TW480274B - Composition impeding polymerisation of monomers containing an ethylene type unsaturated bond, and a process for its preparation - Google Patents
Composition impeding polymerisation of monomers containing an ethylene type unsaturated bond, and a process for its preparation Download PDFInfo
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- TW480274B TW480274B TW087115818A TW87115818A TW480274B TW 480274 B TW480274 B TW 480274B TW 087115818 A TW087115818 A TW 087115818A TW 87115818 A TW87115818 A TW 87115818A TW 480274 B TW480274 B TW 480274B
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Abstract
Description
480274 五、發明說明(1) - 本發明係有關一種組合物,其在室溫至-2 0 °C的溫度範 圍内為液體,其可用來抑制含乙烯型不飽和鍵的單體發生 自由基聚合反應。更特別者,其係有關乙烯型單體。 本發明也有關一種製備該組合物的方法。 含乙烯型不飽和鍵的單體於受熱時傾向於自然地聚合。 於彼等體的製造,純化與貯存之中必須避免過早聚合。於 製造或純化中,過早聚合係一項問題,因其會促成產率下 降且設備堵塞,而需要時常矩暫停止生產以進行維修,導 致過度的生產成本。由於聚合反應的放熱本質,也會有火 災與***之危險。 含有乙烯型不飽和鍵的某些單體特別易於發生彼種聚合 反應。特別是單烯烴與二烯烴之情況,更特別者為含有共 軛雙鍵的烯烴,例如異戊二烯與1,3 - 丁二烯,以及乙烯型 化合物。 為了遏止含乙烯型不飽和鍵的單體發生聚合反應,先前 技藝述及添加一或多種聚合抑制劑或滯缓劑,作為製造中 的預防手段,或作為直接針對使用前的單體者。彼等化合 物通常為自由基聚合抑制劑。 於此技術領域中也為有用者提出一種緊急抑制劑,其可 在工廠中發生技術問題時,在傳統聚合合成中停止彼等單 體的聚合。 最常用的抑制劑為4-第三丁基兒茶酚,其係單獨加入或 可能與其它抑制劑混合後加入。 於此方面,美國專利 US-A-2 4 7 8 7 1 0,US-A- 3 4 0 5 1 8 9480274 V. Description of the invention (1)-The present invention relates to a composition which is a liquid in a temperature range from room temperature to -20 ° C, and can be used to inhibit the occurrence of free radicals of monomers containing ethylenically unsaturated bonds. Polymerization. More specifically, it relates to vinyl monomers. The invention also relates to a method for preparing the composition. Monomers containing ethylenic unsaturated bonds tend to polymerize naturally when heated. In their manufacture, purification and storage must be avoided prematurely. In manufacturing or purification, premature polymerization is a problem because it will lead to a decrease in yield and equipment blockage, and it is necessary to temporarily stop production for maintenance from time to time, resulting in excessive production costs. Due to the exothermic nature of the polymerization reaction, there is also the danger of fire and explosion. Certain monomers containing ethylenically unsaturated bonds are particularly susceptible to that type of polymerization. In particular, in the case of monoolefins and diolefins, olefins containing conjugated double bonds such as isoprene and 1,3-butadiene, and ethylene-based compounds are more particular. In order to prevent the polymerization reaction of the monomer containing an ethylenically unsaturated bond, the prior art described the addition of one or more polymerization inhibitors or retarders as a preventive measure in manufacturing or as a direct targeting of monomers before use. Their compounds are usually free-radical polymerization inhibitors. In this technical field, an emergency inhibitor is also proposed for the useful person, which can stop the polymerization of their monomers in the traditional polymerization synthesis when a technical problem occurs in the factory. The most commonly used inhibitor is 4-tert-butylcatechol, which is added alone or possibly mixed with other inhibitors. In this regard, US patents US-A-2 4 7 8 7 1 0, US-A- 3 4 0 5 1 8 9
