TW442517B - Control system for continuous polyamidation process - Google Patents
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- TW442517B TW442517B TW088108917A TW88108917A TW442517B TW 442517 B TW442517 B TW 442517B TW 088108917 A TW088108917 A TW 088108917A TW 88108917 A TW88108917 A TW 88108917A TW 442517 B TW442517 B TW 442517B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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Abstract
Description
4425 1 7 五、發明說明（υ I.發明之領域 本發明大致關於由二羧酸單體與二胺單體製造聚醯胺之 方法。更特別地，本發明係關於改良之聚醯化系統及其控 制系統，其藉由在聚合引發後測量反應物之莫耳比例，及 調整熔融反應物進料之流速，而維持熔融反應物之所需質 量流速。 I I ·先行技藝之說明 聚醯胺製造之主要挑戰為確定反應物以足以平衡生成聚 醯胺中羧與胺端基數量之量提供。如果反應物組合而保持 過里之鲮或胺端基，其可負面地影響生成聚醯胺之特定特 徵。例如’在由己二酸及伸已二胺（HMD)製造耐綸6,6時， 發現端基不平衡可負面地影響耐綸之染色力，而且減弱製 造高分子量耐綸6, 6之能力。結果，為了使聚醯胺之品質 最佳，製造者強調在聚合時平衡反應物之莫耳比例。 一種製造聚醯胺之先行技藝技術涉及一種二步驟方法， 其中二羧酸與二胺在水中反應以形成鹽，然後鹽加熱以造 成聚合。、然而，此二步驟聚合方法為不利的，因為其需要 水之加成及瘵發槽之使用以去除在形成鹽時增加之水。 難以控制此方法以確定最终聚合物之適#莫耳平衡， 療發槽為非常不可預測的且 ^ 許多控制機構已用於此二步驟一種已 制機構涉及物理地移除方法中物質之樣品以用心：控 析。然而’其為不利的，因為實行為耗時的，而且；：樣 品亚非總是適當地反映方法中物f之特徵而趨於發生不準4425 1 7 V. Description of the invention (υ I. Field of invention The present invention relates generally to a method for producing polyamines from dicarboxylic acid monomers and diamine monomers. More particularly, the present invention relates to an improved polyfluorination system And its control system, which maintains the required mass flow rate of the molten reactants by measuring the mole ratio of the reactants after the initiation of the polymerization and adjusting the flow rate of the molten reactant feed. II. Explanation of the Prior Art Polyamide The main challenge of manufacturing is to determine that the reactants are provided in an amount sufficient to balance the number of carboxyl and amine end groups in the polyamine. If the reactants are combined to retain the fluorene or amine end groups, it can negatively affect the production of polyamines. Specific characteristics. For example, 'In the manufacture of nylon 6,6 from adipic acid and hexamethylene diamine (HMD), it was found that the imbalance of end groups can negatively affect the dyeing power of nylon, and weaken the manufacture of high molecular weight nylon 6, 6. As a result, in order to optimize the quality of polyamide, the manufacturer emphasized that the mole ratio of reactants should be balanced during polymerization. A prior art technique for manufacturing polyamide involves a two-step process in which dicarboxylic acid It reacts with diamine in water to form a salt, and then the salt is heated to cause polymerization. However, this two-step polymerization method is disadvantageous because it requires the addition of water and the use of a hair tank to remove the increase in salt formation. It is difficult to control this method to determine the proper polymer balance of the final polymer. Hair troughs are very unpredictable and many control mechanisms have been used in these two steps. A prepared mechanism involves physically removing the substances in the method. The sample is intentional: controlled analysis. However, 'it is disadvantageous because the implementation is time consuming, and: the sample Asian and African always tend to reflect the characteristics of the object f in the method and tend to be inaccurate
442 5 1 7 五、發明說明（2) _ 確。 其他之已知控制機構涉及進行線上端基分析，以提供生 成聚醯胺中之適當莫耳平衡。這些線上控制機構關於避免 將方法中物質物理地取樣為有助益的。一種技術涉及莫耳 平衡之間接評定’其藉由測量在二步驟聚合方法中形成之 鹽之pH。然而’此pH測量技術為受限制的，因為pH並非生 成聚醯胺中端基之特別準確之平衡指示。 另一種線上端基分析技術涉及在聚合時測量端基比例， 及基於此測定將適量之反應物注射至熔融聚合混合物中， 以提供生成聚酿胺之所需莫耳平衡。此系統為不利的，因 為其需要昂貴之額外計量裝置及電路以將額外之反應物注 射至炫融之聚合混合物中。此系統亦為受限制的，因為其 需要額外之時間以在以後加入反應物組合熔融之聚合現a 物。 已嚐試直接由單體製造聚醯胺而不加入水。然而，已證 明控制反應物組合之程度為相當困難的’因為其中任何: 種之過量負面地影響產物之分子量因此及物理性質。此直 接聚合方法之其他問題包括單體及/或聚合物產物之降 解’其為（1)長時間（例如，數小時）保持在高溫，（2)垃 單體與氧之接觸，及（3)對物質中由方法裝置製造之殘量 金屬雜質之暴露之結果。 里 對於改良之聚合系統與其控制系統仍有克服先行技藝 上述缺點之長期持續需求。 τ .發明之概要442 5 1 7 V. Description of the invention (2) _ Yes. Other known control mechanisms involve performing on-line end-group analysis to provide an appropriate mole balance in the production of polyamide. These online control agencies are helpful in avoiding the physical sampling of substances in the method. One technique involves indirect evaluation of Mohr's equilibrium by measuring the pH of the salt formed in the two-step polymerization process. However, this pH measurement technique is limited because pH is not a particularly accurate indication of the equilibrium at which end groups are generated in polyamides. Another on-line end-group analysis technique involves measuring end-group ratios during polymerization and injecting an appropriate amount of reactants into the molten polymerization mixture based on this determination to provide the required mole balance to form the polyamine. This system is disadvantageous because it requires expensive additional metering devices and circuits to inject additional reactants into the fused polymer mixture. This system is also limited because it requires additional time to add the polymerized melt of the reactant combination to melt later. Attempts have been made to make polyamines directly from monomers without adding water. However, it has proven to be quite difficult to control the extent of the combination of reactants because an excess of any of these species negatively affects the molecular weight of the product and therefore the physical properties. Other problems with this direct polymerization method include degradation of the monomer and / or polymer product, which is (1) maintained at high temperature for a long time (e.g., several hours), (2) contact of waste monomer with oxygen, and (3 ) The result of the exposure of the residual metal impurities in the substance produced by the method device. There is still a long-term continuing need for improved aggregation systems and their control systems to overcome the aforementioned disadvantages. τ. Summary of the invention
442 5 1 f -—- — "" 五'發明說明（3) 本發明之一種 二羧酸單體與熔 將熔融二羧酸單 融二胺單體之供 使得組合熔融二 以形成炼融之聚 以聚合此聚合混 二羧酸單體與熔 連接至偵檢裝置 地調整熔融二羧 速，以平衡聚合 之莫耳比例。 本發明之另一 造聚醯胺之聚合 羧酸單體之供應 體之供應至溶融 合混合物。提供 與熔融二胺單體 及第一與第二計 據來自偵檢裝置 第二計量裴置至 胺單體至少之一 羧酸單體與熔融 此控制系統連 狀態為一種改良之聚 融之二胺單體製造。 體之供應計量。提# 應計量。第一與第 羧酸單體之供應與@ 合混合物。提供炱少 合物。提供裝置以摘 融二胺單體之莫 及第一與第二計量裝 酸單體與熔融二胺單 混合物中炫融二羰@ 種狀態為一種自二羧 控制系統。提供第一 計量提供第二計量 二羧酸單體之供應計 裝置以偵檢聚合混合 之莫耳比例。提供傳 量襄置至少之一之控 之莫耳比例輸入信號 少之一，以調整熔融 之質量流速，以平衡 二胺單體之莫耳比例 續地操作以確定反應 合系統’以由熔融之 提供第一計量裝置以 第二計量裝置以將熔 計量裝置連接在一起 融二胺單體之供應， 一個不通風反應容器 檢聚合混合物中熔融 例。控制裝置傳導地 置。控制裝置選擇性 體至少之一之質量流 單體與熔融二胺單體 酸單體與二胺單體製 計量裝置以將熔融二 裝置以將熔融二胺單 量’以形成熔融之聚 物中熔融二羧酸單體 導地連接至偵檢裝置 制器裝置。控制器根 控制第一計量裝置與 二羧酸單體與熔融二 聚合混合物中溶融二 〇 物以生成聚醯胺中等442 5 1 f -—- — " " Five 'invention description (3) The present invention provides a dicarboxylic acid monomer and a melted dicarboxylic acid monomelt diamine monomer so that the melted dimer is combined to form a remelt. Melt polymerization is to polymerize the polymer mixed dicarboxylic acid monomer and adjust the melted dicarboxylic acid speed to connect to the detection device to balance the mole ratio of polymerization. The supply of the polymer of another polymerized carboxylic acid monomer of the present invention to the molten mixture. Provided with the molten diamine monomer and the first and second data from the detection device. The second measurement is that at least one of the amine monomer and the carboxylic acid monomer is connected to the melting. This control system is in a state of improved fusion. Amine monomer manufacturing. Physical supply measurement.提 # Should be measured. Supply of first and second carboxylic acid monomers and mixtures. Provide oligomeric compounds. A device is provided to dissolve the diamine monomer and the first and second metered acid monomers and the molten diamine monomer in a mixture of dicarbonyl and various states as a self-dicarboxylic control system. A first meter is provided and a second meter is provided. A meter is provided to detect the mole ratio of the polymer mixture. Provides at least one of the controllable mole ratio input signal and one less to adjust the mass flow rate of the melt to balance the mole ratio of the diamine monomer. Continuous operation to determine the reaction system A first metering device and a second metering device are provided to connect the melt metering device together to melt the supply of the diamine monomer, and an unvented reaction vessel is used to check the melt in the polymerization mixture. The control device conducts ground. The control device selects at least one of the mass flow monomer and the molten diamine monomer, the acid monomer and the diamine monomer to make a metering device to melt the second device to melt the diamine unit to form a molten polymer The molten dicarboxylic acid monomer is conductively connected to the detection device controller device. The controller controls the first metering device and the dicarboxylic acid monomer and the melted dimerization mixture to dissolve the two compounds to form polyamide.
