TWI712619B - Manufacturing method of vinyl ether polymer using onium salt - Google Patents
Manufacturing method of vinyl ether polymer using onium salt Download PDFInfo
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Abstract
[課題] 本發明之課題為提供一種乙烯基醚聚合物之製造方法,其係不使用金屬觸媒及有機溶劑兩者,且不以低溫反應為必要的簡便之乙烯基醚聚合物之製造方法。 [解決手段] 一種乙烯基醚聚合物之製造方法,其係包含將下述通式(1): (式中,R 1表示碳數1~3之烷基,n為1~10之整數) 表示之乙烯基醚單體之至少1種,及/或 下述通式(2): (式中,R 2為碳數1~10之脂肪族烴基、脂環式烴基、烯丙基) 表示之乙烯基醚單體之至少1種,使用鎓鹽作為聚合起始劑於無溶劑下聚合之步驟而成。 [Problem] The subject of the present invention is to provide a method for producing a vinyl ether polymer, which is a simple and convenient method for producing a vinyl ether polymer that does not use both metal catalysts and organic solvents and does not require low-temperature reaction . [Solution] A method for producing vinyl ether polymer, which includes the following general formula (1): (In the formula, R 1 represents an alkyl group with a carbon number of 1 to 3, and n is an integer of 1 to 10) at least one of the vinyl ether monomers represented, and/or the following general formula (2): (In the formula, R 2 is a C 1-10 aliphatic hydrocarbon group, alicyclic hydrocarbon group, allyl group) represents at least one of the vinyl ether monomers, using onium salt as polymerization initiator in the absence of solvent The steps of polymerization are made.
Description
本發明係關於使用鎓鹽之乙烯基醚聚合物之製造方法。The present invention relates to a method for producing vinyl ether polymers using onium salts.
乙烯基醚聚合物係使用作為接著劑、塗料、潤滑劑之摻合成分。又,具有如熱刺激應答性或生物體適合性之特徵,利用其特徵,可應用於分散劑、金屬回收樹脂、抗血栓性材料等。Vinyl ether polymers are used as blending ingredients for adhesives, coatings, and lubricants. In addition, it has characteristics such as thermal stimulus responsiveness or biocompatibility, and can be used in dispersants, metal recovery resins, anti-thrombotic materials, etc., using its characteristics.
乙烯基醚聚合物之原料的乙烯基醚單體,為具有陽離子聚合性之單體。因此,一般而言為使用路易士酸之聚合。The vinyl ether monomer, which is the raw material of the vinyl ether polymer, is a monomer with cationic polymerizability. Therefore, generally speaking, it is polymerization using Lewis acid.
例如,專利文獻1中,揭示使用三氟化硼二乙基醚錯合物之乙烯基醚聚合物之製造方法。更詳細而言,係藉由將n-丁基乙烯基醚與三環癸烷乙烯基醚之兩種單體,在甲苯中,使用三氟化硼二乙基醚錯合物於-30℃聚合,來合成隨機共聚物。For example, Patent Document 1 discloses a method for producing a vinyl ether polymer using boron trifluoride diethyl ether complex. In more detail, by using two monomers of n-butyl vinyl ether and tricyclodecane vinyl ether in toluene, using boron trifluoride diethyl ether complex at -30°C Polymerization to synthesize random copolymers.
又,專利文獻2中,揭示使用烷基鋁作為路易士酸的乙烯基醚聚合物之製造方法。更詳細而言,係藉由將環己基乙烯基醚與甲氧基乙基乙烯基醚之兩種單體,在甲苯中,使用1,4-二噁烷作為添加鹼,使用Et1.5AlCl1.5作為路易士酸,於0℃聚合,來合成嵌段共聚物。In addition, Patent Document 2 discloses a method for producing a vinyl ether polymer using aluminum alkyl as Lewis acid. In more detail, by using two monomers of cyclohexyl vinyl ether and methoxyethyl vinyl ether, in toluene, 1,4-dioxane is used as the added base, and Et1.5AlCl1 is used. 5 As Lewis acid, polymerize at 0°C to synthesize block copolymer.
上述聚合均係使用半金屬觸媒或金屬觸媒,於有機溶劑中,以0℃以下之低溫反應來實施。但是,使用半金屬觸媒或金屬觸媒時,觸媒之去除步驟係必要的,因此必需有聚合後之純化步驟。又,使用有機溶劑時,於純化步驟中將有機溶劑餾去亦為必要。進一步地,0℃以下之低溫反應,必需要大型的冷卻裝置,因此有難以規模放大之問題。The above-mentioned polymerization is carried out by using a semi-metal catalyst or a metal catalyst in an organic solvent at a low temperature reaction below 0°C. However, when using a semi-metal catalyst or a metal catalyst, the removal step of the catalyst is necessary, so a purification step after polymerization is necessary. In addition, when an organic solvent is used, it is also necessary to distill off the organic solvent in the purification step. Furthermore, low-temperature reactions below 0°C require a large-scale cooling device, so there is a problem that it is difficult to scale up.
