1232775 玖、發明說明： 相關申請案 之美國臨時申請案第 本發明係主張2〇〇〇年】月7曰申請 6〇/1 75,006號之優先權。 本發明係關於—種製造聚酯之方法 草酸氧鈦如草酸氧鈦鋰作έ寻別疋—關於使用 略 作為觸媒與觸媒增強劑如金屬直妒 鹽例如草酸鋰組合供該反應，以對快迷反廡々 =媒位準下對所得聚酯提供改良特性如減少之乙搭含量 ㈣性。在草酸氧鈦觸媒與觸媒增強劑之間發現 二文關係。亦在草酸氧鈦觸媒、觸媒增強劑與金屬輔觸媒 如虱化銻或三醋酸銻之間發現增效關係。 ” 習知技藝之說明 產生聚酯之聚縮合反應需要極長時間，其顯然由適當觸 媒減少。各種觸媒被用以縮短反應時間。例如，三氧化銻' 三醋酸銻及三甘油氧化銻通常用作聚縮合觸媒。 曾提議草酸氧鈦化合物作為觸媒供聚縮合反應以產生聚 酯。然而，當草酸氧鈦觸媒用作聚酯之聚縮合觸媒時會造 成所得聚酯之顏色問題。 聚酯係藉酯化、酯交換或二元酸如對酜酸及異酞酸或其 酯、酸氣化物及二醇類如乙二醇及四亞曱二醇或其氧化物 之官能衍生物及碳酸衍生物之官能衍生物之聚縮合獲得。 在此情況，當使用一種二元酸成份及二醇成份時，可得單 聚酯。當至少二種或多種二元酸成份及二醇成份被混合、1232775 发明 Description of the invention: United States provisional application No. of the related application The present invention claims priority of application No. 60/1 / 1,75,006, dated January 7, 2000. The present invention relates to a method of manufacturing polyester, such as titanium oxalate oxalate, lithium lithium oxalate, and the like. Regarding the use of a combination of a catalyst and a catalyst enhancer such as a metal direct jealous salt such as lithium oxalate for the reaction, Respond to fast fans = provide improved properties to the obtained polyester such as reduced ethylene content at the medium level. A secondary relationship was found between the titanyl oxalate catalyst and the catalyst enhancer. Synergistic relationships have also been found between titanium oxalate catalysts, catalyst enhancers, and metal auxiliary catalysts such as antimony lice or antimony triacetate. Description of the know-how. Polycondensation reaction to produce polyester takes an extremely long time, which is obviously reduced by appropriate catalysts. Various catalysts are used to shorten the reaction time. For example, antimony trioxide 'antimony triacetate and antimony triglyceride It is usually used as a polycondensation catalyst. A titanium oxalate compound has been proposed as a catalyst for the polycondensation reaction to produce polyester. However, when the titanium oxalate catalyst is used as a polycondensation catalyst for polyester, it will cause Color problems: Polyesters are based on esterification, transesterification or dibasic acids such as p-acid and isophthalic acid or their esters, acid gases and glycols such as ethylene glycol and tetramethylene glycol or their oxides. The polycondensation of functional derivatives and functional derivatives of carbonic acid derivatives is obtained. In this case, when a dibasic acid component and a diol component are used, a monopolyester can be obtained. When at least two or more dibasic acid components and The diol ingredients are mixed,
O:\68\68625-9303 10 DOC 1232775 酯化或受酯交換然後受聚縮合時，可得混合之共聚酯。當 I聚醋或二種或多種混合之共聚醋之最初聚縮合物受聚: 口時，可仔有次序聚酯。在本發明中，術語聚酯為此三種 類型之一般標示。 白知之文件揭不草酸氧鈦化合物用作聚酯之聚縮合觸 媒。所揭不之草酸氧鈦化合物包括草酸氧鈦鉀、草酸氧鈦 鉍、草酸氧鈦鋰、草酸氧鈦鈉、草酸氧鈦鈣、草酸氧鈦鳃、 草酸氧鈦鋇、草酸氧鈦鋅及鈦酸氧鈦鉛。然而，根據該等 文件芩考之貝例，僅草酸氧鈦鉀及銨真正被用以催化形成 聚酯之反應。參照例如日本專利公告案42_13〇3〇, 1967, 7， 25公告。歐洲專利申請案Ep 〇6997〇〇 A2，1996，3，^公告， 讓渡於Hoechst，標題為”熱安定性天然顏色不含銻之聚酯 之製造方法及自其製造之產品”，揭示聚縮合觸媒之用途， 然而僅草酸氧鈦鉀及異丙酸鈦被用於該觸媒，且當揭示改 良顏色及不含銻之聚酯時，亦使用鈷或光學拋光劑。其他 專利揭示草酸氧鈦鉀作為製造聚酯之聚縮合觸媒，例如， 美國專利4,245,086，發明人為Keiichi Uno等人，曰本專利 06丨28464，發明人為Ishida，Μ·等人。