L:\EXT\55\55041.PTD 第4頁 五、發明說明(2) 與日本專利j p 1 9 fi q q / e j +、上 戊二烯及環戊二稀之安^白a及丁二烯,異戊二烯,工,3一 6qfi 171,一烯文疋化。類似地,法國專利FR-A-2 關十,7 @丨—A_3 3 90 1 98與歐洲專利EP_A —〇 4 03 6 72皆 闡述乙稀型單ϋ的^. L ^ 449 和 US-A-4 48 7 98 1。 者,可參#US_A-2 9 25 Z基兒茶盼為一種在室溫下為固禮之化合物。立 熔點為d4 c。因此為了你廿+ θ t '、 笑 ^ σσ 為了使其容易地注射到工業裝置的再沸 态,儲器,反麻哭,…+ # ^ ^L: \ EXT \ 55 \ 55041.PTD Page 4 V. Description of the invention (2) and Japanese patent jp 1 9 fi qq / ej +, upper pentadiene and cyclopentadiene ^ white a and butadiene , Isoprene, Ig, 3-6qfi 171, monoenzyme. Similarly, French patent FR-A-2 Guan Shi, 7 @ 丨 —A_3 3 90 1 98 and European patent EP_A —〇4 03 6 72 both describe ^. L ^ 449 and US-A- 4 48 7 98 1. For more details, please refer to # US_A-2 9 25 Z Catechin is a compound that solidifies at room temperature. The melting point is d4 c. So for you 廿 + θ t ', laugh ^ σσ In order to make it easy to inject into the reboiled state of the industrial plant, the reservoir, anti-hemp, ... + # ^ ^
A u. ^ ^ ^ Φ ^ " 財存官線與頂部回流管線之内,必須 无將其熔在要安定彳卜 W 因此,4-第^其^早體内^容於有機溶劑内。 , —讲^丄一 &兒余酚係由RHONE-POULENC以在水 合物之形式銷售。〃 丁知中,在曱苯中與在二甲苯中的組 彼等組合物並不完八 〇 °C以下,不是液體王7人滿意,因彼等在負溫度,亦即 甲醇,甲苯和二甲^之故。事實上,4 一第三丁基兒茶酚在 特殊條件下且特別^ 2具有鬲於〇。0之結晶點。此外,在 溫度下,也從對鹿的在振動或機械應力下,於高於〇 t的 第三丁基兒茶酚:卹^水與異丁醇内之組合物内觀察到4- μ °卜份結曰。 因此,為了遏止4_ 日日。 售溶液都先預熱到2 〇。〜丁基兒茶酚的結晶,上文所述市 注射到製備標的'單释C與60 °C之間並保持在彼等溫度以期 的工業管線。 斤用程序内,意謂著必須用到經恒溫 本發明的目標在於、^ 、 合物,其可用為聚人 以4-第三丁基兒荼紛為基質的組 + θ抑制劑且其不具先前技藝組合物的缺A u. ^ ^ ^ Φ ^ " Within the Treasury's official line and the top return line, it must not be melted in the to-be-stabilized W. Therefore, the 4-th ^ ^ early body ^ is contained in organic solvents. --Speak ^ 丄 一 & catechol is sold by RHONE-POULENC as a hydrate. 〃 Ding Zhizhong, their composition in xylene and xylene is not more than 80 ° C, which is not satisfactory for 7 liquid kings, because they are at negative temperature, that is, methanol, toluene and dioxin. A ^ the reason. In fact, 4-tert-butylcatechol has a specific value of less than 0 under special conditions. Crystallization point of 0. In addition, 4-μ ° was also observed in the composition of tertiary butyl catechol: water and isobutanol above 0 t under vibration or mechanical stress on deer at temperature. Bu share said. Therefore, to curb 4_ day. The commercial solutions were preheated to 20 ° C. ~ The crystallization of butyl catechol, as described above, was injected into the preparation of the target 'mono release C and 60 ° C and maintained at that temperature for industrial pipelines. In the application program, it means that the target of the present invention is to be used at constant temperature. The compound can be used as a group based on 4-third butyl cyanine + θ inhibitor and it does not have The lack of prior art compositions
L:\EXT\55\55041.PTD 第5頁 480274 五、發明說明(3) 點,亦即,其在室溫至約-2 0 °C的溫度下皆為液體。在這 些溫度之下,本發明組合物保持為液體且未觀察到4 -第三 丁基兒茶酚的結晶或振動。 更精確而言,在室溫至-2 0 °C範圍内呈液體的本發明組 合物包括至少一種兒茶盼衍生物與至少一芳族醚。 π室溫π —詞通常指在1 5 °C至2 5 °C範圍内的溫度。 必須提及者該溫度範圍的上限在本質上係不具關鍵性 者。 本發明組合物較佳者包括至少一種式(I)兒茶S分衍生 物:L: \ EXT \ 55 \ 55041.PTD Page 5 480274 V. Description of the invention (3) Point, that is, it is liquid at room temperature to about -20 ° C. At these temperatures, the composition of the invention remained liquid and no crystallization or vibration of 4-tert-butylcatechol was observed. More precisely, the composition of the present invention which is liquid at a temperature ranging from room temperature to -20 ° C includes at least one catechin derivative and at least one aromatic ether. π Room temperature π — The word usually refers to a temperature in the range of 15 ° C to 25 ° C. It must be mentioned that the upper limit of this temperature range is not critical in nature. The composition of the present invention preferably includes at least one catechin S-derived derivative of formula (I):
