TW448292B - On-line quantitative analysis of chemical compositions by Raman spectrometry - Google Patents

Abstract

A method for quantitatively monitoring in situ by Raman spectrometry one or more selected constituents of a chemical composition comprises: simultaneously irradiating with a substantially monochromatic radiation source a reference material and a chemical composition containing one or more constituents, the radiation being transmitted from the source to the chemical composition by an excitation conduit connecting the source to an optical probe that interfaces with the composition; simultaneously acquiring at more than one wavelength convolved Raman spectra of the reference material and the chemical composition by means of a spectrograph, which is connected to the optical probe by a collection conduit; chossing the standard Raman spectrum of the reference material; determining the convolution function of the convolved spectra from the convolved Raman spectrum and the standard Raman spectrum of the reference material; applying the convolution function to adjust the convolved Raman spectrum of the composition to produce the standard Raman spectrum of the chemical composition; and applying predetermined calibration means to the standard Raman spectrum of the chemical composition, by which the chemical constitution of the composition at the time of acquisition of the convolved Raman spectra can be ascertained.

Description

4482 9 2 A7 B7 經濟部中央橾準局員工消費合作杜印製 五、發明説明（ 發明之領域 本發明關於拉曼光譜分析，而尤其關於〜 ,種以拉曼光譜 術於原位定量監測化學组合物之成份的方法。 發明之背景 在分析實驗室，利用光譜儀於測量材料之鉍 科 物理和分析性 员’係一項成熟之技術。拉曼光譜術即係此等技術之其 一項，其可提供關於組合物及/或化學物質夕八7 、 Λ I分子結構的 疋性和足量訊息。當入射輻射與物質產生交互作用時，其 可能會經歷一種稱爲散射之過程。散射輻射可爲彈性或非 彈性：在散射輻射爲彈性之情況下，入射波長在散射輻射 中不會發生變化，而在散射輻射爲非彈性之情況下，散射 輻射和入射輻射則有不同之波長。其中一種形式之非彈性 輻射散射，稱爲拉曼散射’其入射光子之散射伴随著能量 的獲得或損耗。而在散射輻射和入射輻射間之能量差一般 稱爲拉曼位移（Raman shift)。所得之拉曼位移光譜可提供 各種分子振動運動之能量，而傳達關於所探討之物質的化 學和分子訊息。拉曼散射效慮相當地弱；典型情況爲於數 百萬個彈性散射光子中’僅存在有少許的拉曼散射光子。 測定化學組合物之组成，或監測化學反應之進行，經常 係在物質處於相當嚴苛之環境下進行。常常必須分析處於 高溫及/或高壓或有腐蝕性物質或強力溶劑存在之情況下 的程序物流《例如，可能必須監測在高溫之連續或分批式 方法中’由較低分子量之反應物生成聚合物之反應的進行 。同樣地’可能須要監測分批反應之組合物或在蒸餾塔頂 -4- 本紙择尺度適用中國國家標準（CNS ) Μ規格（2献加公麥） C請先聞讀背面之.，¾意事項再 ？本頁) ’裝·4482 9 2 A7 B7 Consumption cooperation with employees of the Central Bureau of Standards and Commerce of the Ministry of Economic Affairs of the People's Republic of China 5. Production Description (Field of Invention) The present invention relates to Raman spectroscopy, and in particular, ~, Raman spectroscopy is used to quantitatively monitor chemistry in situ. Methods for the composition of the composition. BACKGROUND OF THE INVENTION In analytical laboratories, the use of spectrometers to measure bismuth physics and analysts of materials is a mature technology. Raman spectroscopy is one of these technologies, It can provide natural and sufficient information about the molecular structure of the composition and / or chemical substance, and the Λ I molecular structure. When incident radiation interacts with the substance, it may undergo a process called scattering. Scattered radiation Can be elastic or inelastic: When the scattered radiation is elastic, the incident wavelength does not change in the scattered radiation, and when the scattered radiation is inelastic, the scattered radiation and the incident radiation have different wavelengths. Among them A form of inelastic radiation scattering, called Raman scattering, where the scattering of incident photons is accompanied by the gain or loss of energy. The energy difference between radiation is generally referred to as Raman shift. The resulting Raman shift spectrum can provide the energy of various molecular vibrational motions, and convey the chemical and molecular information about the substance in question. Raman scattering has considerable concerns Ground weakness; typically, there are only a few Raman scattered photons among millions of elastically scattered photons. Measuring the composition of a chemical composition, or monitoring the progress of a chemical reaction, often occurs when the substance is in a relatively harsh environment It is often necessary to analyze process logistics in the presence of high temperatures and / or high pressures or the presence of corrosive substances or powerful solvents. "For example, it may be necessary to monitor the reaction of lower molecular weight in continuous or batch processes at high temperatures. The reaction of polymer to polymer is carried out. Similarly, the composition of batch reaction may need to be monitored or the top of the distillation column -4- This paper applies the Chinese National Standard (CNS) M standard (2 gram added) C Please First read and read the back. What do you want? This page)

丁 -S A7 B7 4482 92 五、發明説明（2 之禪發性物料随時間的變化。可能 ， = 聚達離欲㈣位進行分析之物料二:如: 物科諸如生成聚合物之组合物和蒸館混合物，· f經由包含光學纖維㈣射導管與裝I相連。 當^ ’本發明之方法並不僅限於應用在以 =較《度之環境下^若可取得衫之光探針，則j 據本發明之定量原位拉曼光譜測量可在各種環境，包括活 的有機體中進行3 聚㈣-種在其主聚合物鏈中包含㈣結的合成樹脂。 甲售&可作爲衣物纖維、容器包裝等等使用之重要的聚酯 係由各種反應物製得。例如，其可經由將二元幾酸與二元 醇進行酯化、將二元羧酸酯與二元醇進行酯交換、或使羥 基羧酸自行縮合而製得。 a達到某種聚酯之特定用途的性質，需要嚴格地控制製 造過程在反應容器中之物料的成份比例或組成。起始組合 物中之微小的變化，即可大大地影響最終聚酯產品的效用 3而依係使用二元酯或二元政之不同，亦需要控制酯端基 或酸端基之轉化成反應性羥端基，以確保製成之聚酯產品 具有可靠的特性》在第一階段之反應中的低轉化率，將會 限制聚縮合反應過程的反應性，且對聚酯材料之最终用途 的性質有不利之影響。因此，獲知第—階段之反應的轉化 率或反應程度係相當重要的。其他重要的组成控制參數， 包括各二元酸和二元醇部份之量、反應容器中之全部二元 醇對全部二元酸及/或二元酯之比例、以及聚合程度、分 本紙張尺度適用中ga家標準（CNS > A4規格（210X297公廣） 請 先 閱 蟓 背 面 之Ding-S A7 B7 4482 92 V. Description of the invention (2 The change of zen materials over time. Possibly, = Juda material for analysis from the desired position II: For example: Materials such as polymer composition and polymer The steaming room mixture, f is connected to the device I through a fiber-optic emission catheter. When the method of the present invention is not limited to the application in the environment where the temperature is relatively high, if the light probe of the shirt can be obtained, then j The quantitative in situ Raman spectroscopy measurement according to the present invention can be performed in a variety of environments, including living organisms, 3 polyfluorenes-a type of synthetic resin that contains tritium in its main polymer chain. For sale & The important polyesters used in containers and packaging are made from various reactants. For example, they can be prepared by esterifying a dibasic acid with a diol, transesterifying a dicarboxylic acid ester with a diol, Or it can be prepared by the self-condensation of hydroxycarboxylic acid. A To achieve the specific purpose of a certain polyester, it is necessary to strictly control the proportion or composition of the ingredients in the reaction container during the manufacturing process. Minor changes in the starting composition Can greatly affect the most The effectiveness of polyester products3 depends on the use of dibasic esters or dibasic politics. It is also necessary to control the conversion of ester or acid end groups to reactive hydroxyl end groups to ensure that the finished polyester products have reliable characteristics. 》 The low conversion rate in the first-stage reaction will limit the reactivity of the polycondensation reaction process and adversely affect the properties of the final use of the polyester material. Therefore, the conversion rate of the first-stage reaction is known Or the degree of reaction is very important. Other important composition control parameters include the amount of each diacid and glycol portion, the ratio of all glycols to all diacids and / or dibasic esters in the reaction vessel , As well as the degree of aggregation and the size of the paper, apply the Chinese standard (CNS > A4 size (210X297)) Please read the back