作為解決上述課題之方法,專利文獻3中,揭示使用雜多酸之乙烯基醚單體之聚合方法。更詳細而言,係藉由將乙基乙烯基醚單體,於環己烷中、磷鎢酸存在下,於室溫聚合來合成乙烯基醚聚合物。專利文獻3記載之發明中,可於室溫反應,但所使用的觸媒為金屬觸媒,且使用有機溶劑,因此未同時解決3個課題。As a method for solving the above-mentioned problems, Patent Document 3 discloses a polymerization method using a vinyl ether monomer of heteropoly acid. In more detail, the vinyl ether polymer is synthesized by polymerizing ethyl vinyl ether monomer in cyclohexane in the presence of phosphotungstic acid at room temperature. In the invention described in Patent Document 3, the reaction can be performed at room temperature, but the catalyst used is a metal catalyst and an organic solvent is used, so the three problems have not been solved simultaneously.
另一方面,有提出不使用金屬觸媒,且可高溫反應的聚合方法。例如,非專利文獻1中,記載使用鹽酸醚化物觸媒之聚合方法。更詳細而言,係藉由將各種乙烯基醚單體,於甲苯或己烷中、二噁烷及鹽酸醚化物觸媒存在下聚合,來合成乙烯基醚聚合物。非專利文獻1記載之發明中,係不使用金屬觸媒,且可於最高65℃之高溫反應,但必需添加致癌性物質的二噁烷,進而有機溶劑亦為必需,因此於此系統中亦未同時解決3個課題。 [先前技術文獻] [專利文獻] On the other hand, a polymerization method that does not use a metal catalyst and can react at a high temperature has been proposed. For example, Non-Patent Document 1 describes a polymerization method using a hydrochloric acid etherate catalyst. In more detail, a vinyl ether polymer is synthesized by polymerizing various vinyl ether monomers in toluene or hexane in the presence of dioxane and hydrochloride etherate catalysts. The invention described in Non-Patent Document 1 does not use a metal catalyst and can react at a high temperature of up to 65°C. However, it is necessary to add dioxane, which is a carcinogenic substance, and an organic solvent is also necessary, so it is also used in this system. Three issues were not solved simultaneously. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本特開2007-231227號公報 [專利文獻2]日本特開2016-50266號公報 [專利文獻3]日本特開2000-143711號公報 [非專利文獻] [Patent Document 1] JP 2007-231227 A [Patent Document 2] JP 2016-50266 A [Patent Document 3] JP 2000-143711 A [Non-Patent Literature]
[非專利文獻1]J. Polym. Sci. Part A: Polym. Chem. 46, 1913 (2008)[Non-Patent Document 1] J. Polym. Sci. Part A: Polym. Chem. 46, 1913 (2008)
[發明所欲解決之課題][The problem to be solved by the invention]
本發明之課題為提供乙烯基醚聚合物之製造方法,其係不使用金屬觸媒及有機溶劑兩者,且不以0℃以下之低溫反應為必要的簡便之乙烯基醚聚合物之製造方法。 [用以解決課題之手段] The subject of the present invention is to provide a method for producing vinyl ether polymers, which is a simple and convenient method for producing vinyl ether polymers that does not use both metal catalysts and organic solvents, and does not require low-temperature reactions below 0°C . [Means to solve the problem]
本發明者等人,為了解決上述課題,重複深入研究的結果,發現藉由不使用金屬觸媒,且使用特定之聚合起始劑,於無溶劑下使乙烯基醚單體聚合,可得到乙烯基醚聚合物。進一步地,發現藉由於聚合系統中添加環狀碳酸酯,可抑制聚合系統之溫度上昇,而完成本發明。In order to solve the above-mentioned problems, the inventors of the present invention repeated intensive studies and found that by not using a metal catalyst and using a specific polymerization initiator to polymerize vinyl ether monomers without solvent, ethylene can be obtained. Base ether polymer. Furthermore, it was discovered that by adding a cyclic carbonate to the polymerization system, the temperature rise of the polymerization system can be suppressed, and the present invention has been completed.
亦即,本發明提供以下之<1>~<7>。 <1>一種乙烯基醚聚合物之製造方法,其係包含將下述通式(1): (式中,R 1表示碳數1~3之烷基,n為1~10之整數) 表示之乙烯基醚單體之至少1種,及/或 下述通式(2): (式中,R 2為碳數1~10之脂肪族烴基、脂環式烴基、芳香族烴基) 表示之乙烯基醚單體之至少1種,使用鎓鹽作為聚合起始劑於無溶劑下聚合之步驟而成。 That is, the present invention provides the following <1> to <7>. <1> A method for producing a vinyl ether polymer, which includes the following general formula (1): (In the formula, R 1 represents an alkyl group with a carbon number of 1 to 3, and n is an integer of 1 to 10) at least one of the vinyl ether monomers represented, and/or the following general formula (2): (In the formula, R 2 is a C1-C10 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group) represents at least one of the vinyl ether monomers, using onium salt as a polymerization initiator in the absence of solvent The steps of polymerization are made.
<2>如<1>之製造方法,其中前述鎓鹽,為選自由錪鹽、氧鎓鹽、鋶鹽,及溴鎓鹽所成之群的至少1種。<2> The production method according to <1>, wherein the onium salt is at least one selected from the group consisting of iodonium salt, oxonium salt, sulphur salt, and bromium salt.