OHOH
式中: •心,R2,R3和R4可相同或相異,各表氫原子,烷基或烷氧 基; • Ri,R2,R3或1?4中至少有一取代基表一氫原子; • h,R2,R3和1^4中至少有三取代基表一氫原子。 π烷基’’ 一詞在本發明範疇内係指線型或分枝烴鏈例如曱 苯,正丁基,第三丁基,正丙基,異丙基或辛基。 ”烷氧基”一詞於本發明範疇内係指其烷基係上文所定義 者之烧氧基。該烧氧基較佳者為異丙氧基。In the formula: •, R2, R3 and R4 may be the same or different, and each of them represents a hydrogen atom, an alkyl group or an alkoxy group; • at least one substituent in Ri, R2, R3 or 1-4 represents a hydrogen atom; h, R2, R3 and 1 ^ 4 have at least three substituents representing a hydrogen atom. The term πalkyl '' within the scope of the present invention refers to a linear or branched hydrocarbon chain such as toluene, n-butyl, third butyl, n-propyl, isopropyl or octyl. The term "alkoxy" within the scope of the present invention refers to an alkyloxy group as defined above. The alkoxy group is preferably isopropoxy.
L:\EXT\55\55041.PTD 第6頁 480274 五、發明說明(4) 於本文中,兒茶酚衍生物”一詞涵蓋式(丨)人 除二其中,R2,,和IV全部都是氫原子的兒茶‘以,但 第一較佳的兒茶酚衍生物組合係由式(〗)中κ 。 R4可相同或相異地選自氫原子,c「Ci2烷基,較件二,I和 及匕-义2烷氧基,較佳者^ —q之中者的化合物二rC4, 另一較佳兒余酚衍生物組合係由式(丨)化合 、 基K ’ R2,R3和1中至少有三者表氫原子者所構成的、取复代 中,K ’ R2 ’ R3,和r4中的該第四取代基係選 /、 基,較佳m「c4,及Cl —Ci2院氧基,較佳者1 更有利者。 1、之中者係 第三組較佳化合物係由3—曱基兒茶酚,4 — 3:異丙基兒茶齡,3_ 丁基_5_甲基兒茶齡,4_第基三兒余齡, 余酚,3, 5-二-第三丁基兒茶酚,4, 6_二_第三丁美土欠 驗,3_辛基_5~甲基兒茶齡,4-異丙氧基兒茶齡,土3, 6_木二一 異丙基兒余酚,及彼等的混合物。 必須提及者所有的兒茶酚衍生物皆 由熟練者順利製成者。 』付者次了 於諸兒茶酚衍生物中,4—第三丁基兒茶酚為較佳的化合 物。 本發月、、且e物的另一特點為包括一種芳族峻作為溶劑。 a於本發明揭示内容的剩餘部份中,”芳族醚”一詞意指芳 私,化广物中一直接鐽結到芳環的氫原子被一醚基所取代, 芳θ族化合物” 一詞意指習用的芳香性概念,如在文獻, erry MARCH, Advanced Organic ChemistryfiL: \ EXT \ 55 \ 55041.PTD Page 6 480274 V. Description of the invention (4) In this article, the term catechol derivative encompasses the formula (丨) except for the two, where R2, and IV are all Catechin is a hydrogen atom, but the first preferred combination of catechol derivatives is κ in formula (). R4 may be the same or differently selected from a hydrogen atom, c, Ci2 alkyl, more than two , I, and d-syl-2alkoxy, preferably the compound di rC4 of ^ -q, and another preferred phenol compound combination is a compound of the formula (丨), the group K'R2, R3 In the substitution of at least three of 1 and 1 representing a hydrogen atom, the fourth substituent in K'R2'R3, and r4 is an optional group, preferably m "c4, and Cl-Ci2 Oxygen, preferably 1 is more favorable. 1. The third group is the preferred compound of the 3-group catechol, 4-3: isopropylcatechin age, 3-butyl-5 _Methyl catechin age, 4_three tri-cate, age, phenol, 3, 5-di-tertiary butyl catechol, 4, 6_ di_tertiary butyl methacrylate, 3_ octyl 5--5 methyl catechin age, 4-isopropoxy catechin age, soil 3, 6_ wood-diisopropyl catechu Phenol, and their mixtures. Must mention that all catechol derivatives are made by skilled ones. "The payer is inferior to catechol derivatives, 4-tert-butyl catechin. Phenol is a preferred compound. Another feature of this invention is that it includes an aromatic compound as a solvent. A In the remainder of the present disclosure, the term "aromatic ether" means aromatic Privately, a hydrogen atom directly bonded to an aromatic ring is replaced by an ether group, and the term "aromatic θ compound" means a conventional aromatic concept, such as in the literature, erry march, advanced organic chemistryfi