美國專利 3,957,886，標題為"製造聚酯樹脂之方法”，mde〇, Μ•等人， column 3，59行至c〇lumn 4，1〇行，包含聚酯用之草酸氧鈦 觸媒包括許多類型草酸氧鈦觸媒名單之揭示。但是，僅草 酸氧鈦鉀及草酸氧鈦銨用於實例中而在其較佳草酸氧鈦觸 媒中甚至未列示草酸氧鈦鋰。 發明之概述 O:\68\68625-930310.DOC η 1232775 本發明乃基於草酸非氧鈦可增強草酸氧鈦觸媒之催化官 月匕度之發現。本發明提供—種新穎催化組合物，包括草酸 氧鈦觸媒及金屬草酸鹽觸媒增強劑以及視需要包含金屬輔 觸媒如銻基礎之觸媒。在草酸氧鈦觸媒與觸媒增強劑之間 么現增效關係在草酸氧鈦觸媒、觸媒增強劑與金屬輔觸 媒如氧化銻或三醋酸娣之間㈣現增效關係、。亦提供一種 在催化有效量之聚縮合觸媒存在下，藉形成聚醋之試劑之 ?么縮合製造聚酯之改良方法’其中該改良包括使用含有草 酸氧鈦如草酸氧鈦減觸媒增㈣如非氧鈦金屬草酸鹽如 草酸鐘以及視需要含有金屬觸媒如氧化銻或三醋酸録之新 穎觸媒組合物作為聚縮合觸媒。該改良方法製造具有較低 乙《及良好顏色之改良聚§旨。草酸氧鈦/觸媒增強劑組合 物可與其他觸媒組合用作聚縮合觸媒，以達成增效催化活 性。較佳者為草酸氧鈦鐘、Li2Ti〇(C2〇4)2、草酸鐘、 Li2(C2〇4)2與氧化銻或三醋酸銻之組合。 發明之詳細說明 藉形成聚醋之試劑之聚縮合來製造聚醋為熟悉聚醋技藝 者已知。反應用之傳統觸媒為氧化銻。本發明乃基於一項 發現’即’在草酸氧鈦觸媒與金屬草酸鹽觸媒增強劑（即草 酸經）間之增效關係在藉製造優異顏色（白色）之聚醋之聚縮 合反應之觸媒性能方面較其他草酸氧鈦觸媒更優異。因而 可除去含銻之觸媒之需要’而不含銻之聚酉旨可用草酸氧鈦 鐘作為觸媒製成。當草酸氧鈦鐘與其他聚縮合觸媒組合使 用以製造聚酯時’只要草酸氧鈦鋰基於反應混合物内鈦之O: \ 68 \ 68625-9303 10 DOC 1232775 When esterified or transesterified and then subjected to polycondensation, a mixed copolyester can be obtained. When the initial polycondensate of I polyacetate or two or more mixed copolyesters is polymerized, the polyester can be ordered. In the present invention, the term polyester is a generic designation for these three types. The white paper discloses that titanium oxalate compound is used as a polycondensation catalyst for polyester. The disclosed oxytitanium oxalate compounds include potassium oxotitanate, bismuth oxotitanate, lithium oxotitanium oxalate, sodium oxotitanate, sodium oxotitanate calcium, oxotitanium gill, barium oxotitanate, zinc oxotitanate, and titanium Acid Titanium Lead. However, according to examples cited in these documents, only potassium titanyl oxalate and ammonium are really used to catalyze the reaction to form polyesters. For example, refer to Japanese Patent Publication No. 42-1330, 1967, 7, 25. European Patent Application Ep 06997900A2, 1996, 3, ^ Announcement, assigned to Hoechst, entitled "Thermally stable natural color antimony-free polyester manufacturing method and products made therefrom" The use of condensation catalysts, however, only potassium titanyl oxalate and titanium isopropoxide are used for this catalyst, and cobalt or optical polishing agents are also used when polyesters with improved color and antimony-free are disclosed. Other patents disclose potassium titanyl oxalate as a polycondensation catalyst for manufacturing polyesters. For example, U.S. Patent No. 4,245,086, Keiichi Uno et al., Japanese Patent No. 06, 28464, and Ishida, M. et al. U.S. Patent 3,957,886, entitled " Method for Manufacturing Polyester Resin, " mde0, M •, et al., Columns 3,59 to column 4,10, containing titanium oxalate catalysts for polyesters including A list of many types of titanyl oxalate catalysts is disclosed. However, only potassium titanyl oxalate and ammonium titanyl oxalate are used in the examples and even their preferred titanyl oxalate catalysts are not even listed for lithium titanyl oxalate. SUMMARY OF THE INVENTION O: \ 68 \ 68625-930310.DOC η 1232775 The present invention is based on the discovery that non-oxytitanium oxalate can enhance the catalytic activity of oxytitanium oxalate