200932778 % \ 5 ❹ 10 15❹ 20 六、發明說明：【發明所屬二 發明背景 本發明有關轉化一在室温為液體之環氧樹於為 温為固體之環氧樹脂的製程。【先前技J 環氧樹脂塗層可由一塗層配方形成，其可勺人 ^ c ° 各在至温 (〜25C)為液體之環氧樹脂或包含在室溫為固體之環氧樹 脂。使用在室温為固體之環氧樹脂，例如為粉末塗層配方: -在室温為祕之環氧樹脂(如由環氧氣㈣與雙反應 而形成的已知之液體環氧樹脂）可轉化為在室溫是固體： 其係藉由在-催化劑存在下混合液體環氧樹脂 與方香雜(較佳—雙盼如㈣A)並接著加熱混合物以使 樹脂可催化的與芳香族較應以轉化液體環氧樹 月曰為在至温是固體的環氧 ^ _環氧樹脂可催化與雙心【明内】 發明概要 本發明為前述問題的— 樹脂至在室温為__^決手段。需要轉化液體環氧 發明之製程而減少約23%或更多脂所需的時間可藉由使用本 -技術領域】 3 200932778 10 15 20 * 在-實施例中，本發明為—用於製造轉化 製程’其包含步驟：⑷加熱—液體環氧樹脂以&之 之液體環氧樹脂；（b)加熱一若巷灶^ 王—加熱 方香族酚以產生—加埶 祕·，⑷混合加熱之液體環氧樹脂及加熱 :方香 實質上未加入或除去熱能量以產生— 、酚，其 至約14代範_的液體環氧樹脂 ⑷混合⑴可增加芳香_與液體環氧樹脂間反:物: 料與⑼液體環氧樹脂與芳香_的混合物㈣力 紛與液體環氧樹脂之反應速率而生成轉化之環二.^ 1==芳香_液體環氧樹脂間反應速率二料 及液體％氧樹脂與芳香族盼之混合物的组合物均質 於約20秒中為大於約0.95。 夕 在另-實施例中，本發明為—用於製 之製程，其包含步驟：⑷加轨可 環氧樹月曰 β Λ Λ 、 θ方香族酚與液體環氧 樹月曰間反應速率的材料與液體環氧樹脂的混合物 樹脂與可增加芳香_與液體環氧樹脂間反錢 率㈣料之加熱混合物；（b)加熱—芳香族_產p加熱 之方香族t及⑷混合液體環氧樹脂與可增加芳香紐與 =體環氧樹脂間反應速率的材料之加㈣合物及加熱之芳 _ ’其實f上未加人或除去熱能量以產生—且有最初 温度在約至約14(rc__反應混合物故芳香族 盼與液體環氧樹脂反應以製造轉化之魏樹脂；其中混合 =體環氧樹脂與可增加芳香祕與液體環氧樹脂間反應速 ”的材料之加熱混合物與加熱之芳香族盼的組合物均質性 〇 ❺ 4 200932778 在少於約20秒中為大於約〇 95。 匕在又另一實施例中，本發明為一用於製造轉化環氣樹 脂之製程’其包含步驟：（a)加熱可增加芳香族齡與液體環 乳樹脂間反應速率的材料與芳香族紛的混合物以產生一芳 香族紛與可增加芳香族盼與液體環氧樹脂間反應速率的材 料之加熱混合物，（b)加熱液體環氧樹脂以產生加熱之液體 環氧樹脂；及(c)混合芳香族盼與可增加芳香族紛與液體環 ，樹脂間反應速率的材料之加熱混合物及加熱之液體環氧 树月曰，其實質上未加入或除去熱能量以產生一具有最初温 10度在約U0°C至約140°c範圍間的反應混合物，故芳香族酚 與液體環氧樹脂反應以製造轉化之環氧樹脂；其中混合芳 香族酚與可增加芳香族酚與液體環氧樹脂間反應迷率的材 料之加熱混合物與加熱之液體環氧樹脂的組合物均質性在 少於約20秒中為大於約0.95。 15圖式簡單說明 本發明配合附圖藉由本發明之例示的非限制實施例更 詳盡描述如下，其中： 第1圖為習知技藝反應器及製程的橫切面剖視圖. 第1A圖為第1圖之習知技藝反應器沿1八4八線的頂視 20 橫切面剖視圖； 第2圖為本發明反應器及製程的橫切面剖視圖；及 第2A圖為第2圖本發明反應器沿2A-2A線的頂視橫切 面剖視圖。 【貧施方式3 5 200932778 較佳實施例之詳細說明 質性，詞係以下列方式式界定： Η机充分混合]，卩時] 其作-充錢合]=在充以合後_添 1 你及[C.㈣]=添加_SP㈣h 的均質混合物。 U 1葸扣7〇王 “實質上未加人統錢，，—詞 除為少於混合物熱能的約1〇%。較二：、的加入或去 10 15 20 去除為無法避免的且少&任何熱的加入或 兄的且夕於混合物熱能的約$ 在一實施例中，本發明 程’其包含四步驟。第—步驟==之環氧樹脂的製 加熱之液體環氧樹脂。第加熱讀環氧樹脂以產生 加熱之芳香族紛。第驟為加熱—芳香族盼以產生 加熱之芳香細，其實質為^合加熱之液體環氧樹脂及 具有温度在約11(TC至約14()。=^或除去減量以產生-香族紛之混合物1四的液體環氧樹脂與芳 體環氧樹脂間反應逮率：此合一可增加芳香族酚與液 的混合物以增加芳香族紛與錄樹脂與芳香· 成轉化之環氧触，可^ 他之反應速率而生 應速率的材料及液體環二料族_液體環氧樹脂間反 物均質性在少於約脂與芳香族狀混合物的組合 約0.95少於約15秒佳為大於 式反應器中進行，則轉混合在—具有轉動動葉輪的批 約5至約14英吋處。加熱:輪較=低於混合物高度之 、液體環氧樹脂及加熱之芳香族紛 200932778 的混合實質無熱能加人(或去除)在本發”為重要的，其可 增加製程的產能並減少反應容器之固體相硬結的形成;對 於可增加芳香族紛與液體環氧樹脂間反應速率的材料及液 體環氧樹脂與芳香族酴之混合物的組合物均質性在少於約 5 20秒中為大於約0.95之要求為減少凝膠的形成。 在另-實施财，本發縣1於製造轉化環氧樹腊之 製程’其包含三步驟。第-步驟為加熱可增加料㈣與液 體環氧樹關反應速率的材料與液體環氧樹腊的混合物以產 生-液體環氧_與可增加芳香族_液體環氧樹脂間反應 10速率的材料之加熱混合物。第二步驟為加熱—芳香族紛以產 生-加熱之芳香雜。此第三步驟為混合液體環氧樹脂與可 增加芳香祕無體環氧樹脂肢應鱗的材料之加熱混合 物及加熱之芳香麟其實質上未加人或除去熱能量以產生I 具有最初温度在約1UTC至約14(rc範圍間的反應混合物故芳 15香族龄與液體環氧樹脂反應以製造轉化之環氧樹脂，液體環 氧樹脂與可增加芳香騎與㈣環氧樹關反應速率的材料 之加熱混合物與加熱之芳香騎的組合物均質性在少於約扣 秒中為大於約0.95 ;且較佳在少於約15秒為大於約〇 95。若此 —混合在—具有轉動動葉輪的批式反應器中進行，則轉動動 20 =輪較佳在低於混合物高度之約5至約14英对處。加熱之液體 環乳樹脂及加熱之芳香麵的混合實f無熱能加人(或去除） 在本發明巾為重要的，其可增加製㈣產能並減少反應容器 之固體相硬結的形成。對於混合的組合物均質性在少於約加 秒中為大於·95之要求為減少凝膠的形成。 7 200932778 5 在又另一實施例中，本發明為一用於製造轉化環氣樹 脂之製程’其包含三步驟。第—步驟為加熱可增加芳香埃 盼與液體環氧樹脂間反應速率的材料與芳香彡嫌的混合物 以產生一芳香族酚與可增加芳香族酚與液體環氧樹脂間反 應速率的材料之加熱混合物。第二步驟為加熱液體環氣樹 脂以產生加熱之液體環氧樹脂。第三步驟為混合芳香族酚 與可增加芳香族盼與液體環氧樹脂間反應速率的材料之加 10 15 20 熱物及加熱之液體環氧樹脂，其實質上未加入或除^ 熱能里以產生-具有最初温度在約11(rc至約範圍^ 的反應混合物，故Μ㈣錢贿氧樹脂反應以製造專 化之環氧樹脂，料祕與可增加芳香贿與液體環氧名 脂間反應速率的材料之加熱混合物與加熱之液體環氧樹月 的組合物均質性在少於約20秒中為大於約0.95 ;且，較<: 為大於約G·95少於約15秒。若此—混合在-具有轉動動| 輪的批式反絲巾進行，麟動動葉輪較佳在低於混合4 高度之約5至約14糾處。加熱之㈣環氧樹脂及加熱之; 香祕的混合實質無熱能加入(或去除)在本發明中為幻 的，其可增加製程的產能並減少反應容器之固體相硬結白 形成。對於混合的組合物均質性在少於約2()秒中為大於乡 〇·95之要求為減少凝膠的形成。 雖然在本發明中可使用任何在室温為液體的環氧樹月 (包括一液體環氧基_酚醛樹脂），但較佳為含有二莫耳之宠 氧氣丙境與—莫耳之雙齡的反應產物之液體環氧樹脂。虽 然在本發明中可使用任何芳香族紛，較佳為—雙齡(如雙酉BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for converting an epoxy resin which is liquid at room temperature to a solid epoxy resin. [Previously, the epoxy resin coating can be formed by a coating formulation which can be scooped at a temperature of (~25C) as a liquid epoxy resin or as a solid epoxy resin at room temperature. Use epoxy resin which is solid at room temperature, for example, powder coating formulation: - Epoxy resin at room temperature (such as known liquid epoxy resin formed by double reaction of epoxy gas (4)) can be converted into room The temperature is solid: it is obtained by mixing a liquid epoxy resin with a fragrant (preferably-bend as (4) A) in the presence of a catalyst and then heating the mixture to make the resin catalyzed with the aromatic to convert the liquid ring Oxygen tree ruthenium is an epoxy at a temperature which is solid. _ Epoxy resin can be catalyzed and double-hearted. [Inventive Summary] The present invention is the above-mentioned problem - the resin is at a room temperature. The time required to convert a liquid epoxy invention process to reduce about 23% or more of the fat can be achieved by using the present technology. 