I 訂 經濟部中央樣準局負工消費合作社印裝 4482 9 2 A7 B7 經濟部中央標準局貝工消費合作杜印製 五、發明説明（3 ) 子量、或聚合物鏈之大小β 於製造過程，可將少量之樣品取出，於遠處的實驗室中 進行分析試驗，而決定反應容器中之物料的化學组成。可 使用常用的分析方法，以獲知第一階段之反應程度、混合 物中之反應物和產物的莫耳量'以及反應程度。經常用以 求得選定樣品之组成訊息的實驗室方法，包括核磁共振 (NMR)光譜儀、氣相層析術（GC)、和液相層析術（LC)。此 等方法要求將選定之樣品加以溶解，且在某些情況下，必 須進行衍生化。NMR方法能提供可靠之訊息；然而，其所 需之儀器昂貴且複雜，同時在進行測量前，必須正確地製 備得樣品。 有待本發明解決之問題 於化學製造程序中’重覆進行取樣和分析測量，存在有 數項重要的潛在問題。 . 首先’將樣品自熱程序物流中取出，即存在有危險性； 尤其當此物流係黏性，如於生成聚合物之程序中之物流時 3必須將大的絕緣閥打開，A使物料流入小的樣品容器中 。其中聚合物管線中之取樣口，經常會部份阻塞，而使熱 物料出人意料地自開口噴出。 其次，取出樣品之步驟可能會改變樣品之組成β例如， 在一平常之聚酯製造程序中的第—階段反應，通常係在反 應器中存在有過量乙二醇（EG)的情況下進行。eg較寡聚 物料更具揮發性，因此當自程序中取出樣品時，其將優先 自樣品中揮發，以致所得之樣品不具有代表性。此外，由 _____-6- 本紙張尺度適用中國國家標準（CNS ) A4規格（2Ϊ0Χ297公瘦\ '------ ---------装------1T------.fei (請先slti背面之汰意事項再ΐ 本頁) A482 92 A7 B7 經濟部中央標隼局員工消費合作社印裝 五、發明説明（4 於取樣之物料具有黏性，其會黏於取樣閥口上，因此可能 會造成此次之樣品與先前取得之樣品的殘留物彼此混合。 第三’取樣和分析步驟極爲耗時。在將樣品取出、進行 製備、和進行分析所需之時間内，可能即有數千镑之物料 被製造出。因此由樣品獲得之分析數據，對於預先進行程 序控制之價値有限。 最後’由於伴隨取樣之危險性而來的困難和成本問題， 因而通常很少進行分析取樣。而以極少的分析數據點，很 難對程序變化獲得具統計效力的暸解，或對程序進行適當 的控制調整。 較佳的分析方法應能随時監測物料之製造0此一方法應 能減低自製造環境取出樣品之需求、減小安全顧慮、並易 於更頻繁且更快速地進行測量。 然而’仍存在著重大的障礙，而使大多數的分析技術無 法在程序環境中提供原位、線上的化學组成訊息。首先， 此分析方法必須能正確地測得所要的性質，並具有足夠的 精確度3其次，分析儀器必命能承受加工區域之物理環境 ’或必須能由遠處感測所要的组成性質s第三，儀器與程 序間之介面，必須能承受化學程序管線内之嚴苛的壓力和 溫度環境s第四，濁度、氣泡、和其他常見之加工現象不 可阻擾分析測量。所有此等障礙，皆可被本發明之方法所 克服。 發明之概述 本發明提供一種以拉曼光譜術，於原位定量監測化學组 本紙浪尺度適用中囷1家標隼（CNS ) A4規格（210X297公釐） I 裝 II 訂 線 (請先閲11背面之孓意事項再一 本頁}, 4482 92 A7 _______ B7 五、發明説明（5 ) 合物中之一種或多種選定成份之方法，其包括：將參考物 質和包含一種或多種成份之化學組合物，同時以實質上之 單色輻射源進行照射，此輻射自輻射源，經由連接輻射源 和與化學组合物形成界面之光探針的激發導管，而傳輸至 化學组合物上，經由以收集導管與光探針相連接之攝譜儀 ，同時在多個波長處’取得參考物質和化學組合物之捲積 拉曼光譜（convolved Raman spectra);選擇參考物質之標準 拉曼光譜；由麥考物質之捲積拉曼光譜和標準拉曼光错， 決定捲積光譜之捲積函數；應用此捲積函數於調整化學組 合物之捲積拉曼光譜’而產生組合物之標準拉曼光諸：以 及應用預先決定之校準方法，於化學組合物之標準拉曼光 睹上’由此而可確疋在取得捲積拉曼光譜之當時，组合物 中的化學組成。 本發明之優點 本發明之方法較傳統分析方法的顯著改良處，在於可在 較短時間内’獲得更可靠之測量結果，且沒有連續取出樣 品之困難。所得之資訊可用’以訂定反饋或前授控制政策 以改良產品品質、減少廢棄物、改良程序產量、以及減低 伴隨自化學製造程序中抽出樣品而來的危險= 附圖之簡單説明 圖1係聚（對苯二甲酸乙二酯）之中間體的拉曼光譜。 圖2係拉曼光譜系統之示意圖。 圖3係用於決定生成聚合物之組合物中，甲基端基的相 關圖。 -8- 本紙浪尺度適用中國國&標隼（CNS > A4規格（210X297公1〉 ---------^------1T------^ <請先閱承背面之法意事項再..~本頁) 經濟部中央標準局負工消費合作社印製 448^92 經濟部中央標準局員工消費合作社印裝 A7 ----- —_ B7__ 五、發明説明（6 ) 圖4係概述對苯二甲酸二曱酯與乙二醇之反應動力的圖 〇 圖5係比較在聚酯生產線上之拉曼和nmR光譜分析數據 的圖。 發明之詳細説明 市售之有用的化學品諸如聚酯，舉例來説，通常係經由 大規模的連續式方法’在高溫下進行製造β此等製備聚酯 之方法包括酯化反應，諸如二元羧酸之酯化，或將二元羧 酸醋以二元醇化合物進行酯交換。 二元醇化合物包含兩個羥官能基β有許多二元醇可用於 聚醋之製造上’其包括，例如，乙二醇（EG) '二甘醇、二 縮三乙二醇、聚乙二醇、聚4_ 丁二醇、聚丙二醇、聚異 丙二醇、1，4-丁二醇、新戊二醇、和1>4·環己烷二甲醇 (CHDM)。 二元羧酸包含兩個羧酸部份。可用於製造聚酯材料之代 表性的二元羧酸包括：對苯二曱酸（TpA)、間苯二甲酸、答 二羧酸 '莕二羧酸、1,4-環己*烷二羧酸（CHDA)、和各種脂 鏈二元幾酸。 —元幾酸酯包含兩個酯官能基。可使用之二元酯的實例 ’包括任何前述所提之二元酸的酯化衍生物。—種經常用 於製造聚酯材料之重要的二元酯爲對苯二甲酸二甲醋 (DMT)。 聚（對苯二甲酸乙二酯），PET ,係市售之有用聚酯的— 個實例。此聚合物通常係由DMT或TPA和EG，一般係分兩 _ -9- 本紙張尺度適用中國國家標準)·Α4規格（210X297公癸1 一 一 " (請先閱漆背面之.ίί-^w項-S-. ί本育) .装 —訂 線 448292 A7 ------ --B7__ 五、發明説明（7 ) 1¾段方式製得，如說明於0dian,聚合原理（Principles 〇f ^Serizationl，第三版 ’ Wiley，紐約，1991，第 97至 ι〇〇 頁，以及Billmeyer，物科學敎科書（Textb〇〇k 〇f Polymer Science) ’第三版，Wiley ’ 紐約，1934，第 442至 445頁之中的方法。在第一階段中，過量的EG與βΜτ或 TPA反應而生成中間體一對苯二甲酸雙（2_羥乙基）酯（bhet) ，其拉咒光譜不於圖i。此過程一般係在丨5〇_23〇1之溫度 下進行，而依係使用〇1^7或ΤΡΑ之不同，會分別產生甲醇 或水，其則經由蒸餾而持續地被移除.在屬於聚縮合反應 之第二階段中’物料被加熱至270_300»c之溫度。聚合係 透過EG之移除而進行，且通常係使用部份眞空[〇〇133至 0.133仟帕斯卡（〇.1至1毫米汞柱）]而促進其進行。聚合過程 將使分子量和分子大小增加，因而使許多化學和物理性質 發生改變a 經濟部中央標準局負工消費合作社印装 餐-- - ί (請先聞黎背面之：忠意事項再 ~本頁) 聚酿材料之性質，可藉由將不同的二元醇、二元酯、或 一元酸成份’併入聚合物結構中，而加以改質。舉例來說 ，可以CHDM取代EG，用於Pet之第一階段反應中，而生 成性質和用途異於以EG爲基礎之產品的不同聚酯。此外 ’尚可使用各種二元醇、二元酯、二元酸之混合物，或其 組合’而獲得具有獨特性質之其他聚酯材料β例如，可將 二元醇CHDM和EG摻合，使與DMT反應，.而生成二元醇改 質的PET。有許多此種經改質的聚酯，說明於專利文獻中 ，包括美國專利編號4,259,478、3,772,405、和 3,〇33,822。 典型的拉曼光譜術包括輻射源'將輻射源之輻射傳輸至 -10- 本紙張尺度適用中國國家標準（CNS )八#見格（210Χ297公釐） A482 92 A7 B7 經濟部中央標準局負工消費合作社印製 五、發明説明（8 ) 才水TO之構件、收集由樣品散射出之輻射的構件、散射輻射 I能量分離或分散構件'以及偵測輻射之構件。 有許多輻射源可自材料產生拉曼散射，但爲配合分析測 量使用，此等輻射源必須能放出高強度的單色光。就此而 論，雷射係相當適合之輻射源。美國專利第3,556,659號即 説明一種拉曼光譜術，其中將容納於管中之樣品，以雷射 光沿著管軸進行照射。 雷射輻射源有各種不同之種類，其中包括：氣體雷射， 諸如氦-氖、氮、氬離子和氪離子；固態雷射，諸如紅寶 石w射和Nd:YAG(钕：釔-鋁-石榴石）雷射；染料雷射；化學 雷射’·及固態雷射’諸如單型及多型二極體雷射。 其中’由於氣體雷射具有高度的波長穩定性，因此一般 皆認爲其特別適用於分散拉曼光譜術。但不幸地，其通常 價格昂貴、需要經常維修、或者輸出功率低。而从⑽名和 McCreery ?免-杜化學（Anal. ChemJ^ 1990，第 62册，2647· 2651頁，則説明將半導體二極體雷射應用於拉曼光譜術中 ’其可在小巧簡單的裝置中；提供大的功率輸出，但其可 能存在輸出性質天生不穩定的問題a 由於拉曼散射方法係與入射波長之位移有關，因此使用 不同的雷射’可提供不同波長區域之光譜。然而，在彼等 區域之拉曼位移光譜均頗類似，因此經由使用不同之入射 雷射波長，基本上可獲得相同的結構訊息， 螢光係一種由吸收輻射誘發範圍廣大之放射的作用，其 係分子結構之特性。而如可觀察到的話，感應勞光信號通 -11- 本紙張尺度適用中國國家縣(_CNS ) A4^ d〇X297公〜----— (請先閱I背面之士意事項再'·本頁) 裝-I Order Printed by the Central Procurement Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, printed 4482 9 2 A7 B7 Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed by V. Invention Description (3) Sub-quantity, or the size of the polymer chain β In manufacturing In the process, a small amount of samples can be taken out and analyzed in a remote laboratory to determine the chemical composition of the materials in the reaction vessel. Common analytical methods can be used to know the degree of reaction in the first stage, the moles of reactants and products in the mixture, and the degree of reaction. Laboratory methods often used to obtain information on the composition of selected samples include nuclear magnetic resonance (NMR) spectrometers, gas chromatography (GC), and liquid chromatography (LC). These methods require that the selected sample be dissolved and in some cases derivatized. The NMR method can provide reliable information; however, the equipment required is expensive and complicated, and samples must be properly prepared before measurement. PROBLEMS TO BE SOLVED BY THE INVENTION There are several important potential problems in the chemical manufacturing process where repeated sampling and analytical measurements are performed. First, 'take the sample out of the heating process stream, that is, there is danger; especially when the stream is viscous, such as in the process of generating a polymer's stream 3, the large insulation valve must be opened, and A will allow the material to flow in. In a small sample container. Among them, the sampling port in the polymer pipeline is often partially blocked, and the hot material is unexpectedly ejected from the opening. Second, the step of taking out the sample may change the composition β of the sample. For example, the first-stage reaction in a normal polyester manufacturing process is usually performed in the presence of excess ethylene glycol (EG) in the reactor. eg It is more volatile than oligomeric materials, so when a sample is taken from the program, it will preferentially volatilize from the sample, so that the resulting sample is not representative. In addition, by _____- 6- This paper size applies to China National Standard (CNS) A4 specifications (2Ϊ0 × 297 male thin \ '------ --------- installation ----- 1T- -----. fei (please refer to the item on the back of slti first, and then ΐ this page) A482 92 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (4 The sampled materials are sticky, It sticks to the sampling valve port, so it may cause residues of this time sample and previously obtained samples to mix with each other. The third 'sampling and analysis step is extremely time consuming. The sample is taken out, prepared, and analyzed. Thousands of pounds of material may be manufactured within the required time. Therefore, the analysis data obtained from the sample has limited value for the pre-programmed control. Finally, due to the difficulties and costs associated with the danger of sampling, Therefore, analysis sampling is rarely performed. With very few analysis data points, it is difficult to obtain a statistically effective understanding of program changes, or to make appropriate control adjustments to the program. A better analysis method should be able to monitor the manufacture of materials at any time. This method should reduce The need to take samples out of the manufacturing environment, reduce security concerns, and make measurements more frequent and faster. However, there are still significant obstacles that prevent most analytical techniques from providing in-situ, online in the programming environment First, this analysis method must be able to correctly measure the required properties and have sufficient accuracy3 Second, the analytical instrument must be able to withstand the physical environment of the processing area 'or must be capable of being sensed from a distance Third, the composition and the interface between the instrument and the process must be able to withstand the severe pressure and temperature environment in the chemical process pipeline. Fourth, the turbidity, bubbles, and other common processing phenomena must not disturb the analysis and measurement. All these obstacles can be overcome by the method of the present invention. SUMMARY OF THE INVENTION The present invention provides a method for quantitatively monitoring in situ the chemical wave size of chemical papers using Raman spectroscopy. (210X297mm) I installed II ordering line (please read the intentions on the back of 11 and then another page}, 4482 92 A7 _______ B7 V. Description of the invention (5) A method for selecting one or more of the ingredients, comprising: irradiating a reference substance and a chemical composition containing one or more ingredients with a substantially monochromatic radiation source, the radiation from the radiation source, and by connecting the radiation source and The excitation probe of the optical probe that forms an interface with the chemical composition is transmitted to the chemical composition, and through a spectrograph connected to the collection probe and the optical probe, the reference material and chemical combination are obtained at multiple wavelengths at the same time Convolved Raman spectra of matter; select the standard Raman spectrum of the reference substance; the convolution function of the convolution spectrum is determined by the convolutional Raman spectrum of the McCaw substance and the standard Raman optical error; apply this The convolution function adjusts the convolution Raman spectrum of the chemical composition to generate the standard Raman light of the composition: and applies a predetermined calibration method to the standard Raman light of the chemical composition. The chemical composition in the composition was confirmed at the time when the convolutional Raman spectrum was obtained. Advantages of the present invention The method of the present invention is a significant improvement over the traditional analysis method in that a more reliable measurement result can be obtained in a shorter time, and there is no difficulty in continuously taking out samples. The information obtained can be used to establish feedback or pre-control policies to improve product quality, reduce waste, improve process yields, and reduce the risks associated with taking samples from chemical manufacturing processes = a brief description of the drawings. Raman spectrum of poly (ethylene terephthalate) intermediate. Figure 2 is a schematic diagram of a Raman spectroscopy system. Figure 3 is a correlation diagram of the methyl end groups used to determine the polymer-forming composition. -8- The scale of this paper is applicable to China & standard (CNS > A4 specification (210X297 male 1> --------- ^ ------ 1T ------ ^ < Please read the legal and legal matters on the back .. ~ This page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, printed 448 ^ 92 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, printed A7 ----- —_ B7__ 5 Explanation of the invention (6) Figure 4 is a diagram summarizing the reaction kinetics of dimethyl terephthalate and ethylene glycol. Figure 5 is a diagram comparing the Raman and nmR spectral analysis data on a polyester production line. Details of the invention Description of commercially useful chemicals such as polyesters, for example, are usually produced through large-scale continuous processes' produced at elevated temperatures. [Beta] These methods of preparing polyesters include esterification reactions, such as the use of dicarboxylic acids. Esterification, or transesterification of a dicarboxylic acid vinegar with a diol compound. The diol compound contains two hydroxy-functional groups β. There are many diols that can be used in the manufacture of polyesters. This includes, for example, ethylene glycol Alcohol (EG) 'Diethylene glycol, diethylene glycol, polyethylene glycol, poly 4-butanediol, polypropylene glycol, polyisopropyl glycol, 1,4- Diols, neopentyl glycols, and 1> 4. Cyclohexanedimethanol (CHDM). Dicarboxylic acids contain two carboxylic acid moieties. Representative dicarboxylic acids that can be used to make polyester materials include: Terephthalic acid (TpA), isophthalic acid, dicarboxylic acid, hydrazone dicarboxylic acid, 1,4-cyclohexane * anedicarboxylic acid (CHDA), and various lipid dibasic dibasic acids. Several esters contain two ester functional groups. Examples of dibasic esters that can be used include any of the esterified derivatives of the dibasic acids mentioned previously. An important dibasic ester often used in the manufacture of polyester materials is Dimethyl terephthalate (DMT). Poly (ethylene terephthalate), PET, is an example of a commercially useful polyester. This polymer is usually made of DMT or TPA and EG, and is generally Divided into two _ -9- This paper size applies to Chinese national standards) · A4 size (210X297 male december 1 one by one " (please read first. Ί- ^ w item-S-. Ί this education) on the back of the paint). Packing — Order line 448292 A7 ------ --B7__ V. Description of the invention (7) Manufactured in 1¾ steps, as described in 0dian, Principles of Aggregation (Principles 〇f ^ Serizationl, 3rd edition 'Wiley, New York, 1991 Pages 97 to ιο〇, and Billmeyer, Textb 00k Polymer Science 'Third Edition, Wiley' New York, 1934, Methods from pages 442 to 445. In the first In this stage, excess EG reacts with βMτ or TPA to form the intermediate bis (2-hydroxyethyl) phthalate (bhet) terephthalate, whose spectrum is not as shown in Figure i. This process is generally carried out at a temperature of 50 ~ 23〇1, and depending on the use of 〇1 ^ 7 or TPA, methanol or water will be produced, which will be continuously removed by distillation. In the second stage of the polycondensation reaction, the 'material is heated to a temperature of 270-300 »c. Polymerization is carried out by removal of EG, and is usually facilitated using partial emptying [00133 to 0.133 Pascals (0.1 to 1 mm Hg)]. The polymerization process will increase the molecular weight and molecular size, which will cause many chemical and physical properties to change. A. Printed meals by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. (Page) The properties of polymer materials can be modified by incorporating different glycols, dibasic esters, or monoacids into the polymer structure. For example, EG can be replaced by CHDM and used in the first-stage reaction of Pet to produce different polyesters with different properties and uses from EG-based products. In addition, it is possible to use various glycols, mixtures of dibasic esters, dibasic acids, or combinations thereof to obtain other polyester materials with unique properties. For example, the glycols CHDM and EG can be blended to DMT reaction, and generate glycol modified PET. There are many such modified polyesters described in the patent literature, including U.S. Patent Nos. 4,259,478, 3,772,405, and 3,033,822. Typical Raman spectroscopy includes a radiation source to transmit the radiation from the radiation source to -10-. This paper size applies Chinese National Standards (CNS) Eight # See grid (210 × 297 mm) A482 92 A7 B7 Central Standards Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative V. Description of the Invention (8) The components of Caishui TO, the components that collect the radiation scattered by the sample, the scattered radiation I energy separating or dispersing components', and the components that detect radiation. There are many sources of radiation that can produce Raman scattering from materials, but to be used in conjunction with analytical measurements, these sources must be capable of emitting high-intensity, monochromatic light. In this connection, lasers are quite suitable sources of radiation. U.S. Patent No. 3,556,659 describes a Raman spectroscopy in which a sample contained in a tube is irradiated with laser light along the tube axis. There are various types of laser radiation sources, including: gas lasers such as helium-neon, nitrogen, argon ions, and krypton ions; solid-state lasers such as ruby w radiation and Nd: YAG (neodymium: yttrium-aluminum-pomegranate) Stone) lasers; dye lasers; chemical lasers; and solid-state lasers such as single- and multi-type diode lasers. Among them, because gas lasers have a high wavelength stability, they are generally considered to be particularly suitable for dispersive Raman spectroscopy. Unfortunately, it is usually expensive, requires frequent maintenance, or has low output power. From Anonymous and McCreery® Free-Du Chemical (Anal. ChemJ ^ 1990, Vol. 62, 2647 · 2651, it shows that the application of semiconductor diode lasers to Raman spectroscopy can be used in a small and simple device ; Provide large power output, but it may have the problem of inherently unstable output properties a. Because the Raman scattering method is related to the shift of the incident wavelength, the use of different lasers can provide spectra in different wavelength regions. However, in The Raman shift spectra of these regions are quite similar. Therefore, by using different incident laser wavelengths, basically the same structural information can be obtained. Fluorescence is a kind of radiation that induces a wide range of radiation by absorbing radiation. Its molecular structure is And if it can be observed, the induction light signal is -11- This paper size is applicable to China's national counties (_CNS) A4 ^ d〇X297 male ~ ----— (Please read the notes on the back of I first Again '· this page) loaded-