480274 五、發明說明(5) 第4 版,John Wiley & Sons, 1992, ρρ· 40 ff,中所定義 者。 有許多準則可決定溶劑的選擇。 該兒茶酚衍生物必須可溶於該芳族醚内且必須不在使用 溫度下結晶。 該芳族醚必須在使用溫度範圍内為液體且必須具有低於 0 °C,較佳者低於-20 °C的結晶溫度。 更精確而言,本發明芳族醚可用通式(II)表之:480274 V. Description of Invention (5) 4th edition, as defined in John Wiley & Sons, 1992, ρρ · 40 ff. There are many criteria that can determine the choice of solvent. The catechol derivative must be soluble in the aromatic ether and must not crystallize at the temperature of use. The aromatic ether must be liquid within the use temperature range and must have a crystallization temperature below 0 ° C, preferably below -20 ° C. More precisely, the aromatic ether of the present invention can be represented by the general formula (II):
基 丁 正 •’ 基 基 丙 烷異 : 枝 , 為 :分 基 醚 者或丙 族 (U述型 正。。芳Butyl-n -'- propylpropane iso: branch, as: branched ether or propyl (U-type n. Aromatic
L:\EXT\55\55041.PTD 第8頁 480274 五、發明說明(6) • 4~氯茴香謎; • 2 -氟茴香驗; • 4-氣茴香_。 菌香醚為較適用於本發明 發生興趣的性質:其為非毒性中:溶劑。其具有令人 有高濟點(154。〇且其具有古貝/其具熱安定性,其具 士政 口口 ’ 呵閃點(5 1 °C ) 〇 一構成份的重量比例可由孰^ =酚衍生物與一芳族鍵。每 必須確s兒茶酚的最大安“ J =衫。所得組合物 範圍中固化或結晶。…,其必須不在所考慮的溫度 較佳的本發明組合物包括: • 3 0至6 0重量%的兒茶酚衍生物; •40至70重量%的芳族醚。 為了得到在-1 0 °C以下的溫度呈液體 為使用下列者: -至液體之組合物’較佳者 • 30至50重量%的兒茶酚衍生物; • 50至70重量%的芳族醚。 必須參照諸實施例,其中依溫度界定所得組人 有關製備本發明組合物的方法,可導致 ")式。 何方法皆可以使用。 一、、且合物的任 經揭示組合物所含諸構成份可在室溫或較言 如在5 0 C至6 0 °C範圍内者,以任何順序混合。° 、’風度,例 本發明組合物為聚合抑制劑。彼等可因^用 、 合所劣化的含乙稀型不飽和鍵的單體之安定南丨7 =易被聚 M 可經由直L: \ EXT \ 55 \ 55041.PTD Page 8 480274 V. Description of the invention (6) • 4 ~ chlorofennel puzzle; • 2-fluorofennel test; • 4-gas fennel. Mycelium ether is more suitable for the present invention. The property of interest: It is non-toxic. Solvent. It has a high point (154.〇) and it has Gubei / its thermal stability, its Shi Zhengzhengkou 'flash point (5 1 ° C) 〇 One component weight ratio can be 孰 ^ = Phenol derivative and an aromatic bond. Each must be determined for the maximum safety of catechol "J = shirt. Cured or crystallized in the range of the composition obtained ...., it must not be a composition of the invention that is better than the temperature considered Including: • 30 to 60% by weight of catechol derivatives; • 40 to 70% by weight of aromatic ethers. To obtain a liquid at a temperature below -10 ° C use the following:-to liquid The composition is 'better' • 30 to 50% by weight of a catechol derivative; • 50 to 70% by weight of an aromatic ether. Reference must be made to the examples in which the resulting group is defined by temperature in relation to the preparation of the composition of the invention The method can lead to the formula "). Any method can be used. First, the composition of any disclosed composition can be at room temperature or more specifically in the range of 50 ° C to 60 ° C The internal ones are mixed in any order. °, 'Feng degree, for example, the composition of the present invention is a polymerization inhibitor. The stability of monomers containing ethylenically unsaturated bonds that can be deteriorated due to the use and combination of 7 and 7 can be easily polymerized.