3 200932778 10 15 20 * In the embodiment, the present invention is used for manufacturing conversion The process 'includes the steps: (4) heating - liquid epoxy resin & liquid epoxy resin; (b) heating a furnace stove ^ Wang - heating Fangxiang phenol to produce - adding secrets, (4) mixing heating Liquid epoxy resin and heating: square incense does not substantially add or remove thermal energy to produce -, phenol, which is about 14 generations of liquid epoxy resin (4) mixed (1) can increase the aroma _ and liquid epoxy resin : material: material and (9) mixture of liquid epoxy resin and aromatic _ (four) force and liquid epoxy resin reaction rate to form a conversion ring II. ^ 1 = = aromatic _ liquid epoxy resin reaction rate two materials and liquid% The composition of the mixture of oxygen resin and aromatic mixture is homogeneously greater than about 0.95 in about 20 seconds. In another embodiment, the present invention is a process for the preparation of the process comprising the steps of: (4) the reaction rate of the epoxiconium ruthenium, the quaternary aromatic phenol and the liquid epoxy resin a mixture of a material and a liquid epoxy resin and a heating mixture which can increase the aromatic content and the liquid epoxy resin (4); (b) heating-aromatic_producing p-heating square incense t and (4) mixed liquid The addition of the epoxy resin to the material which increases the reaction rate between the aromatic and the epoxy resin and the heating of the material _ 'in fact, no added or removed thermal energy to produce - and the initial temperature is about Approximately 14 (rc__reaction mixture, aromatics are expected to react with a liquid epoxy resin to produce a converted Wei resin; wherein a mixed mixture of a body epoxy resin and a material which increases the reaction speed between the aromatic and liquid epoxy resins) The composition is homogeneous with heated aromatics 〇❺ 4 200932778 is greater than about 〇95 in less than about 20 seconds. In yet another embodiment, the invention is a process for making a conversion loop gas resin. 'It contains the steps: (a) heating a mixture of a material and an aromatic mixture which increases the reaction rate between the aromatic age and the liquid ring-containing latex resin to produce a heated mixture of a material which increases the reaction rate between the aromatic expectant and the liquid epoxy resin, and (b) heating a liquid epoxy resin to produce a heated liquid epoxy resin; and (c) a mixed aromatic mixture of a material which is expected to increase the reaction rate between the aromatic liquid and the liquid ring, the resin, and a heated liquid epoxy resin. It does not substantially add or remove thermal energy to produce a reaction mixture having an initial temperature of 10 degrees between about U0 ° C and about 140 ° C, so the aromatic phenol reacts with the liquid epoxy resin to produce a converted epoxy resin. The composition homogeneity of the mixed mixture of the aromatic phenol and the material which increases the reaction rate between the aromatic phenol and the liquid epoxy resin and the heated liquid epoxy resin is greater than about 0.95 in less than about 20 seconds. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a more detailed description of the non-limiting examples of the invention by way of example, in which: FIG. 1 is a prior art reactor and process 1A is a cross-sectional view of a top view 20 of a conventional art reactor of FIG. 1 along a line 1880; FIG. 2 is a cross-sectional view of the reactor and process of the present invention; and FIG. 2A is a view Figure 2 is a cross-sectional view taken along the line 2A-2A of the reactor of the present invention. [Purity mode 3 5 200932778 The detailed description of the preferred embodiment is qualitative, and the words are defined in the following manner:卩时] Its work - charge the money] = after filling the _ add 1 you and [C. (four)] = add _SP (four) h of a homogeneous mixture. U 1 葸 buckle 7 〇 Wang "substantially no added people, , - the word is less than about 1% of the thermal energy of the mixture. Compared with the second:, the addition or removal of 10 15 20 is unavoidable and less & any hot addition or brother's heat of the mixture of about $ In one embodiment, the invention comprises four steps. The first step == the epoxy resin is made of heated liquid epoxy resin. The first reading of the epoxy resin is heated to produce a heated aromatic. The first step