第7頁 4425 1 7 五'發明說明（4) 端基之平衡方式聚合。在熔融聚合混合 ’ :J订反應物流速之任何修改 — ：成 改變炫融二緩酸單體與炼融二胺單體至; ΐί。混合後無需加入額外之二羧酸單體或二胺單： 聚人系：2控制系統特別適用於直接由單體製造聚醯：： =系統内…方式，無需將水加入二賴，二 熔融之聚合混合物。 胺或 ”久至少一個不通風反應容器中之聚合混合物之溫度為約 約300 C。較佳為，至少一個不通風反應容器中之壓 力為約0-50 0 psig，更佳為約5〇-2 50 psig，最佳為約 120-180 psig。聚合混合物在至少一個不通風反應容器之 停留時間較佳為約0. 0 1分鐘至約3 0分鐘，更佳為約〇 . 5 -30分鐘，最佳為約1-5分鐘。離開至少一個不通風反應容 器之聚合混合物一般含少於4 〇重量％之未聚合單體，較佳 為少於10重量％之未聚合單體。 在特定具體實施例中，可在至少一個不通風反應容器之 下游視情況地使用至少一個通風反應容器，以去除在聚合 方法及/或進一步聚合時形成之水。在如此使用時，聚合 混合物在至少一個通風反應容器之停留時間較佳為約1分 鐘至約6 0分鐘。 亦可使用廢氣回收系統以回收至少一個通風反應容器製 造之廢氣中之蒸發二胺單體及/或二羧酸單體。此廢氣流 一般包含水蒸氣與蒸發之二胺單體。廢氣在回收管柱中接 觸熔融之二羧酸單體，而至少一部份之蒸發二胺單體反應Page 7 4425 1 7 Five 'invention description (4) Balanced polymerization of end groups. In the melt polymerization and mixing ′: J order any modification of the flow rate of the reactant —: to change the melamine diamine monomer and the melamine diamine monomer to; ΐί. There is no need to add additional dicarboxylic acid monomer or diamine monomer after mixing: Poly-human system: 2 control system is especially suitable for making polyfluorene directly from monomer :: = system ... way, no need to add water to di-lai, di-melt Its polymerization mixture. The temperature of the amine or polymerization mixture in at least one unvented reaction vessel is about 300 C. Preferably, the pressure in the at least one unvented reaction vessel is about 0-50 0 psig, more preferably about 50- 2 50 psig, most preferably about 120-180 psig. The residence time of the polymerization mixture in at least one unvented reaction vessel is preferably from about 0.01 minute to about 30 minutes, more preferably about 0.5 to 30 minutes. It is preferably about 1-5 minutes. The polymerization mixture leaving at least one airless reaction vessel generally contains less than 40% by weight of unpolymerized monomer, preferably less than 10% by weight of unpolymerized monomer. In specific embodiments, at least one vented reaction vessel may be used optionally downstream of the at least one unvented reaction vessel to remove water formed during the polymerization process and / or further polymerization. When so used, the polymerization mixture is in at least one The residence time of the ventilated reaction vessel is preferably from about 1 minute to about 60 minutes. An exhaust gas recovery system may also be used to recover the evaporated diamine monomer and / or dicarboxylic acid monomer in the exhaust gas produced by at least one vented reaction container. This offgas stream typically comprises water vapor and diamine monomer evaporated. Column recovery of the exhaust gas contact the molten dicarboxylic acid monomer and at least a portion of the reaction was evaporated diamine monomer
442517 五、發明說明（5) ~ 二叛酸單體而形成聚醯胺。其用以在包含聚醯胺與未反應 熔融二缓酸單體之回收管柱内形成液態溶析流。液態溶析 流可繼而混合熔融之二胺單體。 在一個具體實施例中’離開不通風反應容器之聚合混合 物中之财論6, 6之相對黏度（RV)為約〇至約3，而離開通風 反應容器之聚合混合物中之耐綸6，6之相對黏度為約3至約 1 5。在此使用之相對黏度為聚醯胺在9〇%甲酸（9〇重量％之 甲酸與10重量％之水）之8· 4重量％溶液在25。〇之黏度（厘泊） 對9 0 %曱酸單獨在2 5 °C之黏度之比例。 本發明之聚醯化方法可製造其最終產物而無需將水加入 反應物，而且無需形成鹽之中間步驟。此外，本發明之方 法可連續地及以熔融反應物與熔融聚合物在方法之高溫部 :之非常短停留時間操作。…大地減少水使用，廢水 生，及方法之能量消耗。纟亦排除先行技藝方法中發現 裝置之需要或所需A小，#己用以擔加入之 :理水之热發15。此外，避免反應物與產物之過量熱暴 有關如己二酸之二敌酸之 續供應熔融二羧酸以用於聚 經濟之方法。此方法提供高 之熱降解。透明熔融酸之製 〇 連續熔化之本發明狀態提供連 酿化方法或其他用途之實際且 品質之熔融酸而無變色或其他 造有利於高品質聚醯胺之製 園式之簡要說明 民表醯化乐統之方塊圓；442517 V. Description of the invention (5) ~ Diamine acid monomer to form polyamine. It is used to form a liquid eluate stream in a recovery column containing polyamidamine and unreacted molten dilute acid monomer. The liquid eluate stream can then be mixed with the molten diamine monomer. In a specific embodiment, the relative viscosity (RV) of the financial theory 6, 6 in the polymerization mixture leaving the unventilated reaction vessel is about 0 to about 3, and the nylon 6, 6 in the polymerization mixture leaving the vented reaction vessel The relative viscosity is about 3 to about 15. The relative viscosity used herein was 25% of a 8.4% by weight solution of polyamide in 90% formic acid (90% by weight formic acid and 10% by weight water). 〇Viscosity (centipoise) to 90% acetic acid alone at 25 ° C viscosity ratio. The polymerization method of the present invention can produce its final product without adding water to the reactants and without the intermediate step of forming a salt. In addition, the method of the present invention can be operated continuously and with a very short residence time in the high temperature part of the method: molten reactants and molten polymers. … The earth reduces water use, waste water generation, and energy consumption of methods.纟 also excludes the need for the device found in the prior art method or the required A is small, # has been used to add: the heat of the water 15. In addition, avoid excessive heat storms of reactants and products related to the continuous supply of dicarboxylic acids, such as adipic acid, to a molten dicarboxylic acid for use in a polymer economy. This method provides high thermal degradation. Production of transparent molten acid. The state of the present invention, which is continuously melted, provides a practical and high quality molten acid without discoloration or other purposes. It is a brief description of a garden system that is conducive to high-quality polyamines. The square circle of Huatong
圖1為描述本發明之改良來 4Fig. 1 illustrates a modification of the present invention.
