均質化混合哭。夕_ 時自高速均質化混合器排出的均質化單體/輔觸媒/觸5 = 合物裝入20公升反應器,並同時起始反應。此時,混二= 片之旋轉速度保持在80 rpm。反應時間為1小時。接二求 空反應益以完全收集未反應單體並打開反應器之閱以彳貧$曰 聚合物粉末。在反應器以及混合器之内壁上未發現〒八 物。使用含有少量HC1之過量曱醇充分洗滌所獲&合 並在真i爐中乾餘。定置所付產物。結果,粉末聚合產物 之量為2300公克(產率:63.7%)。聚合產物具有3^,〇= 重量平均分子量為及2.65之分子量分佈。NMR分析的結 果為·聚合產物展示93。/。或更大的間規立體規則性。 比較性實例 除使用女裝有包括45 FIG,齒節葉片(pitch blade)之發 性驅動型混合器而非高速均質化混合器之反應器以在 1,200 rpm下將單體/輔觸媒混合物以及觸媒混合物混合之 分鐘外,試驗條件與實例1相同。反應完全進行後,洗滌、 乾燥並定量反應產物。結果所得聚合物粉末之量為],57丨 公克’並強制移除附著至反應器與混合器之内壁上之殘餘The rate of 5 liters to 10 liters per minute flows through the high-speed homogenization mix and cry. At the same time, the homogenized monomer/auxiliary catalyst/touch 5 = compound discharged from the high-speed homogenization mixer was charged into a 20-liter reactor, and the reaction was started at the same time. At this time, the rotation speed of the mixed two = piece was maintained at 80 rpm. The reaction time was 1 hour. The second emptying reaction is used to completely collect the unreacted monomer and open the reactor to deplete the polymer powder. No sputum was found on the reactor and on the inner wall of the mixer. The resulting mixture was thoroughly washed with an excess of sterol containing a small amount of HCl and allowed to dry in a true furnace. Set the product to be paid. As a result, the amount of the powder polymerization product was 2,300 g (yield: 63.7%). The polymerization product had a molecular weight distribution of 3, 〇 = weight average molecular weight and 2.65. The result of the NMR analysis was that the polymerization product exhibited 93. /. Or larger syndiotactic stereo rules. A comparative example uses a reactor comprising a 45 FIG. pitch blade driven mixer rather than a high speed homogenizing mixer to provide monomer/auxiliary catalyst at 1,200 rpm. The test conditions were the same as in Example 1 except that the mixture and the catalyst mixture were mixed. After the reaction is completely carried out, the reaction product is washed, dried and quantified. As a result, the amount of the obtained polymer powder was,, 57 gram, and the residue attached to the inner wall of the reactor and the mixer was forcibly removed.
19 1327575 19721pif 聚合物。所移除殘餘聚合物的量為233公克。亦即,所產 生聚合物的全部量為1,804公克(產率:50.0%),但僅能 夠收集全部聚合物之87%,而當如實例1至5使用高速均 質化混合器時,所產生聚合物100%可收集。聚合產物具 有388,000之重量平均分子量,分子量分佈為2.52,且間 規立體規則性為93%或更大。19 1327575 19721pif polymer. The amount of residual polymer removed was 233 grams. That is, the total amount of the polymer produced was 1,804 g (yield: 50.0%), but only 87% of the total polymer was collected, and when the high-speed homogenization mixer was used as in Examples 1 to 5, the polymerization was produced. 100% can be collected. The polymerization product had a weight average molecular weight of 388,000, a molecular weight distribution of 2.52, and a stereoregularity of 93% or more.
根據本發明,使用高速均質化混合器將觸媒快速分散 於單體中,使得可基本上防止當間規苯乙烯聚合物產生時 所出現的凝膠形成,且可製備具有高活性、優良立體規則 性以及均勻分子分佈的苯乙烯聚合物。 雖然本發明已以較佳實施例揭露如上,然其並非用以 限定本發明,任何熟習此技藝者,在不脫離本發明之精神 和範圍内,當可作些許之更動與潤飾,因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】According to the present invention, the catalyst is rapidly dispersed in the monomer using a high-speed homogenization mixer, so that gel formation which occurs when the syndiotactic styrene polymer is produced can be substantially prevented, and high activity and excellent stereoscopic rules can be prepared. Sexual and uniform molecular distribution of styrene polymers. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. [Simple description of the map]
為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂,上文特舉較佳實施例,並配合所附圖式,作詳細說 明。 圖]為說明使用根據本發明之一實施例之高速均質化 混合器及反應器的製備苯乙烯聚合物之方法的示意圖。 圖2為說明使用根據本發明之另一實施例之多個串聯 連接高速均質化混合器的製備苯乙烯聚合物之方法的示意 圖。 圖3為說明使用根據本發明之另一實施例之高速均質 20 1327575 1972lpif 化混合器及反應器的製備苯乙烯聚合物之方法的示意圖。 圖4為說明使用根據本發明之另一實施例之多個串聯 以及並聯連接高速均質化混合器的製備苯乙烯聚合物之方 法的示意圖。 【主要元件符號說明】 1 :單體 2 :輔觸媒混合物The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the invention. Figure] is a schematic view showing a method of producing a styrene polymer using a high-speed homogenization mixer and reactor according to an embodiment of the present invention. Fig. 2 is a schematic view showing a method of producing a styrene polymer using a plurality of series-connected high-speed homogenization mixers according to another embodiment of the present invention. 3 is a schematic diagram illustrating a method of preparing a styrene polymer using a high speed homogenizing 20 1327575 1972 lpif mixer and reactor in accordance with another embodiment of the present invention. Fig. 4 is a schematic view showing a process for producing a styrene polymer using a plurality of high-speed homogenization mixers connected in series and in parallel according to another embodiment of the present invention. [Main component symbol description] 1 : Monomer 2 : Auxiliary catalyst mixture
3 :均質化混合流體 4 :觸媒混合物 5 :均質化混合流體 a :反應器 b :反應器 bl :第一高速均質混合器 b2 :第二高速均質混合器 b3 :高速均質混合器 c :反應器3: Homogenized mixed fluid 4: Catalyst mixture 5: Homogenized mixed fluid a: Reactor b: Reactor bl: First high-speed homogenizer b2: Second high-speed homogenizer b3: High-speed homogenizer c: Reaction Device
i 21i 21
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