200523291 九、發明說明： 發明所屬之技術領域 本發明是關於在一種使用至少一種反應器系、统的設施 中由一種聚合物熔融液生產一種聚合物的方法，此反應系 統是在聚合物熔融液中進行一種形成聚合物的化學反應， 該反應是由至少一種反應參數所決定，藉由此方法取得聚 合物熔融液的至少一種狀態變數，並依據此種狀態變數來 控制此種反應器系統的至少一個反應參數。 此外，本發明也是關於一種使用至少一種反應器系統 由種聚合物溶融液生產一種聚合物的設施，其中此種反 應器系統適合在1合物溶融液中進行一種化學反應，，反 應疋由反應參數所決定，它是利用一種感測器取得聚合物 嫁融液的至少一種狀態變數’並且利用一種與此種感測器 連接的控制單元來轉換數據，藉此可依據此種狀態變數來 控制至少一種反應參數。 此種反應器系統的一種反應參數可表示一種物理的 量，藉此可以決定在反應器中反應進行的反應平衡，例如 此種反應的量可以是溫度、壓力和/或一種化學的量（例如聚 合物成分的濃度和/或其克-分子量）。藉由此種反應參數可 以定義並控制在反應器系統中的反應進行。聚合物溶融液 的狀態依據此反應的反應參數而改變，此聚合物熔融液的 狀態是藉由此聚合物溶融液的狀態變數所決定，例如次要 產物的濃度、聚合度、溫度及黏度等等。最後，此設施的 體積圍出-個空間，在此空間中，聚合物熔融液與次要產 200523291 物和裂解的產物，以及在聚合物生產過程中由聚合物熔融 液所形成的氣體和蒸氣一起流動。 先前技術 在開頭所提的方法及系統是先前的技術所熟知的。 US-A-5 155 184專利中描述利用紅外線光譜儀的吸收 測量來決定聚合物的分子結構，流經反應器的物質和反應 器的排放週期是依據吸收測量的結果來控制。依據專利 US-A-5 155 184,此方法適合用於控制一種或更多烯烴或 疋乙稀基單體的聚合。 US-A-5 155 184專利中所有依靠光學測量方法的缺點 是透明的區域（例如玻璃窗）必需被建構在測量點的設施的 外壁上，如果沒有此種透明的區域，聚合物熔融液的光學 檢查將無法在設施的體積内進行。此種裝置的缺點是管件 系統的機械強度顯著降低，對某些類型的聚合物而言（特別 疋自行放熱的反應性聚合物），此種機械強度的降低是不被 容許的，因為對於自行放熱的反應的情形會有破裂的風險。 另一種測量原理可由US-A-4 448 943專利得知，利用 此種測量原理可藉由一種交變電磁場來決定一種聚合物的 介電常數，因為聚合物生產程序的程序變數被控制，所以 測得的介電常數會接近具有所需組合物的聚合物的介電常 數。除了介電常數外，也可以計算出一種消散因子，並且 用於決定聚合物的狀態。依據US-A-4 448 943專利的解 說’在低於20 kHz的頻率下，介電常數會大大地受到離子 200523291 的污染物所影響，可以利用此種頻率範圍來控制聚合物熔 融液的組合物。依據此發表内容，頻率介於2〇 kHz到丄 MHz之間時，此物質的介電常數達到一個固定的數值。 US-A-5 208 544專利中描述一種環形的介電感測器和 一種連續式的測量方法，其中聚合物的黏度可以依據介電 消散因子來決定。此種感測器產生具有介於〇·5Ηζ到2〇〇 kHz之間的頻率的電磁交變場，而且只適用於最大内徑為8 公分的導管，使用此種管徑對大規模的公司而言是太小了。 大體來說，在聚合物生產的領域中，特別是在生產聚 合物的領域中，沒有耐用、準確且可靠的方法及控制系統。 然而，尤其使用現代化生產聚合物的方法有必要將反 應條件保持特別穩定並且固定在特定的值。這不只是生產 品質均一的產物所必要的，也能抑制因為設定的反應條件 超出或過低而發生不想要的次要反應，此種次要反應不只 對產品品質及產品產率有影響，也需要特別的測量來保持 此方法的環保及不具污染性。尤其因為生產方法的環保觀 念愈來愈重要，所以精確地維持反應條件是特別重要的。 發明内容 根據本發明，本案開頭所提的方法達成了上述目標， 其中聚合物熔融液所產生的柯氏力被用於當作至少一種狀 態變數’並用於控制至少一種反應參數。 本發明所謂的，，聚合物熔融液，，是指依據本發明的系统 所產生的所有液體，它們可以包含寡聚合物和/或聚合物， 200523291 同時部分的這些混合物也可以被稱為溶液。 對本案開頭所提的設施而言，本發明達成此目標的方 供-種柯氏力的感測器’並且提供—種適合依據測 付的柯氏力進而控制至少—種反應參數的控制器。 …兩種達成目標的答案都很簡卩，因為柯氏力感測器已 經被用於聚合物生產的設施。 依據本發明，由柯氏力感測器所取得的柯氏力被用於 仔到有關聚合物熔融液狀態的資訊，並用它來控制反應与 糸統中的反應，可以藉由評估柯氏力瞬間的值和/或評估柯 氏力隨時間的變化來達成。隨時間變化的評估是注意在— 段時間内柯氏力如何發展’例如是否發生突然間的改變及 暴增’或疋是否連續緩慢地降低。柯氏力隨時間的變化在 下面被稱為柯氏力的“時間軌跡“，可做為計算第一及其他 短暫區間所得的例子。 本發月利用柯氏力感測器來控制在聚合物生產期間的 反應’基纟上它與在生產聚合物或三元纖維素混合物的加 工中使用柯氏力感測器的已知方法（例如在fr 2 82i 175 A1 和 DE 1〇〇 44 491 A1 或 DE-A-199 49 726 和 WO-A-01 W17中所描述的）是不同的，在這些前案中，柯氏力感測 器並非真正用於控制反應，反而只是用於控制聚合物或纖 維素混合物的組合物，其一部份進入溶液但未進行反應。 FR 2 821 175 A1是關於一種用於控制產物性質的方 法，例如疋合成或聚加成的產物，此方法是藉由一種數學 模型的協助來控制，此種數學的模型可複製產物性質與獨 200523291 特的私序變數之間的關係、’例如由流變儀、光譜儀或超音 波的方法來決定熔融液的流動性。在FR 2 82i i75 ai中也 杬述由一種柯氏感測器取得一種反聚合試劑的產量。 因此相較於本發明，這些刊物中並未提及利用聚合物 熔融液所產生的柯氏力來控制至少一種反應的參數。FR 2 821 175 A1真正只有描述由柯氏感測器來取得反應過程中 反聚合試劑的產量 在DE 100 44 491 A1中描述使用一種柯氏測量槽來決 定一種充氣且在壓力下的液體（特別是一種可流動的塑性 體）密度的一種密度測量裝置。另外，DE1〇〇 44 491 A論及 一種用於取得並控制液體的氣體充填的裝置，其中充氣測 量裝置包含密度測量裝置。 DE 100 44 491 A1取得並控制在壓力下的充氣流液體 (例如塑膠泡沫）的組合物，然而並沒有化學反應發生也沒 有控制此反應，因此在DE 100 44 491 A1中並未揭示由至 少一種反應參數來決定一種利用柯氏感測器的輔助來監控 及控制生成聚合物的化學反應。 在WO_A-01 25517中，三元纖維素溶液的密度及質量 流量是由一種柯氏力感測器所得到，纖維素溶液的水含量 是依據密度而決定，並且啟動氧化胺進料管線的閥門。 DE-A_ 199 49 725的具體實例也描述纖維素、水及胺氧 化物的三元纖維素溶液的密度是使用一種柯氏力感測器來 測量，密度是控制纖維素溶液組合物的兩種狀態變數中的 一種。 200523291 DE-A-199 49 726 及 WO-A-Ol 25517 中的柯氏力感測 器不被用於生產一種聚合物也不被用於控制一種化學反應 器的反應，而是用於控制一種不反應的溶液，其中所含的 纖維素已經是一種聚合物，不再需要被製造。 依據柯氏力的測量或是代表柯氏力的一種狀態變數， 在一個至少一種反應器系統中，當至少一種反應參數改變 時，反應平衡會偏移或改變。隨著反應平衡的偏移，在反 應改變期間反應器系統中所產生的反應產物的量及濃度會 改變。此外，可能產生新的反應產物或可能會防礙反應產 物的形成。此種改變也可以是聚合度的改變，例如在一種 生成長鏈聚酯的聚縮合反應中，聚合度也可以藉由柯氏力 感測器來決定，當鏈長增加時，聚合物熔融液的黏度會增 加並影響柯氏力。 9 例如當作反應參數時，可以控制各種物質之間或單體 與另一種單體反應之間的比例和/或觸媒的濃度。尤其優選 的是聚合物熔融液的溫度可以進一步葬ώ ^ ^猎由柯氏力感測器來 加以控制，在反應中，溫度可以同時影響單體與另一個單 體的反應以及黏度，藉由柯氏力的測量可以簡單且快速地 發現此種常見的效應。 在一個相似且尤其優選的方案中 7示甲，反應器中聚合物熔 R9虫液上方的氣恶空間的壓力可以获士 」Μ鞛由柯氏力感測器來控 制。此種壓力也會影響單體與另一個取 1固早體或聚合物鏈與另 一個聚合物鏈的反應，另外也會影變 Ρ I黏度，因為它會影響 聚縮合反應所生成水份由聚合物熔融液的移除。 10 200523291 純經驗的測量來控制及麻51会Μ & f j &應m不需要知道測得的狀態 變數、柯氏力及反應參數之間的¥ & 乂双心间的理論關係。此種方法的優 點是藉由柯氏力來取得狀離及批击丨e處 π π狀也汉徑制反應可成功地被運用在 本發明的一種特別有益的 物炼融液的狀態或組合物之間 地檢查’而是可以以一種點對 制的聚合物熔融液狀態依據實 可以定義出一種特性攔位，它 的狀態歸屬於測得的柯氏力。 許多完全不同的生產方法。 改善是測得的柯氏力和聚合 的關係不需要預先以分析性 點的校正方法利用各種被控 驗來決定。由各自的測量點 特定地將某些聚合物熔融液 使用此種特性攔位可以基於 在控制單元内，可以各種不同的方法實施特性棚位。 第-種可能性是將特性攔位储存成為參照表，其中所測得 的一種柯氏力或所測得的一種柯氏力的時間軌跡被關聯至 反應系統中所設定的某些反應參數，如果測得的柯氏力落 在參照表的數值之間，則此表可以被内插。 另一種可能性是將控制單元中的特性欄位儲存成一種 已經適用於測量點的内插的方程式，例如是一種多項式或 是一種傅立葉級數。利用此種方程式，反應器系統中被設 定的反應參數可以被特定地歸屬於所测量的柯氏力。 另一種可能性是使用測量點來訓練出一種電腦執行的 類神經網路，一方面柯氏力的測量點做為訓練用的數值， 另一方面，基於所使用的取得狀態，為了得到想要的聚合 物熔融液的狀態，在反應器系統中那些反應參數必需被設 定0 200523291 當然可以使用-種簡單的PID控制器，其中在反應器 系統中的反應參數是依冑測得的柯氏力與參考的柯氏力之 間的誤差來設定，例如測量的柯氏力可以與先前所決定的 參考數值（代表聚合物熔融液的參考狀態）來比較，反應器 系統可以根據比較的結果來控制。 當然不只是所設定的反應參數可以藉由不同形式的特 性攔位來具體說明其絕對值，而且目前能被設定的反應參 數的變化更可以具體地以相對值來說明。 此種反應器系統尤其可以依據柯氏力來控制，因此在 反應器系統中聚合物熔融液的至少一種成分的比例是依據 所述的柯氏力而改變，當聚合物的密度及黏度受此種成分 影響時特別有利。與這種活性成分有關的聚合物的組合物 特別容易被發現使用柯氏力測量。 因為聚合物熔融液的黏度及密度會隨溫度變化，如果 設施體積中或測量體積中的聚合物熔融液的溫度被測量並 且被考慮用於控制反應器系統，則反應器系統控制的準確 性可以進一步的提高。例如以一種簡單的方式來實行，藉 由實驗地（或分析地）方法來決定溫度對柯氏力測量的影 響’並且/或是將溫度導入特性欄位當作另一種用來控制的 量。另一種可能性是利用一種補償的方程式來補償因為溫 度所引起的柯氏力的變化，在這種補償方程式中考慮到溫 度對柯氏力的影響。 此種控制系統的構成具有優勢，所以可以適合現行的 設施’特別是此種控制系統的測量單元可以被裝配成為一 12 200523291 種元件，元件中的至少一種感測器被單一地結合在現行的 設施上。另外，此種控制系統適合與一種已經存在的柯氏 力感測器連接，因此現行的設施完全不需修改或只是稍微 修改。 本發明的方法及測量系統可以用於例如由聚合物熔融 液生產聚合物或是用於改變一種聚合、聚加成或是聚縮合 過程中成分的濃度、末端基或是聚合度。 在由酯化反應形成聚合物的反應器的後面使用此種方 法及測量系統是有利的，此種酯化反應是在高於200°C的 溫度下由芳香族及脂肪族的二羧酸或二羧酸酯與二醇類或 羥基酸形成聚酯（例如對苯二甲酸或二甲基對苯二甲酸酯 與乙二醇、i，2-，1，3_丙二醇或1，4-丁二醇形成聚酯），由雙 紛及二苯基以及二芳基碳酸酯形成聚碳酸酯，或是由芳香 族二酸與芳香族二酚形成聚丙烯酸酯，在一種固定的操作 模式下藉由接近達到熱力學的極限可達成產率的提高。 