442517 ^ _案號881Q8917 左/年"月?曰 修正|_ 五、發明說明（5) 圖2為描述本發明之聚合控制系統之方塊圖； 圖3為描述圖2所示之本發明聚合控制系統之第二方塊 圖； 圖4為描述本發明之另一種聚合控制系統之方塊圖a442517 ^ _Case No. 881Q8917 Left / year " Month? Revision | _ V. Description of the invention (5) Fig. 2 is a block diagram describing the polymerization control system of the present invention; The second block diagram of the control system; FIG. 4 is a block diagram describing another aggregation control system of the present invention a
O:\58\58727.ptc 主要元件代表符號 20 熔 融HMD儲存槽 22 HMD計量系統 24 己 二 酸 儲 存儲倉 26 大 型 氧 去 除 槽 28 真 空 泵 30 己 -— 酸 熔 化 容 器 32 熔 融 己 二 酸計量系 統3 4 炫 融HMD流 36 熔 融 己 酸流 38 Y - 接 π 40 次 一 管 段 42 靜 態 混 合 器 44 熱 交 換 器 46 通 風 之 預 聚 物 反應器 48 反 應 器 底 部流 50 再 循 環 流 52 第 二 流 54 塔 頂 流 56 HMD回收管柱 58 進 料 水 60 縮 合 流 62 熱 交 換 器 64 廢 氣 流 66 近 紅 外 線 分 析 儀 67 控 制 器 67a 终 端 機 67b 前 進 模 型 控制器 68 閃 蒸 器 70 第 _ 反 應 器 72 底 部 流 74 塔 頂 流 76 洗 滌 器 78 水 流 80 排 水 管 水 流 82 塔 頂 流 84 粒 化 器 86 旁 通 線 88 乾 燥 器 第10頁 2000.11.06.010 442517 次ί年Μ月？O: \ 58 \ 58727.ptc Symbols for main components 20 Fused HMD storage tank 22 HMD metering system 24 Adipic acid storage bin 26 Large oxygen removal tank 28 Vacuum pump 30 Hexacid-acid melting vessel 32 Fused adipic acid metering system 3 4 Hyun Rong HMD stream 36 molten hexanoic acid stream 38 Y-connected to pi 40 times one tube section 42 static mixer 44 heat exchanger 46 vented prepolymer reactor 48 reactor bottom stream 50 recirculation stream 52 second stream 54 tower Top stream 56 HMD recovery column 58 Feed water 60 Condensed stream 62 Heat exchanger 64 Exhaust gas stream 66 Near-infrared analyzer 67 Controller 67a Terminal 67b Forward model controller 68 Flash evaporator 70 No._ Reactor 72 Bottom stream 74 tower Top stream 76 Scrubber 78 Water stream 80 Drain water stream 82 Tower stream 84 Granulator 86 Bypass line 88 Dryer Page 10 2000.11.06.010 442517 times
修正I 案號 88108917 五、發明說明（?Ά) 90 氮 氣 進 料 92 氮 氣 吹 風 機 94 氮 氣 加 執 器 96 喷 水 冷 卻 器 98 過 濾 器 100 吹 風 機 102 產 物 儲 存 區 域 120 控 制 系 統 124 二 胺 計 量 泵 126 二 胺 流 速 計 組 件 128 主 驅 動 馬 達 ISO- 134 主 泵 取 頭 136 修 正 頭 138 主 軸 140 速 度 送 碼 器 142 速 度 控 制 器 144-1 48 伺 服 馬 達 150 伺 服 馬 達 152-1 58 衝 程 位 置 送 碼 器 1 60- 166 衝 程 位 置 控 制器 168 流 速 計 170 流 動 傳 送 機 172 己 二 酸 計 量 泵 174 流 速 計 組 件 176 主 驅 動 馬 達 1 78- 182 頭 184 單 驅 動 主 軸 186 速 度 送 瑪 器 188 速 度 控 制 器 190- 1 94 手 動 衝 程 控 制器 196 流 速 計 198 流 動 傳 送 機 200 分 析 儀 元 件 202 分 析 傳 送 機 描 述 性 具 體實施 例之 說 明 本發1 明之 聚 合 系 統 與 聚 合 控制系 統可 用· 以 白- 二( 暖： 與- 二胺 a 單體製造許多種聚醯胺。這些系統在由己二酸與伸己二胺 製造耐綸6，6特別有用。 圖1顯示本發明具體實施例之一種方法流程。由熔融HMD 儲存槽20提供熔融之伸己二胺（HMD)。有許多種提供熔融 HMD之適當方式。其一為相鄰製造HMD之設備安置聚醯化方Amendment I Case No. 88108917 V. Description of the invention (? Ά) 90 Nitrogen feed 92 Nitrogen blower 94 Nitrogen applicator 96 Water spray cooler 98 Filter 100 Hair dryer 102 Product storage area 120 Control system 124 Diamine metering pump 126 Diamine Tachometer assembly 128 Main drive motor ISO- 134 Main pumping head 136 Correction head 138 Spindle 140 Speed encoder 142 Speed controller 144-1 48 Servo motor 150 Servo motor 152-1 58 Stroke position encoder 1 60- 166 Stroke position controller 168 flow meter 170 flow conveyor 172 adipic acid metering pump 174 flow meter assembly 176 main drive motor 1 78- 182 head 184 single drive spindle 186 speed feeder 188 speed controller 190- 1 94 manual stroke control 196 flow meter 198 flow conveyor 200 analyzer elements 202 analysis conveyor descriptive and concrete Examples: The polymerization system and the polymerization control system of the present invention are available. · Many kinds of polyamines are produced from white-di (warm: and-diamine a monomers. These systems are used to produce nylon from adipic acid and hexamethylene diamine. 6, 6 are particularly useful. Figure 1 shows a method flow of a specific embodiment of the invention. The molten HMD storage tank 20 provides molten hexamethylene diamine (HMD). There are many suitable ways to provide molten HMD. One is the phase Set up a polymerization plant next to HMD manufacturing equipment
O:\58\58727.ptc 第10a頁 2000.11.06.011 4 4251 7 _案號88108917 0年丨\月7 a 修正|)_ 五、發明說明的>) 法裝置，使得熔融HMD流可直接以管輸送至槽20。另——種^ 方式為提供HMD水溶液，蒸發水，及熔化HMD。 熱可視情況地提供於此槽2 0，例如，藉圍繞槽2 0之熱轉 移外套。此槽之溫度較佳為約70 °C。熔融HMD然後經HMD計 量系統22泵送，其精確地控制進料至下游裝置之HMD量。 一般為無水結晶形式之己二酸由己二酸儲存儲倉2 4供應 。來自儲倉之己二酸流至大型氧去除槽26。在此槽26去除 空氣。較佳為，槽26之空氣去除藉由分批模式以氮置換之 循環真空完成。真空可藉真空泵28誘發。可調整真空與氮 壓間之循環頻率以得到所需之氧去除程度。 較佳為，大型氧去除槽26包含一個壓力容器，其具有形 成朝其底部直徑遞減之漏斗之底部。大型氧去除槽之漏斗 部份之側較佳為與水平形成至少7 0 °之角度，以利於流出O: \ 58 \ 58727.ptc Page 10a 2000.11.06.011 4 4251 7 _Case No. 88108917 0year 丨 \ Month 7 a Correction |) _ V. The device of the >) method described in the invention makes the molten HMD flow directly The tube is conveyed to the tank 20. The other way is to provide HMD aqueous solution, evaporate water, and melt HMD. Heat may optionally be provided in this slot 20, for example, by transferring heat to the jacket around the slot 20. The temperature of this tank is preferably about 70 ° C. The molten HMD is then pumped through the HMD metering system 22, which precisely controls the amount of HMD fed to the downstream device. Adipic acid, generally in the form of anhydrous crystals, is supplied from adipic acid storage bins 24. Adipic acid from the silo flows to the large oxygen removal tank 26. Air is removed in this groove 26. Preferably, the air removal from the tank 26 is accomplished by a circulating vacuum replaced with nitrogen in a batch mode. Vacuum can be induced by the vacuum pump 28. The cycle frequency between vacuum and nitrogen pressure can be adjusted to obtain the required degree of oxygen removal. Preferably, the large-scale oxygen removal tank 26 includes a pressure vessel having a bottom portion forming a funnel that decreases in diameter toward its bottom portion. The side of the funnel part of the large-scale oxygen removal tank is preferably at an angle of at least 70 ° to the level to facilitate the outflow.
O:\58\58727.ptc 第10b頁 2000.11.06.012 4425 1 7 五、發明說明（7) —--- 槽底。 大多無分子氧之己二酸結晶然後自大型氧去除槽Μ 較佳為藉重力，及大型氧去除槽中氮壓之壓力幫助） 酸熔化容器30。熔化容器30較佳為連續攪拌外套容器 在稍高於己二酸熔點之溫度（即，高於153。〇以氮稍毛 壓而操作。經其頂部進入此容器之己二酸結晶在其中 己二酸之表面快速地熔化。因此，此方法可連續地熔 二酸β較佳為，熔化容器3〇具有反圓錐入口喷嘴以減 動阻力。亦較佳為，熔化容器30由含極少或盔負面地 熔融單體之雜質之金屬合金製成。赫史特合金〇與31 鋼為適合之物質。 為了自此熔化容器之進一步氧去除而包括額外之方 有用的，以使熱降解之可能最小。一種進行之方式為 化容器30中之熔融己二酸供應振動能量，例如，藉超 裝置。振動能量可利於來自熔融酸之輸送空氣之散^ 成氣泡上升至炫融酸之表面。 熔化容器30中熔融己二酸之停留時間較佳為最小以 反應物之熱暴露。較佳為，停留時間小於三小時，更 約卜2小時。熔融己二酸離開熔化容器3〇之底部且泵彳 融己二酸計量系統3 2，其精確地控制進料至下’ 二酸之量。 "'置 大型氧去除槽26與己二酸熔化容器30之組合使己二 晶可連續炫化而無熱降解或變色。 HMD計量系統22與己二酸計量系統32以化學計量之— 流至 己二 ，其 1加 溶融 化己 少流 影響 不銹 法為 對熔 音波 ，造 降低 佳為 L熔 之己 酸結 t供O: \ 58 \ 58727.ptc Page 10b 2000.11.06.012 4425 1 7 V. Description of the invention (7) ----- The bottom of the tank. Most of the molecular oxygen-free adipic acid crystallizes and then is assisted from the large-scale oxygen removal tank M by gravity and the pressure of nitrogen pressure in the large-scale oxygen removal tank.) The acid melting vessel 30. The melting vessel 30 is preferably a continuously stirred jacket vessel operating at a temperature slightly above the melting point of adipic acid (ie, higher than 153.0 ° with a slight gross pressure of nitrogen. Adipic acid crystals entering the vessel through its top are crystallized therein. The surface of the diacid melts rapidly. Therefore, this method can continuously melt the diacid β. Preferably, the melting vessel 30 has an anti-conical inlet nozzle to reduce the movement resistance. It is also preferred that the melting vessel 30 is made up of Made of a metal alloy that negatively melts the impurities of the monomer. Hirst alloys 0 and 31 steel are suitable materials. In order to further remove oxygen from the vessel, it is useful to include additional methods to minimize the possibility of thermal degradation. One way to do this is to provide vibrational energy to the molten adipic acid in the chemical tank 30, for example, by means of a supersonic device. The vibrational energy can help the air from the molten acid to disperse into air bubbles and rise to the surface of the molten acid. The residence time of the molten adipic acid in 30 is preferably the smallest by the thermal exposure of the reactants. Preferably, the residence time is less than three hours, and more about 2 hours. The molten adipic acid leaves the melting vessel 30%. The bottom is pumped with an adipic acid metering system 32, which precisely controls the amount of adipic acid fed to the bottom. &Quot; The combination of a large oxygen removal tank 26 and adipic acid melting vessel 30 makes adipic acid available Continue to dazzle without thermal degradation or discoloration. HMD metering system 22 and adipic acid metering system 32 flow stoichiometrically to the second one. The first solution is melted and the second stream is flown. For the melting of caproic acid