，1T 經濟部中央標隼局員工消費合作社印装 448292 A7 ______B7 五、發明説明（9 ) 常較拉曼信號大數個數量，級，且纟某些情況了，將會完全 遮蔽拉曼位移光譜。因此，須要選擇—個可使營光放射作 用減至最小之入射波長。 一種熟知之降低螢光背景問題的方法，係使用產生紅光 或近紅外光之雷射，其波長約爲660毫微米至11〇〇毫微米 ，如説明於 D.B. Chase，t m ^ (J. Am. Ch,m ^1，1986,第108册，7485_7488頁中者。由於螢光放射 分佈與入射波長無關，而拉曼作用則係關於入射波長之位 移，因此此一方法可行。在此範圍内操作之典型輻射源包 括氪離子氣體雷射、單型二極體雷射、多型二極體雷射、 和Nd:YAG雷射。 在種種可取得之輻射源中，雷射由於其效力高、及單色 光之特性，因而特別佳。在市售之各種類型的雷射中，以 二極體雷射較佳，因其在長期使用壽命中之維修需求最低 3此項優點對序分析儀器之组件而言，係相當必要的a此 外，利用預先連結至光纖電纜之雷射將特別佳s稱爲柔引 二極體雷射（pigtailed diode lasers)之纖維偶合二極體雷射 裝置可於市面上購得。 柔引二極體雷射較其他雷射源’具有數項實際之優點。 首先’其已連結至光纖電纜，因此可省去可能發生未聚焦 ，而造成信號損失之複雜的光學對準機構。此項便利性使 於必要時，能簡單地進行卸除和更換。此外，二接體雷射 之特色爲具有長的使用壽命，因此僅需極少的維修。再者 ’二極體雷射在一小的波長範圍内，係可以溫度進行調整 -12- 本紙崁尺度適用中國國家樣準（CNS ) A4規格（2丨0X297公釐） . ^----^------1T------^ (請先閱汰背面之汰意事項再一 本頁) 4482 92 A7 經濟部中央標準局員工消費合作社印製 B7五、發明説明（10 ) 的，因而其對任何可能發生之微小的波長位移，提供了一 種補償方式。最後，可購得具有高功率之二極體雷射，其 可獲得較大的信號，因此可以縮短測量時間。關於較高功 率之二極體雷射的一個顧慮，爲其係在所謂之11多型”下 操作，其中有許多雷射模式同時進行活動。此等各.別之模 式彼此間並不穩定，而可能使裝置無法精確的進行定量分 析測量。如Carrabba等人，於"供程序和環境監測用之小型 拉曼儀器(Compact Raman Instrumentation for Process and Environmental Monitoring)”，SPIE，1991，1434册，環境感 測 及燃燒診斷(Environmental Sensing and Combustion Diagnostics)，第127-134頁之中所説明者，經由適當的控 制溫度和不必要之放射，可以降低二極體雷射之不穩定性 ，但無法完全將其消除。而爲控制不必要的雷射放射， Carrabba等人描述一種在雷射波長上，具有非常高之光密 度的全像邊緣;慮光器（holographic optical edge filters)。 若未施行諸如彼等所述之控制，則二極體雷射將不穩定 ，因此一般認爲其對拉曼光_研究的用途不大。此外，任 何二極體雷射裝置之波長，將隨裝置之老化，而逐漸發生 位移。二極體雷射裝置，即使有短時間的穩定，但其特徵 爲具有會產生緩慢位移的長期不穩定性，而使儀器之可靠 度降低。 可於市面上購得可在各種入射波長下運作的二極體雷射 。宜利用波長在約700毫微米和900毫微米間之雷射較佳。 在700毫微米以下，某些背景干擾作用，諸如螢光，較於 -13- ----;------^------ΐτ------.^ (請先閔讀」背面之.ΪΪ-意事項再\ .本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 4482 92 經濟部中央標準局負工消費合作社印製 A7 B7 五、發明説明（11 ) 較高波長下時更常發生。然而，超過900毫微米之波長， 則對目前市面上之多路偵測系統的偵測能力有不利影響。 在本發明方法之一個較佳具禮實例中，係使用包括高功 率、柔引、多型二極體雷射之拉曼光譜術裝置，其中該二 極體雷射可放出在約780毫微米和830毫微米間之輻射。然 而’本發明中所述之方法並不受限於此種儀器。 由於彈性散射光子與拉曼散射光子間之大的比例差異， 因此需要一種有效的光子分離方法。傳統上，此項工作已 經由分別係由兩個或三個分散元件構成之雙重或三重攝譜 儀系統完成》而其他的濾光装置則可充份地除去彈性散射 光子，因而可以使用較小、較有效的單一分散元件攝譜儀 裝置；例如，描述於Carrabba等人’應用光譜（Appl. Spec.) ’ 1990’第44册' 1558-1561頁中之全像布拉格繞射濾光器 (holographic Bragg diffraction filters)。 偵檢器元件對拉曼儀器之適當性能係相當重要的，其必 須能夠識別相當低的輻射訊號。傳統之掃描式單色器系統 ，係使用可以測得低光子訊堯之光電倍増管》較新之儀器 則使用陣列偵檢器，諸如光電二極體陣列（pda : photodiode arrays)或電荷偶合裝置（CCD ; charge coupled devices)。陣列偵檢器係由多個可以同時監測一個光譜區 域以至整個拉曼光譜的光學元件所組成^ CCD偵檢器係多 因次，其可同時在多個波長下監測多個拉曼光譜，如於 Vess等人，SPIE，1992，1637册，118-125頁，及於 Angd 等人’ SPIE，1991，1587册，219-231頁之中所敘述者。 14- 本紙朵尺度逋用中菌國家揉準（CMS ) A4規格（210X 297公釐) ---^------ΐ衣------iT------0 (請先閲靖背面之法意事項再(；本頁) 4 4 8 2 9 2 Λ7 Α7 Β7 經濟部中央標準局員工消費合作社印裳 五、發明説明（12 ) 前面提到之Wang和McCreery的論文，述及將電荷偶合裝 置與近紅外光二極體雷射一起用於高靈敏度之拉曼光譜術 中。同時，Newman等人，應用光譜，1992，第46册，262-265頁，則敘述使用CCD和二極體雷射以及設有與樣品間 之光纖界面的平場影像攝譜儀（flat field imaging spectrograph) 3 結合單一分散光柵攝譜儀與CCD偵檢器、單型二極體雷 射、光纖電纜、光纖探針、以及適當電腦的拉曼光譜術器 適用於進行快速分析測量。然而，攝譜儀和偵檢器系統及 其他光學介面的機械穩定性，以及前述之二極體雷射的不 穩定性，則限制了儀器的定量能力。已有建議使用傳立葉 轉換（FT)拉曼光譜術進行定量化學分析。然而，如 Seasholtz等人，應用光譜（Appl. Spec·)，1989，第 43册， 1067-1072頁所説明者，由於儀器之偏差，再現性通常至 多不過一個百分比。 傳統的實驗室拉曼儀器使用一系列之透鏡、鏡子、及其 他光學元件，以及輻射源之4射傳輸並聚焦至樣品上。而 光纖電境之進步，例如，説明於Allred和McCreery，應用 光譜，1990，第 44册，1229-1231 頁，及 Schwab和 McCreery ，分析化學（Anal. Chem.)，1984，第 56册，2199-2204頁之 中者，則提供一種將輻射導向樣品的簡化方法。光纖電纜 之便利、柔軟性、及輸出效率，使搖控感測之前景可期3 雖然光纖電纜之熔融二氧化矽核心，係弱的拉曼散射器 ，但當所使用之纖維長度長時，則可能成爲背景干擾訊號 -15- ---------装------、1Τ------0 <請先閱諫背面之法意事項再 ，Γ本頁) 本紙张尺度適用中國國家標準（CNS ) Α4規格（2丨0 X 297公釐） 4Λ82 9 2 經濟部中央標隼局負工消費合作社印聚 A7 B7 五、發明説明（13 ), 1T Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 448292 A7 ______B7 V. Description of Invention (9) Often several orders of magnitude larger than the Raman signal, and, in some cases, it will completely obscure the Raman shift spectrum . Therefore, it is necessary to select an incident wavelength that can minimize the effect of camper radiation. A well-known method to reduce the problem of fluorescent background is to use lasers that produce red or near-infrared light with a wavelength of about 660 nm to 1100 nm, as described in DB Chase, tm ^ (J. Am Ch, m ^ 1, 1986, Vol. 108, pages 7485-7488. Since the fluorescence emission distribution is independent of the incident wavelength, and the Raman effect is a displacement of the incident wavelength, this method is feasible. Within this range Typical radiation sources for operation include krypton ion gas lasers, single-type diode lasers, multi-type diode lasers, and Nd: YAG lasers. Among the various sources available, lasers are highly effective due to their high efficiency. And monochromatic light characteristics, so it is particularly good. Among the various types of lasers on the market, diode lasers are better, because they have the lowest maintenance requirements in the long-term service life. It is quite necessary for the components of the instrument. In addition, a fiber-coupled diode laser device called a “pigtailed diode lasers” which is particularly good using lasers that are pre-connected to optical fiber cables can be used. Commercially available. Flexible diode laser Compared with other laser sources, it has several practical advantages. First, it is connected to the fiber optic cable, so it can eliminate the complicated optical alignment mechanism that may cause unfocusing and cause signal loss. This convenience is necessary Can be easily removed and replaced. In addition, the diode laser is characterized by a long service life, so only minimal maintenance is required. Furthermore, 'diode lasers are within a small wavelength range, The temperature can be adjusted. -12- The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm). ^ ---- ^ ------ 1T ------ ^ ( (Please refer to the remarks on the back of the page, please refer to the next page) 4482 92 A7 The B7 printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China (5) Invention Description (10). Therefore, it provides A compensation method is finally available. Finally, a diode laser with a high power can be purchased, which can obtain a larger signal, so that the measurement time can be shortened. One concern about higher power diode lasers is that Operating under the so-called 11 polytypes, of which Many laser modes are active at the same time. These other modes are not stable with each other, which may prevent the device from accurately performing quantitative analysis and measurement. For example, Carrabba et al., "Small pull for program and environmental monitoring "Compact Raman Instrumentation for Process and Environmental Monitoring", SPIE, 1991, volume 1434, Environmental Sensing and Combustion Diagnostics, pages 127-134, with appropriate controls Temperature and unnecessary radiation can reduce the instability of diode lasers, but they cannot be completely eliminated. To control unnecessary laser radiation, Carrabba et al. Describe a holographic optical edge with very high light density at the laser wavelength; holographic optical edge filters. If controls such as those described above are not implemented, the diode laser will be unstable, so it is generally considered to be of little use for Raman light research. In addition, the wavelength of any diode laser device will gradually shift as the device ages. Diode laser devices, even if they are stable for a short period of time, are characterized by long-term instability that can produce slow displacements, reducing the reliability of the instrument. Diode lasers are commercially available that can operate at various incident wavelengths. A laser with a wavelength between about 700 nm and 900 nm should preferably be used. Below 700 nm, some background interference effects, such as fluorescence, are better than -13- ----; ------ ^ ------ ΐτ ------. ^ (Please "Min Xian Du" on the back of the page. 意-Italian matters, then \. This page) This paper size applies to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) 4482 92 Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 B7 5. Description of the invention (11) Occurs more often at higher wavelengths. However, wavelengths exceeding 900 nanometers have a negative impact on the detection capabilities of multi-channel detection systems currently on the market. In a preferred courtesy example of the method of the present invention, a Raman spectroscopy device including a high-power, flexible, multi-type diode laser is used, wherein the diode laser can emit at about 780 nm And radiation between 830 nm. However, the method described in the present invention is not limited to such an apparatus. Due to the large ratio difference between elastically scattered photons and Raman scattered photons, an effective photon separation method is needed. Traditionally, this work has been done by a dual or triple spectrograph system consisting of two or three dispersive elements, respectively, while other filters can adequately remove elastic scattered photons, so smaller ones can be used. A more effective single-dispersion spectrograph device; for example, the Carragb et al. 'Appl. Spec.' 1990 1990 Vol. 44 1558-1561 Holographic Bragg Diffraction Filter ( holographic Bragg diffraction filters). Detector components are important to the proper performance of Raman instruments, and they must be able to identify relatively low radiation signals. Traditional scanning monochromator systems use low-photon photomultipliers. Newer instruments use array detectors, such as photodiode arrays (pda: photodiode arrays) or charge coupling devices ( CCD; charge coupled devices). Array detectors are composed of multiple optical elements that can simultaneously monitor a spectral region or the entire Raman spectrum ^ CCD detectors are multi-dimensional, which can monitor multiple Raman spectra at multiple wavelengths at the same time, such as In Vess et al., SPIE, 1992, vol. 1637, pages 118-125, and in Angd et al. 'SPIE, 1991, vol. 1587, pages 219-231. 14- This paper is in the standard size (CMS) A4 size (210X 297 mm) --- ^ ------ ΐ 衣 ------ iT ------ 0 ( Please read the legal and legal matters on the back of Jing before (; this page) 4 4 8 2 9 2 Λ7 Α7 Β7 Yin Chang, a staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) Wang and McCreery's paper mentioned earlier , Describes the use of a charge coupling device with near-infrared diode lasers for high-sensitivity Raman spectroscopy. At the same time, Newman et al., Applied Spectroscopy, 1992, Volume 46, pages 262-265, describes the use of CCD And diode lasers and a flat field imaging spectrograph with an optical fiber interface to the sample 3 Combines a single dispersion grating spectrograph with a CCD detector, a single-type diode laser, and an optical fiber Cables, fiber optic probes, and appropriate computerized Raman spectrometers are suitable for fast analytical measurements. However, the mechanical stability of spectrograph and detector systems and other optical interfaces, as well as the aforementioned diode laser Instability limits the quantitative capabilities of the instrument. The use of a Fourier transform has been suggested (FT) Raman spectroscopy for quantitative chemical analysis. However, as described by Seasholtz et al., Appl. Spec., 1989, Vol. 43, pp. 1067-1072, reproducibility is usually at most due to instrumental variation. But a percentage. Traditional laboratory Raman instruments use a series of lenses, mirrors, and other optical components, as well as the radiation of a radiation source to transmit and focus on the sample. The advancement of fiber optics, for example, is illustrated by Allred and McCreery, Applied Spectroscopy, 1990, Vol. 44, pp. 1229-1231, and Schwab and McCreery, Anal. Chem., 1984, Vol. 56, pp. 2199-2204, provide a way to direct radiation Sample simplification method. The convenience, flexibility, and output efficiency of fiber optic cables make remote sensing possible. Although the fused silica core of fiber optic cables is a weak Raman diffuser, When the fiber length is long, it may become the background interference signal -15- --------- install --------, 1T ------ 0 < Please read the legal notice on the back Furthermore, this page) This paper is applicable to China Standard (CNS) Α4 specification (2 丨 0 X 297 mm) 4Λ82 9 2 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13)