is heating - the aromatic is expected to produce a heated aromatic fine, which is essentially a heated liquid epoxy resin and has a temperature of about 11 (TC to about 14 (). = ^ or remove the reduction to produce - aroma The reaction rate between the liquid epoxy resin and the aromatic epoxy resin in the mixture of 14: This combination can increase the mixture of aromatic phenol and liquid to increase the aromatic touch and resin and aromatic conversion. The material can be reacted at the rate of the reaction rate and the liquid ring two-group _ liquid epoxy resin intermediate homogeneity in less than about a combination of a lipid and aromatic mixture of about 0.95 less than about 15 seconds is preferably greater than In the reactor, it is mixed and mixed in a batch with a rotating impeller of about 5 to about 14 inches. Heating: round comparison = lower than the mixture height, liquid epoxy resin and heated aromatic mixture 200932778 Substantially no heat can be added (or removed) in the present invention, which increases the capacity of the process and reduces the formation of solid phase induration of the reaction vessel; for materials that increase the rate of reaction between aromatic and liquid epoxy resins And liquid epoxy resin and aromatic The composition homogeneity of the mixture of the aromas of the genus of the genus is greater than about 0.95 in less than about 520 seconds to reduce the formation of the gel. In another implementation, the county is in the process of manufacturing the converted epoxy tree wax. 'It consists of three steps. The first step is to heat the mixture of material and liquid epoxy wax to increase the reaction rate of the material (4) with the liquid epoxy tree to produce - liquid epoxy - and to increase the aromatic - liquid epoxy resin The reaction mixture is a mixture of materials that react at a rate of 10. The second step is heating-aromatic production - heating of the aromatic impurities. This third step is a mixture of liquid epoxy resin and can increase the aroma of the invisible epoxy resin. The heated mixture of the material and the heated aromatic lining substantially without adding or removing thermal energy to produce I having an initial temperature in the range of from about 1 UTC to about 14 (r range of reaction mixture fragrant 15 fragrant age and liquid epoxy resin Reacting to produce a converted epoxy resin, the composition of the liquid epoxy resin and the heated mixture of the material which increases the rate of reaction between the aromatic rider and the (4) epoxy tree and the heated aromatic rider is greater in less than about seconds. Preferably, at about 0.95; and preferably less than about 15 seconds, greater than about 〇95. If this is done in a batch reactor having a rotating impeller, then the rotation 20 = the wheel is preferably below the mixture height. From about 5 to about 14 inches. The combination of heated liquid ring emulsion resin and heated aromatic surface is not added to heat (or removed). It is important in the present invention to increase the production capacity and reduce the reaction. Formation of a solid phase of the container. The homogeneity of the mixed composition is less than about 95 in less than about plus seconds to reduce gel formation. 7 200932778 5 In yet another embodiment, the invention is The process for producing a converted cycloolefin resin comprises three steps. The first step is heating to increase the reaction rate between the aromatic and liquid epoxy resin and the aromatic mixture to produce an aromatic phenol and increase A heated mixture of materials having a reaction rate between an aromatic phenol and a liquid epoxy resin. The second step is to heat the liquid ring resin to produce a heated liquid epoxy. The third step is the addition of 10 15 20 hot material and heated liquid epoxy resin to the mixed aromatic phenol and the material which can increase the reaction rate between the aromatic expectant and the liquid epoxy resin, which is substantially not added or removed. Produce - a reaction mixture having an initial temperature of about 11 (rc to about range ^, so Μ (4) ethoxy brittle resin reaction to produce a specialized epoxy resin, which can increase the reaction rate between aromatic bribe and liquid epoxy The composition of the heated mixture of the heated material and the heated liquid epoxy resin has a homogeneity of greater than about 0.95 in less than about 20 seconds; and, more than about G.95 less