442517442517
五、發明說明（8) 應熔融單體，使得熔融MD與熔融己二酸在^ 而^以下稱為“聚合混合物，，者。換言之，炫融草體在 Y:接口 Μ合及共混而引發聚合方法。聚合混合物通過次一 官段40前進至不通風混合器42，其較佳為線上靜態混合器 在較佳具體實施例中，炫融己二酸流36為約七之溫 度，及炫融HMD流34為約70 °C，而且在γ “接口 μ之壓力為 約150 psig ^線上靜態混合器較佳為具有24個元件之一 Kernes靜態混合器接口與線上混合器42之壁較佳為保 持在約2 6 8 °C。單體在混合器42之停留時間較佳為約ι_3〇'' 秒’更佳為約3秒。離開混合器42之聚合混合物進入不通 風管’例如，在260 °C及1 50 psig為另外1〇-6〇秒之反應時 間。 … 雖然反應物無需包括水即可操作本發明之方法，其不需 要反應物為完全無水的。例如，Η M D進料流可含多達約5重 量％，及已二酸流可含多達約2重量！，而此方法仍應適當 地作用。具有此低水濃度之反應物流在此稱為“本質上乾 燥”。 HMD與己二酸之一些反應由其在Y-接口 38彼此接觸之時 間持續發生至其進入熱交換器44之時間&可選擇用於方法 此部份之溫度與停留時間以造成在此處完全聚合，或防止 在此處發生完全聚合。在後者之情形，單體之接觸產生之 部份反應產物在此稱為“預聚物”。混合器42之管下游中 之預聚物質量一般為60-90%轉化成耐綸6, 6。不發生阻塞V. Description of the invention (8) The monomer should be melted so that the molten MD and the molten adipic acid are hereinafter referred to as "polymeric mixture," or in other words, the Xuanrong grass is combined and blended at Y: Initiating the polymerization process. The polymerization mixture advances to the unventilated mixer 42 through the next stage 40, which is preferably an on-line static mixer. In a preferred embodiment, the adipic acid stream 36 is at a temperature of about seven, and Hyun Rong HMD flow 34 is about 70 ° C, and the pressure at the γ "interface μ is about 150 psig. The on-line static mixer is preferably one of 24 elements. The wall of the Kernes static mixer is compared with the wall of the on-line mixer 42. It is best to keep it at about 2 6 ° C. The residence time of the monomers in the mixer 42 is preferably about 3 to 30 seconds, more preferably about 3 seconds. The polymerized mixture leaving mixer 42 enters an airless duct ', for example, at a reaction time of 260 ° C and 1 50 psig for another 10-60 seconds. ... Although the reactants need not include water to operate the method of the present invention, it does not require the reactants to be completely anhydrous. For example, the ΗMD feed stream can contain up to about 5 weight percent, and the adipic acid stream can contain up to about 2 weight! , And this method should still work properly. A reactant stream having this low water concentration is referred to herein as "essentially dry." Some reactions of HMD and adipic acid continue from the time they touch each other at the Y-interface 38 to the time they enter the heat exchanger 44 & the temperature and residence time can be selected for this part of the method to cause here Complete polymerization, or prevent complete polymerization from occurring here. In the latter case, a portion of the reaction products resulting from the contact of the monomers are referred to herein as "prepolymers". The mass of the prepolymer downstream of the tube of the mixer 42 is generally 60-90% converted to nylon 6,6. No blocking
第12頁 4425 1 7 五、發明說明（9) ’因為使用之條件防止低炼化中間產物之結晶。管4 〇與混 合器42為不通風，及其中之壓力相當低，例如，約0_5〇〇 Psig ’最佳為約150 psig，對此方法之最適操作為重要的 在圖1所示之具體實施例中，預聚物其次通過熱交換器 44且至通風之預聚物反應器46中。在此使用熱交換器並不 重要。任何所需之熱應可以反應器4 6内之内部加熱線圈， 或以反應器周圍之外套取代。離開熱交換器44之加熱預聚 物較佳為在低於其中液態物質表面之處進入反應器Μ 6在 此反應器46可發生進一步之聚合，其較佳為連續攪拌槽反 應器。反應器底部流48視情況地可分成再循環流5〇及引導 以進步處理之第二流5 2 β如果使用再循環，再循環流5 〇 流速較佳為比至反應器46之新鮮預聚物進料之流速大至少 1 5倍》反應器46較佳為以約50%滿之液態物質操作，以提 供大蒸氣/液體脫離表面。 在此方法中非常希望提供聚合物端基之後混合，高表面 積界面產生，其利於熔融物質之去揮發，及高熱轉移速率 ，其可快速地增加熔融物質之溫度。這些優點可藉例 々Hr!槽反應器之使用或阻流反應器與產物流之再 循裱一起使用而完成。 來自反應器46之塔頂流54為包括水蒸氣（即，多 應產生之揮發之水）及一般為一些HMD之水 汉0 送入_回收管柱56中，其中亦進料水⑽。含—此。頂:： 之縮合細再循環至反應器46，同時其餘之蒸氣Page 12 4425 1 7 V. Description of the invention (9) ′ Because of the conditions used, the crystallization of the low refining intermediate product is prevented. The tube 40 and the mixer 42 are not ventilated, and the pressure therein is relatively low. For example, about 0-5500 Psig 'best is about 150 psig. The optimal operation of this method is important. The specific implementation shown in Figure 1 In the example, the prepolymer passes through the heat exchanger 44 and into a vented prepolymer reactor 46. It is not important to use a heat exchanger here. Any required heat should be replaced by internal heating coils in the reactor 46, or by a jacket around the reactor. The heated prepolymer leaving the heat exchanger 44 preferably enters the reactor M 6 below the surface of the liquid substance therein, where further polymerization can take place in the reactor 46, which is preferably a continuous stirred tank reactor. The reactor bottom stream 48 can optionally be divided into a recycle stream 50 and a second stream 5 2 that is directed for progressive treatment. If a recycle is used, the recycle stream 50 has a flow rate that is preferably better than the fresh prepolymerization to the reactor 46 The flow rate of the material feed is at least 15 times greater> The reactor 46 is preferably operated with about 50% full liquid material to provide a large vapor / liquid release surface. In this method, it is very desirable to provide polymer end groups and then mix them. A high surface area interface is generated, which facilitates the devolatization of the molten material and a high heat transfer rate, which can quickly increase the temperature of the molten material. These advantages can be achieved by using, for example, the use of a Hr! Tank reactor or the use of a choke reactor with recycling of the product stream. The overhead stream 54 from the reactor 46 is composed of water vapor (i.e., the volatile water produced by the reactor) and water, which is generally some HMD. Han 0 is sent to the recovery column 56, which also feeds water leeches. With—this. Top :: The condensation is recycled to reactor 46, while the remaining vapor