之因素，如於美國專利第5，112，127、Vess等人，SPIE， 1992 ’ 1637册 ’ 118-125 頁 ' Schoen等人，應用光皋 fAppl 1992’ 第 36册，7707-7715 頁 '及 Schoen等人，SPIE ，199：»，1857册，116-12S頁之中所論及者。用以克服此項 因難之基本技術’係使用位在靠近樣品處的濾光器。此等 濾光器可在干擾產生前，將造成背景之輻射移除s 光纖探針通常係與光學纖維同時使用，以提供—種將輕 射傳輸向樣品’並收集散射輻射之構件，例如，説明於美 國專利第4,573,761號之中者a此種探針可由光學纖維、透 鏡、及/或筑子之组合構成3在其中一種構造中，將兩根 以上之光學纖維一起緊密地固定於樣品端。此等光學纖維 之一或多根係用於將輻射傳輸至樣品，而其他之—或多根 光學纖維則用於收集散射輻射，並將其傳輸至偵檢器β 散射輻射經收集和傳輸後，使用分散元件將其分離3分 散元件通常與聚焦和照準光學元件一起包括於攝错儀中， 其有助於散射輻射之各種能階的彼此分離。經常使用兩個 以上之分散元件’以更元全‘除去雜散光，並提高鑑別度 。然而’使用具有適當濾光較小、較有效率、單—光拇的 攝譜儀則具有相當多之優點’如説明於前述之八^^和 McCreery及Wang和McCreery之論文中，以及於Carrabba等 人’ SPIE ’ 1991，1434册，127-134頁之中者。因此所達到 之大的訊龍輸出增加’則供一種相當靈敏且再現性佳的 測量方法。 已有數篇參考文獻論及將拉曼光譜術作爲線上分析方法 -16- 本纸張尺度適用中圉國家標準（CNS ) A4^格（2丨0\297公澄^' ---- ---；---；----^------1T------^ (請先閲沐背面之；王意事項再--^7本頁) 經濟部中央標準局員工消費合作社印繁 482 92 A7 B7 五、發明説明（14 ) 之基礎 ° 例如，Garrison’ SPIE’ 1992’ 1681 册，291-293 頁，敘述應用FT-拉曼系統於監測蒸餾塔中之组合物，其 中將少量物流自蒸餾塔盤移入控溫樣品室中》再將拉曼探 針***此環境中以收集數據；此方法之相對精確度約爲2 個百分比。前述之Seasholtz等人的論文説明以具有限定量 能力之FT-拉曼實驗室方法發展出石油燃料產品之校準線 。James，PCT國際申請案W0 87/06011及Nguyen等人，法 國專利第2,571,144號則説明由遠處進行原位、線上測量化 學品或化學成份之組合之分析性質的拉曼輻射監測裝置和 方法：但其並未指出由所述方法可以達到的精確度。 本發明之方法特別適用於原位監測聚酯製造程序。早已 有用拉曼光譜術進行聚酯之分析的實例；例如，參見 Bulkin等人，巨大分子（Macromolecules) ’ 1987，第 20册， 830-835 頁；Bower等人，聚合物（Polymer)，1982，第 23册 ’ 645-649頁；Adar等人，聚合物，1985，第 26册，1935-1943頁；及DeBlase等人，聚合物科學期刊（J, p〇lym, Sci.) ’ 1985，第23册’ 109-115頁。大致上，最終產物聚酯材 料係經由線外實驗室分析進行研究，以測定其構像、取向 、及結晶度性質9已觀察到與程序差異一致之在聚合材料 振動光譜中的重大變化。構像、取向、及結晶度皆會影響 最終之產品性質，及對特定用途之有效性。 PET單體樣品之典型拉曼光譜示於圖1 β此光譜之特徵在 於各種指示分予中之特定振動運動的波峰。例如在約1610 公分―1處之波峰，係與對苯二甲酸環系統之對稱膨脹/鬆弛 ______-17, 本紙味尺度適用中國國家標隼（CN’S ) Α4規格（210X297公釐） ' ---------装------1T------線 (請先鬩諫背面之法意事項再^本頁) 448292 A7 B7 經濟部中央標隼局員工消費合作社印製 五、發明説明（15 ) 有關聯。此振動運動一般稱爲"環呼吸模式（ring modeH參見Grasselli和Bulkin，編者，”分析拉曼光譜術 (Analytical Raman Spectrometry)» -也學分析 fChemkal Analysis)，第 14册，1991，Wiley，紐約，223 至 252 頁）。 於拉曼光譜中測得之分子的振動運動，係分子本性及組 成物之特性》由於拉曼光譜術所可取得之結構訊息的豐富 性，使其成爲在聚酯之生成過程中，明瞭其组成之高度必 要的技術。但尚不瞭解如何以線上之例行方法完成此一工 作。然而在聚酯之製造過程中，持續監測形成聚合物之組 合物的目標，則已在本發明中達成。因此，任何聚酯於其 合成過程之組成性質，皆可根據本發明之方法進行監測， 其中該聚酷之起始物料可包括二元酸和二元醇、二元酯和 二元醇、羥基羧酸、羥基羧酸酯、或其组合。 在拉曼光譜測定中，觀測到之訊號將係期望訊號與儀器 響應之捲積（convolution)。大致上，儀器響應將會加寬、 改變、或者扭曲期望訊號a而本發明之方法則得以測量並 補仏拉趸光術裝置之組件岛長期和短期變化以及不穩定 性。此項工作係經由參照敘述於美國專利第5;455,673號中 之技術而達成’其係同時取得反應物流中之化學樣品和參 考物質之捲積光譜’其中所有光譜皆承受相同之不穩定性 ϋ 雖然捲積過程在觀測光譜中係爲非線性，但可將其表現 成時域中之乘法。而一般係使用FT技巧於完成與時域之 間的轉換。在時域中，解捲積（deconv〇iuti〇n)方法係直接 18- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---_---^----^.------ΐτ------^ (诗先聞请背面之：^意事磅再.r本頁) 經濟部中央標準局員工消費合作社印裝 4482 92 A7 B7 五、發明説明（16) 的除法’其係使用觀測訊號之複數（其係由實部和虛部所 組成），除以儀器之響應函數而求得。 偵檢器持續不斷地監測取樣化學組合物和適當參考物質 之光譜a參考物質之捲積光譜-此處亦稱爲捲積參考光譜_ 係由已知光譜特性之光譜片段，與所有在輻射源中之隨機 不穩疋性’及/或儀器中之機械不穩定性捲積而成。捲積 參考光譜係由裝置以如取樣化學组合物之捲積光譜·此處 亦稱爲捲積樣品光譜-的相同方式進行捲積。 適當之數學常式亦有助於本發明之實行。收集得之光譜 以標準化方法經數學處理，以補償除隨機偵檢器雜訊變異 外的所有變異》在此方法中，有以下之重要的光譜訊息； 捲積樣品光譜、捲積參考光譜' 標準參考光譜、標準樣品 光譜、以及捲積函數。 捲積樣品光譜-s'(?〇-係未知樣品物質之拉曼光譜的數位 表示法’其係得自攝譜儀偵檢器。此光譜受到來自儀器（ 雷射及/或機械）不穩定性和樣品中之結構改變之變異的影 響。 . 如前所述，捲積參考光譜-R，(x)_包含形狀特性己知之光 譜片段與所有儀器不穩定性的捲積β此光譜片段必須與如 捲積樣品光譜相同之捲積函數進行捲積a 可以補償來自輕射源之變異及/或儀器之機械不穩定性 的捲積函數-C(x)-包含將標準光譜轉換成捲積光譜所需之 訊息，反之亦然3 標準參考光譜-R(X)-應係爲捲積參考光譜之基礎形狀眞 ~ 19 - 本紙法尺度適用中國國冬標準（CNS }八4既格（2ΐ〇χ297公楚） ---^---^----裝------訂------線 (诗先聞沐背面之：出意事項再.r本頁) 經濟部卡央標準局貝工消費合作社印製 4482 92 A7 __ B7 — - 五、發明説明（17 ) 實表現的選定光譜。標準參考光譜可爲捲積參考光譜之不 變部份的理論數學表示法；其亦可爲已經調整或平滑化之 參考物質之先前取得的捲積光譜3其宜爲將多個先前重覆 取得之參考物質之捲積光譜平均而得之光譜較佳。須要將 收集得之光譜對橫座標作”線性化"；其可經由各種内插方 法完成，諸如彼等說明於W H. Press等人，數値祕訣：科皋 !十-事_^^~^___(Numerical Recipes: The Art of Scientific Computing) ’ 1986’劍橋大學出版部，第77_S9頁之中的方 法。説明於第86_89頁之三次樣條函數（cubic SpHne)内插法 特別適用於此目的。用以作爲標準參考光譜之光譜，不必 取自用於取得樣品和參考物質之捲積光譜的相同儀器。 於獲得光譜R’(x)和S，(x)後，宜使用FT法將其轉換至時域 較佳’該FT法係，例如，説明於數値秘訣：科學計算之藝 复’第381-383頁及4〇7_412頁之中者》同時並將r⑻轉換 至時域，及以R(x)之FT除R，⑻之FT而求得c(x)。由於R(x) 和R'(x)之FT的矩陣包含複數，故此除法必需正確地説明其 實部和虛部。 ’ 計算得之捲積函數-C (X)-包含譯解在光譜收集過程，儀 器發生之變異和不穩定性的必要訊息，然後將SI(X)之FT( 同樣地兩矩陣背包含複數）以c(x)除，而得到s(x)之FT。經 由汁算此結果之逆FT，即得正確代表樣品组合物的標準 樣品光譜-S(x)。 若須要，可將S(x)進行，例如，使曲線平滑化或求得光 譜導數的處理步驟。此等步驟當光譜係用作可重覆選用之 -20* ϋ尺度適用中國國家標準（CN'S ) A4現格（210X297公H -- ^---^----^------1T------.^ (请先閲填背面之ΐ£·意事項再 Γ本頁) 經濟部中央標準局員Η消費合作杜印裝 4482 92 Λ7 Α7 — Β7 五、發明説明（18 ) 定量组成訊息時可能有用。曲線平滑方法敘述於A Savitsky和 M.J.E. Golay，分析化學（Anal. Chem.)，1964， 第 36册，1627-1639頁。 於本發明方法中求得之標準樣品光譜-S(x)-係於除去所 有除了随機偵檢器雜訊以外之隨機儀器變異後，所得之取 樣化學組合物的光譜。此光譜將根據化學組合物而異，因 此使樣品可進行精確的定量分析。 概述於圖2之典型的拉曼光譜系統包括輻射源丨、光學導 波管2、分光器1〇、將輻射傳達至遠處之樣品位置的構件 ’包括激發導管2Α及2Β及2C及2D、濾光器3Α及3Β、光探 針4及13 '濾光器5八及5Β、收集導管6Α及6Β、攝譜儀界面 7、及包含光學分散元件的攝譜儀8、陣列偵檢器16、以及 *又有適當之數學常式的電腦19。此系統可以同時取得樣品 17和參考物質18之捲積光譜。此系統係由説明於下之各種 組件所構成。 在較佳具體實例中，其中輻射可來回傳輸至樣品和參考 物質間的導管2Α、2Β、2C、’2D、6Α、6Β、6C、及 6D，包 含光纖電纜。可使用各種其他之光的傳輸引導元件以補足 此項目的’其包括光學元件諸如鏡子、透鏡、或中空燈管 的組合。而以包含熔融二氧化矽核心 '摻雜熔融二氧化矽 外覆層、和聚醯胺緩衝層的光學纖維較佳，由於其在較佳 二極體雷射的波長範圍内，可提供最簡單且最有效之傳輸 輻射的構件。 如先前論及者，長距離使用光學纖維有相關 _______ ~21 - 本紙乐尺度適用中ί國家標嗥（CNS )戌4規播（21〇父297公逢） ---；----------裝------1Τ------^ (請先閱I背面之企意事項再；'/本頁) A7 B7 4482 92 五、發明説明（19 装φ切敍^疋許多万法’足以使長纖維可應用於遠處。 圭之方法應係構造簡[且具有簡單之構件，經由 件可將其在儀器内***和更換。 在較佳具體實例中’上述導管更包括濾光器3A、3B、 5A和）B，其各可位在兩個小的照準透鏡之間。此等經 最適化以致有最大輸出的遽光器裝置，係連接至相關的激 發和收集光纖_。此_光器裝置’由^其小而精巧、 強勒、且容易拆卸和更換，因此較佳。亦可考慮使用其他 敘述於又獻中，及/或市售之濾光構件，以移除不必要之 =射輻射。根據本發明，A射輻射在進人#品和參考物質 W會先通過通帶濾光器（band-pass filters) 3 A和3B ;以及 於收集之後，通過斥拒濾光器5八和5B。 作爲與程序物流之樣品物質17，及與參考物質18間之界 面的光探針4和13，必需具有可使本發明之方法圓滿操作 的正崔特性。在此程序界面’探針將入射輻射傳輸至樣品 ，同時自樣品收集得散射輻射。此界面在加工線之操作條 件下必須穩定’·界面上之小$變化即可造成輸出效率的極 大損耗。化學程序條件通常均相當嚴苛；例如，典型的聚 酯加工線係在150和3〇(rc間之溫度，和及於2〇 685仟帕斯 卡（3000磅/平方吋）之壓力下操作β此種嚴苛之條件，對可 用於構成界面之材料的類型造成限制。 在本發明之較佳具體實例中，所使用之光纖探針係經由 將塗佈金屬之熔融二氧化矽光纖電纜焊入保護性金屬護套 中所構成，此探針説明於Buchanan等人，1995年5月25日 -22 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐 :——.----1------、玎------^ (請先閲讀背面之ii意事項再4 •本頁} 經濟部中央標準局員工消費合作社印製 經濟部中央標準局負工消費合作社印裝 4482 92 A7 B7 五、發明説明（20 ) 提出申請之共同申請中的美國申請案编號08/450,597，標 題爲"強靭的光譜光探針（ROBUST SPECTROSCOPIC OPTICAL· PROBE)”之中β此探針係直接***程序線中，且 先前所述之選擇性的濾光器装置係連接在探頭尖稍的另一 端=此種探頭設計，提供一種在製造程序之嚴苛的物理環 境中，將化學組合物進行光學取樣之簡單但可靠的方法。 此種設計另具有在發生損壞時，可簡單地將探針卸下並進 行更換，五可免除在例行使用過程，需要進行光學對準的 好處。 -光分散元件係用以分離不同能階之散射輕射。大致上攝 譜儀S必需具有適當的解像力，以將幅射能階分離至所須 要之程度。同時，其應能有效地減小輻射損耗。 市售之有用的攝譜儀係由劃線光柵作爲分散元件而構成 。依攝譜儀箱之大小和光柵之線條間間隔的不同，儀器將 具有不同的解像力。其他市售之攝譜儀則使用輸出特性提 高之特殊設計的全像分散元件。本發明之一種較佳具體實 例利用單一光柵之攝譜儀，灰具有分散輻射之固定光栅， 以致在800毫微米至1000毫微米範圍内之波長係入射在偵、 檢範圍内+。可由不同廠商購得此種類型之高品質儀器。 陣列偵檢器16對儀器之有效運作係相當重要的。爲於程 序物流中存在有氣泡和粒子時，仍能獲得有用的光譜，則 偵檢器必需具有許多緊密間隔的波道，以同時進行收集。 兩種現有之經常供此目的使用的偵檢系統爲電荷偶合裝置 (CCD)和光電二極體陣列（PDA)。其中以CCD較佳，因爲此 ______ 23 - 本纸張从適用令國國家^T^TT^7^ox 297^·)---~~-— - 1 III I ~ ; 訂! I 線 (請先閲緣背面之洫意事項再；..本頁} 4482 92 A? B7 經漭部中央標準局wa;工消費合作杜印策 五、發明説明（21 ) 等偵檢益具有相當低之夤景雜訊値，相當靈敏，且可作爲 二度空間陣列，而可使多個光譜顯像在單—的债檢器上。 此種多工能力有助於降低儀器成本，並能提供可利用雙重 光束標準化方法的構件’如說明於美國專利第5,455,673號 之中者。此標準化方法可提高精確度’並有助於降低取樣 成本。 市售有各種形狀和大小之CCD偵檢降列〇常見之陣列爲 512 X 512像元（pixels)及3 86 X 576像元。亦可購得其他較大 之陣列形式’諸如256 X 1024或1024 X 1024像元。此種偵 檢器必需冷卻至室溫以下’以使產生干擾之背景雜訊値減 至最小3其可藉由以液態氮、水或空氣進行冷卻而達成。 某些CCD裝置利用一種稱爲多銷調整（MPP ; multi-pin phasing)之技術’其可降低背景訊號値和雜訊，以在由空 氣冷卻而降溫之溫度下，達到期望的性能。 在本發明之較佳具體實例中，須要減小雜訊，放大訊號 ’以及減小儀器所需之維修量s因此，須要經適當空氣冷 卻之MPP的CCD偵檢器。其+以512 X 512像元之陣列較佳 ’因其具有適當的光譜解像度/通達範圍，並可同時偵檢 多個波道。 光講系統之攝>f儀' 偵檢器 '和雷射组件，一般並未設 計成可以承受製造區域之環境效應。因此，宜將此等裝置 ’放置在遠離於程序取樣點之安全的控制環境下較佳。光 學纖維則延伸於控制環境和程序點之間，並連接至光探針 ’此探針則***程序線中。 -24- 本紐尺度適财ig家縣（CNS )如祕 QX297/># ) ----^-------装------、玎------,^ (請先閱讀背面之法意事項再「本頁) 448 2 9 2 A7 B7 五、發明説明（22 ) 收集於所述之拉曼光譜***上之光譜，係指示流動於製 造程序中之物’的化學組成。此方法之精確度和正確性， 可經由使用儀器之較佳具體實例而予以提升，雖然其他組 件之組合亦有效3 必需瞭解並控制數種會造成最終分析結果之干擾或不精 確的現象，以獲得最大可能的正確性和精確度。此等現象 包括：”宇宙射線"事件；程序中之氣泡、粒子、和濁度： 校準點取樣；實驗室取樣誤差；及儀器组件之振動、運動 、和移動。 ”宇宙射線”事件-通常稱爲尖光（spikes)-係以隨機方式發 生於CCD偵檢器上。據信其係由來自外太空之高能粒子與 CCD偵檢器元件碰撞’產生大的污染性光譜尖光所造成。 由此等事件而來之尖光一般均非常狹窄，典型情況爲寬1 至5像元。宇宙射線事件極少發生，且無法加以預測，雖 然有些證據顯示此事件之頻率與太陽閃光之活動力和每曰 的時刻有關。 經濟部中央標牟局員工消费合作社印掣 ； 私衣— (請先閏I背面之：/i*意事項再..、本頁) 線 宇宙射線尖光係相當令人_擾之問題，因其會在光譜内 加入一個與程序物質無關之大訊號。幸而有數種簡單的數 學常式’可用以校正或消去此光譜資料。此種常式之一説 明於Takeuchi.等人，應用光譜，1993，第47册，129-131頁 〇 氣泡、粒予、和濁度可因使部份之取樣區域發生混亂， 產生與樣品體積之變化相關的光譜強度變化，而影響測得 之光譜。透過多路偵檢系統之使用，可於同時觀測散射輻 -25- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐〉 4 4 8 2 9 2 經濟部中央標準局貝工消費合作社印策 A7 ____B7 五、發明説明（23 ) 射之所有能階。氣泡 '粒子、和濁度係以類似於乘上一亂 數之方式’作用在光譜響應上’其可利用校正而使光譜正 規化。一般應用於標準樣品光譜之正規化步驟，可校正由 入射輻射之取樣造成之物質的體積差異。 最簡單之正規化方式，係利用可指示取樣物質之量的内 部標準品。對PET類型之聚酯材料，將位在約161〇公分-1 處之環呼吸模式之面積正規化的方式，係方便且有效的。 此振動模式與取樣之對苯二甲酸環的數目直接相關，而使 其可被用於校正樣品體積之變化。此方法雖因其簡單性而 較佳’但其並非進行正規化的唯一方式，其他可將光譜正 規化的數學方法亦可以使用。 觀測得之拉曼光譜係與取樣物質中之組合物相關之振動 能帶的組合。然而，各別之振動運動的散射效率係與此振 動運動之極化度有關。因此’單純地分析振動能帶，並無 法直接獲得期望的组成訊息。由於無法直接獲得樣品组合 物之測量結果’因此必須建立使測得之光譜·特性與期望分 析訊息間產生關聯的权準方4。爲建立校準方法，將時間 上與各別取得之光譜一致的樣品自化學程序中移出，並進 行分析測量’以獲得其化學組成訊息，由於取得之光譜係 與儀器之不穩定性捲積，因此宜將其在建立校準方法前， 轉換成標準光譜較佳。此項工作可經由決定並應用發表於 美國專利第5,455,673號t之捲積函數而完成。對此方法， 靖石係較佳之參考物質。 經由比較多數個已知組成之化學组合物，其拉曼光譜的 -26- 本紙張尺度適用中國國家標準（CNs ) a4規格（210x29?公釐） (请先閲ti-背面之注意事項再. ί本I ) -裝·Factors, such as in U.S. Patent Nos. 5,112,127, Vess et al., SPIE, 1992 'Vol. 1637', pp. 118-125, 'Schoen et al., Applicants fAppl 1992' Vol. 36, pp. 7707-7715 'and Schoen et al., SPIE, 199: », volume 1857, pages 116-12S. The basic technique to overcome this difficulty is to use a filter located near the sample. These filters remove background radiation before interference occurs. Fiber optic probes are often used with optical fibers to provide a means of transmitting light to the sample and collecting scattered radiation. For example, This type of probe is described in US Patent No. 4,573,761 a. Such a probe may be composed of a combination of optical fibers, lenses, and / or bricks. 3 In one of the configurations, two or more optical fibers are tightly fixed to the sample end together. One or more of these optical fibers are used to transmit radiation to the sample, while the other—or multiple optical fibers—are used to collect scattered radiation and transmit it to the detector. Β The scattered radiation is collected and transmitted They are separated using a dispersing element. 3 Dispersing elements are usually included in the error detector together with focusing and collimating optics, which help separate the various energy levels of the scattered radiation from each other. Frequently, two or more dispersing elements are used to more completely remove stray light and improve discrimination. However, 'the use of a spectrometer with a smaller, more efficient, single-thumb spectrophotometer with appropriate filtering has considerable advantages' as explained in the aforementioned papers by McCreery and Wang and McCreery, and in Carrabba Et al. 'SPIE' 1991, volume 1434, pages 127-134. Therefore, the large increase in the output of the dragon's signal achieved is provided for a rather sensitive and reproducible measurement method. Several references have been made on the use of Raman spectroscopy as an online analysis method. -16- This paper is scaled to the China National Standard (CNS) A4 ^ grid (2 丨 0 \ 297 Gongcheng ^ '------ -; ---; ---- ^ ------ 1T ------ ^ (Please read the back of Mu; Wang Yi matters first-^ 7 page) Staff of Central Bureau of Standards, Ministry of Economic Affairs Consumer cooperatives Yinfan 482 92 A7 B7 V. The basis of the invention description (14) ° For example, Garrison 'SPIE' 1992 'Vol. 1681, pages 291-293, describes the composition of the FT-Raman system for monitoring distillation columns, Among them, a small amount of stream is moved from the distillation tray into the temperature-controlled sample chamber. Then the Raman probe is inserted into this environment to collect data; the relative accuracy of this method is about 2%. The aforementioned paper by Seasholtz et al. The FT-Raman laboratory method with a limited amount of capacity has developed calibration lines for petroleum fuel products. James, PCT International Application WO 87/06011 and Nguyen et al., French Patent No. 2,571,144 shows that in situ, An analytical Raman radiation monitoring device and method for online measurement of chemicals or combinations of chemical components: but The accuracy achievable by the method is not indicated. The method of the present invention is particularly suitable for monitoring polyester manufacturing procedures in situ. Examples of polyester analysis by Raman spectroscopy have long been available; see, for example, Bulkin et al., Huge molecules (Macromolecules) '1987, Vol. 20, 830-835; Bower et al., Polymer, 1982, Vol. 23' 645-649; Adar et al., Polymers, 1985, Vol. 26, 1935 -1943 pages; and DeBlase et al., Journal of Polymer Science (J, polim, Sci.) '1985, Volume 23' 109-115. Roughly, the final product polyester material was analyzed by an off-line laboratory Conduct research to determine its conformation, orientation, and crystallinity properties9 Significant changes in the vibrational spectrum of polymeric materials have been observed consistent with program differences. Conformation, orientation, and crystallinity all affect the final product properties, And its effectiveness for specific applications. A typical Raman spectrum of a PET monomer sample is shown in Figure 1. β This spectrum is characterized by various peaks indicating specific vibrational movements in the distribution. For example, a peak at about 1610 cm-1, system Symmetrical expansion / relaxation of terephthalic acid ring system ______- 17, the paper flavor standard applies to China National Standard (CN'S) Α4 specification (210X297 mm) '--------- installation ----- -1T ------ line (please refer to the legal matters on the back before ^ this page) 448292 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The invention description (15) is related. This vibrational motion is commonly referred to as "ring mode" (see Grasselli and Bulkin, editor, "Analytical Raman Spectrometry"-also fChemkal Analysis), Book 14, 1991, Wiley, New York (Pp. 223 to 252). The vibrational motion of molecules measured in Raman spectroscopy is the nature of the molecules and the properties of the composition. "Due to the richness of the structural information available in Raman spectroscopy, it has become a polyester In the process of production, the highly necessary technology of its composition is known. However, it is not yet known how to accomplish this work through the online routine method. However, during the polyester manufacturing process, the target of the polymer-forming composition is continuously monitored. It has been achieved in the present invention. Therefore, the composition and properties of any polyester in its synthesis process can be monitored according to the method of the present invention, wherein the starting material of the polycool may include a dibasic acid and a diol, Esters and glycols, hydroxycarboxylic acids, hydroxycarboxylic acid esters, or combinations thereof. In Raman spectroscopy, the signal observed will be the volume of expected signal and instrument response. Convolution. In general, the instrument response will widen, change, or distort the desired signala, and the method of the present invention can measure and compensate for the long-term and short-term variations and instabilities of the component islands of the photoluminescence device. This work was achieved by referring to the technique described in U.S. Patent No. 5; 455,673, 'It is to obtain the convolutional spectrum of the chemical sample and the reference substance in the reaction stream at the same time'. All the spectrums are subject to the same instability. Although the convolution process is nonlinear in the observed spectrum, it can be expressed as a multiplication in the time domain. Generally, the FT technique is used to complete the conversion to the time domain. In the time domain, deconvolution ( deconv〇iuti〇n) method is directly 18- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ---_--- ^ ---- ^ .------ ΐτ- ----- ^ (please read the back of the poem first: ^ It's a pound. This page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4482 92 A7 B7 V. Division of Invention Note (16) 'It's the system Use the complex number of the observation signal (which consists of real and imaginary parts), divide The response function of the instrument is obtained. The detector continuously monitors the spectrum of the sampled chemical composition and the appropriate reference substance.a The convolution spectrum of the reference substance-also referred to herein as the convolution reference spectrum. Spectral fragments are convolved with all random instabilities in the radiation source 'and / or mechanical instability in the instrument. A convolution reference spectrum is a convolution spectrum from a device such as a sampled chemical composition. Convolution is performed in the same manner, which is also referred to as convolution of the sample spectrum. Appropriate mathematical formulas are also helpful in the practice of the present invention. The collected spectra are mathematically processed by a standardized method to compensate for all variations except random detector noise variations. In this method, there are the following important spectral information: Convolution sample spectrum, convolution reference spectrum 'standard Reference spectra, standard sample spectra, and convolution functions. Convolutional sample spectrum -s '(? 〇- is a digital representation of the Raman spectrum of an unknown sample substance' which is derived from a spectrograph detector. This spectrum is subject to instability from the instrument (laser and / or mechanical) And the variation of the structural changes in the sample. As mentioned earlier, the convolution reference spectrum -R, (x) _ contains the spectral segment with known shape characteristics and the convolution of all instrument instability β This spectral segment must The convolution function a, which is the same as the spectrum of the convolution sample, can compensate for the variation from light sources and / or the mechanical instability of the instrument. The convolution function -C (x)-contains the conversion of the standard spectrum into a convolution. The information required for the spectrum, and vice versa 3 The standard reference spectrum -R (X)-should be the basic shape of the convolution reference spectrum-~ 19-The paper method scale is applicable to the Chinese National Winter Standard (CNS) 8 4 both grid (2ΐ) 〇χ297 公 楚) --- ^ --- ^ ---- install -------- order ------ line (on the back of the poem first heard Mu: unexpected matters, then this page.) Economy Printed by the Kayang Standards Bureau, Shellfish Consumer Cooperative, 4482 92 A7 __ B7 —-V. Selected Spectra of the Presentation of the Invention (17) The standard reference spectrum can be a volume The theoretical mathematical representation of the invariant part of the product reference spectrum; it may also be a previously obtained convolution spectrum of a reference substance that has been adjusted or smoothed. 3 It is preferably a convolution of multiple previously obtained reference substances. The spectrum obtained by averaging the spectrum is better. The collected spectrum needs to be "linearized" to the abscissa; it can be done through various interpolation methods, such as those described in W H. Press et al. Ke 皋! Ten-Things _ ^^ ~ ^ ___ (Numerical Recipes: The Art of Scientific Computing) '1986' Cambridge University Press, page 77_S9. The cubic spline function (cubic) on page 86_89 (SpHne) interpolation method is particularly suitable for this purpose. The spectrum used as the standard reference spectrum does not have to be taken from the same instrument used to obtain the convolution spectrum of the sample and the reference substance. To obtain the spectra R '(x) and S, ( x), it is better to use the FT method to convert it to the better time domain. 'The FT method system, for example, is explained in the mathematical secret: The Renaissance of Scientific Computing' on pages 381-383 and 407_412. At the same time, transform r⑻ to the time domain and FT with R (x) R, ⑻ of FT to find c (x). Since the matrix of FT of R (x) and R '(x) contains complex numbers, the division must correctly describe the real and imaginary parts.' Calculated convolution function -C (X)-Contains the necessary information to interpret the variation and instability of the instrument during the spectral collection process, and then divides the FT of SI (X) (the same two matrix backs contain complex numbers) by c (x), The FT of s (x) is obtained. By calculating the inverse FT of this result, the standard sample spectrum -S (x) representing the sample composition is obtained correctly. If necessary, S (x) can be performed, for example, a processing step for smoothing a curve or obtaining a spectral derivative. These steps when the spectrum is used as a repeatable -20 * ϋ scale is applicable to the Chinese National Standard (CN'S) A4 (210X297 male H-^ --- ^ ---- ^ ------ 1T ------. ^ (Please read the ΐ £ · intentions on the back page first and then Γ page) Member of the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperation Du printed 4482 92 Λ7 Α7 — Β7 5. Description of the invention (18) May be useful in quantifying compositional information. Curve smoothing methods are described in A Savitsky and MJE Golay, Anal. Chem., 1964, Vol. 36, pp. 1627-1639. Standard sample spectra obtained in the method of the present invention- S (x)-is the spectrum of the sampled chemical composition obtained after removing all random instrument variations other than random detector noise. This spectrum will vary depending on the chemical composition, so that the sample can be accurately measured. Quantitative analysis. A typical Raman spectroscopy system outlined in Figure 2 includes a radiation source 丨, an optical waveguide 2, a beam splitter 10, and a member that transmits radiation to a distant sample location. 'Includes excitation catheters 2A and 2B and 2C And 2D, filters 3A and 3B, light probes 4 and 13 'filters 5A and 5B, collection ducts 6A and 6 , Spectrograph interface 7, and spectrograph 8 containing optically dispersed elements, array detector 16, and * computer 19 with appropriate mathematical routines. This system can simultaneously obtain volumes of sample 17 and reference material 18 Product spectrum. This system consists of various components described below. In a preferred embodiment, where radiation can be transmitted back and forth to the conduits 2A, 2B, 2C, '2D, 6A, 6B, 6C between the sample and the reference material. , And 6D, including fiber optic cables. Various other light transmission guide elements can be used to complement the project's 'combination including optical elements such as mirrors, lenses, or hollow tubes. And doped with fused silica core' Optical fibers with a hybrid fused silica dioxide coating and a polyamide buffer layer are preferred, as they provide the simplest and most effective means of transmitting radiation, as they are within the wavelength range of the preferred diode laser. As mentioned earlier, the use of optical fibers over long distances is relevant _____ ~ 21-This paper is applicable to the National Standards (CNS) 戌 4 standard broadcast (21〇 Father 297 public meetings) ---; ----- ----- 装 ------ 1Τ ------ ^ (Please Read the business ideas on the back of I again; '/ this page) A7 B7 4482 92 V. Description of the invention (19 sets of φ cuts ^ 疋 many ways 足以) is enough to make long fibers can be used in the distance. Gui's method should be simple structure [And has a simple component, which can be inserted and replaced in the instrument through the piece. In a preferred embodiment, the above-mentioned catheter further includes filters 3A, 3B, 5A, and B), each of which can be located in two small The collimator devices, which are optimized for maximum output, are connected to the associated excitation and collection fibers. This optical device is better because it is small, compact, strong, and easy to remove and replace. It is also possible to consider the use of other filter elements described in additional and / or commercially available filters to remove unnecessary radiation. According to the present invention, the A radiation entering the product and the reference substance W will first pass through the band-pass filters 3 A and 3B; and after collection, it will pass through the rejection filters 58 and 5B. . The optical probes 4 and 13 as the interface between the sample substance 17 and the reference substance 18 of the program stream must have the positive characteristics that enable the method of the present invention to operate satisfactorily. In this program interface, the probe transmits incident radiation to the sample and collects scattered radiation from the sample. This interface must be stable under the operating conditions of the processing line. 'Small changes in the interface can cause great losses in output efficiency. Chemical process conditions are usually quite severe; for example, a typical polyester processing line is operated at a temperature between 150 and 30 (rc), and at a pressure of 2,0685 Pascals (3,000 psi). This kind of severe condition restricts the type of materials that can be used to form the interface. In the preferred embodiment of the present invention, the fiber optic probe used is protected by soldering a metal-coated fused silica fiber cable This probe is described in Buchanan et al., May 25, 1995-22 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm: --------- 1 ------ 、 玎 ------ ^ (please read the second notice on the back first and then 4 • this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Packing 4482 92 A7 B7 V. Description of the invention (20) US application No. 08 / 450,597 in the joint application filed, titled " Tough Spectrum Optical Probe (ROBUST SPECTROSCOPIC OPTICAL · PROBE) " The probe is inserted directly into the program line and previously described The selective filter device is connected at the other end of the probe tip = this probe design provides a simple but reliable method for optically sampling chemical compositions in the harsh physical environment of the manufacturing process. This design also has the advantage that the probe can be easily removed and replaced in the event of damage, and the benefit of eliminating the need for optical alignment during routine use is eliminated. -The light dispersing element is used to separate different energy levels. Scattered light. Generally speaking, the spectrograph S must have a proper resolution to separate the radiation level to the required level. At the same time, it should be able to effectively reduce radiation loss. Commercially available spectrograph systems The scribing grating is used as the dispersing element. Depending on the size of the spectrometer box and the spacing between the lines of the grating, the instrument will have different resolution. Other commercially available spectrometers use a specially designed full-scale improved output characteristics. Image dispersing element. A preferred embodiment of the present invention utilizes a spectrograph with a single grating. Gray has a fixed grating that disperses radiation so that it is between 800 nm and 1000 nm. The wavelength in the range is incident within the detection and inspection range. + This type of high-quality instrument can be purchased by different manufacturers. The array detector 16 is very important for the effective operation of the instrument. For the existence of bubbles in the program logistics Useful particles can still be obtained, the detector must have many closely spaced channels to collect at the same time. Two existing detection systems often used for this purpose are charge coupled devices (CCD) and Photodiode array (PDA). Among them, CCD is better, because of this ______ 23-This paper is from applicable countries ^ T ^ TT ^ 7 ^ ox 297 ^ ·) --- ~~ ----1 III I ~; Order! I line (please read the notice on the back of the margin first; then .. this page) 4482 92 A? B7 Economic Central Bureau of Standards Wa; Industrial and consumer cooperation Du Yinxue V. Description of invention (21 The other detection and detection benefits have relatively low background noise, are very sensitive, and can be used as a two-dimensional spatial array, which can display multiple spectra on a single debt detector. This multiplexing capability helps to reduce the cost of the instrument and can provide components that can utilize the dual beam normalization method 'as described in U.S. Patent No. 5,455,673. This standardized method improves accuracy 'and helps reduce sampling costs. Commercially available CCD detections of various shapes and sizes are degraded. Common arrays are 512 X 512 pixels and 3 86 X 576 pixels. Other larger array forms are also available, such as 256 X 1024 or 1024 X 1024 pixels. Such a detector must be cooled below room temperature 'to minimize background noise that can cause interference3 which can be achieved by cooling with liquid nitrogen, water or air. Some CCD devices use a technique called multi-pin phasing (MPP), which reduces background signal noise and noise to achieve the desired performance at temperatures that are cooled by air cooling. In the preferred embodiment of the present invention, it is necessary to reduce noise, amplify the signal, and reduce the amount of maintenance required for the instrument. Therefore, an MPP CCD detector with proper air cooling is required. It is better to use an array of 512 X 512 pixels because it has the appropriate spectral resolution / access range and can detect multiple channels at the same time. The photo camera system's 'detector' and laser components are generally not designed to withstand the environmental effects of the manufacturing area. Therefore, it is better to place these devices' in a safe control environment far from the sampling point of the program. The optical fiber extends between the control environment and the program point and is connected to a light probe, which is inserted into the program line. -24- Ben New Zealand Standards Wealth County (CNS) Rubi QX297 / >#) ---- ^ ------- installation ------, 玎 ------, ^ (Please read the legal meanings on the back before "this page") 448 2 9 2 A7 B7 V. Description of the invention (22) The spectrum collected on the Raman spectroscopy system mentioned is an indication of the substance flowing in the manufacturing process 'Chemical composition. The accuracy and correctness of this method can be improved through the use of better specific examples of the instrument, although the combination of other components is also effective. 3 It is necessary to understand and control several kinds of interference that will cause the final analysis result or not. Precise phenomena to obtain the greatest possible accuracy and precision. Such phenomena include: "cosmic rays" events; bubbles, particles, and turbidity in procedures: calibration point sampling; laboratory sampling errors; and instrument components Vibration, motion, and movement. "Cosmic ray" events-often called spikes-occur randomly on a CCD detector. It is believed to be caused by the collision of high-energy particles from outer space with the CCD detector element ', resulting in a large contaminating spectral sharp light. The sharp light from these events is generally very narrow, typically 1 to 5 pixels wide. Cosmic ray events rarely occur and cannot be predicted, although there is some evidence that the frequency of this event is related to the activity of the solar flash and the time of day. Printed by the Consumers' Cooperatives of the Central Bureau of Standards and Mobilization of the Ministry of Economic Affairs; It adds a large signal to the spectrum that has nothing to do with the procedural substance. Fortunately, there are several simple mathematical routines' that can be used to correct or eliminate this spectral data. One of these routines is described in Takeuchi. Et al., Applied Spectroscopy, 1993, Vol. 47, pp. 129-131. Bubbles, particles, and turbidity can cause chaos in part of the sampling area, resulting in sample volume. Changes in the spectral intensity are related to changes in the measured spectrum. Through the use of the multi-channel detection system, it is possible to observe the scattered radiation at the same time. -25- This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) 4 4 8 2 9 2 Consumption Cooperative India A7 ____B7 V. Description of the Invention (23) All levels of radiation. Bubbles' particles and turbidity 'act on the spectral response in a manner similar to multiplying by a random number' which can be corrected by using correction Spectral normalization. It is generally used in the normalization step of the standard sample spectrum to correct the volume difference of the material caused by the sampling of incident radiation. The simplest normalization method is to use an internal standard that can indicate the amount of sampled material. PET type polyester material is a convenient and effective way to normalize the area of the ring breathing mode at about 1610 cm-1. This vibration mode is directly related to the number of terephthalic acid rings sampled. It can be used to correct the change in sample volume. Although this method is better because of its simplicity, it is not the only way to normalize, other mathematical methods that can normalize the spectrum Can be used. The observed Raman spectrum is a combination of vibrational energy bands related to the composition in the sampled material. However, the scattering efficiency of individual vibrational motions is related to the polarization of this vibrational motion. The analysis of the vibrational energy band does not directly obtain the desired composition information. Because the measurement results of the sample composition cannot be obtained directly, it is necessary to establish a weighting method 4 that correlates the measured spectrum and characteristics with the desired analysis information. The calibration method removes the samples that are consistent with the spectra obtained in time from the chemical program and performs analysis and measurement to obtain its chemical composition information. Since the obtained spectrum is convolved with the instability of the instrument, it is appropriate to It is better to convert it into a standard spectrum before establishing a calibration method. This work can be done by determining and applying the convolution function published in US Patent No. 5,455,673 t. For this method, Jingshi is a better reference material. Compared with most chemical compositions of known composition, the Raman spectrum of this paper is -26-. CNs) a4 size (210x29? Mm) (please read the precautions on the ti-back first. Ί 本 I)-installed ·