本發明的方法及裝置可以發現的其他優點是可用於追 縱同時以溶融液和以溶液或以懸浮方式進行聚合反應過程 中的反應進度或是產物的狀態，在此情形中，柯氏力的感 測器可以特別放置於（優選地是立即放置於）各別反應器系 統之後。如果在酯化、酯交換或聚縮合反應器之後使用柯 氏力感測器，則在這些測量點的聚合物尚未完全被轉換， 所以藉由控制醋化、酯交換及聚縮合反應器系統的反應參 數，可以對進入聚縮合的聚合物熔融液進行一種修正的或 後調整的干預。 13 200523291 在這些聚縮合反應器中會進一步進行聚合到所要的最 終產物，尤其是聚合物最終的黏度可使用柯氏力感測器來 監控，一旦有偏差的情形，可以隨意地干預反應器的控制。 例如聚乙烯對苯二甲酸酯的生產中，當最終的黏度下降並 低於參考值時，可以減低聚縮合反應器的氣態空間的壓力 以增加聚合物熔融液中水分的移除，進而促進更長鏈的聚 乙烯對苯二甲酸酯的形成。 另種柯氏力感測器可以放置於一種回流管柱上，以 便能平衡回流量並且考慮到聚合物的進料量。 實施方式 以下將參照圖表來舉例說明本發明的單一具體實例， 因為本發明從以上一般性描述清楚易懂，如果在特定的使 用中與這些特色相關的優點不是很重要時，此具體實例的 單一特色可以省略。 圖1以示意圖顯示由對苯二甲酸TPA(第一單體2)與乙 籲 -醇EG(第一單體3)生產聚乙稀對苯二甲酸醋pET的設施 卜對苯二甲酸及乙二醇是以1:18的莫耳比進行反應，並 加入200 Ppm的銻當作觸媒4,反應是在一個醋化反應器5 中於25〇〇C到280W之間的溫度以及17〇〇 mbar到〇 5 mbar 之間的壓力下進行，產量為100 kg/h。例如在DE_A_3 544 5 5 1中有描述一個相似原理的設施。 一 酯化反應器5的產物經由管件系統6傳送到酯交換反 應器7’並由那裏傳送到兩個連續進行預聚縮合的反應器8 14 200523291 及9。聚合物熔融液由最後的預聚縮合反應器9傳送到最 終的反應器或是環形盤狀的反應器10，並得到最終的產物 11(聚乙烯對苯二甲酸酯的聚合物）。藉由真空產生設備13 將次要產物由反應器系統8，9，10經由排放管12吸出， 再經由收集管線14傳送到一個裂解產物的精餾15，並以 裂解產物16離開此設施。佔裂解產物最大部分的酯化反應200523291 IX. Description of the invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a polymer from a polymer melt in a facility using at least one reactor system. The reaction system is a polymer melt A chemical reaction for forming a polymer is performed in the reaction. The reaction is determined by at least one reaction parameter. By this method, at least one state variable of the polymer melt is obtained, and the reactor system is controlled according to the state variable. At least one response parameter. In addition, the present invention also relates to a facility for producing a polymer from a polymer melt using at least one reactor system, wherein such a reactor system is suitable for carrying out a chemical reaction in a 1-solution melt. Determined by the parameters, it uses a sensor to obtain at least one state variable of the polymer melt solution and uses a control unit connected to the sensor to convert data, so that it can be controlled based on this state variable. At least one response parameter. A reaction parameter of such a reactor system can represent a physical quantity, thereby determining the reaction equilibrium in which the reaction proceeds in the reactor. For example, the quantity of this reaction can be temperature, pressure, and / or a chemical quantity (such as The concentration of the polymer component and / or its gram-molecular weight). With such reaction parameters, the reaction in the reactor system can be defined and controlled. The state of the polymer melt changes according to the reaction parameters of the reaction. The state of the polymer melt is determined by the state variables of the polymer melt, such as the concentration, polymerization degree, temperature, and viscosity of the secondary product. Wait. Finally, the volume of this facility encloses a space in which the polymer melt and secondary production 200523291 products and cracked products, as well as the gases and vapors formed from the polymer melt during the polymer production process Flowing together. Prior art The methods and systems mentioned at the outset are well known in the prior art. The US-A-5 155 184 patent describes the use of infrared spectrometer absorption measurements to determine the molecular structure of the polymer. The material flowing through the reactor and the discharge cycle of the reactor are controlled based on the results of the absorption measurements. According to patent US-A-5 155 184, this method is suitable for controlling the polymerization of one or more olefins or ethylene monomers. The disadvantage of all US-A-5 155 184 patents that rely on optical measurement methods is that transparent areas (such as glass windows) must be constructed on the outer wall of the facility at the measuring point. Without such transparent areas, the polymer melt Optical inspections will not be performed within the facility's volume. The disadvantage of this device is that the mechanical strength of the pipe system is significantly reduced. For certain types of polymers (especially reactive polymers that exothermic themselves), this reduction in mechanical strength is not allowed, because The exothermic reaction situation is at risk of cracking. Another measuring principle can be known from the US-A-4 448 943 patent. Using this measuring principle, the dielectric constant of a polymer can be determined by an alternating electromagnetic field. Because the program variables of the polymer production process are controlled, so The measured dielectric constant will be close to that of the polymer having the desired composition. In addition to the dielectric constant, a dissipation factor can also be calculated and used to determine the state of the polymer. According to the explanation of US-A-4 448 943 patent, 'at a frequency below 20 kHz, the dielectric constant will be greatly affected by the pollutants of the ion 200523291. This frequency range can be used to control the combination of polymer melts. Thing. According to this publication, when the frequency is between 20 kHz and 丄 MHz, the