<3>如<1>或<2>之製造方法,其中相對於前述乙烯基醚單體之總量而言,前述鎓鹽之量為0.1~15質量%之範圍。<3> The manufacturing method of <1> or <2>, wherein the amount of the onium salt is in the range of 0.1-15% by mass relative to the total amount of the vinyl ether monomer.
<4>如<1>~<3>中任一項之製造方法,其中前述聚合步驟中,進一步使用環狀碳酸酯。<4> The production method according to any one of <1> to <3>, wherein in the aforementioned polymerization step, a cyclic carbonate is further used.
<5>如<4>之製造方法,其中前述環狀碳酸酯為碳酸伸丙酯。<5> The manufacturing method of <4>, wherein the cyclic carbonate is propylene carbonate.
<6>如<1>~<5>中任一項之製造方法,其中前述聚合步驟之聚合溫度為20℃以上。<6> The manufacturing method of any one of <1> to <5>, wherein the polymerization temperature in the aforementioned polymerization step is 20°C or higher.
<7>如<1>~<6>中任一項之製造方法,其中前述乙烯基醚單體之重量平均分子量為1000~50000之範圍內。 [發明之效果] <7> The manufacturing method of any one of <1> to <6>, wherein the weight average molecular weight of the aforementioned vinyl ether monomer is in the range of 1,000 to 50,000. [Effects of Invention]
依照本發明之乙烯基醚聚合物之製造方法,藉由不使用金屬觸媒,且使用特定之聚合起始劑,於無溶劑下使乙烯基醚單體聚合,可得到乙烯基醚聚合物。依照如此的製造方法,可於常溫至高溫條件使聚合反應進行,而非0℃以下之低溫條件,因此不需冷卻裝置,工業上的優點大。According to the manufacturing method of the vinyl ether polymer of the present invention, the vinyl ether polymer can be obtained by polymerizing the vinyl ether monomer without a solvent without using a metal catalyst and using a specific polymerization initiator. According to such a manufacturing method, the polymerization reaction can be carried out under normal temperature to high temperature conditions instead of low temperature conditions below 0°C. Therefore, no cooling device is required, and the industrial advantage is great.
<乙烯基醚聚合物之製造方法> 本發明之乙烯基醚聚合物之製造方法,其特徵為包含於特定條件下使乙烯基醚單體聚合之步驟。以下,詳細說明該聚合步驟。 <Method of manufacturing vinyl ether polymer> The method for producing a vinyl ether polymer of the present invention is characterized by including a step of polymerizing a vinyl ether monomer under specific conditions. Hereinafter, the polymerization step will be described in detail.
<單體成分> 本發明之聚合所用的乙烯基醚單體,可為下述通式(1): (式中,R 1表示碳數1~3之烷基,n為1~10之整數) 表示之單體。 <Monomer component> The vinyl ether monomer used in the polymerization of the present invention may have the following general formula (1): (In the formula, R 1 represents an alkyl group with a carbon number of 1 to 3, and n is an integer of 1 to 10) represents the monomer.
通式(1)中,R 1表示之烷基之碳數為1~3,較佳為1或2。烷基可為直鏈狀亦可為分支狀,具體而言,可列舉甲基、乙基、n-丙基、異丙基。此等之中,作為烷基,尤以甲基、乙基為佳;更佳為甲基。 In the general formula (1), the carbon number of the alkyl group represented by R 1 is 1 to 3, preferably 1 or 2. The alkyl group may be linear or branched, and specific examples include methyl, ethyl, n-propyl, and isopropyl. Among these, as the alkyl group, methyl and ethyl are particularly preferred; and methyl is more preferred.
通式(1)中,n為1~10之整數,較佳為1~6之整數、更佳為1~4之整數、特佳為1~3之整數。In the general formula (1), n is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and particularly preferably an integer from 1 to 3.
通式(1)表示之單體的例子,可列舉2-甲氧基乙基乙烯基醚、2-乙氧基乙基乙烯基醚、2-(2-甲氧基乙氧基)乙基乙烯基醚、2-(2-乙氧基乙氧基)乙基乙烯基醚、2-(2-(2-甲氧基乙氧基)乙氧基)乙基乙烯基醚(三乙二醇單甲基乙烯基醚)、2-(2-(2-乙氧基乙氧基)乙氧基)乙基乙烯基醚、2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)乙基乙烯基醚等。Examples of monomers represented by the general formula (1) include 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-(2-methoxyethoxy)ethyl Vinyl ether, 2-(2-ethoxyethoxy) ethyl vinyl ether, 2-(2-(2-methoxyethoxy) ethoxy) ethyl vinyl ether (triethylene two Alcohol monomethyl vinyl ether), 2-(2-(2-ethoxyethoxy)ethoxy)ethyl vinyl ether, 2-(2-(2-(2-methoxyethoxy) Group) ethoxy) ethoxy) ethyl vinyl ether and the like.