'1T 4482 9 2 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（24 ) 多數個波長，可以建立組成一強度相關（CIC ; constitution-intensity correlation) 多 變量校準方法 ，其中 該光譜 宜爲標 準光譜較佳。選定於建立CIC之波長，係依化學组合物中 ，欲決定其濃度之各別成份的光譜特性而定。關於欲於任 何特定時刻，監測其在组合物中之原位濃度的各成份，須 製備其各別的CIC校準。 包括多變量校準和部分最小平方迴歸之校準方法的使用 和建立，説明於Martens等人，多變量校準（Multivariate Calibration)，1989，Wiley，紐約，第 1-6、11-22、25-30' 73-78、和116-125頁中。其他使化學物質之濃度與拉曼光 譜波峰面積間產生關聯之方法，説明於美國專利第 4,620,284號中。 爲由對苯二甲酸二甲酯（DMT)和乙二醇（EG)製備得PET 類型之聚合物-其中可進一步包括有限濃度之二元醇改質 劑，諸如環己烷二甲醇（CHDM)-於程序中，在不同時刻監 測酯交換程度，係相當重要之工作。此項工作可經由測定 生成聚合物之组合物中之甲i酯端基（來自DMT)、羥乙基 端基（來自EG)、及係包含於中間體對笨二曱酸雙（2-羥乙 基）酯（BHET)中之内部伸乙基鍵結的濃度而完成。欲於原 位測定各此等物種，需要有其個別的濃度-強度關係（CICs ;concentration-intensity correlations) 3 而欲測定於任何特 定時刻存在之二元醇改質劑的量，則需要另一個CIC。 各種儀器组件之振動、運動、和移動會對測得光譜造成 意想不到的變化=所發生之此種類型的誤差很難預測，且 -27- 本紙承尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ----^------裝------訂--------線 (請先閱t背面之^意事項再.r 」本頁) 經濟部中央標準局員工消費合作社印家 ^482 92 A7 _ B7 五、發明説明（25 ) 會產生使精確度受限之不正確性。因此，設法消除或減小 儀器之振動、運動、和移動作用係相當重要的，其可經由 其组件之強靭的組合而"固定"於穩固的構造中。若能將 儀器固定的愈佳，.則最終可達到較高的精確度。 可將樣品探針置於化學製造程序物流中的任何位置，但 —般宜將探針放置在使其可提供對於控制程序及對於提供 校準目的用之分析資訊的有用訊息之位置上較爲適當。 在聚醋製造程序中’ 一種較佳的樣品探針位置，係在靠 近於私序中之第一階段反應接近完成的點上。如此提供一 種可快速確定與反應程度相關之分析訊息、二元醇對酸及 /或二元酯之莫耳比、二元醇或二元酸改質劑之百分比、 以及聚合程度之方法。此種訊息可以改良對程序之第一階 段的控制，以及改良對下游的控制。 以下之實施例進一步説明本發明。 复_施例卜證實本方法在分批程序中之能力 本監測方法之技術能力’係於實驗室之反應容器中，在 類似於製造程序環境之條件下進行驗證。將Dmt和eg之 酯交換反應，以拉曼光譜術，随樣品之定期自容器中取出 ，而於原位連續進行監測。接著再進行第二次反應實驗， 以比較拉曼估計數據與量數據，並因而驗證校準法 之有效性。 構建一種包含以氪離子氣體雷射（購自Lexe丨，Fremont CA) ’在752毫微米下操作作爲輻射源之拉曼儀器。將來自 雷射發光過程之電漿線，經由介電帶通濾光器自入射輻射 _________ - 28 - 本紙張尺度通财CNS) ϋ( 2ιαχ29^^ I---------襄------t------線 <请先閲请背面之法意ί項具..本頁) 4482 92 at - — B7 五、發明説明（26 ) 光束中濾出’而輻射聚焦於200微米核心之以聚醯亞胺缓 衝的炫融二氧化矽光纖電纜上。此光學纖維將輻射傳輸至 直接***反應介質中的樣品探針上。 散射輻射由六根緊密位在激發纖維左右之2〇〇微米的纖 維收集》此六根收集纖維則傳送回Instruments SA (Edison ’ NJ) 302型攝譜儀《此纖維係排列成線性陣列形式，且 正位於入口光學元件之前β 入口光學元件首先使輻射照準，然後使其通過實質上可 消除所有彈性散射輻射的凱撒光學元件（Kaiser 0ptics)(安 亞伯，MI)全像一帶拒濾光器，最後再將濾過輻射聚焦於 攝譜儀之入口狹縫上。分散輻射由ISA液態氮冷卻之CCD 偵檢器進行偵測，並將其轉換成電子訊號。 經濟部中央標準局員工消費合作社印製 ----------裝-- (請先閲玫背面之&意事項再i .本頁) 線 儀器由可以連續收集序列資料檔案之軟體控制。取得數 對之每3 0秒取樣一次的序列光譜，並加以比較以移去宇宙 尖光事件β於除去尖光後，將兩光譜平均。使用位在1610 公分-1之芳香環呼吸振動光譜特性，作爲配合發表於美國 專利第5,455,673號中之標準吒方法用的捲積參考光譜，以 移除帶狀和帶位變化。而在1610公分-1之芳香環呼吸模式 的面積，則用於進行正規化。 所得之標準化波形，則由三點半寬的高斯加寬函數 (Gaussian broadening function)，及單點半寬的洛倫茨窄化 函數（Lorenztian narrowing function)，在傅立葉域進行平滑 化。使用部分最小平方（PLS)數據平析套裝軟體（購自特倫 汗（Trondheim)之電腦輔助模型 A/S (Computer Aided -29- 本紙張尺度適用中國國家標準（CNfS)A4規格（2丨OX 297公釐） 448292 經濟部中央標準局員工消費合作社印製 A7 B7___五、發明説明（27 ) Modelling A/S)的UNSCRAMBLER，挪威），於計算數據之 二次微分，並用所得之標準化的平滑數據於建立CIC校準 將大約1065克之DMT和865克之EG加入一大的反應容器 中。將供光學探針用之經特殊設計之具配件的蓋' 熱電偶 、攪拌器、冷凝器、及取樣口固定好。使一溫和的乾淨氮 氣流通過反應混合物之上，以使混合物與氧隔離。 一邊收集拉曼光譜，一邊將反應晶合物小心地加熱至 180°C。於收集數個基線光譜後，將大約0.20克之酯酸錳 觸媒***混合物辛。於數小時後，反應溫度提升至195°C ，並於另一段時間後，再提升至210°C。 在反應過程的一段時間間隔中，取出樣品，並以NMR光 譜儀分析，以夹定下列各物之數目：芳香對苯二甲酸環， 表示爲·Τ·;甲基酯端基，表示爲-CH3 ;羥乙基端基，表 示爲-0H ;内部伸乙基鍵結，表示爲-2-;及游離EG。 圖3顯示甲基端基數目之校準和確認反應値。將測得之 曱基酯端基-CH3的數目，對'對苯二甲酸環-T-正規化，則 得酯交換反應程度的直接量度。此校準曲線具有0.9999的 相關係數，顯示拉曼方法在酯交換反應的整個組成範圍内 ，極適於用來決定分析結果。 圖4所示爲在整個反應中，測得之各種參數的圖。大約 每分鐘收集一次各別的光譜。起始的20分鐘係當容器在 180°C ’且不存在觸媒之情況下所取得。加入觸媒後，反 應快速地增加。於3小時（光譜编號180)後，反應溫度提升 __- 30 -__ 本紙浪尺度適用中國國家榡準（CNS ) A4規格（2丨0乂 297公釐）'1T 4482 9 2 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (24) For most wavelengths, a constitution-intensity correlation (CIC) multivariate calibration method can be established, where the spectrum The standard spectrum should be better. The wavelength chosen to establish the CIC depends on the spectral characteristics of the individual components in the chemical composition whose concentration is to be determined. For each component to monitor its in situ concentration in the composition at any particular moment, its own CIC calibration must be prepared. The use and establishment of calibration methods including multivariate calibration and partial least squares regression, as described in Martens et al., Multivariate Calibration, 1989, Wiley, New York, 1-6, 11-22, 25-30 ' 73-78, and 116-125. Other methods of correlating the concentration of a chemical substance with the peak area of a Raman spectrum are described in U.S. Patent No. 4,620,284. Is a PET type polymer made from dimethyl terephthalate (DMT) and ethylene glycol (EG)-which may further include a limited concentration of glycol modifiers such as cyclohexanedimethanol (CHDM) -Monitoring the degree of transesterification at different times in the program is a very important task. This work can be determined by the methyl ester end group (from DMT), the hydroxyethyl end group (from EG), and the intermediate The concentration of internal ethylenic bonds in the ethyl) ester (BHET) is completed. To measure each of these species in situ requires their own concentration-intensity correlations (CICs) 3 and to determine the amount of glycol modifiers present at any given moment, another CIC. The vibration, movement, and movement of various instrument components will cause unexpected changes in the measured spectrum = this type of error is difficult to predict, and -27- this paper bears the standard applicable to the Chinese National Standard (CNS) A4 specifications ( 210X 297 mm) ---- ^ ------ installation ------ order -------- line (please read the ^ intentions on the back of t first.r '' this page) Yin Jia, a consumer cooperative of employees of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 482 92 A7 _ B7 V. Explanation of the invention (25) will produce inaccuracies that limit the accuracy. Therefore, it is important to try to eliminate or reduce the vibration, movement, and movement of the instrument, which can be " fixed " in a stable construction via a strong combination of its components. The better the instrument can be fixed, the higher accuracy will eventually be achieved. Sample probes can be placed anywhere in the chemical manufacturing process logistics, but it is generally advisable to place the probes where they provide useful information for the control process and for providing analytical information for calibration purposes . A preferred sample probe position in the polyacetate manufacturing process is at a point near the completion of the first-stage reaction in the private sequence. This provides a method for quickly determining analytical information related to the degree of reaction, the molar ratio of glycol to acid and / or dibasic ester, the percentage of glycol or diacid modifier, and the degree of polymerization. Such information can improve control of the first stage of the process, as well as downstream control. The following examples further illustrate the invention. Re-exemplification demonstrates the capability of this method in batch procedures. The technical capabilities of this monitoring method are verified in a laboratory reaction vessel under conditions similar to those in the manufacturing process environment. The transesterification reaction of Dmt and eg was carried out by Raman spectroscopy, and the samples were periodically taken out of the container with the sample, and continuously monitored in situ. Then a second reaction experiment was performed to compare the Raman estimation data with the quantity data, and thus verify the validity of the calibration method. A Raman instrument comprising a krypton ion gas laser (purchased from Lexe 丨, Fremont CA) 'was operated at 752 nm as a radiation source. The plasma line from the laser light emission process is radiated from the incident radiation through a dielectric band-pass filter _________-28-CNS of this paper scale ϋ (2ιαχ29 ^^ I --------- xiang ------ t ------ line < please read the meaning of the item on the back first .. this page) 4482 92 at--B7 V. Description of the invention (26) Filtered out of the beam ' The radiation is focused on a 200 micron core polyfluoride-imbedded fused silica optical fiber cable. This optical fiber transmits radiation to a sample probe that is inserted directly into the reaction medium. Scattered radiation was collected by six 200-micron fibers close to the excited fibers. The six collected fibers were transmitted back to Instruments SA (Edison 'NJ) 302 spectrograph. The fibers are arranged in a linear array and Located ahead of the entrance optics, the beta entrance optics first collimates the radiation and then passes it through a Kaiser Optics (Aberber, MI) hologram that rejects virtually all elastically scattered radiation, and finally Focus the filtered radiation on the entrance slit of the spectrograph. The scattered radiation is detected by an ISA liquid nitrogen cooled CCD detector and converted into an electronic signal. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ---------- Installation-(please read the & notice on the back of Mei and then i. This page) Software control. A number of sequence spectra were sampled every 30 seconds and compared to remove the cosmic sharp light event β. After removing the sharp light, the two spectra were averaged. The aromatic ring respiration vibration spectrum characteristic at 1610 cm-1 was used as a convolution reference spectrum in conjunction with the standard 吒 method published in U.S. Patent No. 5,455,673 to remove banding and band position changes. The area of the aromatic ring breathing pattern at 1610 cm-1 is used for normalization. The resulting normalized waveform is smoothed in the Fourier domain by a three-point half-width Gaussian broadening function and a single-point half-width Lorenztian narrowing function. Uses part of the least squares (PLS) data analysis package software (Computer Aided -29 purchased from Trondheim) (Computer Aided -29- This paper size applies to China National Standard (CNfS) A4 specifications (2 丨 OX 297 mm) 448292 Printed by A7 B7___ of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (5) UNSCRAMBLER (Norway) Modelling A / S), calculate the second derivative of the data, and use the resulting normalized smoothing The data was used to establish a CIC calibration. Approximately 1065 grams of DMT and 865 grams of EG were added to a large reaction vessel. Fix the specially designed cover 'thermocouple, stirrer, condenser, and sampling port for the optical probe. A gentle stream of clean nitrogen was passed over the reaction mixture to isolate the mixture from oxygen. While collecting the Raman spectrum, the reaction crystal was carefully heated to 180 ° C. After collecting several baseline spectra, approximately 0.20 g of manganese ester catalyst was inserted into the mixture. After a few hours, the reaction temperature increased to 195 ° C, and after another period of time, it increased to 210 ° C. During a period of time during the reaction, samples were taken out and analyzed by NMR spectroscopy to determine the number of each of the following: aromatic terephthalate ring, represented by · T ·; methyl ester end group, represented by -CH3 Hydroxyethyl end groups, expressed as -0H; internal ethylenyl bond, expressed as -2-; and free EG. Figure 3 shows the calibration and confirmation reactions for the number of methyl end groups. A direct measurement of the degree of transesterification is obtained by normalizing the number of fluorenyl ester end groups -CH3 and the 'terephthalic acid ring-T-. This calibration curve has a correlation coefficient of 0.9999, showing that the Raman method is well-suited to determine the analysis results over the entire composition range of the transesterification reaction. Figure 4 shows a graph of various parameters measured throughout the reaction. Individual spectra are collected approximately every minute. The first 20 minutes were obtained when the container was at 180 ° C ′ and no catalyst was present. After the catalyst was added, the response increased rapidly. After 3 hours (spectrum number 180), the reaction temperature increases __- 30 -__ This paper wave scale is applicable to China National Standard (CNS) A4 specification (2 丨 0 乂 297 mm)