第13頁 442517 五、發明說明（10) 器62冷卻且如廢氣流64之一部份而去除。 在一個具體實施例中，預聚物在熱交換器44加熱至約 260 C ’且反應器46在約260 °C及150 psig操作。至於適當 相對流速之實例，如果新鮮預聚物以每小時丨〇 〇磅之速率 進料至反應器4 6，反應器底部再循環流速較佳為每小時約 2: 000碎。在這些條件下操作之反應器46可產生大於95%之 單體成為耐綸6, 6之轉化，其在反應器46為2〇分鐘之停留 時間後具有3重量％之水濃度。 一依照^發明，提供控制系統以調整熔融二羧酸單體與熔 融二胺早體至少之一之進料速率或質量流速，以確定聚合 扣σ物中之適當單體比例。在較佳具體實施例中視聚合 物内羧端基與胺端基之平衡調整反應物至少之一之質 s :速-此線上端基測量可在γ_接口 下游任何之處實行 ^ 农〜貫知1例’此端基平衡測量在離開反應器46 _ ^ ^ ^ 尤術為測量聚合混合物内羧與胺端基之平 ^ m R R « ^ 在較佳具體實施例中，近紅外線（NIR)分 析儀b b藉由ί平仝#丄 物中之缓與胺端基2體之光譜光度含量^貞檢聚合混合 在具體實施么丨士 (ΝΠΟ裝置66 計量系統22 T ©里。η 中’本發明之控制系統包括近紅外線 自NIR分析儀66接收輪入之控制器67，HMD NIR分析儀66及以炫融己二酸計量系統32 ° 内熔融二羧酸„實例之方式提供，且非測定聚合混合物 制。N I R分析.早體與炼融二胺單體之莫耳比例之裝置之限 儀6 6藉由連續偵檢離開反應器4 6之部份聚合Page 13 442517 V. Description of the invention (10) The device 62 is cooled and removed as part of the exhaust gas stream 64. In a specific embodiment, the prepolymer is heated to about 260 C ' at heat exchanger 44 and reactor 46 is operated at about 260 ° C and 150 psig. As an example of a suitable relative flow rate, if fresh prepolymer is fed to reactor 46 at a rate of 1000 pounds per hour, the recycle flow rate at the bottom of the reactor is preferably about 2,000 pieces per hour. The reactor 46 operating under these conditions can produce a conversion of more than 95% of the monomers into nylon 6,6, which has a water concentration of 3% by weight after the reactor 46 has a residence time of 20 minutes. According to the invention, a control system is provided to adjust the feed rate or mass flow rate of at least one of the molten dicarboxylic acid monomer and the molten diamine precursor to determine the appropriate monomer ratio in the polymerized polymer. In a preferred embodiment, depending on the balance of the carboxyl end group and the amine end group in the polymer, adjust the quality of at least one of the reactants s: speed-the end group measurement on this line can be performed anywhere downstream of the γ_ interface Knowing 1 case of this end-group equilibrium measurement before leaving the reactor 46 _ ^ ^ ^ Especially for measuring the level of carboxyl and amine end groups in the polymerization mixture ^ m RR «^ In a preferred embodiment, near infrared (NIR) The analyzer bb is mixed with the spectrophotometric content of the amine end group and the amine end group 2 in the specific implementation. What is the practical implementation? (NΠΟ device 66 measuring system 22 T © .η 中 '本The control system of the invention includes a near-infrared controller 67 that receives the turn-in from the NIR analyzer 66, an HMD NIR analyzer 66, and a dicarboxylic acid within 32 ° of the adipic acid metering system. Made of polymerization mixture. NIR analysis. Limiter of device for mole ratio of early body to smelted diamine monomer 6 6 Partial polymerization leaving reactor 6 by continuous detection
第14頁 4425 1 7 — 五、發明說明（11) 物質中之羧與胺端基量。雖然使用NIR分析儀66較佳，其 意圖本發明之控制系統玎使用任何數量之測定聚合時熔融 二緩醆與熔融二胺之莫耳比例或莫耳平衡之裝置。 N 1 R分析儀66產生輸入信號至控制器67，作為聚合混合 物中羧與胺端基之平衡之表示。控制器67可使用此輸入信 號調整熔融二羧酸單體及/或熔融二胺單體之質量流速， 使得聚合此聚合混合物形成之聚醯胺具有所需之莫耳比 例。在 制演算 胺單體 入控制 有預定 中，其 率而完 制與操 應注 可安置 安置於 應器46 3 8之間 較佳具體實施例中，控制器6 7使用一種進料前進控 法’其視來自NIR分析儀66之輸入信號改變熔融二 之進料速率。使用此進料前進控制演算法，可在輸 熔融二羧酸單體與熔融二胺單體之比例，以製造具 莫耳比例之聚合之最終產物。在較佳具體實施例 藉由經HMD計量系統22修正炫融二胺單體之進料速 成。HMD計量系統22及熔融己二酸計量系統32之控 作在以下參考圖2-4而更詳細地討論。 意，雖然所示為沿流52配置，其意圖NIR分析儀66 於Y-接口 38下游任何之處。例如，nir分析儀66可 反應器Μ内低於液體高度之處，靜態混合器42與反 之間靜態合器42内，或靜態混合器42與乂_接口 〇 · 雖然在本方法此 例中，聚合物之聚 ’並非高達最終產 蒸器6 8以供應額外 處聚合物質，在本 合程度，因此及分 物所需《因此，部 之熱，然後進入第 發明之一些具體實施 子量與相對黏度（RV) 份聚合物質可通過閃 二反應器70中。第二Page 14 4425 1 7 — V. Description of the invention (11) The amount of carboxyl and amine end groups in the substance. Although it is preferable to use the NIR analyzer 66, it is intended that the control system of the present invention uses any number of devices for measuring the molar ratio or the molar equilibrium of the molten dimelamine and molten diamine during polymerization. The N 1 R analyzer 66 generates an input signal to the controller 67 as an indication of the balance of the carboxyl and amine end groups in the polymerization mixture. The controller 67 can use this input signal to adjust the mass flow rate of the molten dicarboxylic acid monomer and / or the molten diamine monomer so that the polyamine formed by polymerizing the polymerization mixture has a desired mole ratio. In the production control calculation of the amine monomer, there is a schedule, the completion rate and the response note can be placed between the reactor 46 3 8 In a preferred embodiment, the controller 6 7 uses a feed forward control method 'It depends on the input signal from the NIR analyzer 66 to change the feed rate of melt two. Using this feed forward control algorithm, the ratio of the molten dicarboxylic acid monomer to the molten diamine monomer can be input to produce the final polymerized product with a molar ratio. In a preferred embodiment, the feed rate of the melted diamine monomer is modified by the HMD metering system 22. The controls of the HMD metering system 22 and the molten adipic acid metering system 32 are discussed in more detail below with reference to Figures 2-4. Note that although shown as being configured along stream 52, it is intended that the NIR analyzer 66 is located downstream of the Y-interface 38. For example, the nir analyzer 66 may be located in the reactor M below the liquid height, in the static mixer 42 between the static mixer 42 and the reverse, or in the static mixer 42 and the 接口 _ interface. Although in this example of the method, The polymer polymer is not as high as the final steamer 6 8 to supply additional polymer materials, to the extent that it is suitable, so it is necessary to divide the material, so the heat of the part, and then enter some specific implementations of the invention and the relative viscosity. (RV) parts of the polymeric substance can pass through the flash two reactor 70. second
第15頁 442 5 1 7 五、發明說明（12) 反應器70之目的為使之進一步聚合及因此增加產物之分子 量與RV ^來自第二反應器70之底部流72之聚合產物應具有 最終產物之所需分子量。較佳為’第二反應器7〇之溫度為 約2 6 0至約2 8 0 °C之間，及壓力為大氣壓力。 在進入洗滌器76之塔頂流74去除第二反應器7〇中之HMD 蒸氣與水蒸氣。水流78亦進料至此洗滌器，使得水蒸氣冷 凝且可如排水管水流80去除。殘餘之蒸氣在塔頂流82離開 洗滌器76且變成廢氣流64之一部份。 聚合物產物可經粒化器84送出或通過旁通線86。如果經 過粒化器，聚合物粒然後送入乾燥器88。使用氮氣進料9〇 ’氣氣吹風機92 ’及氮氣加熱器94以對乾燥聚人顆知夕交 器88供應氣氣。離開乾燥謂底部之乾= ; 器96，過濾器98，而且以吹風機1〇〇移動至產物儲存區域 102 » 現在參考圖2，所示為本發明較佳具體實施例之控制系 統之方塊圖，其通常以120表示’以用於圖}所示之改良聚 合系統。控制系統12〇包括熔融二胺（HMD)計量系統22，熔 融己二酸計量系統32，控制器67，及NIR分析儀66。控制 系統1 2〇用以控制熔融己二酸之量，其在Y-接口 38組合熔 融二胺以形成聚合混合物，其進入至預聚物反應容器46路 線上之靜態混合器4 2。 熔融二胺計量系統22包括二胺計量泵1 24與二胺流速計 組件1 2 6。在較佳具體實施例中，二胺計量泵丨24為具有主 驅動馬達128 ,多個主泵取頭13〇„134，及修正頭136之正Page 15 442 5 1 7 V. Description of the invention (12) The purpose of the reactor 70 is to further polymerize it and thereby increase the molecular weight and RV of the product ^ The polymerization product from the bottom stream 72 of the second reactor 70 should have the final product Desired molecular weight. Preferably, the temperature of the 'second reactor 70' is between about 260 and about 280 ° C, and the pressure is atmospheric pressure. The overhead stream 74 entering the scrubber 76 removes HMD vapor and water vapor from the second reactor 70. Water stream 78 is also fed to this scrubber so that water vapor condenses and can be removed like drain pipe water stream 80. The residual vapor leaves scrubber 76 in overhead stream 82 and becomes part of exhaust stream 64. The polymer product can be sent out through the granulator 84 or through a bypass line 86. If passed through a granulator, the polymer pellets are then sent to a dryer 88. A nitrogen feed 90 'gas blower 92' and a nitrogen heater 94 were used to supply the gas to the drying device 88. Leaving the bottom of the dryer is dry = filter 96, filter 98, and moved to the product storage area 102 with a hair dryer 100 »Referring now to FIG. 2, a block diagram of a control system of a preferred embodiment of the present invention is shown. It is usually denoted at 120 'for the improved polymerization system shown in Figure}. The control system 120 includes a molten diamine (HMD) metering system 22, a molten adipic acid metering system 32, a controller 67, and a NIR analyzer 66. The control system 120 is used to control the amount of molten adipic acid, which combines the melted diamine at the Y-interface 38 to form a polymerization mixture, and enters the static mixer 42 on the line of the prepolymer reaction vessel 46. The molten diamine metering system 22 includes a diamine metering pump 1 24 and a diamine flow meter assembly 1 2 6. In a preferred embodiment, the diamine metering pump 24 has a main driving motor 128, a plurality of main pump taking heads 130 and 134, and a correction head 136.