dielectric constant of the substance reaches a fixed value. US-A-5 208 544 describes a ring-shaped dielectric sensor and a continuous measurement method, in which the viscosity of a polymer can be determined based on a dielectric dissipation factor. This sensor generates an electromagnetic alternating field with a frequency between 0.5 介于 ζ to 2000 kHz, and is only suitable for catheters with a maximum inner diameter of 8 cm. Using this pipe diameter for large-scale companies Too small. Generally speaking, in the field of polymer production, especially in the field of polymer production, there is no durable, accurate and reliable method and control system. However, especially with modern methods of producing polymers, it is necessary to keep the reaction conditions particularly stable and fixed at specific values. This is not only necessary for the production of uniform quality products, but also can prevent unwanted secondary reactions from occurring because the set reaction conditions are excessive or too low. Such secondary reactions not only affect the product quality and product yield, but also Special measurements are needed to keep this method environmentally friendly and non-polluting. Especially since the environmental protection concept of the production method is becoming more and more important, it is particularly important to accurately maintain the reaction conditions. Summary of the Invention According to the present invention, the method mentioned at the beginning of the present case achieves the above-mentioned objective, wherein the Coriolis force generated by the polymer melt is used as at least one state variable 'and used to control at least one reaction parameter. The so-called polymer melt in the present invention refers to all liquids produced by the system according to the present invention, and they may contain oligomers and / or polymers. 200523291 These mixtures of simultaneous parts may also be referred to as solutions. For the facility mentioned at the beginning of this case, the present invention achieves this goal by providing a sensor for Coriolis force and providing a controller suitable for controlling at least one response parameter based on the measured Coriolis force. . ... the answer to both goals is straightforward, because Coriolis force sensors are already used in polymer production facilities. According to the present invention, the Coriolis force obtained by the Coriolis force sensor is used to obtain information about the state of the polymer melt, and it is used to control the reaction and the reaction in the system. The Coriolis force can be evaluated by Instantaneous values and / or evaluation of Coriolis forces over time are achieved. The evaluation over time is to pay attention to how the Coriolis force develops over a period of time, such as whether there is a sudden change and a sudden increase, or whether 疋 decreases continuously and slowly. The change of the Coriolis force with time is hereinafter referred to as the "time trajectory" of the Coriolis force, and can be used as an example of calculating the first and other short intervals. This month, a Coriolis force sensor is used to control the reaction during polymer production. It is based on the known method of using the Coriolis force sensor in processing to produce polymers or ternary cellulose blends ( For example, described in fr 2 82i 175 A1 and DE 1004 491 A1 or DE-A-199 49 726 and WO-A-01 W17) are different. In these previous cases, the Coriolis force sensing The device is not really used to control the reaction, but is only used to control the composition of the polymer or cellulose mixture, a part of which enters the solution but does not react. FR 2 821 175 A1 is a method for controlling the properties of products, such as the products of tritium synthesis or polyaddition. This method is controlled by the help of a mathematical model that can replicate the properties of the product and unique 200523291 The relationship between special private sequence variables, such as rheometer, spectrometer, or ultrasonic method to determine the fluidity of the melt. In FR 2 82i i75 ai, it is also stated that the yield of an anti-polymerization reagent is obtained by a Coriolis sensor. Compared to the present invention, therefore, these publications do not mention the use of the Coriolis force generated by the polymer melt to control at least one parameter of the reaction. FR 2 821 175 A1 only describes the use of Coriolis sensors to obtain the yield of anti-polymerization reagents in the reaction process. DE 100 44 491 A1 describes the use of a Coriolis measuring cell to determine an aerated and pressured liquid (in particular Is a kind of flowable plastic body) a density measuring device. In addition, DE 1004 491 A discusses a device for obtaining and controlling a gas filling of a liquid, in which a gas-filled measuring device comprises a density measuring device. DE 100 44 491 A1 obtains and controls the composition of a gas stream liquid (such as plastic foam) under pressure. However, no chemical reaction occurs and the reaction is not controlled. Therefore, it is not disclosed in DE 100 44 491 A1 that at least one The reaction parameters determine a chemical reaction using a Cole sensor to monitor and control the polymer formation. In WO_A-01 25517, the density and mass flow of the ternary cellulose solution are obtained by a Coriolis force sensor. The water content of the cellulose solution is determined by the density, and the valve of the amine oxide feed line is activated. . The specific example of DE-A_ 199 49 725 also describes the density of the ternary cellulose solution of cellulose, water, and amine oxides. It is measured using a Coriolis force sensor, and the density is two kinds of control cellulose solution composition. One of the state variables. 