C:\Program Files\Patent\5504L ptd 第 9 頁 480274 五、發明說明(7) " ------ 、不過、’ f 一較佳實施例中,本發明組合物係在單體的合 成中用為聚合抑制劑。彼等係在合成程序中的任何步驟二 到反應介質内。 於另 #伤中’本發明係有關阻止含乙烯型不飽和鐽的 單體在單體合成中發生聚合之方法…括將本: 物於合成知序的任何步驟添加到反應介質内。 /小加大里承合抑制劑沒有更多好處。可以添加的最適量 決定於要被安定化的含乙烯型不飽和鍵的單體所具本質。 因此,理想的抑制劑用量必須以個例為基予以評估 一般而言,本發明組合物的添加量為使得兒茶酚衍生物 的辰度在10至300 ppm範圍内,較佳者在5〇至120 ppm範圍 内。 當該含乙烯型不飽和鍵的單體係選自乙烯基單體,環戊 二烯與二環戊二稀之中時,本發明組合物特別有用。 根據本發明’ ”乙烯基單體”(v inyl monomers)涵蓋含有 至少一個乙烯基之所有化合物。彼等包括苯乙烯與其0一 曱基苯乙烯型衍生物,乙烯基曱苯與二乙烯基苯;丙烯酸 及其酯類例如丙烯酸曱酯,丙烯酸乙酯,丙烯酸丁 曱 基丙烯酸酯例如甲基丙烯酸曱酯;甲基乙烯基酮;丙烯 烯;氯丁二烯 腈;異戊間二烯;2, 3-二甲基-1,3 >臭丁一稀,氣丁一稀,氯乙稀與1,3 -戊二婦。 當該含乙烯型不飽和鍵的單體為1,3 -丁二烯或異戊間二 稀時,本發明方法特別有效。 其亦可用於從石油餾份蒸汽裂解流中分離和純化q烯混C: \ Program Files \ Patent \ 5504L ptd Page 9 480274 V. Description of the Invention (7) " ------, However, 'f In a preferred embodiment, the composition of the present invention is in the monomer Used as a polymerization inhibitor in synthesis. They are in any step of the synthesis procedure into the reaction medium. In the other #injury ’the present invention is a method for preventing the polymerization of monomers containing ethylenically unsaturated fluorene in the synthesis of the monomers, including adding any of the following steps in the synthesis sequence to the reaction medium. / Xiao Jiali Li Cheng He inhibitors have no more benefits. The optimum amount that can be added depends on the nature of the ethylenically unsaturated bond-containing monomer to be stabilized. Therefore, the ideal amount of inhibitor must be evaluated on a case-by-case basis. Generally speaking, the amount of the composition of the present invention is such that the catechol derivative has a degree of 10 to 300 ppm, preferably 50 To 120 ppm. The composition of the present invention is particularly useful when the monosystem containing an ethylenically unsaturated bond is selected from vinyl monomers, cyclopentadiene and dicyclopentadiene. "Vinyl monomers" according to the present invention encompass all compounds containing at least one vinyl group. They include styrene and its 0-methyl styrene-type derivatives, vinyl benzene and divinyl benzene; acrylic acid and its esters such as ethyl acrylate, ethyl acrylate, and butyl ethyl acrylate such as ethyl methacrylate ; Methyl vinyl ketone; allene; chloroprene nitrile; isoprene; 2, 3-dimethyl-1,3 > styrene butadiene, gas butadiene, chloroethene and 1 , 3-two women. The method of the present invention is particularly effective when the ethylene-type unsaturated bond-containing monomer is 1,3-butadiene or isoprene. It can also be used to separate and purify q-olefin mixtures from steam cracking streams of petroleum fractions.