than about 15 seconds. - mixing in a batch-type spiral scarf with a rotating motion | wheel, preferably the rivet impeller is about 5 to about 14 at a height below the mixing height 4. Heated (4) epoxy resin and heated; The mixing of substantially no thermal energy is added (or removed) in the present invention, which increases the throughput of the process and reduces the formation of hard phase whitening of the solid phase of the reaction vessel. The homogeneity of the mixed composition is less than about 2 () seconds. The medium is greater than the requirement of nostalgic 95 to reduce the formation of gel. Although any epoxy resin which is liquid at room temperature (including a liquid epoxy-phenolic resin) can be used in the present invention, it is preferably a two-year-old containing the oxygen of the two molars. Liquid epoxy resin of the reaction product. Although any aromatics may be used in the present invention, it is preferably - two years old (such as biguanide)
8 200932778 5 ❹ 10 15 ❹ 20 A)。雖然許多材料可用以增加液體環氧樹脂與芳香族紛間 的反應速率，較佳為乙基苯基醋酸鎮且可以例如，為固體、 為在例如甲醇或DowanolDB中之溶液使用。較佳在本發明 中使用下列的量：由約51 wt%至約80 wt%液體環氧樹脂. 由約49 wt%至約20wt%芳香族酚；及由約1〇〇 ppm至約 ppm催化劑。額外成份可加至反應物及/或反應產物中， 如 流動改質劑、勒化劑及溶劑。 本文之“液體環氧樹脂”為指一在室温為液體的纟且合物 且其每分子具有至少一相鄰環氧基，亦即每分子至少〜j 2 環氧基。通常’此化合物為一飽和或未飽和脂族、環脂埃、 芳香族或雜環化合物，其具有至少一 1，2_環氧基。此化合物 若需要可以至少一非-干擾取代基取代，如齒素原子、趣 基、醚基、低級烷基及其相似者。 可用於本發明之液體環氧樹脂為此技已知者。可用於 實施本發明之說明用聚環氧化合物為述於H. 1^6及1<： Neville著1967年由美國紐約市McGraw_Hill公司出版之认e 丹aWZwoA: 〇/母似少办命5與美國專利第4,〇66 628號，其等 全文併入本案做為參考。 可用於實施本發明之特別有用的化合物為具有下列化 學式的液體環氧樹脂： 0Η8 200932778 5 ❹ 10 15 ❹ 20 A). While many materials may be used to increase the rate of reaction of the liquid epoxy resin with the aromatics, it is preferably ethyl phenylacetic acid and may, for example, be a solid, for use in a solution such as methanol or Dowanol DB. Preferably, the following amounts are used in the present invention: from about 51 wt% to about 80 wt% liquid epoxy resin. from about 49 wt% to about 20 wt% aromatic phenol; and from about 1 〇〇 ppm to about ppm catalyst . Additional ingredients may be added to the reactants and/or reaction products such as flow modifiers, tolerants and solvents. By "liquid epoxy resin" herein is meant a hydrazine compound which is liquid at room temperature and which has at least one adjacent epoxy group per molecule, i.e., at least ~j 2 epoxy groups per molecule. Typically, the compound is a saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compound having at least one 1,2-epoxy group. This compound may be substituted with at least one non-interfering substituent if desired, such as a dentate atom, an interesting group, an ether group, a lower alkyl group and the like. Liquid epoxy resins useful in the present invention are known to those skilled in the art. The descriptions that can be used to practice the invention are described in H. 1^6 and 1<: Neville, published in 1967 by McGraw_Hill, Inc., New York, USA. AWZwoA: 〇/母似少少命5 U.S. Patent No. 4, No. 66,628, the entire disclosure of which is incorporated herein by reference. A particularly useful compound useful in the practice of this invention is a liquid epoxy resin having the following chemical formula: 0Η
η 9 0 200932778 其中η具有一由0至2的平均值。 可用於本發明之環氧樹脂包括，例如，多元紛與多元 醇的縮水甘油聚醚。如本發明之說明，可用於本發明之已 知環氧樹脂的範例包括例如間苯二紛之二縮水甘㈣、鄰 5苯二盼、對苯二盼、雙盼、雙酚Α、雙紛八叩’丨-雙(4·經基i 苯基)-1-苯基乙院）、雙盼F、雙鼠、四漠雙盼A、紛甲經 _樹脂、炫基取代之紛-甲盤樹脂、紛_經基苯甲盤樹脂、 甲盼-經基苯甲酸樹脂、二環戊二稀★樹脂、二環戍二稀 取代之紛樹脂四甲基雙紛、四曱基四漠雙盼、四甲基三漠 10 雙驗、四氯雙盼A及其等之任何組合。 特別可用於本發明之二環氧化物範例包括2,2-雙(4·經 基苯基）丙炫(通常稱之為_A)之二縮水甘㈣及Μ雙 (3,5-二浪-4-經基苯基）丙烧(通常稱之為四漠雙龄々之二縮 水甘油醚。二或二以之聚環氧化物混合物亦可用於實施本 15 發明。 其他可用於實施本發明之二環氧化物包括二麵基紛之 二縮水甘油醚，如述於美國專利第5,246,751 ; 5,ii5 〇乃. 5,089,588;4,480,082及4,438,254號中者，其等全文併入本 案參考，或二羧酸之二縮水甘油6旨如揭露於美國專利第 20 5，171，820號。其他合宜之二環氧化物包括例如，l二縮 水甘油基異亞丙基-雙酚-系環氧樹脂（商業產品如 D.E.R.®300及600系列環氧樹脂，為美國密西根州密德I市 陶氏化學公司產品）。 可用於實施本發明之環氧樹脂亦包括藉由二祕盼之 200932778 由二羥基酚與環氧氯丙 已知為“乳脂（taffy)樹 二縮水甘油醚與二羥基酚反應或藉 烧反應而製得之液體環氧樹脂（亦 脂”）。 