又,本發明之聚合所用的乙烯基醚單體,可為下述通式(2): (式中,R 2為碳數1~10之脂肪族烴基、脂環式烴基、芳香族烴基) 表示之單體。 In addition, the vinyl ether monomer used in the polymerization of the present invention may be the following general formula (2): (In the formula, R 2 is a C 1-10 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group) represents a monomer.
通式(2)中,R 2表示之脂肪族烴基、脂環式烴基、芳香族烴基之碳數,為1~10,較佳為1~8。脂肪族烴基可為直鏈狀亦可為分支狀。 In the general formula (2), the carbon number of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group represented by R 2 is 1-10, preferably 1-8. The aliphatic hydrocarbon group may be linear or branched.
通式(2)表示之單體的例子,可列舉甲基乙烯基醚、乙基乙烯基醚、n-丙基乙烯基醚、異丙基乙烯基醚、n-丁基乙烯基醚、sec-丁基乙烯基醚、異丁基乙烯基醚、tert-丁基乙烯基醚、n-戊基乙烯基醚、n-己基乙烯基醚、n-庚基乙烯基醚、n-辛基乙烯基醚、乙基己基乙烯基醚、n-壬基乙烯基醚、n-癸基乙烯基醚、環己基乙烯基醚、三環癸基乙烯基醚、苯基乙烯基醚等。Examples of monomers represented by the general formula (2) include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec -Butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-heptyl vinyl ether, n-octyl ethylene Base ether, ethylhexyl vinyl ether, n-nonyl vinyl ether, n-decyl vinyl ether, cyclohexyl vinyl ether, tricyclodecyl vinyl ether, phenyl vinyl ether, etc.
通式(1)及(2)中之R 1、R 2部分,亦可具有取代基,取代基可列舉矽烷基、酯基、鹵素等。 The R 1 and R 2 moieties in the general formulas (1) and (2) may have a substituent, and examples of the substituent include a silyl group, an ester group, and a halogen.
<鎓鹽> 本發明之聚合所用的鎓鹽,例如可列舉雙(2,4,6-三甲基吡啶)溴鎓六氟磷酸鹽等之溴鎓鹽;(4-甲基苯基)[4-(2-甲基丙基)苯基]錪六氟磷酸鹽、雙(4-tert-丁基苯基)錪六氟磷酸鹽、二苯基錪六氟磷酸鹽、二苯基錪氯化物、二苯基錪錪鹽、4-異丙基-4’-甲基二苯基錪肆(五氟苯基)硼酸鹽、(4-硝基苯基)(苯基)錪三氟甲烷磺酸鹽等之錪鹽;2,6-二-tert-丁基-4-甲基吡喃鎓三氟甲烷磺酸鹽、2,4,6-三甲基吡喃鎓四氟硼酸鹽等之氧鎓鹽;(2-溴乙基)二苯基鋶三氟甲烷磺酸鹽、(2-羧基乙基)二甲基鋶氯化物、(2-羧基乙基)二甲基鋶溴鎓鹽、三苯基鋶溴鎓鹽等之鋶鹽等。此等之中,就反應性之觀點,尤以選自由(4-甲基苯基)[4-(2-甲基丙基)苯基]-錪六氟磷酸鹽、雙(4-tert-丁基苯基)錪六氟磷酸鹽、二苯基錪六氟磷酸鹽、二苯基錪錪鹽、4-異丙基-4’-甲基二苯基錪肆(五氟苯基)硼酸鹽、2,6-二-tert-丁基-4-甲基吡喃鎓三氟甲烷磺酸鹽、(2-溴乙基)二苯基鋶三氟甲烷磺酸鹽、雙(2,4,6-三甲基吡啶)-溴鎓六氟磷酸鹽所成之群的至少1種為佳。 <Onium salt> The onium salt used in the polymerization of the present invention includes, for example, bis(2,4,6-trimethylpyridine)bromonium hexafluorophosphate and the like bromide; (4-methylphenyl)[4-(2 -Methylpropyl) phenyl) iodonium hexafluorophosphate, bis(4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium chloride, diphenyl Iodonium salt, 4-isopropyl-4'-methyldiphenyl iodonium (pentafluorophenyl) borate, (4-nitrophenyl) (phenyl) iodonium trifluoromethanesulfonate, etc. The iodonium salt; 2,6-di-tert-butyl-4-methylpyrylium trifluoromethanesulfonate, 2,4,6-trimethylpyrylium tetrafluoroborate and other oxonium salts ; (2-Bromoethyl) diphenyl sulfonium trifluoromethane sulfonate, (2-carboxyethyl) dimethyl sulfonium chloride, (2-carboxyethyl) dimethyl sulfonium bromide, triphenyl Caenium bromium salt and other sulfonium salts. Among these, from the viewpoint of reactivity, it is particularly selected from (4-methylphenyl)[4-(2-methylpropyl)phenyl]-Igonia hexafluorophosphate, bis(4-tert- Butylphenyl) iodonium hexafluorophosphate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium salt, 4-isopropyl-4'-methyl diphenyl iodonium (pentafluorophenyl) boric acid Salt, 2,6-di-tert-butyl-4-methylpyrylium trifluoromethanesulfonate, (2-bromoethyl)diphenyl sulfonate trifluoromethanesulfonate, bis(2,4 At least one of the group of ,6-trimethylpyridine)-bromonium hexafluorophosphate is preferred.