L:\EXT\55\55041.PTDL: \ EXT \ 55 \ 55041.PTD
第10頁 480274 五、發明說明(8) · 合物之中,更特別者當彼等含有至少43%的1,3- 丁二烯之 時。 本發明組合物可以有利地在用含乙烯型不飽和鍵的單體 進行聚合物合成之中用為緊急抑制劑,較佳者該單體為苯 乙烯和其衍生物之時。 下列實施例係用為闡明本發明且視為本發明較佳實施例 者。 實施例中所給百分比係為重量百分比。 實施例1至8 於這些實施例中,以4 -第三丁基兒茶酚與茴香醚為基的 組合物係經由將該兩種構成份在室溫下以下面表1所示比 例予以混合而製備成者。 該等組合物係使用MettlerR DSC 30設備,在-150°C與 1 0 0 °C之間以差示熱量計分析顯示固體/液體轉變進行研 究。 包括20%,4 0%和60%4-第三丁基兒茶酚的組合物係用DSC 予以研究。 結果顯示對於20%,40°/◦和6 0%4 -第三丁基兒茶酚而言, 沒有觀察到固體/液體轉變且其玻璃轉變溫度為低於-80 °C 以下。 將所有混合物貯存在不同溫度,包括在室溫,冰箱,或 冷康庫内。 在貯存時觀察到的結果列於下表中:Page 10 480274 V. Description of the invention (8) · Among the compounds, more particularly when they contain at least 43% of 1,3-butadiene. The composition of the present invention can be advantageously used as an emergency inhibitor in polymer synthesis using a monomer containing an ethylenically unsaturated bond, preferably when the monomer is styrene and its derivatives. The following examples are intended to illustrate the present invention and are considered as preferred embodiments of the present invention. The percentages given in the examples are weight percentages. Examples 1 to 8 In these examples, a composition based on 4-tert-butylcatechol and anisole was mixed by mixing the two constituents at room temperature in the ratio shown in Table 1 below. And prepared. These compositions were studied using MettlerR DSC 30 equipment and differential calorimetry analysis between -150 ° C and 100 ° C to show solid / liquid transitions. Compositions including 20%, 40%, and 60% of 4-tert-butylcatechol were studied using DSC. The results show that no solid / liquid transition is observed for 20%, 40 ° / ◦ and 60% 4-tert-catechol and its glass transition temperature is below -80 ° C. Store all mixtures at different temperatures, including room temperature, refrigerator, or cold store. The results observed during storage are listed in the following table:
L:\EXT\55\55041.PTD 第11頁 480274 五、發明說明(9) 表丨 實施例 編號 4-第三丁基 兒茶酚(%) 窗香鍵 % 20°C 5°C -10°C -18°C 1 85 15 兩相 - - - 2 70 30 兩相 - 丨 - - 3 60 40 液體 液體 結晶 - 4 50 50 液體 液體 液體 結晶 5 40 60 液體 液體 液體 結晶 6 30 70 液體 液體 液體 液體 7 20 80 液體 液體 液體 液體 8 10 90 液體 •液體 液體 液體L: \ EXT \ 55 \ 55041.PTD Page 11 480274 V. Description of the invention (9) Table 丨 Example No. 4- Third butyl catechol (%) Window fragrance key% 20 ° C 5 ° C -10 ° C -18 ° C 1 85 15 two-phase---2 70 30 two-phase-丨--3 60 40 liquid liquid crystal-4 50 50 liquid liquid liquid crystal 5 40 60 liquid liquid liquid crystal 6 30 70 liquid liquid liquid Liquid 7 20 80 Liquid Liquid Liquid Liquid 8 10 90 Liquid • Liquid Liquid Liquid