200523291 DE-A-199 49 726 and WO-A-Ol 25517 Coriolis force sensors are not used to produce a polymer or to control the reaction of a chemical reactor, but to control a The non-reactive solution, which contains cellulose, is already a polymer and no longer needs to be manufactured. According to the measurement of Coriolis force or a state variable representing Coriolis force, in at least one reactor system, the reaction equilibrium will shift or change when at least one reaction parameter is changed. As the reaction equilibrium shifts, the amount and concentration of reaction products produced in the reactor system during the reaction change will change. In addition, new reaction products may be generated or the formation of reaction products may be hindered. This change can also be a change in the degree of polymerization. For example, in a polycondensation reaction that produces a long-chain polyester, the degree of polymerization can also be determined by a Coriolis force sensor. When the chain length increases, the polymer melt The viscosity will increase and affect the Coriolis force. 9 For example, when used as a reaction parameter, the ratio and / or catalyst concentration between various substances or between a monomer and another monomer can be controlled. It is particularly preferred that the temperature of the polymer melt can be further controlled by the Koch force sensor. In the reaction, the temperature can affect the reaction and viscosity of a monomer with another monomer at the same time. The measurement of Coriolis force can easily and quickly find this common effect. In a similar and particularly preferred solution, as shown in Fig. 7, the pressure of the gas-evil space above the polymer melt R9 in the reactor can be determined by the Koch force sensor. This pressure will also affect the reaction of the monomer with another solid precursor or polymer chain with another polymer chain, and it will also affect the viscosity of PI, because it will affect the water content of the polycondensation reaction. Removal of polymer melt. 10 200523291 A purely empirical measurement to control the numbness 51 & f j & should not need to know the measured state variables, Coriolis forces, and the reaction parameters between the &; 的 theoretical relationship between the two hearts. The advantage of this method is the use of Coriolis force to obtain the dissociation and strike. The π π shape at e can also be successfully used in the state or combination of a particularly beneficial smelting solution of the present invention. Inspection between objects' can be based on a point-to-point polymer melt state that can actually define a characteristic stop, and its state is attributed to the measured Coriolis force. Many completely different production methods. The improvement is that the relationship between the measured Coriolis force and the aggregation does not need to be determined in advance by using various controlled tests with an analytical point correction method. Certain polymer melts are specifically targeted by their respective measurement points. The use of such characteristic stops can be based on the control unit, which can be implemented in a variety of different ways. The first possibility is to store the characteristic stop as a reference table, in which the measured Coriolis force or the measured time course of the Coriolis force is associated with certain reaction parameters set in the reaction system, If the measured Coriolis force falls between the values in the reference table, the table can be interpolated. Another possibility is to store the characteristic field in the control unit as an interpolation equation that has been applied to the measurement point, such as a polynomial or a Fourier series. Using this equation, the reaction parameters set in the reactor system can be specifically assigned to the measured Coriolis force. Another possibility is to use the measurement points to train a computer-like neural network. On the one hand, the measurement points of the Coriolis force are used as training values. On the other hand, based on the used acquisition status, in order to obtain the desired The state of the polymer melt, those reaction parameters must be set in the reactor system. 