— 裝 訂 線 (請先聞讀·背面之忒意事項再1*本頁J 經濟部中央標準局員工消費合作社印製 4 4 8 2 9 2 Λ7 Α7 Β7 五、發明説明（28 ) 至195°C ’及於4小時（光譜編號230)後，溫度再提升至210 X。 圖4中之數據，證實本發明對於測定反應中之數種重要 成份的優異能力3甲基酯端基之數目係指示中間體BHET 之生成程度，其係優良聚合物製品的重要指標。内部伸乙 基單元與聚合程度及分子量直接相關，其係另一項重要之 性質。 實施例2 -聚酯製造反應物流之分析 爲證實本發明在製造環境中作爲原位、線上定量分析工 具之效用，將拉曼儀器裝設在靠近於聚酯生產線處，將一 構造，如發表於前述之1995年5月25日提出申請之共同申請 中的美國申請案編號08/450,597,標題爲"強靭的光譜光探 針"中之強靭的探針裝設好，以使取樣尖稍突出入流動中 之溶融的聚醋物流中。指定個別的程序線，以由DMT、 EG和CHDM製造二元醇改質的PET。測量過程進行六個星 期β取得關於第一階段（酯交換）反應程度之分析數據、二 元醇對酸之莫耳比、及CHDNi二元醇改質劑之百分组成α 拉曼儀器係構造成包含一以800毫微米激發進行操作之 2.0瓦特的多型二極體雷射；其係接續至一100微米二氧化 矽石英核心之光纖電纜（Spectra Diode Lab, Inc.,聖約瑟 (SanJose)’ CA型號SDL-2372-Pj)。入射輕射由光纖分光器 (Oz Optics Ltd.，Carp，安大略’加拿大，型號FOBS-12-555- MMM-750-50/50)***成兩束輻射。兩束輻射均聚焦於個別 之200微米核心、聚酿亞胺緩衝的石英二氧化夕光纖電境 -31 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ；—.----裝— (請先閔讀*背面之;1*意事項再>*'.本頁) 訂 線 AA82 92 A7 B7 29 經濟部中央標準為貝工消費合作社印^ 五、發明説明（ (hberguide lndustries，Sdrling，NJ)上。此兩光學纖維將輻 射傳輪至樣品探針和參考探針。其中樣品探針係直接*** 大約40米遠之程序物流中。 各光纖電纜中之輻射在進入其個別之探針前，均經過濾 光 連光器（〇mega Optical, Brattleboro, VT型號 800 BP1 0) 係設計成僅能傳輸狹窄的能帶，且係***固定光纖濾光器 失持裝置（〇z〇ptics，Ltd‘，型號ND-200-55-750-M-30)内。參 考探針係用於照亮作爲參考物質之小碎鑽。樣品探針則係 經由凸緣口而***程序物流中。 來自參考物質和樣品之散射輻射，由個別之緊密位在激 發纖維左右之200微米的纖維收集。收集到之散射輻射， 於進入回路纖維前，再經過濾光，以大致將所有的雷來散 射輻射移除。此遽光器（〇mega 〇ptjcal，型號rEflp)係 固定於固定的光纖濾光器夹持裝置（〇z 〇ptics, ud，型號 ND-200-55-750-M-30)内，且係設計成可有效地排拒不必要 之輻射’同時得以收集必要的拉曼散射福射。 兩條回路纖維皆傳送回IS A 3 20攝譜儀。此纖維係排列成 線性陣列形式，且正位於入口狹缝之前方。經分散之輕射 由ISA液態氮冷卻之CCD偵檢器進行偵測，並轉換成電子 訊號。 儀器係以可連續收集序列資料檔案之軟體控制。取得數 對之30秒取樣一次的序列光譜，並加以比較以移去宇宙尖 光事件’再將兩去除尖光之光譜平均。使用說明於數値秘 座：科學算U直，86-89頁中之三次樣條函數内插法， -32 本紙張尺度適用中國g家標準（CNS ) A4規格（210X297公釐） . 1 I I ^ 訂一i —i ™I - ---線-I--—— (讀先閱讀"·面之注，意事項再^本頁) ip Λ482 92 A7 B7 經濟部中央標準局員工消費合作社印策 五、發明説明（30 於獲得捲積參考和樣品光譜之等距的橫座標數據 。進行如 實施例1所述之標準化和正規化步驟。所得之標準化波形 ，由九點半寬的高斯加寬函數，及七點半寬的洛倫茨窄化 函數，在傅立葉域進行平滑化。將五個連續的平滑標準波 形平均在一起，以獲得每5分鐘一個的數據點。 樣印探針係位在程序物流中’認爲酯交換反應已幾近完 全的位置上。在程序環境内之溫度大約爲235i，及壓力 大約爲206.85仟帕斯卡（規測）(3〇1^4卜一取樣口位在靠近 於樣品探針處，且每隔12小時取出一次少量的寒聚物樣品 。此樣品以NMR進行分析，以決定其酯交換反應程度。 使用在時間上與已知濃度之分析组合物一致的二次微分 標準化平滑光譜於建立CIC校準。校準之建立係使用部分 最小平方（PLS)數據分析套裝軟體（購自特倫汗之電腦輔助 模型A/S的UNSCRAMBLER，挪威）進行。 圖5顯示在大約六週之期間内，酯交換反應程度之取出 樣品的NMR結果（如空心圓圈之記號點所示）與拉曼儀器所 得之數據（如實線所示）^其f NMR數據顯示程序的變化相 當大’其中數據中之點與點間有顯著發生偏差的趨勢》變 化的主要來源’推測係由於取樣步驟，程序本身之變化， 以及分析測量之結果所致。 拉曼數據中之不連續性，係由於未重新填充液態氮容器 ’或數據之意外損失所致。 程序數據之統計分析證實，拉曼數據較NMR測量結果， 有更低之點與點間變化的觀察結果。拉曼方法經證實有約 -33- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ---------裝------訂------線 (請先閲讀*背面之汰意事項再i*本頁) 4482 92 A7 經濟部中央標隼局員工消费合作社印製 B7 五、發明説明（31 ) 〇.1°/。之優良的相對精確度。NMR數據之最大偏差來源係在 於取樣方法上，一旦考慮到樣品自程序中取出之方法後， 其並不會令人感到驚訝。 除了有較高之精確度外，拉曼方法明顯地可提供更頻繁 之取樣’免除取出樣品之需求，且較NMR分析有更快速的 處理時間。較頻繁之取樣’可提供更透徹瞭解程序中之特 性’和眞正變化期間的方法。減少取出樣品之需求，可大 大地降低發生傷害之危險。較快速之處理時間，使其得以 it出更主動之程序控制對策。因此利用本發明，很明類地 可以對變數進行更頻繁及精確之測量β 堂捭㈣3 -證實本方法對分析混合二甲苯之能力 本方法對於決定其他化學組合物之組成的技術能力，經 由製備；昆合二甲苯之樣品組而加以證實。樣品係經由小心 稱重各成份之不同量，將其配成混合物而製備得。計算莫 耳濃度百分比，將其作爲眞實値，示如以下之表i中的 STD。 拉曼儀器係構造成包含一以800毫微米激發進行操作之 2.0瓦特的多型二極禮雷射，其係接續至一 1〇〇微米二氧化 碎石英核心之光纖電境（Spectra Diode Lafc^ Inc_，聖約瑟’ CA型號SDL_2372-P3)。入射輻射由光纖分光器（〇2; 〇ptics— Gutter (please read and read the notice on the back first) * This page J Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 4 8 2 9 2 Λ7 Α7 Β7 5. Description of the invention (28) to 195 ° C 'And after 4 hours (spectrum number 230), the temperature increased to 210 X. The data in Figure 4 confirms the superior ability of the present invention to determine several important components in the reaction. The number of 3 methyl ester end groups is an indication The degree of formation of the intermediate BHET is an important indicator of excellent polymer products. The internal ethylenic unit is directly related to the degree of polymerization and molecular weight, which is another important property. Example 2-Analysis of the reaction stream of polyester manufacturing In order to confirm the effectiveness of the present invention as an in-situ, online quantitative analysis tool in a manufacturing environment, a Raman instrument is installed near the polyester production line, and a structure is applied, as published on May 25, 1995. U.S. Application No. 08 / 450,597 in the joint application, entitled "Tough Spectral Light Probe", the tough probe is installed so that the sampling tip protrudes slightly into the flowing polyacetate stream in. Specify individual program lines to produce glycol-modified PET from DMT, EG, and CHDM. The measurement process is performed for six weeks. Β Analytical data on the degree of reaction in the first stage (transesterification), glycol to acid Morby ratio and percent composition of CHDNi glycol modifiers. The Raman instrument is configured to contain a 2.0 watt multi-type diode laser operating with 800 nm excitation; it is connected to a 100 Fiber Optic Cable with Micron Silica Quartz Core (Spectra Diode Lab, Inc., San Jose 'CA Model SDL-2372-Pj). The incident light is transmitted by a fiber optic splitter (Oz Optics Ltd., Carp, Ontario) Canada, model FOBS-12-555- MMM-750-50 / 50) is split into two beams of radiation. Both beams of radiation focus on individual 200 micron cores, polyimide-buffered quartz dioxide fiber optic electrical environment -31 -This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm); —.---- install — (please read the * on the back; 1 * the matter of interest and then > * '. This page) Order Line AA82 92 A7 B7 29 The central standard of the Ministry of Economic Affairs is printed for Shellfish Consumer Cooperatives ^ V. Description of the invention ((hbergu ide lndustries, Sdrling, NJ). These two optical fibers transfer radiation to the sample probe and the reference probe. The sample probe is directly inserted into the program stream about 40 meters away. The radiation in each fiber optic cable is entering Before the individual probes, they are all filtered by optical connectors (〇mega Optical, Brattleboro, VT model 800 BP1 0). They are designed to transmit only narrow energy bands, and are inserted into fixed fiber filter loss holding devices ( (P.ptics, Ltd ', model ND-200-55-750-M-30). The reference probe is used to illuminate a small crushing diamond as a reference substance. The sample probe is inserted into the process stream through the flange opening. Scattered radiation from reference materials and samples is collected by individual fibers that are closely spaced about 200 microns from the excitation fiber. The scattered radiation collected is filtered before it enters the loop fiber to remove almost all the scattered radiation from the mine. This calender (〇mega 〇ptjcal, model rEflp) is fixed in a fixed fiber filter holding device (〇z 〇ptics, ud, model ND-200-55-750-M-30), and Designed to effectively reject unnecessary radiation 'while collecting necessary Raman scattering radiation. Both loop fibers are sent back to the IS A 3 20 spectrograph. The fibers are arranged in a linear array directly in front of the entrance slit. The scattered light is detected by the ISA liquid nitrogen cooled CCD detector and converted into an electronic signal. The instrument is controlled by software that can continuously collect serial data files. Obtain a number of sequence spectra sampled every 30 seconds, and compare them to remove the cosmic sharp light event 'and then average the two spectra without the sharp light. Instructions for use in Mathematical Secrets: Scientific Straight U, Straight Spline Function Interpolation on pages 86-89, -32 This paper size is applicable to China Standard (CNS) A4 (210X297 mm). 1 II ^ Order one i —i ™ I---- line-I --—— (read first read " · Notes on the surface, and then note the matter ^ this page) ip Λ482 92 A7 B7 Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Imprint V. Explanation of the invention (30: Obtain the horizontal coordinate data of the equidistant reference between the convolution reference and the sample spectrum. Perform the normalization and normalization steps described in Example 1. The resulting normalized waveform is Gaussian with a width of nine and a half. The widening function and the Lorentz narrowing function at seven and a half width are smoothed in the Fourier domain. Five consecutive smooth standard waveforms are averaged together to obtain a data point every 5 minutes. Sample probe The position in the program stream is that the transesterification reaction is considered to be almost complete. The temperature in the program environment is about 235i, and the pressure is about 206.85 Pascal (measurement) (3〇1 ^ 4) Mouth is near the sample probe and removed every 12 hours The amount of cold polymer sample. This sample is analyzed by NMR to determine the degree of transesterification reaction. The secondary differential normalized smooth spectrum consistent with the analysis composition of known concentration in time is used to establish the CIC calibration. The establishment of the calibration This was performed using a partial least squares (PLS) data analysis suite (UNSCRAMBLER, Computer Aided Model A / S from Trenhan, Norway). Figure 5 shows the extent of transesterification reactions taken over a period of approximately six weeks. The NMR results (shown by the marked points in the open circles) and the data obtained by the Raman instrument (shown by the solid line) ^ The f NMR data shows that the program has changed considerably. Among them, there is a significant deviation between the points in the data The main source of the "change" is speculated as a result of changes in sampling steps, procedures themselves, and results of analytical measurements. Discontinuities in Raman data are due to unrefilled liquid nitrogen containers or unexpected loss of data The statistical analysis of the program data confirmed that the Raman data has lower observation points and point-to-point changes than the NMR measurement results. The Mann method has been confirmed to be about -33- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) --------- Installation ------ Order ------ Line (please read the * description on the back side before i * this page) 4482 92 A7 Printed by the Consumers Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, printed B7 V. Description of the invention (31) 0.1 ° /. Excellent relative accuracy The source of the largest deviation of NMR data is the sampling method. Once the method of taking the sample from the program is taken into account, it will not be surprising. In addition to the higher accuracy, the Raman method is obviously applicable. Provides more frequent sampling 'eliminates the need to take samples and has faster processing time than NMR analysis. More frequent sampling ' provides a more thorough understanding of the characteristics of the procedure ' and the period of positive change. Reducing the need to remove samples greatly reduces the risk of injury. Faster processing time allows it to come up with more proactive program control countermeasures. Therefore, with the present invention, it is clear that variables can be measured more frequently and accurately. Β 捭 ㈣ 3-Demonstrates the ability of the method to analyze mixed xylene. The method's technical ability to determine the composition of other chemical compositions is ; Kunhe xylene sample group to confirm. Samples were prepared by carefully weighing different amounts of each component and formulating them into a mixture. Calculate the percentage of molar concentration and use it as the actual value as shown in the STD in Table i below. The Raman instrument is configured to include a 2.0 watt multi-type diode laser operating at 800 nm excitation, which is connected to the fiber optic environment of a 100 micron quartz quartz core (Spectra Diode Lafc). ^ Inc_, San Jose 'CA Model SDL_2372-P3). Incident radiation is split by a fiber optic splitter (〇2; 〇ptics