第16頁 442517 五、發明說明（13) 向置換泵。主驅動馬達128包括驅動主軸138，其延伸至各 主泵取頭130-134與修正頭136中。個別之活塞（未示）配置 於主泵取頭130-134與修正頭136内》活塞（未示）連接至驅 動主軸138以提供來自熔融二胺容器2〇之熔融二胺單體通 過流速計組件1 2 6及朝Y -接口 3 8前進，以進入靜態混合器 42中之正向置換。 主驅動馬達128亦包括速度送碼器140與速度控制器142 ’其概括地形成封閉迴圈反饋系統以控制主驅動馬達1 2 8 之速度。速度送碼器140監測主驅動馬達128之速度及傳送 表示馬達速度之信號至控制器67。速度控制器142接收來 自控制器6 7之信號以控制主驅動馬達1 2 8之速度。 主系取頭130-134裝有飼服馬達144-148，衝程位置送碼 器1 52- 1 56，及衝程位置控制器16〇_164〇伺服馬達144_ 148連接配置於各主栗取頭130-134内之活塞（未示）。衝程 位置送瑪器152-156監測各飼服馬達144-148之主韩位置及 傳送表示衝程體積（0-100%)之信號至控制器67。衝程位置 控制器1 6 0 - 1 6 4接收來自控制器6 7之信號以控制伺服馬達 1 44-1 48之主軸位置，以在主泵取頭13〇_134内製造預定之 衝程趙積（0-100%)。主泵取頭130〜134較佳為可視應用之 大小提供系統適合提供足夠熔融二胺容量之流速。 修正頭1 36類似地裝有伺服馬達1 50，衝程位置送碼器 158 ’及衝程位置控制器166。伺服馬達150，衝程位置送 碼器158 ’及衝程位置控制器166以如在主泵取頭130-134 發現之相同方式協同操作》主要差別為修正頭丨36具有實Page 16 442517 V. Description of the invention (13) Directional displacement pump. The main drive motor 128 includes a drive spindle 138 that extends into each of the main pumping heads 130-134 and the correction head 136. Individual pistons (not shown) are configured in the main pumping heads 130-134 and the correction head 136. The pistons (not shown) are connected to the driving spindle 138 to provide the molten diamine monomer from the molten diamine container 20 through the flow meter. Modules 1 2 6 and Y-ports 3 8 are forwarded for positive displacement in the static mixer 42. The main drive motor 128 also includes a speed encoder 140 and a speed controller 142 ', which generally form a closed loop feedback system to control the speed of the main drive motor 128. The speed encoder 140 monitors the speed of the main drive motor 128 and transmits a signal indicating the speed of the motor to the controller 67. The speed controller 142 receives a signal from the controller 67 to control the speed of the main drive motor 1 2 8. The main system pick heads 130-134 are equipped with feeding motors 144-148, stroke position feeders 1 52- 1 56 and stroke position controllers 16_164〇 servo motors 144_ 148 are connected to each main chest pick head 130 -134 piston (not shown). The stroke position sender 152-156 monitors the position of the main Korean of each feeding motor 144-148 and sends a signal indicating the stroke volume (0-100%) to the controller 67. The stroke position controller 1 6 0-1 6 4 receives the signal from the controller 6 7 to control the spindle position of the servo motor 1 44-1 48 to make a predetermined stroke within the main pump pick-up head 13〇_134 ( 0-100%). The main pump extraction heads 130 to 134 are preferably a size-providing system suitable for the application, and are suitable for providing a sufficient flow rate of molten diamine capacity. The correction head 1 36 is similarly equipped with a servo motor 150, a stroke position encoder 158 ', and a stroke position controller 166. The servo motor 150, the stroke position encoder 158 'and the stroke position controller 166 operate in the same manner as found in the main pump pickup head 130-134. The main difference is that the correction head
第17頁 442517 五、發明說明（14) 質上比主果取頭130-134小之流速能力s其乃因為為了微 调整炫融一胺至靜態混合器4 2之總供應，修正頭1 3 6用以 供應相當小流速之熔融二胺至來自主泵取頭丨3〇_134之較 大流速。如在以下所更詳細地解釋，此特點為重要的，因 為其使本發明之控制系統120在混合前改變起初反應物（熔 融己一酸與熔融二胺）之比例’使得生成之聚醯胺具有化 學計量平衡之莫耳比例。 熔融二胺計量系統22之流速計組件丨26包括流速計丨68鱼 流動傳送機170 «流動傳送機170組態成監測如流速計168、 所偵檢之熔融二胺單體流速，同時傳送輸出信號至控制器 67，表示至靜態混合器42中之二胺流速。流速計1 68與流 動傳送機170可包含任何商業可得之流速計與流動傳送機 ,概括地，流速計組件丨2 β與二胺泵丨2 4協同操作控制器δ ? γ开/成封閉迴圈反饋配置’以選擇性地調整溶融二胺至靜 態混合器42中之流速。 己—酸計量系統32包括己二酸計量泵172及流速計 Ϊ as 。在較佳具體實施例中，己二酸計量泵1 72為具有 ，動馬達176與多個頭178_182之正向置換栗。主驅動馬 β ^延伸至各頭178_182中之單驅動主軸184 ^個別 X摇彳不）配置於頭178_182内，且連接至驅動主轴184 ;*自己—酸計量容器3 0之熔融己二酸單體通過流速 Τ 2要秘4及朝Υ~接口 3 8前進’以進入靜態混合器42中之 正向置換。 主驅動馬達176亦包持速度送蜂器186與速度控制器188Page 17 442517 V. Description of the invention (14) The flow rate capacity s is lower than the main fruit taking head 130-134 in quality because it is used to finely adjust the total supply of melamine to the static mixer 4 2 and correct the head 1 3 6 To supply a relatively small flow rate of molten diamine to a larger flow rate from the main pump pick-up head. As explained in more detail below, this feature is important because it allows the control system 120 of the present invention to change the ratio of the initial reactants (melted adipic acid and molten diamine) before mixing, such that the resulting polyamide is Molar ratio with stoichiometric balance. Flow meter assembly of molten diamine metering system 22 丨 26 includes flow meter 丨 68 fish flow conveyor 170 «The flow conveyor 170 is configured to monitor the flow rate of the molten diamine monomer detected such as the flow meter 168, while transmitting the output The signal to the controller 67 indicates the diamine flow rate to the static mixer 42. The flow meter 1 68 and the flow conveyor 170 may include any commercially available flow meter and flow conveyor. In summary, the flow meter assembly 丨 2 β and the diamine pump 丨 2 4 cooperative operation controller δ? Γ open / closed The loop feedback configuration is used to selectively adjust the flow rate of the molten diamine into the static mixer 42. The adipic acid metering system 32 includes an adipic acid metering pump 172 and a flow meter 计 as. In a preferred embodiment, the adipic acid metering pump 1 72 is a positive displacement pump with a moving motor 176 and a plurality of heads 178_182. The main driving horse β ^ extends to the single driving spindle 184 of each head 178_182 ^ individual X is not configured) is arranged in the head 178_182 and is connected to the driving spindle 184; * self-melted adipic acid monomer of the acid measuring container 30 The body passes through the flow rate T 2 and 4 and advances toward the interface 3 8 'to enter the positive displacement in the static mixer 42. The main drive motor 176 also includes a speed beeper 186 and a speed controller 188
第18頁 442517 五、發明說明（15) ~ -- ^概括地形成封閉迴圈反饋系統以控制主驅動馬達1 76 度。速度送碼器186監測主驅動馬達176之速度及傳送 不馬，速度之信號至控制器67 »速度控制器188接收來 ，制器67之信號以控制主驅動馬達176之速度。提供手 衝程控制器190-194以調整頭178-182内之活塞衝程體積 ’較佳為0-100%。 溶融己一酸计量系統3 2之流速計组件1 74包括流速計1 9 6 ”流動傳送機1 9 8。流動傳送機1 9 8組態成監測如流速計 196所/貞檢之熔融己二酸單體流速，同時傳送輸出信號至 控制器67 ’表示至靜態混合器42中之己二酸流速。流速計 1 96與流動傳送機1 98可包含任何商業可得之流速計與流動 傳送機。 提供控制器6 7以接收各種輸入信號及輸出各種控制信號 以協調控制系統1 2 〇之操作。較佳為，控制器6 7應程式化 以依照進料前進控制演算法進行。在此控制體系下，測量 敌與胺端基數量以決定聚合混合物内之端基平衡。控制器 6 7由此測量可使用搜哥表決定在混合前起初反應物必須改 變至何種程度，使得提供具有化學計量平衡莫耳比例之反 應物與生成聚醯胺。 NIR分析儀66包括分析儀元件200及分析傳送機202。分 析儀元件200直接連接預聚物反應器46，以在其離開預聚 物反應器4 6時偵檢聚合混合器内之羧與二胺端基數量。分 析傳送機20 2連接於分析儀元件200與控制器67之間，以傳 送分析儀元件200之輸.出至控制器67。NIR分析儀66可包含Page 18 442517 V. Description of the invention (15) ~-^ A closed loop feedback system is formed to control the main drive motor 1 76 degrees. The speed encoder 186 monitors the speed and transmission of the main drive motor 176. The speed signal is received by the controller 67. The speed controller 188 receives the signal from the controller 67 to control the speed of the main drive motor 176. A hand stroke controller 190-194 is provided to adjust the piston stroke volume ' within the heads 178-182, preferably 0-100%. The flow meter assembly 1 74 of the melt caproic acid metering system 32 includes a flow meter 196 "flow conveyor 198. The flow conveyor 198 is configured to monitor the melted hexahedron such as the flow meter 196 / Chastity. Acid monomer flow rate, while transmitting the output signal to the controller 67 'indicating the adipic acid flow rate to the static mixer 42. The flow meter 1 96 and flow conveyor 1 98 may include any commercially available flow meter and flow conveyor Provide the controller 67 to receive various input signals and output various control signals to coordinate the operation of the control system 120. Preferably, the controller 67 should be programmed to perform the control algorithm in accordance with the feed forward control. Under the system, the number of enemy and amine end groups is measured to determine the end group balance in the polymerization mixture. From this measurement, the controller can be used to determine the extent to which the reactants must be changed before mixing to provide a chemical The reactants and polyamines are metered to balance the molar ratio. The NIR analyzer 66 includes an analyzer element 200 and an analysis conveyor 202. The analyzer element 200 is directly connected to the prepolymer reactor 46 to leave the prepolymer reactor 46 The polymer reactor detects the number of carboxyl and diamine end groups in the polymerization mixer at 6:00. The analysis conveyor 20 2 is connected between the analyzer element 200 and the controller 67 to transmit the output of the analyzer element 200. To controller 67. NIR analyzer 66 may include