200523291 Of course, a simple PID controller can be used, in which the reaction parameters in the reactor system are measured by the Coriolis force. Set the error with the reference Coriolis force. For example, the measured Coriolis force can be compared with the previously determined reference value (representing the reference state of the polymer melt). The reactor system can be controlled according to the comparison result. . Of course, not only the set reaction parameters can specify their absolute values through different forms of characteristic stops, but also the changes of the currently set reaction parameters can be specifically described with relative values. Such a reactor system can be controlled in particular according to the Coriolis force. Therefore, the ratio of at least one component of the polymer melt in the reactor system is changed according to the Coriolis force. When the density and viscosity of the polymer are affected by this, This is particularly advantageous when it is affected by these ingredients. Compositions of polymers associated with this active ingredient are particularly easily found using Coriolis force measurements. Because the viscosity and density of polymer melts vary with temperature, if the temperature of the polymer melt in the facility volume or measurement volume is measured and considered for controlling the reactor system, the accuracy of the reactor system control can be Further improvement. For example, in a simple way, experimentally (or analytically) determine the effect of temperature on the Coriolis force measurement 'and / or use the temperature introduction characteristic field as another quantity for control. Another possibility is to use a compensation equation to compensate for the change in Coriolis force due to temperature. In this compensation equation, the effect of temperature on the Coriolis force is taken into account. The structure of this control system has advantages, so it can be adapted to existing facilities. In particular, the measurement unit of this control system can be assembled into a 12 200523291 element. At least one of the sensors is integrated into the existing unit. On facilities. In addition, this control system is suitable for connection with an existing Coriolis force sensor, so existing facilities require no modification or only slight modification. The method and measurement system of the present invention can be used, for example, to produce polymers from polymer melts or to change the concentration, end groups, or degree of polymerization of a component during a polymerization, polyaddition, or polycondensation process. It is advantageous to use this method and measuring system behind a reactor that forms a polymer from an esterification reaction. This type of esterification reaction is carried out by aromatic and aliphatic dicarboxylic acids or Dicarboxylic esters form polyesters with glycols or hydroxy acids (eg, terephthalic acid or dimethyl terephthalate with ethylene glycol, i, 2-, 1, 3-propanediol, or 1, 4- Butanediol forms a polyester), polycarbonates from bis (diphenyl) and diaryl carbonates, or polyacrylates from aromatic diacids and aromatic diphenols, in a fixed mode of operation An increase in yield can be achieved by approaching the thermodynamic limit. Other advantages found by the method and device of the present invention are that they can be used to track the progress of the reaction or the state of the product during the polymerization reaction in a molten solution and in a solution or suspension. In this case, the Coriolis force The sensors may be placed in particular, preferably immediately after, the respective reactor system. If a Coriolis force sensor is used after the esterification, transesterification, or polycondensation reactor, the polymer at these measurement points has not been completely converted, so by controlling the acetification, transesterification, and polycondensation reactor system The reaction parameters can be a modified or post-adjusted intervention on the polymer melt entering the polycondensation. 13 200523291 In these polycondensation reactors, polymerization will further proceed to the desired final product, especially the final viscosity of the polymer can be monitored using a Coriolis force sensor. Once there is a deviation, you can freely interfere with the reactor. control. For example, in the production of polyethylene terephthalate, when the final viscosity decreases and is lower than the reference value, the pressure of the gaseous space of the polycondensation reactor can be reduced to increase the removal of water from the polymer melt, thereby promoting the removal of water from the polymer melt. Formation of longer chain polyethylene terephthalate. Another Coriolis force sensor can be placed on a return string to balance the return flow and allow for the polymer feed. Embodiments A single specific example of the present invention will be exemplified below with reference to the drawings, because the present invention is clear and understandable from the above general description. If the advantages related to these features are not very important in a particular use, the single example of this specific example is