結果顯示有多種組合物在寬廣溫度範圍内保持液態。因 此彼等可以不必預先再加熱而直接用於工業單元中。 實施例9至1 3 於下面的實施例中,以4 -第三丁基兒茶酚與苯***為基 的組合物係經由將該兩種構成份在室溫下以表I I所示比例 混合而製備成。 所有混合物都貯存在不同的溫度下8天並將觀察結果摘 列於下表中: 表II 實施例 編號 4-第三丁基 兒茶酚(%) 苗香鍵 % 20°C 5°C -3°C -18°C 60 40 液體 液體 結晶 結晶· 、10 50 50 液體 液體 液體 結晶 __ 40 60 液體 液體 液體 結晶 30 > ·、 70 液體 液體 液體 結晶 13 20 ' 80 液體 液體 液體 結晶The results show that many compositions remain liquid over a wide temperature range. They can therefore be used directly in industrial units without reheating in advance. Examples 9 to 1 In the following examples, a composition based on 4-tert-butylcatechol and phenylethyl ether was prepared by mixing the two constituents at room temperature in the ratio shown in Table II. And prepared into. All mixtures were stored at different temperatures for 8 days and the observations are summarized in the following table: Table II Example No. 4-Third-Butylcatechol (%) Miaoxiang Bond% 20 ° C 5 ° C- 3 ° C -18 ° C 60 40 liquid liquid crystal crystallization · 10 50 50 liquid liquid liquid crystal __ 40 60 liquid liquid liquid crystal 30 > · 70 liquid liquid liquid crystal 13 20 '80 liquid liquid liquid crystal
L:\EXT\55\55041.PTD 第12頁 480274L: \ EXT \ 55 \ 55041.PTD Page 12 480274
L:\EXT\55\55041.PTD 第Γ3頁 480274 案號87115818 年月 日 修正L: \ EXT \ 55 \ 55041.PTD Page Γ3 480274 Case No. 87115818 Month Day Amendment
O:\55\55041.ptc 第14頁 480274 附頁 OH "Λοη R^Y^R4 R3 (I) \ or5 ό Y (ID l\^t tier® 表1 i 實施例 編號 4-第三丁基 兒茶酚(%) 菌香謎 % 20°C 5V -10°C -18°C 1 85 15 兩相 - - - 2 70 30 兩相 - - - 3 60 40 液體 液體 結晶 - 4 50 50 液體 液體 液體 結晶 5 40 60 液體 液體 液體 結晶 6 30 70 液體 液體 液體 液體 7 20 80 液體 液體 液體 液體 8 10 90 液體 液體 液體 液體 表Μ 實施例 編號 4-第三丁基 兒茶酚(%) 茴香醚 % 20°C 5°C -3°C -18°C 9 60 40 液體 液體 結晶 結晶 10 50 50 液體 液體 液體 結晶 11 40 60 液體 液體 液體 結晶 12 30 70 液體 液體 液體 結晶 13 20 80 液體 液體 液體 結晶 C:\Program Files\Patent\55041. ptd 第,气頁O: \ 55 \ 55041.ptc Page 14 480274 Attachment OH " Λοη R ^ Y ^ R4 R3 (I) \ or5 ό Y (ID l \ ^ t tier® Table 1 i Example No. 4-Third Ding Base catechol (%) Mycorrhizal mystery% 20 ° C 5V -10 ° C -18 ° C 1 85 15 two-phase---2 70 30 two-phase---3 60 40 liquid crystal-4 50 50 liquid Liquid Liquid Crystal 5 40 60 Liquid Liquid Liquid Crystal 6 30 70 Liquid Liquid Liquid Liquid 7 20 80 Liquid Liquid Liquid Liquid 8 10 90 Liquid Liquid Liquid Liquid Table M Example No. 4-Third Butylcatechol (%) Anisyl Ether % 20 ° C 5 ° C -3 ° C -18 ° C 9 60 40 Liquid liquid crystals 10 50 50 Liquid liquid liquid crystals 11 40 60 Liquid liquid liquid crystals 12 30 70 Liquid liquid liquid crystals 13 20 80 Liquid liquid liquid crystals C: \ Program Files \ Patent \ 55041. Ptd
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FR9711890A FR2768723B1 (en) | 1997-09-24 | 1997-09-24 | COMPOSITION PREVENTING POLYMERIZATION OF ETHYLENICALLY UNSATURATED MONOMERS AND METHOD FOR PREPARING THE SAME |
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DE102013204950A1 (en) | 2013-03-20 | 2014-09-25 | Evonik Industries Ag | Process and composition for inhibiting the polymerization of cyclopentadiene compounds |
JPWO2022230915A1 (en) * | 2021-04-28 | 2022-11-03 | ||
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