可用於本發明之較佳環氧樹脂包括例如，雙齡之二縮 5水甘油鍵；4,4，_續醯基二齡；4趣基二盼；4,4，•二經基二 苯甲鋼；間苯二紛·，對苯二盼；9,9，_雙㈣基苯_; 4 4, 二赵基雙苯基或H録及如前及的二幾酸之 二縮水甘油酯η 9 0 200932778 where η has an average value from 0 to 2. Epoxy resins useful in the present invention include, for example, glycidyl polyethers which are polyhydric and polyhydric alcohols. Examples of known epoxy resins useful in the present invention, such as the description of the present invention, include, for example, meta-diphenyl sulphate (tetra), o- 5 benzophenone, para-phenylene, bis, bisphenol quinone, double Gossip '丨-双(4·经基i phenyl)-1-phenyl 乙院), 双盼F, 双鼠,四漠双盼A, 甲甲经_Resin, 炫基换的纷-甲Resin, styrene-based benzoyl resin, acetaminophen-benzoic acid resin, dicyclopentadiene ★ resin, bicyclo quinone di-disubstituted resin tetramethyl bis, tetrakisyl Hope, tetramethyl three deserts 10 double test, tetrachloropyrene A and any combination thereof. Examples of diepoxides that are particularly useful in the present invention include 2,2-bis(4-.pyridylphenyl)propane (commonly known as _A) bis-glycolate (tetra) and bismuth (3,5-two waves) 4--4-Phenylphenyl)propane burned (generally referred to as quaternary glycidyl ether of the quaternary sorghum. The polyepoxide mixture of two or two may also be used to carry out the invention of the 15th. Others may be used in the practice of the invention The bis-epoxides include di-glycidyl diglycidyl ethers as described in U.S. Patent No. 5,246,751, 5, ii, 5, 089, 588, 4, 480, 082, and 4, 438, 254, the entire contents of which are incorporated herein by reference. Acid diglycidyl 6 is disclosed in U.S. Patent No. 20,171,820. Other suitable diepoxides include, for example, diglycidylisopropylidene-bisphenol-based epoxy resin (commercial Products such as DER® 300 and 600 series epoxy resins are manufactured by The Dow Chemical Company, Midland, Michigan, USA. The epoxy resins that can be used to practice the invention also include dihydroxyphenols by the second secret of 200932778. Known as "milk (taffy) tree diglycidyl ether and dihydroxyphenol Liquid epoxy resin (also known as "battery") obtained by the calcination reaction. Preferred epoxy resins useful in the present invention include, for example, double condensed condensed oligohydrin bonds; 4, 4, _ ; 4 interesting base 2; 4, 4, • di-based benzophenone steel; m-benzoic acid, p-benzoic acid; 9,9, bis-bis(tetra)ylbenzene _; 4 4, dizinc bisphenyl or H recorded as before and after the di-acid diglycidyl ester
10 其他可用於實施本發明之有用環氧化合物為環脂族環 氧化物。-環脂族環氧化物由-環氧基氧鍵結至碳環上二 相鄰原子的碳環組成，例如由下通式說明者：Other useful epoxy compounds useful in the practice of this invention are cycloaliphatic epoxides. The cycloaliphatic epoxide is composed of a carbon ring in which an epoxy group is bonded to two adjacent atoms on the carbocyclic ring, for example, as illustrated by the following formula:
其中R為一羰基，其可選擇的包含一或一以上的雜原子(如， 未限制為Cl、Br及S)，或一原子或一組原子（如，未限制為 15 Sl' P及B)與碳形成一安定鍵結且其中η為大於或等於i。 環脂族環氧化物可為單環氧化物、二環氧化物、聚環氧 化物、或其等之混合物。例如，本發明可使用任何述於美國 專利第3,686,359號之環脂族環氧化物，其全文併入本案做為 參考。如一說明，可用於本發明之環脂族包括例如(3,4_環氧 20基環已基-甲基)-3,4-環氧基-環己烷羰酸、雙_(3,4-環氧基環 己基）己二酸酯、一氧化乙烯環己烯及其等之混合物。 可催化所述反應之材料在此技中為已知的且因本發明 200932778 目的提出參考。範例之催化劑為說明於美國專利第 2,216,099 ； 2,633,458 ； 2,658,855 ； 3,377,406 ； 3,694,407 ； 3,948,855 ; 4,389,520 ; 4,354,015 ;及 3,477,990與Η丄ee及 K. Neville著1967年由美國紐約市McGraw-Hill公司出版之 5 The_Handbook of Epox^^Resins ’其等全文併入本案做為參 考。描述之催化劑的代表為二級及三級胺，較佳為三級胺 如苯甲基二甲基胺、三乙基胺及苯甲基二乙基胺；鹼金屬 氫氧化物，例如氫氧化鉀；四級銨化合物如四烷基自化銨， 例如四甲基氣化銨’與鱗及四級鱗鹽如三苯基鱗及乙基三 10 苯基醋酸鎸-乙酸複合物。 催化劑基本上以傳統用量使用。此些量可依使用之特定 催化劑、聚環氧化物及芳香族酚而變化但較佳在芳香族酚與 聚縮水甘油醚組份總重之約0.005至約i重量百分比間變 化。更較佳地’使用由約〇.〇1至約〇·5重量百分比間之催化 15劑’該重量百分比基於芳香族酚及聚環氧化物組份的總重。 現配合第1圖，其中顯示一習知技術的系統1〇。此系統 1〇包括一具有一加熱套14的批式反應器11。一熱交換流體 (如蒸氣或一加熱之液體)經喷嘴15引入套14中並經噴嘴16 引出套14。此反應器η具有至少一固定隔板17(在第1圖中 20 顯示2個）安裝於反應器内側。一馬達18轉動軸桿19。一上 動葉輪及一下動葉輪置於轴桿19上，分別為20a及20b。反 應混合物21的組份經喷嘴12導引至反應器11且加熱至所期 待的溫度。一催化劑加至反應混合物21 ;且該反應進行時， 可此期待一冷卻劑取代加熱之液體，其經喷嘴15至套14以 200932778 5 10 15 e 20 除去之來自反應混合物21組份的反應熱之熱。當反應性組 份21的密度為1.1 g/cm3時’當反應性組份21的黏度為20厘 泊時且當馬達18在全速操作時，反應混合物21之組份的組 合物之均質性在約33秒内為約0.95。產物由喷嘴13自反應 器11中流出。 現參考第2圖，其中顯示一本發明系統30，其包括一批 式反應器31。一部份(例如，約75 wt%)之加熱組份38經由 喷嘴32加至反應器31。反應器31具有至少一固定隔板34(在 第2圖中顯示2個）安裝於反應器内侧。一馬達35轉動軸桿 36。一上動葉輪7a及一下動葉輪37b置於軸桿36上。加熱之 組份38在反應器31中的量39為在高於上動葉輪37a之約5英 吋至約14英吋（約13公分及約35公分）間距離。當反應性組份 38的密度為1.1 g/cm3，當反應性組份38的黏度為20厘泊且 當馬達35在全速操作時，反應混合物38之組份的組合物之 均質性在約10秒内為約0.95。加熱之組份的殘餘量接著加 至反應器且進行反應。產物由反應器31經喷嘴33方式流出。 在第2圖中’如前述參考本發明’僅顯示一入口噴嘴32 及一出口 33。然而，本發明已藉由參考前述相較佳實施例 而描述，且因此其他的變化，如反應器31可分別對入口噴 嘴32及出口喷嘴33使用一或多個喷嘴。此外，反應器31中， 動葉輪37a及37b可包括多個動葉輪。任一熟於此項技術人 士可瞭解本發明並未限制至第2圖的說明；且其他的變化、 修飾及相等型式為包括於本發明之範嘴中。 下列實施例為僅用於說明之用而非用限制本發明的範_。 13 200932778 實施例1 75重量百分比的7683磅加熱之液體環氧樹脂與2516磅 熔融之雙酚A餵料加至具有轉動動葉輪的批式反應器中，其 中當轉動的動葉輪在低於液體環氧樹脂與雙紛A的混合物 5高度的5英吋至14英吋且該混合物具有13(TC温度時，接著 在全動葉輪動力下加入溶解在曱醇中的8·4磅乙基三苯基 醋酸鱗。然後，加熱之液體環氧樹脂與熔融之雙酚六的殘餘 物加至反應器。在反應器中混合物的温度增加至19〇°c，因 為液體環氧樹脂與雙酚A間反應以產生轉化之環氧樹脂為 10放熱反應。轉化之環氧樹脂由反應器流至一粒片切削機， 在該處冷卻轉化之環氧樹脂並包裝為粒片切削之固體。 竟施例2 75重量百分比的7510磅的加熱之液體環氧樹脂與274〇 峙熔融之雙酚A餵料加至具有轉動動葉輪的批式反應器 15中，其中當轉動的動葉輪在低於液體環氧樹脂與雙酚a的混 合物高度的5英忖至Μ英对且該混合物具幻饥温度時， 接著在全動葉輪動力下加入溶解在甲醇中的7 6碎乙基二 笨基醋酸鱗。然後，加熱之液體環氧樹脂與嫁融之雙盼A 扣的殘餘物加至反應器。在反應器中混合物的温度增加至i95 〇 C，因為液體環氧樹脂與雙酚A間反應以產生轉化之環氧樹 月曰為放熱反應。轉化之環氧樹脂由反應器流至一粒片切削 機，在該處冷卻轉化之環氧樹脂並包裝為粒片切削之固體。 