鎓鹽之使用量,相對於單體成分之總量而言,較佳為0.1~15質量%、更佳為0.1~10質量%、特佳為0.1~5質量%。鎓鹽之使用量若為上述範圍內,能夠以適切的聚合速度進行聚合反應。The amount of onium salt used is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.1 to 5% by mass relative to the total amount of monomer components. If the amount of the onium salt used is within the above range, the polymerization reaction can be carried out at an appropriate polymerization rate.
<環狀碳酸酯> 本發明之聚合反應,亦可進一步使用環狀碳酸酯。藉由使用環狀碳酸酯,可抑制聚合系統內之溫度上昇,可調整聚合系統內之內溫上昇幅度及聚合速度。環狀碳酸酯可列舉碳酸伸乙酯、碳酸伸丙酯、碳酸伸丁酯等。此等之中,就抑制溫度上昇之觀點,尤以碳酸伸丙酯為佳。本發明中之內溫上昇幅度,係使用熱電偶,以聚合開始前之內溫為基準,由聚合中之一時的內溫之上昇幅度所測定的值。 <Cyclic Carbonate> In the polymerization reaction of the present invention, cyclic carbonate may be further used. By using cyclic carbonate, the temperature rise in the polymerization system can be suppressed, and the range of the internal temperature rise in the polymerization system and the polymerization speed can be adjusted. Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, and butyl carbonate. Among these, from the viewpoint of suppressing temperature rise, propylene carbonate is particularly preferred. The increase in internal temperature in the present invention is a value measured from the increase in internal temperature during one of the polymerizations based on the internal temperature before the start of polymerization using a thermocouple.
環狀碳酸酯之使用量,相對於單體成分之總量而言,較佳為0.1~20質量%、更佳為0.1~10質量%、特佳為0.1~5質量%。The amount of cyclic carbonate used is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.1 to 5% by mass relative to the total amount of monomer components.
<乙烯基醚聚合物> 本發明中,乙烯基醚聚合物之重量平均分子量(Mw),可依其用途適當設定,無特別限定。例如,就展現高分子性之觀點,重量平均分子量(Mw),較佳為1000~50000之範圍內、更佳為1000~30000之範圍內。又,就使聚合物之性質均一化的觀點,分子量分布(Mw/Mn),較佳為1.2~4.0、更佳為1.3~3.9、特佳為1.5~2.0。 <Vinyl ether polymer> In the present invention, the weight average molecular weight (Mw) of the vinyl ether polymer can be appropriately set according to its use and is not particularly limited. For example, from the viewpoint of exhibiting high molecular weight, the weight average molecular weight (Mw) is preferably in the range of 1,000 to 50,000, more preferably in the range of 1,000 to 30,000. In addition, from the viewpoint of homogenizing the properties of the polymer, the molecular weight distribution (Mw/Mn) is preferably 1.2 to 4.0, more preferably 1.3 to 3.9, and particularly preferably 1.5 to 2.0.
<聚合步驟> 本發明之聚合反應中之聚合溫度,係依所使用之鎓鹽種類、單體成分、有機溶劑之有無、環狀碳酸酯之有無而異,但可為常溫至高溫,而非0℃以下之低溫,通常係20℃以上,較佳為30℃以上;較佳為100℃以下,更佳為90℃以下,又更佳為80℃以下,特佳為70℃以下。 <polymerization step> The polymerization temperature in the polymerization reaction of the present invention varies depending on the type of onium salt used, the monomer components, the presence of organic solvents, and the presence of cyclic carbonates, but it can be from room temperature to high temperature instead of below 0°C The low temperature is generally above 20°C, preferably above 30°C; preferably below 100°C, more preferably below 90°C, still more preferably below 80°C, particularly preferably below 70°C.
本發明之聚合反應中之聚合時間,雖依系統而異,但通常為1小時~36小時,較佳為1小時~24小時、更佳為1小時~18小時。Although the polymerization time in the polymerization reaction of the present invention varies depending on the system, it is usually 1 hour to 36 hours, preferably 1 hour to 24 hours, and more preferably 1 hour to 18 hours.
本發明之聚合系統內之內溫上昇幅度,通常調整為0.1℃~120℃,較佳調整為0.1℃~100℃、更佳調整為0.1℃~80℃、特佳調整為0.5℃~80℃。The internal temperature rise in the polymerization system of the present invention is usually adjusted to 0.1°C to 120°C, preferably 0.1°C to 100°C, more preferably 0.1°C to 80°C, particularly preferably 0.5°C to 80°C .
本發明之聚合反應亦可遮光來進行。藉由遮光來進行聚合反應,可抑制鎓鹽之光開裂所致之乙烯基醚單體的失控反應。The polymerization reaction of the present invention can also be performed by shielding light. By shielding light to carry out the polymerization reaction, the runaway reaction of the vinyl ether monomer caused by the photocracking of the onium salt can be suppressed.