single. Features can be omitted. Figure 1 shows a schematic diagram of a facility for the production of polyethylene terephthalate pET from terephthalic acid TPA (first monomer 2) and ethylene-alcohol EG (first monomer 3). The diol was reacted at a molar ratio of 1:18, and 200 Ppm of antimony was added as the catalyst 4. The reaction was performed in an acetation reactor 5 at a temperature between 2500C and 280W and 17 °. It is carried out at a pressure between 0 mbar and 0 5 mbar with a throughput of 100 kg / h. For example, DE_A_3 544 5 5 1 describes a facility with a similar principle. -The product of the esterification reactor 5 is transferred to the transesterification reactor 7 'via the tube system 6 and from there to two reactors 8 14 200523291 and 9 which are continuously subjected to prepolymerization and condensation. The polymer melt is transferred from the final prepolymerization condensation reactor 9 to the final reactor or the annular disk-shaped reactor 10, and the final product 11 (polyethylene terephthalate polymer) is obtained. The secondary products are sucked out of the reactor system 8, 9, 10 via the discharge pipe 12 by means of a vacuum generating device 13, and then transferred via a collection line 14 to a rectification 15 of the cracked product, and leave the facility with the cracked product 16. Esterification reaction which accounts for the largest part of the cleavage product
器5中的裂解產物也是經由排放管線17傳送到裂解產物 的精館15。經由精餾將最初的起始原料分離並且經由一個 回流管1 8再次傳送到酯化反應器5。 由圖1也可以看出測量柯氏力的測量系統19，20，2 1 及22依聚合物熔融液流動的方向被分別放置於反應器系 統5 ’ 7 ’ 8及9之後。另一個柯氏力測量系統23被安置在 由裂化產物的精館1 5到酯化反應器系統5之間的回流管線 上，則里系統19_23可以使用如Krohne的Optimass MFS 7000型或Emerson Process的2_系列的柯氏力感測器。The cracked product in the reactor 5 is also transferred to the fine hall 15 of the cracked product via the discharge line 17. The initial starting material is separated via rectification and transferred to the esterification reactor 5 via a reflux tube 18 again. It can also be seen from Fig. 1 that measurement systems 19, 20, 21, and 22 for measuring the Coriolis force are placed behind the reactor systems 5'7'8 and 9 in the direction of the polymer melt flow, respectively. Another Coriolis force measurement system 23 is placed on the return line from the cracked product 15 to the esterification reactor system 5. The 19-19 system can be used, for example, Krohne's Optimass MFS 7000 or Emerson Process. Coriolis force sensor of 2_ series.
^施中所用的柯氏力測量系統的數目並不重要，使用 了五個測量系統只是當作例子;依據本發明，在設施i中存 在至少—種19-23形式的系統。 代表作為產物的狀態變數的柯氏力的信號由測量系勒 :9-23經由數據線路24或數據轉換區域傳送到一個控制系 认 卞用的控制線路％來控制反應器系 、、克 5，7-1〇，13 , 15。反岸 應益系統中所設定的或是主要的反 應參數是藉由合適的咸 ,^ ^ 妁级應器（圖1並未顯示）來取得，並經 由控制線路26傳送到柝舍丨系始^ 帝]系、、先25。控制系統％可以使用 15 200523291 一種具有處理器及記憶體的微電腦。 一種用於數據轉換的估算系統27也同樣與控制系統 25連接。使用手動的最終產物的產物分析（以箭頭28表 不）’依據柯氏力測量系統的信號並依據反應器系統中所測 得的反應參數，在估算系統27中計算出一種特徵值29， 藉由此種特徵值的辅助讓控制系統25控制反應器系統。 圖1中顯示一個特性攔位的特徵值29的例子，它顯示 的形式是由分離的校正點30所形成的一個區域，其中傳送 到反應器系統5的觸媒4的量[以質量百分率（m_% KAT)表 不]被歸屬於反應器系統5中所測得的溫度T5以及由柯氏 力測量系統1 9所測得的柯氏力Fc。 特性欄位的這種形式的特徵值29可以經由估算系統 27針對每一個柯氏力測量系統（19到22)以及各別歸屬的反 應器系統（5，7 - 10，13，15)計算出來。$ 了做為反應器 系統的此種單一控制的一種替代或是一種補充，可以產生 種夕維的特徵值2 9，但無法舉例說明，這是一種超曲面， 它與所有測量系統所測得的柯氏力以及一些或所有反應器 系統所設定的反應參數有關。利用這種形式的控制，不同 反應系統的反應參數被合併成一種單一的參數場，此種 參數場同時被狀態變數所控制。相較於歸屬於柯氏力的各 別反應器的分離控制，此種形式的控制的優點也就是依據 不同反應器系統的反應參數來考慮。可以以此種方法來控 制的反應參數的例子有在反應系統5中的第一單體、第二 單體及觸媒4的比例，以及每一個反應器系統中的壓力、 16 200523291 停留時間及温度。 以下以依據圖！的設施來生產聚碳酸醋為基礎，舉例 描述特徵值2 9的產生： 依據圖1的測試設施所得的最佳值被加在表i中，首 先是不使用柯氏力測量並維持穩定的連續操作，反應參數 及產物的特徵值被儲存在控制系統中。 之後開啟柯氏力測量系統並且將設施的反應條件保持 固疋’然後以計算且計劃完善的方式特定地改變反應器系 統中的反應條件，以便追蹤它們對柯氏力測量的影響並且籲 儲存它們的效應。在此方法中每一個柯氏力測量系統都用 相同的步驟’直到在設施！的操作過程所預期的眾多狀態 參數中計算出特徵值。 聚碳酸醋（PC)是由當作第一單體的雙酚A (bpa)和當 作第二單體的二苯基碳酸酯（DPC)以及當作 所產生。在設施丨的操作中，所有的反應器系統在= 溫度、固定的產量、壓力以及固定的觸媒濃度下讓兩種$ 體的莫耳比在0.9到2·〇之間做逐步的改變，在每_個步驟 改變之後保持維持所設定的莫耳比的保持相大約兩個小 時。不論在過渡相或是保持相中都要測量柯氏力感測器上 的柯氏力，並且歸屬於反應系統中的反應參數。這個方法 可以得到特性攔位的特徵值29的一個初始校正點3〇，其 中測置系統的柯氏力與反應器系統的反應參數是互相關聯 的圖2顯示由柯氏力感測器所測得的柯氏力如何對應到 莫耳比，由測得的柯氏力可以發現莫耳比。 17 200523291 在改變莫耳比之後，剩餘的反應參數在固定的莫耳匕 (1:1)下進行改變，例如在每一種情況中有十個步驟。、例比 酉旨化反應器的溫度可以在200〇C到3 50〇C之間變各n ^ 文1G且壓力 在2 bar到10 mbar之間變化，在穩定狀態下可以得到各別 數值的土50%的產量以及—50%到+200%的觸媒濃产， ^ 反應參數的期間，剩餘的反應參數保持在穩定操作的數 值。 由這些變化的設定量可以得到大量的校正點，同時也 得到特徵值29，其中反應參數與柯氏力感測器所取得量是 互相關聯的。 在此種設施的操作中，特徵值29可被用於當作一種多 維查找表’利用一組測得的柯氏力來查詢，反應參數的改 變必需被設定以便達到想要的穩定狀況。 另外’特徵值也可用於訓練類神經網路，以測得的柯 氏力當作輸入向量並以所設定的反應參數達到設定狀態的 改變當作輸出向量。此種類神經網路的功能就如RiUer及^ The number of Coriolis force measurement systems used in the application is not important, and the use of five measurement systems is for example only; according to the present invention, at least one type of 19-23 system exists in facility i. The signal representing the Coriolis force as a state variable of the product is transmitted by the measurement system: 9-23 via the data line 24 or the data conversion area to a control system for the control system to control the reactor system. 