第19頁 442 5 1 7Page 19 442 5 1 7
任何數量之可評定生成聚醯胺中羧與二胺端基之商業可得 近紅外線分析儀。 N IR分析儀6 6傳送輸出信號至控制器6 7，作為聚合混合 物内未反應單體之莫耳平衡之表示。控制器67使用一種進 料前進控制演算法，其視來自N i R分析儀6 6之輸出信號改 變熔融二胺單體之進料速率。使用此進料前進控制演算法 ,可在輸入控制熔融二羧酸單體與熔融二胺單體之比例， 以製造具有化學平衡莫耳比例之聚合之最終產物。 在具體實施例中，其藉由經二胺計量系統22修正熔融二 胺單體之進料速率而完成。二胺計量系統22及熔融己二醆 計量系統32之控制與操作在以下參考圖2_4而更詳細地 論。 參考圖3，控制器67可包含任何數量之商業可得可程式 控制器，其包括但不限於分散式控制系統（DCS)，可程式 數位單元’或以微處理器為主之個人電腦。用於控制 之進料前進控制配置為可能的，因為圖丨所示之改良聚 化系統之組件關於其特徵為可預測的，而且在聚醯化方 時進行。'’藉由排除經水之加成形成鹽之步驟，本發： 在聚醯化方法中排除蒸發器之需I。蒸發容器關於 酿化之影響為不可職’而且在處理時可能呈現廣泛》 變化。 < 現在合併參考圖2與3敘述 考圖3，控制系統120之起初 (容量SP)輸入控制器67。為 控制系統1 2 0之操作。首先參 步驟涉及使操作者將設定點 了方便，控制器67以包括輪^Any number of commercially available near-infrared analyzers that can be evaluated to form carboxyl and diamine end groups in polyamines. The N IR analyzer 6 6 sends an output signal to the controller 67 as an indication of the Mohr equilibrium of the unreacted monomer in the polymerization mixture. The controller 67 uses a feed forward control algorithm which changes the feed rate of the molten diamine monomer depending on the output signal from the NiR analyzer 66. Using this feed forward control algorithm, the ratio of molten dicarboxylic acid monomer to molten diamine monomer can be controlled at the input to produce the final polymerized product with a chemically balanced mole ratio. In a specific embodiment, this is accomplished by modifying the feed rate of the molten diamine monomer via the diamine metering system 22. The control and operation of the diamine metering system 22 and the molten adipylene metering system 32 are discussed in more detail below with reference to FIGS. 2_4. Referring to FIG. 3, the controller 67 may include any number of commercially available programmable controllers including, but not limited to, a distributed control system (DCS), a programmable digital unit ', or a personal computer based on a microprocessor. The feed forward control configuration for control is possible because the components of the improved polymerization system shown in Figure 丨 are predictable with regard to their characteristics and are performed during the polymerization process. '' By eliminating the step of forming salt through the addition of water, the present invention: Eliminates the need for an evaporator I in a polymerization process. The effects of evaporation vessels on brewing are incompetent 'and may show extensive changes during processing. < Now with reference to Figs. 2 and 3 in combination With reference to Fig. 3, the control system 120 initially (capacity SP) is input to the controller 67. To control the operation of the system 120. The first step involves making it easy for the operator to set the point. The controller 67 includes the wheel ^
4425 1 7 五'發明說明（π) 設定點之終端機6 7 a及管理控制系統1 2 0之操作之前進模型 控制器67b而示於圖3。使用者已輸入所需之設定點（容量 SP)之後’電腦終端機67a傳送此資訊至前進模型控制器 67b « 前進模型控制器6 7b然後設定用於己二酸計量泵1 72之主 驅動馬達1 7 6之速度控制器1 8 8用之馬達速度控制。在較佳 具體實施例中，藉由手動調整衝程控制器190-194使得熔 融己二酸以對應操作者選擇之設定點之預定流速前進至靜 態混合器4 2 ’而進一步控制己二酸計量系統32之流速。— 但設疋’較佳為熔融己二酸之流速不應因改變來自控制器 67之控制信號或因調整手動衝程控制器19〇_194而改變。 月_J進模型控制器6 7 b亦設定結合二胺計量泵1 2 4之主驅動 馬達1 28之速度控制器1 42用之馬達速度控制。前進模型控 制器67b連續地監測來自nir分析儀66之輸出信號，以得到 聚合混合物内熔融二羧酸單體與熔融二胺單體之莫耳比例 之评定。在重要之狀態中，前進模型控制器67b使用此N j R 輸出信號產生及傳送修正設定點信號至結合修正頭136之 伺服馬達150之衝程位置控制器166。傳送至衝程位置控制 器1 66之修正設定點信號為基於在控制器67b中發現之進料 刖進控制演算法產生。此進料前進控制演算法可取為記情 體搜尋表之形式，其含表示反應物（熔融己二酸與熔融二'“ 胺）比例必須改變之程度，以得到操作者基於來自NIR分析 儀66選擇之所需容量設定點之數據。 在較佳具體實施例中，連續地調整二胺計量系統22之流4425 1 7 Five 'Invention Description (π) The set point of the terminal 6 7 a and the management control system 1 2 0 are advanced to the model controller 67b and shown in FIG. 3. After the user has entered the required set point (capacity SP), the computer terminal 67a sends this information to the forward model controller 67b «forward model controller 6 7b and then sets the main drive motor for the adipic acid metering pump 1 72 1 7 6 speed controller 1 8 8 for motor speed control. In a preferred embodiment, the adipic acid metering system is further controlled by manually adjusting the stroke controllers 190-194 to advance the molten adipic acid to the static mixer 4 2 'at a predetermined flow rate corresponding to a set point selected by the operator. Flow rate of 32. — But it is preferred that the flow rate of molten adipic acid should not be changed by changing the control signal from the controller 67 or by adjusting the manual stroke controller 19-194. Month_J advance model controller 6 7 b also sets the motor speed control for the speed controller 1 42 combined with the main drive motor 1 28 of the diamine metering pump 1 2 4. The forward model controller 67b continuously monitors the output signal from the nir analyzer 66 to obtain an evaluation of the molar ratio of the molten dicarboxylic acid monomer to the molten diamine monomer in the polymerization mixture. In an important state, the forward model controller 67b uses this NjR output signal to generate and transmit a correction setpoint signal to the stroke position controller 166 of the servo motor 150 combined with the correction head 136. The modified setpoint signal transmitted to the stroke position controller 1 66 is generated based on the feed advance control algorithm found in the controller 67b. This feed forward control algorithm can be in the form of a memory search table, which contains the degree to which the ratio of reactants (fused adipic acid to molten di '"amine) must be changed to obtain an operator based on the data from the NIR analyzer 66 Data on selected desired capacity setpoints. In a preferred embodiment, the flow of the diamine metering system 22 is continuously adjusted
第21頁Page 21
五、發明說明（18) —----- 速，以在混合前提供適當比例之反應物（熔融己二酸與熔 融二胺），使得提供具有化學計量平衡之莫耳比例之生成 聚醯胺。 取 參考圖2，控制器67藉由首先控制主驅動馬達⑵及飼服 馬達1 44-1 48至少之一，使得熔融二胺由主泵取頭丨3〇 — 1以 朝靜癌混合器4 2傳送而完成之。控制器6 7然後調整修正頭 136以微調轉移至靜態混合器42中之反應物比例。修正調 整為基於溶融己二酸之流速（如流速計組件1 7 4所測量）， 熔融二胺之流速（如流速計組件126所測量），各反應物在 反應器4 6内之後之部份聚合混合物之重量百分比之測量 (如NIR分析儀66所測量），及二胺計量泵124内之衝程體積 與馬達速度資訊C如位置送碼器152-158，位置控制器160-1 6 β，速度送碼器1 4 0，及速度控制器丨4 2所測量）》 使兩進料前進控制演算法在本發明之範圍内，其中基於 端基平衡測量而調整熔融二羧酸之質量流速。參考圖4 , 熔融二胺單體之流速維持在固定速率，同時微調二缓酸單 體以製造適當比例之反應物，以製造所需之容量設定點。 應了解’圖4所示之控制電路為由圖2所示者逆轉，使得圖 4具體實施例之操作之完整討論為不必要的。 以上本發明特定具體實施例之說明並不意圖為本發明所 有可能具體實施例之全部表列。