Ltd.，Carp，安大略’加拿大’型號 FOBS-12-555-MMM- 750_50/50)***成兩束輻射。兩束輻射均聚焦於個別之200 微米核心 '聚醯亞胺緩衝的石英二氧化矽光纖電纜 (Fiberguide Industries, Stirling, NJ)上。此兩光學纖維將輻 -34- 本紙張尺度適用中國國家標车（CNS〉A4規格（210 X297公釐） I 0¾ —— (請先閲洗背面之ΪΪ-意事項再..本頁) -^ Δ Λ 8 2 9 2 Α7 Β7 經濟部中央標準局負工消費合作社印製 五、發明説明（32 射傳輸至樣品探針和參考探針。 各光纖電境中之輕射在進入其個別之探針前，均經過濾 光 a 遽光器（Omega Optical, Brattleboro, VT型號 800 BP10) 係設計成僅能傳輸狹窄的能帶，且係***固定的光纖濾光 器夹持裝置（〇z Optics Ud，型號 ND-200-55-750-M-30)内= 參考和樣品光纖探針皆係構造於内部。參考探針係用於 照売作爲參考物質之小碎鑽。樣品探針則係***放置有混 合二甲苯樣品之316不銹鋼樣品管中。 來自參考物質和樣品之散射輕射’由個別之緊密位在激 發纖維左右之200微米的纖維收集。收集到之散射輻射’ 於進入回路纖維前，再經過濾光，以大致將所有的雷來教 射轄射和除。此;慮光器（〇mega 〇pdcal，型號KEflp)係 固定於固定的光纖濾光器夹持裝置（〇z 〇pdcs，Ltd，型號 ND-200-55-750-M-30)内，且係設計成可有效地排拒不必要 之輻射，同時能使必要的拉曼散射輻射通過3 兩條回路纖維皆傳送回Act〇n SpectraPr〇光譜儀（入以⑽Ltd., Carp, Ontario 'Canada' model FOBS-12-555-MMM- 750_50 / 50) split into two beams of radiation. Both beams of radiation are focused on individual 200-micron core 'polyimide-buffered silica silica fiber cables (Fiberguide Industries, Stirling, NJ). These two optical fibers will be spoken -34- This paper size is applicable to Chinese national standard car (CNS> A4 specification (210 X297 mm) I 0¾ —— —— (Please read the precautions on the back of the paper-Issue .. This page)- ^ Δ Λ 8 2 9 2 Α7 Β7 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (32 shots transmitted to the sample probe and reference probe. The light shots in each fiber optic environment enter their individual shots. Before the probes, they are all filtered with a calender (Omega Optical, Brattleboro, VT Model 800 BP10). They are designed to transmit only narrow bands and are inserted into fixed fiber filter holders (〇z Optics Ud, Model ND-200-55-750-M-30) Inside = The reference and sample fiber probes are all built in. The reference probe is used to illuminate small broken diamonds used as reference materials. The sample probe is Inserted into a 316 stainless steel sample tube containing a mixed xylene sample. Scattered light from the reference material and the sample is collected by individual fibers that are closely located about 200 microns around the excitation fiber. The scattered radiation collected is used to enter the loop fiber Before filtering the light to roughly all The Lei Lai Jiao is responsible for shooting and removing. Therefore, the optical filter (〇mega 〇pdcal, model KEflp) is fixed to a fixed fiber filter holding device (〇z 〇pdcs, Ltd, model ND-200-55 -750-M-30), and is designed to effectively reject unnecessary radiation, and at the same time can make the necessary Raman scattered radiation through 3 two loop fibers are transmitted back to ActOn SpectraPr〇 spectrometer (into ⑽

Research Corporation，Acton, ώΑ)。單光器之構造爲具有三 個分散光栅之塔形光柵系統。此等光柵爲· 15〇凹槽/毫米， 於750¾微米發光；300凹槽/毫米，於75〇毫微米發光；及 6〇〇凹槽/毫米，於750毫微米發光β其中3〇〇凹槽/毫米之光 拇係用於進行分析，且提供大約17〇〇厘米.i之光譜通達範 圍。 一具有八個200微米輸入端之纖維承接器，連接於單色 器之入口，以得以同時收集八個拉曼波道。此纖維係 _ -35- 本紙張尺度適用中囤if家標準（CNS ) A4規格（210X297公釐） ϋ 裝 I ; I t ~' .1τ. I I I I- H II ---- (請先閱洗背面之么意事項再'本頁) · d 4 8 2 9 2 A7 B7 經濟部中央標準局貝工消費合作社印裝 五、發明説明（33 ) 成線性陣列形式，且正位於入口狹縫之前方。此八根單色 器纖維的其中一條連接至樣品探針纖維，而另一條纖維則 連接至參考探針纖維。經分散之輻射由普林司通儀器 (Princeton Instruments)(Trei\ton，NJ)熱電冷卻之 CCD偵檢 器進行偵測，並轉換成電子訊號。此CCD晶片係 丁已1：1^〇11丨\512?^512像元之背照偵檢系統。 儀器係由普林司通儀器提供之CSMA資料收集軟體控制 :每3 0秒取得一個光譜。應用如實施例2之三次樣條函數 内插法，將捲積參考和樣品光譜數據對橫座標進行線性化 。.並應用説明於美國專利第5,455,673號中之標準化方法， 於移除帶狀和帶位偏差。所得之標準化波形，由三點半寬 之高斯加寬函數，及兩點半寬之洛倫茨窄化函數，在傅立 葉域進行平滑化a 將取自樣品A-K之標準樣品光譜，配合部分最小平方 (PLS)數據分析套裝軟體（購自特倫汗之電腦輔助模型A/S 的UNSCRAMBLER，挪威）使用，以產生二甲苯混合物中 之各成份的校準。再利用此ά準，以獲得各樣品之组成訊 息。 樣品L-Q構成獨立的確認组。此等樣品係以類似於樣品 Α-Κ之方式進行測量，而取得各樣品之標準光譜。再應用 校準函數於各標準光譜上，以獲得樣品组合物之測量結果 故意將單色器中心由901毫微米改變至899毫微米，以模 擬裝置之不穩定性，並再度測量樣品G及L-Q(重新標註爲 -36- 本紙張尺度適用中國國家標準（CNS ) Α4%格（210X 297公釐） I---；------^------------0 (請先閱讀'背面之'1JE,意事項再J-*·.本頁) ΔΛ82 92 A7 B7 五、發明説明（34 ) 樣品R-X)，而獲得一組新的標準光譜。將校準函數應用於 各標準光譜上，則獲得樣品组合物之測量結果》 在以下之表1中，標註爲"發明"之攔中，所示者爲根據 本發明之方法，由拉曼光譜測得之二甲苯混合物中之组合 物的莫耳百分比。此等値與列於"STD"欄中之實際百分比 間的差異，示於"差別"欄中。各成份簡寫如下： P二對二曱苯，M =間二甲苯，及0 =鄰二甲苯。 表1 經濟部中央標準局員工消費合作社印製 (請先閔讀"背面之汰意事項再一 .·本頁) -37- 樣品 成份 STD 發明 差別 A P 39.86 39.84 -0.02 Μ 35.22 35.19 -0.03 0 24.91 24.97 0.06 B Ρ 39,98 40.10 0.12 Μ 25.01 25.07 0.06 0 35.01 34.83 -0.18 C Ρ 34.97 34.99 0.02 Μ 25:13 25.21 0.08 0 39.91 39.80 -0.11 D Ρ 34.78 34.81 0.03 Μ 39.93 39.94 0,01 0 25.29 25.25 -0.04 E Ρ 39.95 39.83 -0.12 Μ 25.08 24.92 -0.16 0 34.97 35.25 0.28 本紙張尺度適用中國國家標隼（CNS ) A4規潘（210X297公釐） A7 448292 B7 五、發明説明（35 ) 經濟部中央標準局員工消費合作社印^ F Ρ 33.34 33.28 -0.06 Μ ^ -η J J , 33.44 0.12 0 33.33 33.28 -0.05 G Ρ 33.42 33.51 0.09 Μ 33,23 33.11 -0.12 0 33.35 33.37 0.02 Η Ρ 25.12 25.14 0.02 Μ 39.94 39.91 -0.03 0 34.94 34.95 0.01 I Ρ 35.04 35.05 0.01 Μ 39.97 39.93 -0.04 0 24.99 25.02 0.03 J Ρ 39.97 39.93 -0.04 Μ 35.01 35.11 0.10 0 25.02 24.95 -0.07 Κ Ρ 24.97 24.92 -0.05 Μ 35:09 35.11 0.02 0 39.95 39.97 0.02 L Ρ 30.14 30.16 0.02 Μ 29.92 29.92 .0.00 0 39.94 39.92 -0.02 Μ Ρ 30.03 30.07 0.04 Μ 39.90 39.82 -0.08 0 30.07 30.12 0.05 Ϊ . 辦衣« ! 訂 . , .~線 (請先閱讀"'面之汰意事項再;>本頁) -38- 本紙張尺度適用中國國家標準（CNS ) A4g ( 210X 297公釐） A7 4482 92 B7 五、發明説明（36 ) 經濟部中央橾準局員工消资合作社印製 N P 39.96 39.96 0.00 Μ 29.95 30.07 0.12 0 30.09 29.97 -0.12 0 Ρ 35.01 34.85 -0.16 Μ 35.03 34.89 -0.14 0 29.97 30.26 0.29 P Ρ 35.00 35.12 0.12 Μ 30.01 29.90 -0.11 0 34.99 34.98 -0.01 Q Ρ 30.03 ‘ 30.04 0.01 Μ 34.99 35.00 0.01 0 34.98 34.97 -0.01 R Ρ 33.42 33.40 -0.02 Μ 33.23 33.15 -0.08 0 33.35 33.45 0.10 S Ρ 30.14 30.12 -0.02 Μ 29:92 29.76 -0.16 0 39.94 40.12 0.18 τ Ρ 30.03 29.91 -0.12 Μ 39.90 40.08 0.18 0 30.07 30.01 -0.06 υ Ρ 39.96 39.79 -0.17 Μ 29.95 29.88 -0.07 0 30.09 30.33 0.24 -39- (請先閔讀背面之.，¾意事項再 本頁) 本紙法尺度適用中國國家標準（CN:S ) A4規格（210X297公釐） 448292 Α7 Β7 五、發明説明（37 wResearch Corporation, Acton, FREE. The mono-optic device is constructed as a tower grating system with three dispersion gratings. These gratings are · 15 grooves / mm, which emits light at 750¾ micrometers; 300 grooves / mm, which emits light at 7500 nanometers; and 600 grooves / mm, which emits light at 750 nanometers, of which 300 grooves The groove / mm light thumb is used for analysis and provides a spectral reach of approximately 1700 cm.i. A fiber holder with eight 200-micron input terminals is connected to the inlet of the monochromator so that eight Raman channels can be collected simultaneously. This fiber series _ -35- This paper size is suitable for China Standard (CNS) A4 specification (210X297mm) Outfit I; I t ~ '.1τ. III I- H II ---- (Please read first What's the matter of washing the back? Then this page) · d 4 8 2 9 2 A7 B7 Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives 5. The invention description (33) is in the form of a linear array, and it is directly in front of the entrance slit square. One of the eight monochromator fibers is connected to the sample probe fiber and the other fiber is connected to the reference probe fiber. The dispersed radiation is detected by a Princeton Instruments (Trei \ ton, NJ) thermoelectrically cooled CCD detector and converted into an electronic signal. This CCD chip is a 1: 1 back-illuminated detection system for 512 pixels. The instrument is controlled by the CSMA data collection software provided by Princeton Instruments: a spectrum is acquired every 30 seconds. Apply the cubic spline function interpolation method as in Example 2 to linearize the horizontal coordinates of the convolution reference and sample spectral data. And apply a standardized method described in US Patent No. 5,455,673 to remove banding and band offset. The normalized waveform obtained is smoothed in the Fourier domain by a Gaussian widening function of three and a half widths and a Lorentz narrowing function of two and a half widths a. The standard sample spectrum of the sample AK will be taken with the least square (PLS) Data Analysis Suite (UNSCRAMBLER, computer aided model A / S from Trenhan, Norway) was used to generate a calibration of the components in the xylene mixture. This criterion is then used to obtain composition information for each sample. Samples L-Q constitute an independent validation group. These samples were measured in a manner similar to sample A-K, and the standard spectra of each sample were obtained. The calibration function is then applied to each standard spectrum to obtain the measurement results of the sample composition. The center of the monochromator was intentionally changed from 901 nm to 899 nm to simulate the instability of the device, and the samples G and LQ were measured again ( Re-marked as -36- This paper size applies Chinese National Standard (CNS) Α4% grid (210X 297 mm) I ---; -------- ^ ------------ 0 (Please read 1JE on the back of the page, and then J- * .. this page) ΔΛ82 92 A7 B7 V. Description of the Invention (34) Sample RX), and obtain a new set of standard spectra. Applying the calibration function to each standard spectrum, the measurement results of the sample composition are obtained. "In Table 1 below, marked as" Invention ", the one shown is the method according to the present invention. The percentage of moles of the composition in the xylene mixture was measured spectroscopically. The differences between these and the actual percentages listed in the " STD " column are shown in the " difference " column. The components are abbreviated as follows: P-p-xylene, M = meta-xylene, and 0 = o-xylene. Table 1 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read Mind " on the back of the matter again. This page) -37- Sample composition STD Invention difference AP 39.86 39.84 -0.02 Μ 35.22 35.19 -0.03 0 24.91 24.97 0.06 B P 39,98 40.10 0.12 M 25.01 25.07 0.06 0 35.01 34.83 -0.18 C P 34.97 34.99 0.02 M 25:13 25.21 0.08 0 39.91 39.80 -0.11 D P 34.78 34.81 0.03 M 39.93 39.94 0,01 0-25.29 25.29 0.04 Ep 39.95 39.83 -0.12 M 25.08 24.92 -0.16 0 34.97 35.25 0.28 This paper size is applicable to Chinese National Standard (CNS) A4 Regulation Pan (210X297 mm) A7 448292 B7 V. Description of Invention (35) Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer Cooperative Association ^ F Ρ 33.34 33.28 -0.06 Μ ^ -η JJ, 33.44 0.12 0 33.33 33.28 -0.05 G Ρ 33.42 33.51 0.09 Μ 33,23 33.11 -0.12 0 33.35 33.37 0.02 Η P 25.12 25.14 0.02 Μ 39.94 39.91 -0.03 0 34.94 34.95 0.01 I Ρ 35.04 35.05 0.01 Μ 39.97 39.93 -0.04 0 24.99 25.02 0.03 J Ρ 39.97 39.93 -0.04 Μ 35.01 35.11 0.10 0 25.02 24.95 -0.07 Κ Ρ 24.97 24.92 -0.05 Μ 35:09 35.11 0.02 0 39.95 39.97 0.02 L Ρ 30.14 30.16 0.02 Μ 29.92 29.92 .0.00 0 39.94 39.92 -0.02 Μ 30.03 30.07 0.04 Μ 39.90 39.82 -0.08 0 30.07 30.12 0.05 Ϊ. Order.,. ~ Line (please read " 'description of the matter before then > this page) -38- This paper size applies to China National Standard (CNS) A4g (210X 297 mm) A7 4482 92 B7 5 Description of the invention (36) NP 39.96 39.96 0.00 Μ 29.95 30.07 0.12 0 30.09 29.97 -0.12 0 Ρ 35.01 34.85 -0.16 Μ 35.03 34.89 -0.14 0 29.97 30.26 0.29 P ρ 35.00 35.12 0.12 M 30.01 29.90 -0.11 0 34.99 34.98 -0.01 Q P 30.03 '30.04 0.01 M 34.99 35.00 0.01 0 34.98 34.97 -0.01 R P 33.42 33.40 -0.02 M 33.23 33.15 -0.08 0 33.35 33.45 0.10 S P 30.14 30.12 -0.02 M 29: 92 29.76 -0.16 0 39.94 40.12 0.18 τ P 30.03 29.91 -0.12 Μ 39.90 40.08 0.18 0 30.07 30.01 -0.06 υ P 39.96 39.79 -0.17 Μ 29.95 29.88 -0.07 0 30.09 30.33 0.24 -39 -(Please read Min. On the back, and then note the matter on this page) This paper method applies the Chinese national standard (CN: S) A4 specification (210X297 mm) 448292 Α7 Β7 5. Description of the invention (37 w