7-1〇, 13, 15. The set or main response parameters in the anti-shore benefit system are obtained through a suitable salt reactor (not shown in Figure 1) and transmitted to the house through the control line 26. ^ Emperor] Department, first 25. Control system can be used 15 200523291 A microcomputer with a processor and a memory. An estimation system 27 for data conversion is also connected to the control system 25. Using a manual product analysis of the final product (represented by arrow 28) 'based on the signal from the Coriolis force measurement system and based on the reaction parameters measured in the reactor system, a characteristic value 29 is calculated in the estimation system 27, by The assistance of this characteristic value allows the control system 25 to control the reactor system. An example of the characteristic value 29 of the characteristic stop is shown in FIG. 1, and it is shown in the form of an area formed by separate calibration points 30, in which the amount of the catalyst 4 delivered to the reactor system 5 [in mass percentage ( m_% KAT) represents the temperature T5 measured in the reactor system 5 and the Coriolis force Fc measured by the Coriolis force measurement system 19. The characteristic value 29 in this form of the characteristic field can be calculated via the estimation system 27 for each Coriolis force measurement system (19 to 22) and the respective assigned reactor system (5, 7-10, 13, 15). . The $ is used as an alternative or supplement to this single control of the reactor system, which can generate a characteristic value of 9 and 9 dimensional dimensions, but it cannot be exemplified. This is a hypersurface, which is measured with all measurement systems. The Coriolis force is related to the reaction parameters set by some or all reactor systems. With this form of control, the reaction parameters of different reaction systems are combined into a single parameter field, which is controlled by state variables at the same time. Compared with the separation control of the individual reactors that are attributed to the Coriolis force, the advantage of this form of control is that it is considered based on the reaction parameters of different reactor systems. Examples of reaction parameters that can be controlled in this way are the ratio of the first monomer, the second monomer and the catalyst 4 in the reaction system 5, and the pressure in each reactor system, 16 200523291 residence time and temperature. The following is based on the diagram! Based on the facilities to produce polycarbonate, an example is used to describe the generation of eigenvalues 2 9: The best values obtained from the test facility according to Figure 1 are added to Table i. The first is to not use Coriolis force measurement and maintain stable continuous Operation, reaction parameters and characteristic values of the products are stored in the control system. The Coriolis force measurement system is then turned on and the reaction conditions of the facility are kept solid. Then the reaction conditions in the reactor system are specifically changed in a calculated and well-planned manner in order to track their impact on Coriolis force measurements and call for their storage. Effect. In this method, each Coriolis force measurement system uses the same steps ’until at the facility! The eigenvalues are calculated from the many state parameters expected from the operation process of. Polycarbonate (PC) is produced from bisphenol A (bpa) as the first monomer and diphenyl carbonate (DPC) as the second monomer and as a result. In the operation of the facility, all the reactor systems are gradually changed at a temperature, a fixed output, a pressure, and a fixed catalyst concentration between 0.9 and 2.0. After each step change, the maintaining phase of the set mole ratio was maintained for about two hours. The Coriolis force on the Coriolis force sensor is measured both in the transition phase and in the holding phase and is attributed to the reaction parameters in the reaction system. This method can obtain an initial correction point 30 for the characteristic value of the characteristic stop 29. The Coriolis force of the measurement system and the reaction parameters of the reactor system are interrelated. Figure 2 shows the measured by the Coriolis force sensor. How the obtained Coriolis force corresponds to the Morse ratio, and the Morse ratio can be found from the measured Coriolis force. 17 200523291 After changing the Morse ratio, the remaining response parameters are changed under a fixed Morse (1: 1), for example, there are ten steps in each case. For example, the temperature of the reactor can be varied between 200 ° C and 3500 ° C, each with a pressure of 1G and a pressure between 2 bar and 10 mbar. In the steady state, various values can be obtained. The yield of soil is 50% and the catalyst is concentrated from -50% to + 200%. During the reaction parameter period, the remaining reaction parameters are maintained at stable operation values. A large number of correction points can be obtained from these changed setting amounts, and at the same time, a characteristic value 29 is obtained, in which the response parameter and the amount obtained by the Coriolis force sensor are interrelated. In the operation of such a facility, the eigenvalue 29 can be used as a multi-dimensional lookup table 'to query using a set of measured Coriolis forces, and changes in response parameters must be set in order to achieve the desired stable condition. In addition, the eigenvalues can also be used to train a neural network. The measured Coriolis force is used as the input vector and the change in the set response parameter to the set state is used as the output vector. This kind of neural network functions like RiUer and