本發明之聚合反應,係批式、連續式之任意方法均可適合地進行。聚合反應後,亦可依需要,為了去除未反應之單體,而藉由公知方法進行純化處理。 [實施例] The polymerization reaction of the present invention can be suitably carried out by any method of batch type or continuous type. After the polymerization reaction, if necessary, in order to remove unreacted monomers, purification treatment may be performed by a known method. [Example]
藉由以下實施例,以更具體說明本發明,但本發明不受此等實施例之任何限定。再者,實施例中,聚合物之數平均分子量(Mn)、重量平均分子量(Mw)及分子量分布(Mw/Mn),係分別由凝膠滲透層析(GPC)之分子量分析結果(聚苯乙烯換算)求得。分析裝置及測定條件等係如以下所述。 <裝置/條件> ・裝置:東曹股份有限公司製,「HLC-8320GPC」 ・檢測器:RI檢測器 ・移動相:四氫呋喃 ・流量:1mL/分鐘 ・管柱:昭和電工股份有限公司製「Shodex LF-804」×3支 ・管柱溫度:40℃ The following examples are used to illustrate the present invention in more detail, but the present invention is not limited in any way by these examples. Furthermore, in the examples, the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymer are obtained from the molecular weight analysis results of gel permeation chromatography (GPC) (polystyrene Ethylene conversion). The analysis equipment and measurement conditions are as follows. <Device/Conditions> ・Device: "HLC-8320GPC" manufactured by Tosoh Corporation ・Detector: RI detector ・Mobile phase: Tetrahydrofuran ・Flow rate: 1mL/min ・Pipe column: "Shodex LF-804" manufactured by Showa Denko Co., Ltd. x 3 ・Column temperature: 40℃
[實施例1] 將2-甲氧基乙基乙烯基醚(以下,MOVE)30g,與雙(4-tert-丁基苯基)錪六氟磷酸鹽0.45g投入300mL之燒瓶中。藉由將燒瓶以鋁箔被覆,將反應容器內遮光。接著將反應系內進行加熱至50℃。其次,進行攪拌,一邊調節使維持聚合溫度,一邊進行15小時聚合反應。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為16126、Mw/Mn為2.64。 [Example 1] 30 g of 2-methoxyethyl vinyl ether (hereinafter, MOVE) and 0.45 g of bis(4-tert-butylphenyl) hexafluorophosphate were put into a 300 mL flask. The inside of the reaction vessel was shielded from light by covering the flask with aluminum foil. Next, the inside of the reaction system was heated to 50°C. Next, stirring was performed, and the polymerization reaction was performed for 15 hours while adjusting the polymerization temperature to maintain the polymerization temperature. After the completion of the polymerization reaction, as a result of analyzing the properties of the polymer, the Mw of the polymer produced was 16126 and the Mw/Mn was 2.64.
[實施例2] 將MOVE 30g,與二苯基錪六氟磷酸鹽0.45g投入300mL之燒瓶中。藉由將燒瓶以鋁箔被覆,將反應容器內遮光。接著將反應系內進行加熱至50℃。其次,進行攪拌,一邊調節使維持聚合溫度,一邊進行7小時聚合反應。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為25928、Mw/Mn為1.97。 [Example 2] Put 30 g of MOVE and 0.45 g of diphenyl hexafluorophosphate into a 300 mL flask. The inside of the reaction vessel was shielded from light by covering the flask with aluminum foil. Next, the inside of the reaction system was heated to 50°C. Next, stirring was performed, while adjusting the polymerization temperature so as to maintain the polymerization temperature, the polymerization reaction was performed for 7 hours. After the completion of the polymerization reaction, the result of analyzing the properties of the polymer showed that the Mw of the polymer produced was 25928 and the Mw/Mn was 1.97.
[實施例3] 將MOVE 30g,與二苯基錪錪鹽0.45g投入300mL之燒瓶中。藉由將燒瓶以鋁箔被覆,將反應容器內遮光。接著將反應系內進行加熱至70℃。其次,進行攪拌,一邊調節使維持聚合溫度,一邊進行16.5小時聚合反應。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為1259、Mw/Mn為1.30。 [Example 3] Put 30 g of MOVE and 0.45 g of diphenyl iodonium salt into a 300 mL flask. The inside of the reaction vessel was shielded from light by covering the flask with aluminum foil. Next, the inside of the reaction system was heated to 70°C. Next, stirring was performed, and the polymerization reaction was performed for 16.5 hours while adjusting the polymerization temperature to maintain the polymerization temperature. After the completion of the polymerization reaction, the result of analyzing the properties of the polymer showed that the Mw of the polymer produced was 1259 and the Mw/Mn was 1.30.