catalysts. The present invention provides a novel catalytic composition, including titanyl oxalate Catalysts and metal oxalate catalyst enhancers and catalysts containing metal auxiliary catalysts such as antimony based catalysts as required. What is the synergistic relationship between the titanium oxalate catalyst and the catalyst enhancer? A synergistic relationship between catalyst enhancers and metal auxiliary catalysts such as antimony oxide or rhenium triacetate. Also provides a reagent to form polyacetate in the presence of a catalytically effective amount of polycondensation catalyst? Improved method for making polyester by condensation 'wherein the improved package As a polycondensation catalyst, a novel catalyst composition containing titanyl oxalate such as titanyl oxalate is used as a polycondensation catalyst. The improved method produces a modified poly with lower B and good color. The purpose is to use titanium oxalate / catalyst enhancer composition in combination with other catalysts as a polycondensation catalyst to achieve synergistic catalytic activity. The preferred one is a combination of titanyl oxalate clock, Li2Ti0 (C204) 2, oxalate clock, Li2 (C2104) 2, and antimony oxide or antimony triacetate. Detailed description of the invention by polycondensation of reagents forming polyacetate The production of polyacetate is known to those skilled in the art of polyacetate. The traditional catalyst used in the reaction is antimony oxide. The present invention is based on the discovery that the titanium oxide oxalate catalyst and the metal oxalate catalyst enhancer (that is, The synergistic relationship between oxalic acid is superior to other titanium oxyoxalate catalysts in terms of the catalyst performance of polycondensation reaction by producing excellent color (white) polyacetic acid. Therefore, the need for antimony-containing catalysts can be removed. Antimony-free polyfluorinated titanyl oxalate As the catalyst is made. When the clock with other titanyl oxalate polycondensation catalyst for producing a polyester composition enabled 'as long as lithium titanyl oxalate based on the reaction of the mixture of titanium
O:\68\68625-930310 DOC 1232775 乂 ％ /百萬（較佳為1至20)，即可保持由使用草 酸氧鈦鋰所提供之哕辇 更用卓 ”所勺人之立^ 4優異。本文所用之術語"草酸氧鈦鐘 ^⑤義為草酸氧鈦二鐘隊io(C2〇4)2]及草酸氧鈦 早經其中草酸氧鈦二鐘之鐘之一係用另一驗金屬如卸（如 挪咐2〇4)2)及其有或不具水合之水之該化合物所取 代。當鍊之消除並非所得催化產物之條件時，草酸氧欽鐘 觸媒可與娣觸媒組合以達成二觸媒之優點。O: \ 68 \ 68625-930310 DOC 1232775 乂% / million (preferably 1 to 20), which can maintain the superiority of those who are provided by the use of lithium titanyl oxalate ^ 4 Excellent The term used in this article " Otitanium oxalate ^ ⑤ means the second group of oxotitanium oxalate io (C2〇4) 2] and one of the two clocks of the second titanyl oxalate was tested by another test If the metal is unloaded (such as 208) 2) and its compound with or without hydrated water, when the elimination of the chain is not a condition of the obtained catalytic product, the oxalanium oxalate catalyst can be used with the tritium catalyst Combination to achieve the advantages of two catalysts.