75重量百分比的6892傍加熱之液體環氧樹脂與3167碎 14 200932778 熔融之雙酚A餵料加至具有轉動動葉輪的批式反應器中，其 中當轉動的動葉輪在低於液體環氧樹脂與雙酚A的混合物 高度的5英吋至14英吋且該混合物具有丨27。(：温度時，接著 ύ 在全動葉輪動力下加入溶解在甲醇中的12.3磅乙基三笨基 5 醋酸鱗。然後，加熱之液體環氧樹脂與熔融之雙酚Α的殘餘 物加至反應器。在反應器中混合物的温度增加至220°C，因 為液體環氧樹脂與雙酚A間反應以產生轉化之環氧樹脂為 放熱反應。轉化之環氧樹脂由反應器流至一粒片切削機， 〇 在該處冷卻轉化之環氧樹脂並包裝為粒片切削之固體。 10 實施例4 75重量百分比的7278的加熱之液體環氧樹脂與2934傍 熔融之雙酚Α餵料加至具有轉動動葉輪的批式反應器中，其 中當轉動的動葉輪在低於液體環氧樹脂與雙酚A的混合物 高度的5英吋至14英吋且該混合物具有12(rc温度時，接著 15在全動葉輪動力下加入溶解在甲醇中的10.8磅乙基三苯基 醋酸鱗。然後，加熱之液體環氧樹脂與熔融之雙酚A的殘餘 物加至反應器。在反應器中混合物的温度增加至22〇。〇，因 為液體環氧樹脂與雙酚A間反應以產生轉化之環氧樹脂為 放熱反應。轉化之環氧樹脂由反應器流至—粒片切削機， 20在該處冷卻轉化之環氧樹脂並包裝為粒片切削之固體。 實施例5 75重量百分比的6724碎的加熱之液體環氧樹脂與搬 料熔融之雙盼A傲料加至具有轉動動葉輪的批式反應器 中’其中當轉動的動葉輪在低於液體環氧樹月旨與雙盼⑽混 15 200932778 合物高度的5英吋至14英吋且該混合物具有uot溫度時， 接著在全動葉輪動力下加入溶解在甲醇中的16.5镑乙基= 苯基醋酸鱗。然後，加熱之液體環氧樹脂與熔融之雙盼A 的殘餘物加至反應器。在反應器中混合物的温度增加至22〇 5 °C ’因為液體環氧樹脂與雙酚A間反應以產生轉化之環氧樹 脂為放熱反應。轉化之環氧樹脂由反應器流至一粒片切削 機，在該處冷卻轉化之環氧樹脂並包裝為粒片切削之固體。 實施你丨6 75重量百分比的6917磅的加熱之液體環氧樹脂與35〇4 1〇 磅熔融之雙酚A餵料加至具有轉動動葉輪的批式反應器 中，其中當轉動的動葉輪在低於液體環氧樹脂與雙酚A的混 合物高度的5英吋至14英吋且該混合物具有125°C温度時， 接著在全動葉輪動力下加入溶解在甲醇中的1〇·5磅乙基三 笨基醋酸鱗。然後’加熱之液體環氧樹脂與熔融之雙酚A 15 的殘餘物加至反應器。在反應器中混合物的温度增加至225 。(：，因為液體環氧樹脂與雙酚A間反應以產生轉化之環氧樹 脂為放熱反應。轉化之環氧樹脂由反應器流至一粒片切削 機，在該處冷卻轉化之環氧樹脂並包裝為粒片切削之固體。 應已可顯見雖然本發明已由前述二較佳實施例說明， 20 應瞭解本發明益未因此其等受限，且欲涵括在如後附申請 專利範圍中界定之本發明技術思想範疇中所有的變化、修 飾及等效物。 【圖式簡單說明】 第1圖為習知技藝反應器及製程的橫切面剖視圖； 200932778 第1A圖為第1圖之習知技藝反應器沿1A-1A線的頂視 橫切面剖視圖； 第2圖為本發明反應器及製程的橫切面剖視圖；及 第2A圖為第2圖本發明反應器沿2A-2A線的頂視橫切 5 面剖視圖。Wherein R is a carbonyl group which optionally contains one or more heteroatoms (eg, not limited to Cl, Br, and S), or one atom or a group of atoms (eg, not limited to 15 Sl' P and B) Forming a stable bond with carbon and wherein η is greater than or equal to i. The cycloaliphatic epoxide may be a monoepoxide, a diepoxide, a polyepoxide, or a mixture thereof. For example, any of the cycloaliphatic epoxides described in U.S. Patent No. 3,686,359, the entire disclosure of which is incorporated herein by reference. As illustrated, the cycloaliphatic groups useful in the present invention include, for example, (3,4-epoxy 20-cyclohexyl-methyl)-3,4-epoxy-cyclohexanecarboxylic acid, bis-(3,4). - Epoxycyclohexyl) adipate, ethylene oxide cyclohexene and mixtures thereof. Materials which catalyze the reaction are known in the art and are referred to in the context of the present invention 200932778. Exemplary catalysts are described in U.S. Patent Nos. 2,216,099; 2,633,458; 2,658,855; 3,377,406; 3,694,407; 3,948,855; 4,389,520; 4,354,015; and 3,477,990 and Η丄ee and K. Neville, 5 The_Handbook, published by McGraw-Hill, New York, USA, 1967 Of Epox^^Resins 'the full text is incorporated into this case for reference. Representative of the catalysts described are secondary and tertiary amines, preferably tertiary amines such as benzyldimethylamine, triethylamine and benzyldiethylamine; alkali metal hydroxides such as hydroxide Potassium; a quaternary ammonium compound such as a tetraalkylammonium chloride such as tetramethylammonium hydride' with scales and a quaternary scale salt such as triphenyl scale and ethyltris 10 phenyl acetate acetate-acetic acid complex. The catalyst is used essentially in conventional amounts. These amounts may vary depending on the particular catalyst, polyepoxide and aromatic phenol used, but preferably vary from about 0.005 to about i weight percent of the total weight of the aromatic phenol and polyglycidyl ether component. More preferably, the use of a catalyst between about 5% by weight and about 5% by weight is used. The weight percentage is based on the total weight of the aromatic phenol and the polyepoxide component. Now in conjunction with Figure 1, a system of conventional techniques is shown. This system 1 includes a batch reactor 11 having a heating jacket 14. A heat exchange fluid (e.g., a vapor or a heated liquid) is introduced into the sleeve 14 through the nozzle 15 and is led out of the sleeve 14 via the nozzle 16. This reactor η has at least one fixed partition 17 (two shown in Fig. 20 and 20) attached to the inside of the reactor. A motor 18 rotates the shaft 19. An upper impeller and a lower impeller are placed on the shaft 19, 20a and 20b, respectively. The components of the reaction mixture 21 are directed via a nozzle 12 to the reactor 11 and heated to the desired temperature. A catalyst is added to the reaction mixture 21; and when the reaction is carried out, a coolant is expected to replace the heated liquid, which is removed from the reaction mixture 21 by the nozzle 15 to the sleeve 14 at 200932778 5 10 15 e 20 The heat. When the density