[實施例4] 將MOVE 30g,與4-異丙基-4’-甲基二苯基錪肆(五氟苯基)硼酸鹽0.45g投入300mL之燒瓶中。藉由將燒瓶以鋁箔被覆,將反應容器內遮光。接著將反應系內進行加熱至70℃。其次,進行攪拌,一邊調節使維持聚合溫度,一邊進行1小時聚合反應。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為7721、Mw/Mn為2.48。 [Example 4] Put 30 g of MOVE, and 0.45 g of 4-isopropyl-4'-methyldiphenyl bis (pentafluorophenyl) borate into a 300 mL flask. The inside of the reaction vessel was shielded from light by covering the flask with aluminum foil. Next, the inside of the reaction system was heated to 70°C. Next, stirring was performed, and the polymerization reaction was performed for 1 hour while adjusting the polymerization temperature to maintain the polymerization temperature. After the polymerization reaction was completed, the properties of the polymer were analyzed, and the Mw of the polymer produced was 7721 and Mw/Mn was 2.48.
[實施例5] 將MOVE 30g,與2,6-二-tert-丁基-4-甲基吡喃鎓三氟甲烷磺酸鹽0.45g投入300mL之燒瓶中。藉由將燒瓶以鋁箔被覆,將反應容器內遮光。接著將反應系內進行加熱至30℃。其次,進行攪拌,一邊調節使維持聚合溫度,一邊進行1小時聚合反應。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為8203、Mw/Mn為3.89。 [Example 5] Put 30 g of MOVE, and 0.45 g of 2,6-di-tert-butyl-4-methylpyrylium trifluoromethanesulfonate into a 300 mL flask. The inside of the reaction vessel was shielded from light by covering the flask with aluminum foil. Next, the inside of the reaction system was heated to 30°C. Next, stirring was performed, and the polymerization reaction was performed for 1 hour while adjusting the polymerization temperature to maintain the polymerization temperature. After the polymerization reaction was completed, as a result of analyzing the properties of the polymer, the Mw of the polymer produced was 8203 and the Mw/Mn was 3.89.
[實施例6] 將MOVE 30g,與(2-溴乙基)二苯基鋶三氟甲烷磺酸鹽0.45g投入300mL之燒瓶中。藉由將燒瓶以鋁箔被覆,將反應容器內遮光。接著將反應系內進行加熱至50℃。其次,進行攪拌,一邊調節使維持聚合溫度,一邊進行1小時聚合反應。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為27714、Mw/Mn為2.78。 [Example 6] Put 30 g of MOVE and 0.45 g of (2-bromoethyl) diphenyl sulfonate trifluoromethanesulfonate into a 300 mL flask. The inside of the reaction vessel was shielded from light by covering the flask with aluminum foil. Next, the inside of the reaction system was heated to 50°C. Next, stirring was performed, and the polymerization reaction was performed for 1 hour while adjusting the polymerization temperature to maintain the polymerization temperature. After the completion of the polymerization reaction, the properties of the polymer were analyzed, and the resultant polymer had Mw of 27714 and Mw/Mn of 2.78.
[實施例7] 將MOVE 30g,與雙(2,4,6-三甲基吡啶)-溴鎓六氟磷酸鹽0.45g投入300mL之燒瓶中。藉由將燒瓶以鋁箔被覆,將反應容器內遮光。接著將反應系內進行加熱至70℃。其次,進行攪拌,一邊調節使維持聚合溫度,一邊進行9小時聚合反應。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為1734、Mw/Mn為1.52。 [Example 7] Put 30 g of MOVE and 0.45 g of bis(2,4,6-trimethylpyridine)-bromonium hexafluorophosphate into a 300 mL flask. The inside of the reaction vessel was shielded from light by covering the flask with aluminum foil. Next, the inside of the reaction system was heated to 70°C. Next, stirring was performed, and the polymerization reaction was performed for 9 hours while adjusting the polymerization temperature to maintain the polymerization temperature. After the polymerization reaction was completed, the properties of the polymer were analyzed, and the resultant polymer had Mw of 1734 and Mw/Mn of 1.52.
[比較例1] 除了不添加鎓鹽以外,係以與實施例1同樣之方法進行聚合。其結果,未生成聚合物。 [Comparative Example 1] The polymerization was carried out in the same manner as in Example 1 except that the onium salt was not added. As a result, no polymer was produced.
實施例1~7及比較例1之結果示於表1。 The results of Examples 1 to 7 and Comparative Example 1 are shown in Table 1.
由實施例1~7之結果,藉由在鎓鹽存在下,將乙烯基醚單體以高溫條件聚合,得到各種乙烯基醚聚合物。本次的聚合系統中係使用各種鎓鹽,在所有的條件中均確認到進行聚合,生成聚合物。另一方面,由比較例1之結果,確認到於未添加鎓鹽之系統中,未進行聚合,未生成聚合物。From the results of Examples 1 to 7, by polymerizing vinyl ether monomers under high temperature conditions in the presence of onium salts, various vinyl ether polymers were obtained. Various onium salts were used in the polymerization system this time, and it was confirmed that the polymerization proceeded to produce a polymer under all conditions. On the other hand, from the results of Comparative Example 1, it was confirmed that in the system without addition of onium salt, polymerization did not proceed and no polymer was formed.
[實施例8] 除了進一步添加碳酸伸丙酯0.4g以外,係以與實施例1同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為13033、Mw/Mn為1.97。又,聚合系統內之內溫上昇幅度為3℃。 [Example 8] Except for further adding 0.4 g of propylene carbonate, polymerization was carried out in the same manner as in Example 1. After the polymerization reaction was completed, the properties of the polymer were analyzed, and the resultant polymer had Mw of 13033 and Mw/Mn of 1.97. In addition, the internal temperature rise in the polymerization system was 3°C.