除了增強草酸氧鈦催化聚縮合反應之催化功效以外，當 金屬草酸鹽以催化有效量與已知試劑使用以參與酯化或反 式酯化反應時，其亦可增強草酸氧鈦對催化酯化及反式酯 化反應之催化功效。催化有效量為適合。較佳者為基於每 百萬份酯化或反式酯化反應混合物鈦之量約為3份草酸氧 鈦。 藉由聚縮合反應形成聚酯之反應物為熟悉此技藝者已知 且揭示於專利案中，例如，美國專利5，198,530，發明人為 Kyber，M·等人，美國專利4,238,593，發明人為B· Duh，美鲁 國專利4,356,299，發明人為Cholod等人及美國專利 3,907,754’發明人為Tershasy等人，其揭示物被併入本文_ ~ 供參考。此技藝亦述於’’綜合聚合物科學”，Ed· G.C· . Eastmond 等人，Pergamon Press，Oxford 1989，Vol. 5， 275-3 15 頁，及 R.E. Wilfong，J· Polym· Science，54 (1961)， 3 85-4 1 0頁。如此製成之特別重要之商用類型之聚酯為聚對 酉太酸次乙II (PET)。 草酸氧鈦··草酸氧鈦包括金屬草酸氧鈦In addition to enhancing the catalytic efficacy of the titanyl oxalate catalyzed polycondensation reaction, when the metal oxalate is used in a catalytically effective amount with a known reagent to participate in the esterification or trans-esterification reaction, it can also enhance the catalytic effect of titanyl oxalate on the catalytic esterification. Catalytic effect of hydration and trans-esterification. A catalytically effective amount is suitable. Preferred is about 3 parts of titanyl oxalate based on 1 million parts of titanium in the esterification or trans-esterification reaction mixture. Reactants that form polyesters by polycondensation are known to those skilled in the art and are disclosed in patents, for example, U.S. Patent 5,198,530, inventors Kyber, M. et al., U.S. Patent 4,238,593, and inventors B. Duh, U.S. Patent 4,356,299, Cholod et al. And U.S. Patent No. 3,907,754 'Tershasy et al., The disclosures of which are incorporated herein by reference. This technique is also described in "Integrated Polymer Science", Ed · GC ·. Eastmond et al., Pergamon Press, Oxford 1989, Vol. 5, 275-3 pages 15 and RE Wilfong, J. Polym. Science, 54 ( 1961), 3 85-4 1 0. A particularly important commercial type of polyester made in this way is polyethylene terephthalate II (PET). Titanyl oxalate · Titanium oxalate includes the metal titanyl oxalate