of the reactive component 21 is 1.1 g/cm 3 'when the viscosity of the reactive component 21 is 20 cps and when the motor 18 is operated at full speed, the composition homogeneity of the components of the reaction mixture 21 is It is about 0.95 in about 33 seconds. The product flows out of the reactor 11 from the nozzle 13. Referring now to Figure 2, there is shown an inventive system 30 comprising a batch reactor 31. A portion (e.g., about 75 wt%) of the heating component 38 is added to the reactor 31 via the nozzle 32. The reactor 31 has at least one fixed partition 34 (two shown in Fig. 2) attached to the inside of the reactor. A motor 35 rotates the shaft 36. An upper impeller 7a and a lower impeller 37b are placed on the shaft 36. The amount 39 of the heated component 38 in the reactor 31 is between about 5 inches to about 14 inches (about 13 centimeters and about 35 centimeters) above the upper impeller 37a. When the density of the reactive component 38 is 1.1 g/cm3, when the viscosity of the reactive component 38 is 20 centipoise and when the motor 35 is operated at full speed, the composition of the component of the reaction mixture 38 has a homogeneity of about 10 It is about 0.95 in seconds. The residual amount of the heated component is then added to the reactor and the reaction is carried out. The product flows out of the reactor 31 via the nozzle 33. In Fig. 2, 'the present invention' is only shown as an inlet nozzle 32 and an outlet 33 as described above. However, the invention has been described with reference to the preferred embodiments described above, and thus other variations, such as reactor 31, may use one or more nozzles for inlet nozzle 32 and outlet nozzle 33, respectively. Further, in the reactor 31, the moving impellers 37a and 37b may include a plurality of moving impellers. Anybody skilled in the art will appreciate that the invention is not limited to the description of FIG. 2; and other variations, modifications, and equivalents are included in the scope of the present invention. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention. 13 200932778 Example 1 75 weight percent of 7683 pounds of heated liquid epoxy resin and 2516 pounds of molten bisphenol A feed were added to a batch reactor with a rotating impeller, where the rotating impeller was below liquid The mixture of epoxy resin and double A is 5 inches to 14 inches high and the mixture has 13 (at TC temperature, then 8.4 lbs of ethyl three dissolved in sterol is added under full impeller power Phenylacetate scale. Then, the heated liquid epoxy resin and the residue of molten bisphenol VI are added to the reactor. The temperature of the mixture in the reactor is increased to 19 ° C because of the liquid epoxy resin and bisphenol A. The reaction is initiated to produce a converted epoxy resin for an exothermic reaction. The converted epoxy resin is passed from the reactor to a pellet cutting machine where the converted epoxy resin is cooled and packaged as a pellet-cut solid. Example 2 75 weight percent of 7510 pounds of heated liquid epoxy resin and 274 inch molten bisphenol A feed were added to a batch reactor 15 having a rotating impeller, wherein the rotating impeller was below liquid Mixture of epoxy resin and bisphenol a When the height of the object is 5 inches to the Μ 对 pair and the mixture has an illusory temperature, then the 6 6 cumyl ethyl phenyl acetate scale dissolved in methanol is added under full impeller power. Then, the heated liquid epoxy The residue of the resin and the grafted A-Buckle is added to the reactor. The temperature of the mixture in the reactor is increased to i95 〇C because the liquid epoxy resin reacts with bisphenol A to produce a converted epoxy tree. It is an exothermic reaction. The converted epoxy resin flows from the reactor to a pellet cutting machine where the converted epoxy resin is cooled and packaged as a pellet-cut solid. 75 weight percent of 6892 傍 heated liquid epoxy resin And 3167 shard 14 200932778 molten bisphenol A feed is added to a batch reactor with a rotating impeller, wherein the rotating impeller is 5 inches below the height of the mixture of liquid epoxy resin and bisphenol A to 14 inches and the mixture has 丨27. (: At temperature, then 12.3 lbs of ethyltrisyl-5 acetate scale dissolved in methanol is added under full impeller power. Then, heated liquid epoxy and molten Residue of bisphenolphthalein To the reactor. The temperature of the mixture in the reactor is increased to 220 ° C, because the reaction between the liquid epoxy resin and bisphenol A to produce the converted epoxy resin is an exothermic reaction. The converted epoxy resin flows from the reactor to a The pellet cutting machine, where the cooled epoxy resin is cooled and packaged as a pellet-cut solid. 