[實施例9] 除了進一步添加碳酸伸丙酯1.2g以外,係以與實施例1同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mw為11782、Mw/Mn為1.80。又,聚合系統內之內溫上昇幅度為0.5℃。 [Example 9] Except that 1.2 g of propylene carbonate was further added, polymerization was carried out in the same manner as in Example 1. After the polymerization reaction was completed, the properties of the polymer were analyzed, and the resultant polymer had an Mw of 11178 and a Mw/Mn of 1.80. In addition, the internal temperature rise in the polymerization system was 0.5°C.
實施例1、8及9之結果示於表2。 The results of Examples 1, 8 and 9 are shown in Table 2.
由實施例8及9之結果,確認到藉由添加碳酸伸丙酯,可控制溫度上昇。又,確認到藉由調整碳酸伸丙酯之量,可調整聚合系統內之內溫上昇幅度及聚合速度。From the results of Examples 8 and 9, it was confirmed that the temperature increase can be controlled by adding propylene carbonate. In addition, it was confirmed that by adjusting the amount of propylene carbonate, the increase in internal temperature and the polymerization rate in the polymerization system can be adjusted.
[實施例10] 除了將鎓鹽變更為(4-甲基苯基)[4-(2-甲基丙基)苯基]-錪六氟磷酸鹽,且將鎓鹽與碳酸伸丙酯以質量比3:1混合以外,係以與實施例1同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mn為9499、Mw為18544、Mw/Mn為1.95。 [Example 10] Except that the onium salt is changed to (4-methylphenyl)[4-(2-methylpropyl)phenyl]-iphonium hexafluorophosphate, and the onium salt and propylene carbonate are in a mass ratio of 3:1 Except for mixing, polymerization was carried out in the same manner as in Example 1. After the completion of the polymerization reaction, the properties of the polymer were analyzed. The Mn of the polymer produced was 9499, Mw was 18544, and Mw/Mn was 1.95.
[實施例11] 除了使單體成分為乙基己基乙烯基醚(EHVE)以外,係以與實施例10同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mn為2200、Mw為3447、Mw/Mn為1.55。 [Example 11] The polymerization was carried out in the same manner as in Example 10 except that the monomer component was ethylhexyl vinyl ether (EHVE). After the completion of the polymerization reaction, the properties of the polymer were analyzed, and the resultant polymer had an Mn of 2200, Mw of 3447, and Mw/Mn of 1.55.
[實施例12] 除了使單體成分為環己基乙烯基醚(CHVE)以外,係以與實施例10同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mn為1119、Mw為1673、Mw/Mn為1.50。 [Example 12] The polymerization was carried out in the same manner as in Example 10 except that the monomer component was cyclohexyl vinyl ether (CHVE). After the polymerization reaction was completed, the properties of the polymer were analyzed, and the resultant polymer had Mn of 1119, Mw of 1673, and Mw/Mn of 1.50.
[實施例13] 除了使單體成分為2-(2-乙氧基乙氧基)乙基乙烯基醚(EOEOVE)以外,係以與實施例10同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mn為3690、Mw為7365、Mw/Mn為1.99。 [Example 13] The polymerization was carried out in the same manner as in Example 10 except that the monomer component was 2-(2-ethoxyethoxy)ethyl vinyl ether (EOEOVE). After the polymerization reaction was completed, as a result of analyzing the properties of the polymer, the Mn of the polymer produced was 3690, Mw was 7365, and Mw/Mn was 1.99.
[實施例14] 除了使單體成分為2-乙氧基乙基乙烯基醚(EOVE)以外,係以與實施例10同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mn為1107、Mw為1913、Mw/Mn為1.73。 [Example 14] The polymerization was carried out in the same manner as in Example 10 except that the monomer component was 2-ethoxyethyl vinyl ether (EOVE). After the polymerization reaction was completed, the properties of the polymer were analyzed, and the resultant polymer had Mn of 1107, Mw of 1913, and Mw/Mn of 1.73.
[實施例15] 除了使單體成分為三乙二醇單甲基乙烯基醚(TEGVE)以外,係以與實施例10同樣之方法進行聚合。聚合反應結束後,進行聚合物之性狀分析的結果,所生成之聚合物之Mn為3667、Mw為5769、Mw/Mn為1.57。 [Example 15] The polymerization was carried out in the same manner as in Example 10 except that the monomer component was triethylene glycol monomethyl vinyl ether (TEGVE). After the completion of the polymerization reaction, the properties of the polymer were analyzed. The Mn of the polymer produced was 3667, Mw was 5769, and Mw/Mn was 1.57.
實施例10~15之結果示於表3。 The results of Examples 10-15 are shown in Table 3.
由實施例10~15之結果,確認到本次的聚合系統,可應用於側鏈構造相異之各種乙烯基醚單體。From the results of Examples 10-15, it was confirmed that the polymerization system this time can be applied to various vinyl ether monomers with different side chain structures.
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