X Μ Ο Ρ Μ Ο Ρ Μ Ο 35.03 29.97 35.00 30.01 34.99 30.03 34.99 34.98 ^.92 35.03 30.05 35.05 30.15 34.δ〇 29.86 35.07 35.07 -0.09 0.00 0.08 0.05 0.14 -0.19 -0.17 0.08 0.09 以下疋表2顯示混合物Α-Κ進行# Μ , 逆仃权準的標準誤差，以 混合物组L-Q和R-X根據本發明進杆 彳疋，經由應用捲 函數於測得之樣品的拉曼光譜進行預測之棹準嗖差。另 含於表2内以作爲比較之用者，爲未應用本發明之方法 得的校準和預測誤差値。 表2 及 積 包 所 經濟部中失橾隼局貝工消費合作社印製 比較. Μ 一 標準誤差 P Μ 0 Ρ Μ 〇 樣品A-K 0.225 0.191 0.338 0.066 0.084 0.110 樣品L-Q 0.336 0.329 0.591 0.082 0.096 0.134 樣品R-X 3.595 3.949 7.495 0.109 0.116 0.148 由表2之記錄，— 可明顯地看出本發明之標準誤差値有相 當的減少’即使對校準樣品組Α_Κ亦然。而對確認樣品組 L-Q，甚至有更大之改良。然而，在R-χ紕，故意將單色 器中心改變2毫微米，以模擬分光光度系統不穩定性之情 40- 本紙張^度適用中S國家標準（CNS ) Α4規格（210X 297公釐） I I I I —裝 I 訂 . ~'線« . {請先閱水背由之·)i'意Ϋ項再 r本頁) 五、發明説明（3Q ) A7 B7 沉下，本發明之方法最顯著地證實其優點，其造 準誤差之戲劇性的降低。 預 本發明已特別參照其較佳具體實例作詳細之説明，但應 瞭解在本發明之精神和範圍内，可對其内容作各種變化及 修改。 測標 (請先閲讀背面之各意事項再,'·1·.本頁) -裝 訂 線 經濟部中央標準局員工消费合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐）X Μ Ο Ρ Μ Ο Ρ Μ Ο 35.03 29.97 35.00 30.01 34.99 30.03 34.99 34.98 ^ .92 35.03 30.05 35.05 30.15 34.δ〇29.86 35.07 35.07 -0.09 0.00 0.08 0.05 0.14 -0.19 -0.17 0.08 0.09 Below Table 8 shows the mixture A -K performs the standard error of #M, the inverse weighting standard, and uses the mixture group LQ and RX to perform the prediction according to the present invention, and uses the roll function to apply the Raman spectrum of the measured sample to predict the standard deviation. Also included in Table 2 for comparison purposes are the calibration and prediction errors 値 obtained without applying the method of the present invention. Table 2 and the print comparison of the Shellfish Consumer Cooperatives in the Ministry of Economic Affairs of the Jibao Institute. Μ standard error P Μ 0 Ρ 〇 sample AK 0.225 0.191 0.338 0.066 0.084 0.110 sample LQ 0.336 0.329 0.591 0.082 0.096 0.134 sample RX 3.595 3.949 7.495 0.109 0.116 0.148 From the records in Table 2, it can be clearly seen that the standard error of the present invention has a considerable reduction, even for the calibration sample group A_K. For the confirmation sample group L-Q, there are even greater improvements. However, at R-χ 纰, the center of the monochromator was intentionally changed by 2 nm to simulate the instability of the spectrophotometric system. 40- This paper is compliant with the National S (CNS) A4 specification (210X 297 mm) ) IIII — I-booking. ~ 'Line «. {Please read the water back first) i' the meaning of the item and then on this page) 5. Description of the invention (3Q) A7 B7 sinking, the method of the present invention is the most significant To prove its advantages, and its dramatic reduction in alignment error. The present invention has been described in detail with particular reference to its preferred embodiments, but it should be understood that various changes and modifications can be made to its content within the spirit and scope of the invention. Measurement (please read the intent on the back first, then "· 1 .. This page")-Gutter printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) Α4 specification (210 X 297 Mm)

Claims (1)

經濟部中央榇率局W：工消费合作社印製 d482 92 第85m〇64號專利中請案 益 :丨:z..:n 中文申請專利範圍修正本(的年6月）g8g /午〆古：::丄; 六、申請專利範圍 —'· l 一種以拉曼光譜術於原位定量監測化學製程中之有機化 學組合物中之一或多種選定成份之方法，其包括： (a) 以實質上之具波長200 nm至1500 nm之單色輻 射源’同時照射參考物質和包含一或多種化學成份之有 機化學組合物’該輻射係其來源傳輸至與該有機化學組 合物形成界面之光探針上，且該輻射源係利用激發導管 而與探針連接； (b) 利用位在遠離該有機化學組合物之分散攝譜儀或 FT-干涉計’同時在超過一個波長處，取得該參考物質 之捲積拉曼光譜，和該有機化學组合物之捲積拉曼光譜 ’其中該攝譜儀係經由收集導管而連接至該光探針； (c) 選擇該參考物質之標準拉曼光譜； (d) 由該參考物質之捲積拉曼光譜和標準拉曼光譜， 測定捲積函數； (e) 應用該捲積函數以調整該有機化學組合物之捲積 拉曼光譜’因而產生該有機化學组合物之標準拉曼光譜 ;以及 (f) 應用預定之校準方法，於該有機化學组合物之標 準拉曼光譜上； 由此可在取得該捲積拉曼光譜時原位確定化學製程中 之該有機化學组合物t之一或多種選定成份之量。 2. 根據申請專利範圍第1項之方法，其中該輻射源係為雷射 〇 3. 根據申請專利範圍第2項之方法，其中該雷射係為二極體 本紙法疋度遘用中國«家標準（CNS Μ4規接（210Χ297公釐） ---------訂 缘 (請先Μ讀背*之注意事項异填寫本貫) 448292 A8 B8 C8 D8 經濟部令央橾隼局頁工消費合作社印装 六、申請專利範圍 雷射。 4. 根據申請專利範圍第3項之方法，其中該二極體雷射係為 多型二極體雷射。 5. 根據申請專利範圍第1項之方法，其中該激發導管和該收 集導管各包含一個光學波導管。 6. 根據申請專利範圍第5項之方法，其中該激發導管和該收 集導管各更包含一個輻射濾光器= 7. 根據申請專利範圍第1項之方法，其中該光探針包含至少 兩根光學纖維。 8. 根據申請專利範圍第〖項之方法，其中該校準方法包括濃 度-強度相關（CIC)多變量校準，該濃度-強度相關校準係 由已知濃度之化學成份之混合物之拉曼光譜測得。 9. 根據申請專利範圍第8項之方法，其中該混合物之拉曼光 譜包括標準拉曼光譜》 10. 根據申請專利範圍第1項之方法，其中該參考物質包接蹲 石。 11. 根據申請專利範圍第1項之方法，其中該有機化學組合物 包括由單體之反應化合物’藉反應所製得之可形成聚合 物之組合物。 12_根據申請專利範圍第1 1項之方法，其中該單體之反應化 合物’包括二元醇化合物及二羧酸化合物或二叛酸醋化 合物。 13.根據申請專利範圍第1 2項之方法，其中該二元醇化a物 包括乙二醇、1，4-環己烷二甲醇、丨〆· 丁二醇、二 _____-2- 本紙逋用家梂準（CNS >八4祕（2i〇x腕、釐） ---1--：-----^------"------^ (請先閲讀背面之注意事項再填'寫本頁) 448292 A8 B3 C8 D8 '申請專利範圍 醇、三乙二醇 '聚乙二醇、聚丙二醇、對苯二甲酸雙（2-每己基）酯、對苯二曱酸雙（4-超甲基環己基甲基）酯、或 對笨二甲酸（2 -羥乙基）-(4-羥乙基環己基甲基）酯。 14‘根據申請專利範圍第1 2項之方法，其中該二幾酸化合物 包拾對苯二甲酸、間苯二曱酸，1，4-笨二羧酸、2,6 -莕 二羧酸、1,4-環己烷二羧酸、或己二酸。 15. 根據申請專利範園第1 2項之方法，其中該二羧酸酯化合 物包括對苯二甲酸二甲酯、間苯二甲酸二甲酯、2,6-葚 ~羧酸二甲酯、1,4 -環己烷二羧酸二甲酯、己二酸二甲 醋、對苯二甲酸雙（2-趣乙基）酯、對笨二甲酸雙（4 -經甲 基.環己基甲基）酯、或對苯二甲酸（2·羥乙基）-(4-羥甲基 環己基甲基）酯。 16. 根據申請專利範圍第i 2項之方法，其中該單體之反應化 合物包括乙二醇及對苯二甲酸。 Π_根據申請專利範圍第i 6項之方法，其中該反應化合物更 包括環己淀二甲醇。 18. 根據申請專利範圍第i 2項之方法，其中該單體之反應化 合物包括乙二醇及對苯二甲酸二甲酯。 19. 根據申請專利範圍第〖8項之方法，其中該反應化合物更 包括環己烷二甲醇。 20. 根據申請專利範圍第1 1項之方法’其中該有機化學組合 物更包括聚（對苯二甲酸乙二酯）。 21. 根據申請專利範圍第1項之方法’其中該有機化學組合物 包括在溫度南至235 C的蒸備塔頂部之揮發性物質。 -3- 本紙依尺度適用t國困家樣率(CNS ) A4说格（210X297公釐） ---------、装--1 订 ,级， .-4 * * V t锖先閱讀背而之注意事項鼻填寫本萸) 經濟部中夫揉率局頁工洧费合作社印策Central Government Bureau of the Ministry of Economic Affairs W: Industrial and consumer cooperatives printed d482 92 No. 85m〇64 patent claim: 丨: z ..: n Chinese version of the revised patent scope (June of the year) g8g / Wuxi ancient ：:: 六; VI. Patent Application Scope-'· l A method for quantitatively monitoring one or more selected components in an organic chemical composition in situ by Raman spectroscopy in a chemical process, including: (a) using Essentially a monochromatic radiation source with a wavelength of 200 nm to 1500 nm 'simultaneously irradiates a reference substance and an organic chemical composition containing one or more chemical components' The radiation is light transmitted from its source to the interface forming the organic chemical composition On the probe, and the radiation source is connected to the probe using an excitation catheter; (b) using a dispersion spectrograph or FT-interferometer located at a distance from the organic chemical composition to obtain the Convolution Raman spectrum of a reference substance, and convolution Raman spectrum of the organic chemical composition, wherein the spectrograph is connected to the optical probe via a collection duct; (c) selecting a standard Raman of the reference substance Spectrum; (d) by Determine the convolution function by referring to the convolution Raman spectrum and the standard Raman spectrum of the substance; (e) apply the convolution function to adjust the convolution Raman spectrum of the organic chemical composition ', thereby generating a standard for the organic chemical composition Raman spectroscopy; and (f) applying a predetermined calibration method to the standard Raman spectroscopy of the organic chemical composition; thus, the organic chemical combination in the chemical process can be determined in situ when the convolutional Raman spectrum is obtained The amount of one or more selected ingredients. 2. The method according to item 1 of the scope of patent application, wherein the radiation source is a laser 03. The method according to item 2 of the scope of patent application, wherein the laser system is a diode paper method (use China « Standards (CNS Μ4 connection (210 × 297 mm) --------- Determining the margin (please read the precautions of M first and fill in the original)) 448292 A8 B8 C8 D8 Pager Consumer Cooperative Co., Ltd. 6. Laser for patent application scope. 4. The method according to item 3 of the patent application scope, wherein the diode laser is a multi-type diode laser. 5. According to the patent application scope The method according to item 1, wherein the excitation catheter and the collection catheter each include an optical waveguide. 6. The method according to item 5 of the patent application scope, wherein each of the excitation catheter and the collection catheter further includes a radiation filter = 7 The method according to item 1 of the scope of the patent application, wherein the optical probe contains at least two optical fibers. 8. The method according to the item of scope of the patent application, wherein the calibration method includes concentration-intensity correlation (CIC) multivariate calibration. , The concentration-intensity phase Calibration is measured by Raman spectrum of a mixture of chemical ingredients of known concentration. 9. The method according to item 8 of the scope of the patent application, wherein the Raman spectrum of the mixture includes the standard Raman spectrum. The method according to item 1, wherein the reference substance comprises a squat stone. 11. The method according to item 1 of the scope of patent application, wherein the organic chemical composition includes a polymer which can be formed by reacting a monomeric reactive compound 'by reaction. 12_ The method according to item 11 of the scope of the patent application, wherein the monomer's reactive compound 'includes a glycol compound and a dicarboxylic acid compound or a diacid vinegar compound. 13. According to the first scope of the patent application The method according to item 2, wherein the diol a includes ethylene glycol, 1,4-cyclohexanedimethanol, butanediol, di-butanediol, di ___- 2- paper user's standard (CNS > Eight 4 secrets (2i〇x wrist, centimeter) --- 1--: ----- ^ ------ " ------ ^ (Please read the precautions on the back before filling in ' (Write this page) 448292 A8 B3 C8 D8 'Patent application scope alcohol, triethylene glycol' polyethylene glycol, polypropylene glycol , Bis (2-perhexyl) terephthalate, bis (4-supermethylcyclohexylmethyl) terephthalate, or (2-hydroxyethyl)-(4-hydroxyterephthalate) Ethylcyclohexylmethyl) ester. 14 'The method according to item 12 of the scope of the patent application, wherein the dikisuccinic acid compound includes terephthalic acid, isophthalic acid, 1,4-dicarboxylic acid, 2,6-Hydrylene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, or adipic acid. 15. The method according to item 12 of the patent application park, wherein the dicarboxylic acid ester compound includes terephthalic acid Dimethyl formate, dimethyl isophthalate, dimethyl 2,6-fluorene ~ carboxylate, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl adipate, terephthalic acid Bis (2-Ethyl) ester, bis (4-Methyl.cyclohexylmethyl) paraben, or (2 · hydroxyethyl)-(4-hydroxymethylcyclohexyl) terephthalate Methyl) ester. 16. The method according to item i 2 of the patent application range, wherein the reaction compound of the monomer includes ethylene glycol and terephthalic acid. Π_ The method according to item i 6 of the scope of patent application, wherein the reaction compound further includes cyclohexyl dimethanol. 18. The method according to item i 2 of the scope of patent application, wherein the reaction compound of the monomer includes ethylene glycol and dimethyl terephthalate. 19. The method according to item 8 of the application, wherein the reaction compound further comprises cyclohexanedimethanol. 20. The method according to item 11 of the scope of patent application, wherein the organic chemical composition further comprises poly (ethylene terephthalate). 21. The method according to claim 1 of the scope of the patent application, wherein the organic chemical composition comprises a volatile substance at the top of the distillation tower at a temperature of south to 235 ° C. -3- This paper is applicable according to the country's home sample rate (CNS) A4 grid (210X297 mm) ---------, installed-1 order, grade, .-4 * * V t 锖First read the back of the note and fill in this note)) The Ministry of Economic Affairs