10 Example 4 75 weight percent of 7278 heated liquid epoxy resin and 2934 inch molten bisphenolphthalein feed Add to a batch reactor with a rotating impeller, wherein when the rotating impeller is 5 to 14 inches below the height of the mixture of liquid epoxy and bisphenol A and the mixture has 12 (rc temperature) Then, under the full-motion impeller power, 10.8 lbs of ethyltriphenylacetate scale dissolved in methanol was added. The heated liquid epoxy resin and the residue of molten bisphenol A are then added to the reactor. The temperature of the mixture in the reactor was increased to 22 Torr. 〇, because the epoxy resin reacted with bisphenol A to produce a converted epoxy resin as an exothermic reaction. The converted epoxy is passed from the reactor to a pellet cutting machine where the cooled epoxy is cooled and packaged as a pellet-cut solid. Example 5 75 weight percent of 6724 broken heated liquid epoxy resin and moving material molten double expectant A was added to a batch reactor with a rotating impeller "where the rotating impeller is below the liquid ring Oxygen tree month and double hope (10) mixed 15 200932778 The height of the compound is 5 inches to 14 inches and the mixture has a uot temperature, then 16.5 pounds of ethyl group = phenyl dissolved in methanol is added under full-motion impeller power. Acetic acid scales. The heated liquid epoxy resin is then added to the reactor with the residue of molten double A. The temperature of the mixture in the reactor was increased to 22 〇 5 ° C ' because the reaction between the liquid epoxy resin and bisphenol A to produce a converted epoxy resin was an exothermic reaction. The converted epoxy is passed from the reactor to a pellet cutter where the converted epoxy is cooled and packaged as a pellet-cut solid. Implement 丨6 75 weight percent of 6917 lbs of heated liquid epoxy resin and 35 〇 4 1 lbs of molten bisphenol A feed to a batch reactor with a rotating impeller, where the rotating impeller At a temperature of 5 inches to 14 inches below the height of the mixture of liquid epoxy resin and bisphenol A and the mixture has a temperature of 125 ° C, then 1 〇 5 lbs dissolved in methanol is added under full impeller power Ethyl trisyl acetate scale. The heated liquid epoxy resin and the residue of molten bisphenol A 15 are then added to the reactor. The temperature of the mixture in the reactor was increased to 225. (:, because the liquid epoxy resin reacts with bisphenol A to produce a converted epoxy resin as an exothermic reaction. The converted epoxy resin flows from the reactor to a pellet cutting machine where the converted epoxy resin is cooled. And it is to be understood that the present invention has been described in the foregoing two preferred embodiments, and it should be understood that the present invention is not limited thereto, and is intended to be included in the scope of the appended claims. All changes, modifications and equivalents in the scope of the technical idea of the invention are defined. [Simplified illustration of the drawings] Fig. 1 is a cross-sectional view of a conventional art reactor and process; 200932778 Fig. 1A is a first figure A top cross-sectional view of a conventional art reactor along line 1A-1A; Fig. 2 is a cross-sectional view of the reactor and process of the present invention; and Fig. 2A is a second view of the reactor of the present invention taken along line 2A-2A Top view cross-section 5 cross-sectional view.
【主要元件符號說明】 10…習知技術的系統 21…反應混合物 11…批式反應器 30…本發明系統 12…噴嘴 31…批式反應器 13…噴嘴 32…入口喷嘴 14…加熱套 33…出口喷嘴 15…喷嘴 34…固定隔板 16…喷嘴 35…馬達 17…固定隔板 36…轴桿 18…馬達 37a…上動葉輪 19…軸桿 37b…下動葉輪 20a···上動葉輪 38…反應混合物 20b…下動葉輪置 39···力σ熱組份的量 17[Major component symbol description] 10: a conventional system 21... Reaction mixture 11... Batch reactor 30... The present invention system 12... Nozzle 31... Batch reactor 13... Nozzle 32... Inlet nozzle 14... Heating jacket 33... Outlet nozzle 15...nozzle 34...fixed partition 16...nozzle 35...motor 17...fixed partition 36...shaft 18...motor 37a...upper impeller 19...shaft 37b...downper impeller 20a···upper impeller 38 ...reaction mixture 20b...lower impeller setting 39···force σ heat component amount 17