熟悉此領域者應了解，可 對所述之特定具體實施例進行修改，其在本發明之範圍内 e例如*雖然在此所述之詳細具體實施例反應己二酸與伸 己二胺以製造耐綸6，6 熟悉此領域者已知之其他單體亦V. Description of the invention (18) —----- Speed, in order to provide the appropriate proportion of the reactants (melted adipic acid and molten diamine) before mixing, so as to provide a molar ratio of stoichiometric equilibrium to generate polyfluorene amine. Referring to FIG. 2, the controller 67 first controls at least one of the main driving motor ⑵ and the feeding motor 1 44-1 48 so that the molten diamine is taken out of the head by the main pump 丨 30-1 toward the static cancer mixer 4 2 Teleport and complete it. The controller 67 then adjusts the correction head 136 to fine-tune the proportion of reactants transferred to the static mixer 42. The correction is based on the flow rate of molten adipic acid (as measured by the flow meter assembly 174), the flow rate of molten diamine (as measured by the flow meter assembly 126), and the portion of each reactant after the reactor 46 The measurement of the weight percentage of the polymerization mixture (as measured by the NIR analyzer 66), and the stroke volume and motor speed information in the diamine metering pump 124, such as the position encoder 152-158, the position controller 160-1 6 β, Measured by the speed encoder 1 4 0 and the speed controller 4 2) "The two feed forward control algorithm is within the scope of the present invention, in which the mass flow rate of the molten dicarboxylic acid is adjusted based on the end group equilibrium measurement. Referring to Fig. 4, the flow rate of the molten diamine monomer is maintained at a fixed rate, and at the same time, the tartaric acid monomer is fine-tuned to produce an appropriate ratio of reactants to produce the required capacity set point. It should be understood that the control circuit shown in FIG. 4 is reversed by the one shown in FIG. 2 so that a complete discussion of the operation of the specific embodiment of FIG. 4 is unnecessary. The above description of specific embodiments of the invention is not intended to be a complete listing of all possible embodiments of the invention. Those skilled in the art will appreciate that modifications can be made to the specific embodiments described, which are within the scope of the invention, e.g. * although the detailed embodiments described herein react adipic acid and hexamethylenediamine to make Nylon 6,6 Other monomers known to those skilled in the art also
第22頁 442517 五、發明說明（19) 可用以製造其他聚醯胺。 第23頁Page 22 442517 V. Description of the invention (19) It can be used to make other polyamides. Page 23
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8729298P | 1998-05-29 | 1998-05-29 |
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| TW442517B true TW442517B (en) | 2001-06-23 |
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| TW088108917A TW442517B (en) | 1998-05-29 | 1999-07-29 | Control system for continuous polyamidation process |
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| Country | Link |
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| EP (1) | EP1080129A1 (en) |
| JP (1) | JP2002516365A (en) |
| KR (1) | KR20010070956A (en) |
| CN (1) | CN1310736A (en) |
| AU (1) | AU748194B2 (en) |
| BR (1) | BR9910791A (en) |
| CA (1) | CA2332937A1 (en) |
| EE (1) | EE200000695A (en) |
| HU (1) | HUP0101992A3 (en) |
| IL (1) | IL139815A0 (en) |
| MX (1) | MXPA00011755A (en) |
| NO (1) | NO20006013L (en) |
| PL (1) | PL344401A1 (en) |
| RU (1) | RU2000133318A (en) |
| SK (1) | SK17622000A3 (en) |
| TR (1) | TR200003533T2 (en) |
| TW (1) | TW442517B (en) |
| WO (1) | WO1999061510A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172353A1 (en) * | 2000-07-10 | 2002-01-16 | The Procter & Gamble Company | Retardation of discolouration of dicarboxylic acids |
| JP2002194079A (en) * | 2000-12-22 | 2002-07-10 | Mitsubishi Gas Chem Co Inc | Production method for polyamide |
| US7381788B2 (en) | 2002-08-30 | 2008-06-03 | Toyo Boseki Kabushiki Kaisha | Method for continuous production of polyamide |
| JP4177769B2 (en) * | 2004-02-04 | 2008-11-05 | 株式会社日立製作所 | Polymer synthesizer |
| WO2010003277A1 (en) * | 2008-07-11 | 2010-01-14 | 金发科技股份有限公司 | A semi-aromatic polyamide and the process with low amount of waste water discharge for preparing the same |
| JP5487782B2 (en) * | 2008-07-31 | 2014-05-07 | 東レ株式会社 | Polyamide prepolymer and continuous production method of polyamide |
| CN104130131B (en) | 2013-05-01 | 2018-05-29 | 英威达纺织（英国）有限公司 | The preparation of the nylon salt solution carried out from partial equilibrium acid solution |
| TW201446836A (en) | 2013-05-01 | 2014-12-16 | Invista Tech Sarl | Process for producing a partially balanced acid solution |
| TW201529640A (en) | 2013-12-17 | 2015-08-01 | Invista Tech Sarl | Process for producing partially balanced acid solution with vessel having a disperser head for nylon salt production |
| CN108929436A (en) * | 2018-06-12 | 2018-12-04 | 江苏海阳锦纶新材料有限公司 | A kind of preparation method of copolymer nylon |
| CN110684192B (en) * | 2019-11-07 | 2021-09-03 | 蓝星（成都）新材料有限公司 | P-phenylenediamine dissolving system and method for continuous polymerization of aramid fibers 1414 |
| US20230054441A1 (en) * | 2019-12-19 | 2023-02-23 | Dsm Ip Assets B.V. | Continuous solid-state polymerization process and reactor column for use therein |
| CN112062950B (en) * | 2020-03-28 | 2021-06-29 | 成都肆零壹科技有限公司 | Continuous nylon polymerization process |
| CN114196009A (en) * | 2020-08-31 | 2022-03-18 | 中国石油化工股份有限公司 | Method for continuously preparing poly (m-xylylene adipamide) |
| RU2761414C1 (en) * | 2020-09-14 | 2021-12-08 | Общество с ограниченной ответственностью "Спецлак" (ООО "Спецлак") | Method for control by high-frequency titration of the polycondensation stage in the production of alkyd lacquers |
| CN114471426B (en) * | 2022-01-20 | 2024-06-11 | 济宁正东化工有限公司 | Refined sulfonamide integrated preparation system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE756454A (en) * | 1969-09-23 | 1971-03-22 | Fiber Industries Inc | METHOD AND APPARATUS FOR PRODUCTION OF POLYAMIDES BY CONTINUOUS POLYMERIZATION |
| JPS5211354B2 (en) * | 1972-05-18 | 1977-03-30 | ||
| US4582520A (en) * | 1982-09-30 | 1986-04-15 | Owens-Corning Fiberglas Corporation | Methods and apparatus for measuring and controlling curing of polymeric materials |
| CH685003A5 (en) * | 1992-08-11 | 1995-02-28 | Buehler Ag | A method of continuously crystallizing and polymerizing plastic material, and apparatus therefor. |
| US5674974A (en) * | 1994-11-23 | 1997-10-07 | E. I. Du Pont De Nemours And Company | Continuous polymerization process for polyamides |
| US5532487A (en) * | 1994-11-23 | 1996-07-02 | E. I. Du Pont De Nemours And Company | Near-infrared measurement and control of polyamide processes |
| US5674972A (en) * | 1995-07-27 | 1997-10-07 | Albemarle Corporation | Polyamide-based formulations |
-
1999
- 1999-05-26 HU HU0101992A patent/HUP0101992A3/en unknown
- 1999-05-26 CA CA002332937A patent/CA2332937A1/en not_active Abandoned
- 1999-05-26 SK SK1762-2000A patent/SK17622000A3/en unknown
- 1999-05-26 WO PCT/US1999/011577 patent/WO1999061510A1/en not_active Application Discontinuation
- 1999-05-26 BR BR9910791-0A patent/BR9910791A/en not_active Application Discontinuation
- 1999-05-26 AU AU40990/99A patent/AU748194B2/en not_active Ceased
- 1999-05-26 RU RU2000133318/09A patent/RU2000133318A/en not_active Application Discontinuation
- 1999-05-26 EP EP99924508A patent/EP1080129A1/en not_active Withdrawn
- 1999-05-26 TR TR2000/03533T patent/TR200003533T2/en unknown
- 1999-05-26 PL PL99344401A patent/PL344401A1/en not_active Application Discontinuation
- 1999-05-26 JP JP2000550907A patent/JP2002516365A/en not_active Withdrawn
- 1999-05-26 EE EEP200000695A patent/EE200000695A/en unknown
- 1999-05-26 CN CN99809020A patent/CN1310736A/en active Pending
- 1999-05-26 KR KR1020007013251A patent/KR20010070956A/en not_active Application Discontinuation
- 1999-05-26 IL IL13981599A patent/IL139815A0/en unknown
- 1999-07-29 TW TW088108917A patent/TW442517B/en not_active IP Right Cessation
-
2000
- 2000-11-28 NO NO20006013A patent/NO20006013L/en not_active Application Discontinuation
- 2000-11-28 MX MXPA00011755 patent/MXPA00011755A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUP0101992A2 (en) | 2001-09-28 |
| TR200003533T2 (en) | 2001-04-20 |
| AU748194B2 (en) | 2002-05-30 |
| CA2332937A1 (en) | 1999-12-02 |
| CN1310736A (en) | 2001-08-29 |
| PL344401A1 (en) | 2001-11-05 |
| IL139815A0 (en) | 2002-02-10 |
| SK17622000A3 (en) | 2001-05-10 |
| WO1999061510A1 (en) | 1999-12-02 |
| KR20010070956A (en) | 2001-07-28 |
| RU2000133318A (en) | 2002-11-27 |
| EP1080129A1 (en) | 2001-03-07 |
| JP2002516365A (en) | 2002-06-04 |
| NO20006013D0 (en) | 2000-11-28 |
| BR9910791A (en) | 2001-02-13 |
| NO20006013L (en) | 2001-01-25 |
| MXPA00011755A (en) | 2002-04-01 |
| EE200000695A (en) | 2002-04-15 |
| HUP0101992A3 (en) | 2003-01-28 |
| AU4099099A (en) | 1999-12-13 |
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