Helge 等人在"Neuronale Netze·· Eine Einfiihrung in Neuroinformatik selbstorganisierter Netzwerke"(類神經網 路：自組織網路的類神經計算學的導論），Addison-Wesley (199 1年）中所描述的。控制單元25使用由訓練所產生的類 神經網路來控制設施1。 使用此方法及裝置可以有效地生產聚合物並處理聚合 物生產的次要產物。 以三個測試實施例作為基礎於下面說明依據本發明使 200523291 用柯氏力來控制的效果，表1提供測試實施例的綜覽。 實施例1 實施例1中依據上述的生產方法所得到的最終產物i i 是 PET。 由表1可看出使用柯氏力控制可使產物性質變化的幅 度減小達到20%。 實施例2 依據圖1的測試設施中所生產的最終產物丨丨是聚丁稀 對本二曱酸酯（PBT)，它是由當作第一單體的對苯二甲酸 (TPA)與當作第二單體的M_ 丁二醇（BD)(莫耳比為1:2.5) 以及100 ppm的鈦觸媒所生產的，質量產量為丨3〇 kg/h， 一般的反應條件是在220°C到260°C之間的溫度以及0.5 mbar到900 mbar之間的壓力。 由於本發明的控制方法，產物性質變化的幅度可以被 減小達20%以上。 實施例3 依據圖2的測試設施中所生產的最終產物η是聚碳酸 酯（PC) ’它是由當作第一單體的雙酚α(ΒΡΑ)與當作第二單 體的二苯基碳酸酯（DPC)(莫耳比為1:1.2)以及當作觸媒的 100 ppm的酚化鈉所生產，質量產量為i5〇kg/h，反應條件 是在250°C到330°C之間的溫度以及〇.3 mbar到950 mbar 19 200523291 之間的壓力。可由表1看出使用導入柯氏力測量的控制可 以提高黃度係數。 表 1 實 施 例 產物 單體 声曰- 座里 kg/h (不 使用柯 氏力控 制） 末端基 meq/kg (不使用 柯氏力控 制） 次要產物 (不使用柯 氏力控制） 極限 黏度 g/dl 產量 kg/h (使 用柯氏 力控制） 末端基 meq/kg (使用柯 氏力控 制） 次要產物 (使用柯 氏力控 制） 1 PET TPA 100 20 士 4 DEG: 0.64 105 17±2 DEG: EG 0.4% ±0.2 0.2% 土 0.1 2 PBT TPA 130 32 ±5 THF: 1.1 140 24 士 2 THF: BDO 25% 士 3 19% 士 1 3 PC ΒΡΑ 150 酚： 黃度係數： 0.58 160 28 ±2 黃度係數： DPC 20 士 6 96.0 ± 2 98.0 土 1Helge et al. Described in " Neuronale Netze · Eine Einfiihrung in Neuroinformatik selbstorganisierter Netzwerke " (Neural Networks: An Introduction to Neural Computation in Self-Organizing Networks), Addison-Wesley (1991). The control unit 25 controls the facility 1 using a neural-like network generated by training. Using this method and apparatus can effectively produce polymers and process secondary products produced by polymers. Based on the three test examples, the effect of using 200523291 to control by Coriolis force according to the present invention is described below. Table 1 provides an overview of the test examples. Example 1 The final product i i obtained according to the above-mentioned production method in Example 1 was PET. It can be seen from Table 1 that the use of Coriolis force control can reduce the amplitude of product property changes to 20%. Example 2 The final product produced in the test facility according to FIG. 1 is polybutylene terephthalate (PBT), which is composed of terephthalic acid (TPA) as the first monomer and The second monomer is produced by M_ butanediol (BD) (Molar ratio is 1: 2.5) and 100 ppm of titanium catalyst. The mass yield is 30kg / h. The general reaction conditions are at 220 °. Temperatures between C and 260 ° C and pressures between 0.5 mbar and 900 mbar. Due to the control method of the present invention, the magnitude of product property change can be reduced by more than 20%. Example 3 The final product η produced in the test facility according to FIG. 2 is polycarbonate (PC). It is composed of bisphenol α (BPA) as the first monomer and dibenzene as the second monomer. Carbonate (DPC) (Molar ratio of 1: 1.2) and 100 ppm sodium phenolate as catalyst. Mass production is i50kg / h. The reaction conditions are 250 ° C to 330 ° C. Between temperatures and 0.3 mbar to 950 mbar 19 200523291. It can be seen from Table 1 that the control using imported Coriolis force measurement can improve the yellowness coefficient. Table 1 Examples of product monomers in the examples-Block kg / h (without Coriolis force control) End group meq / kg (without Coriolis force control) Secondary products (without Coriolis force control) Limit viscosity g / dl yield kg / h (using Coriolis force control) end group meq / kg (using Coriolis force control) secondary product (using Coriolis force control) 1 PET TPA 100 20 ± 4 DEG: 0.64 105 17 ± 2 DEG : EG 0.4% ± 0.2 0.2% soil 0.1 2 PBT TPA 130 32 ± 5 THF: 1.1 140 24 ± 2 THF: BDO 25% ± 3 19% ± 1 3 PC ΒΡΑ 150 Phenol: Yellowness coefficient: 0.58 160 28 ± 2 Yellowness coefficient: DPC 20 ± 6 96.0 ± 2 98.0 soil 1
圖式簡單說明 圖1以示意圖顯示一種用於聚合物生產的第一設施， 它使用本發明方法及本發明的測量系統的一種具體實例。 圖2顯示一種柯氏力與單體莫耳比之間的關係的示意 圖。 主要元件之符號說明 1··設施；2·.第一單體；3··第二單體；4·.觸媒； 5、7·10、13、15··反應器系統；6..管件系統；11.·產物； 12.. 排放管；14..收集管線；16..裂解產物；17..排放管線； 18··回流管；19-23..柯氏力測量系統；24··數據路線； 25.. 控制系統；26·.控制路線；27..估算系統；29.·特徵值； 3 0..校正點 20Brief Description of the Drawings Figure 1 shows a schematic diagram of a first facility for polymer production using a method of the invention and a specific example of the measurement system of the invention. Figure 2 shows a schematic diagram of the relationship between the Coriolis force and the individual mole ratio. Explanation of symbols of main components 1. Facilities; 2. First unit; 3. Second unit; 4. Catalyst; 5. 7.10, 13. 15. Reactor system; 6 .. Pipe fitting system; 11. product; 12. discharge pipe; 14. collection line; 16. cracked product; 17. discharge line; 18; return pipe; 19-23. Coriolis force measurement system; 24 · Data route; 25. Control system; 26 · Control route; 27. Estimation system; 29. · Characteristic value; 3 0 .. Correction point 20