O:\68\68625-930310 DOC ^32775 :2τ::2〇4)2(Η2〇)η]，其中河各為獨立選自鉀、鐘、鈉及 氧二！氧鈦經及非金屬草酸氧鈦如草酸氧鈦錄。草酸 之水量。 一 Κ σ之水，即，η代表水合 草酸非氧鈦··作為草酸轰# . 虱鈦觸媒之催化增強劑之草酸非 乳鈦包括草酸鐘、Li2C2〇4、草酸納、Na2c2〇4、草酸卸、 草酸链。 仏绝、C截。較佳者為 觸媒.與草酸氧鈦觸媒及金屬草酸鹽增強劑組合起作用 之觸媒包括三醋酸錄、sb(CH3c00)3、甘油氧化錄、 sb2(OCH2CH2〇)3、氧化銻（Sb2〇3)。 增強草酸氧鈦觸媒之催化活性之有效量每份草酸氧鈦觸 媒為至少約i份金屬草酸鹽。較I者為基於草酸氧鈦觸媒及 即使有輔觸媒之全部重量，每份觸媒約丨份至約⑽份增強 將催化有效量之草酸氧鈦加入形成聚酯之反應物内。較 佳者為基於鈦於觸媒中之重量及形成聚酯之反應物之重 里，每百萬觸媒約1份至約40份，其為約相同於基於鈦於觸 媒中之重量之所得聚酯中4〇份/百萬重量觸媒之丨份。 觸媒增強劑與一種或多種觸媒之組合供製造pET樹脂之 聚縮合反應之增效性能示於下列實例。 實例 以在反應器底部設有擠歷螺旋之3 /1 6不錄鋼，1 · 5 l反應 器實施觸媒評估。容器設有3個入口並用具有安培度監視之 O:\68\68625-9303I0 DOC -10- 1232775 電動馬達垂直攪拌。實驗室實驗係使用形成聚酯之反應 物，BHET，及普通瓶樹脂熱屬器處方，皆在4 〇莫耳刻尺 上進行。在BHET裝填時加入實驗用觸媒。 將雙（2-羥基乙基）對酞酸酯（bhet)及觸媒加入反應器 内，内含物用氮氣遮蔽。混合物在減壓下加熱並恆定攪拌。 除去並截留在聚合時產生之EG。當攪拌器轉矩到達一位 準，由安培度標示至攪拌器馬達，對聚合物通常為IV〜〇6 時，停止聚合作用。 使用上述程序及各種觸媒與觸媒增強劑之量進行Μ個實 例。 實例A觸媒—240 Ppm自氧化銻（Sb2〇3)之銻-反應時間 = 127分鐘 實例B觸媒10 ppm自草酸鐘之氧欽_反應時間=1〇〇分鐘實 例1觸媒一1 〇 p p m自蕈酿辟> g力丄」4 λ , 叩日早a文鋰之虱鈦+ 146ppm草酸鋰（或約ΐ5 當量）-反應時間=53分鐘實例2觸媒一 1〇 ppm自草酸氧欽鐘 之鈦+735 Ppm草酸鋰（或約7〇當量）_反應時間=55分鐘 貫例C觸媒—6 ppm自草辦气，丨 ,自卓H缝之鈦+75 ppm自氧化録 (81^2〇3)之錄-反應時間==：1〇5分鐘 貫例D觸媒—6 ppm自草酸g处加 目皁馼虱鈦鋰之鈦+150ppm自氧化 之銻-反應時間=110分鐘 β 實例3觸媒—6 ppm自草酸童 虱鈦鋰之鈦+75 ppm自氧化録 之，367Ppm錢峨約15當量）_反應時間⑷分鐘 貫例4觸媒—3 ppm自草酸第 •礼鈦鐘之鈦+38 ppm自氧化错 之銻+184 ppm草酸鋰（或約 旦 、 田里）-反應時間=90分鐘O: \ 68 \ 68625-930310 DOC ^ 32775: 2τ :: 2〇4) 2 (Η2〇) η], where each is independently selected from potassium, bell, sodium and oxygen two! The titanyl oxide is recorded by non-metal titanyl oxalate such as titanyl oxalate. The amount of oxalic acid. One K σ of water, that is, η represents hydrated non-oxytitanium oxalate ·· as an oxalic acid bomb.. The non-lactate titanium oxalate that is a catalytic enhancer of lice titanium catalyst includes oxalic acid bell, Li2C2O4, sodium oxalate, Na2c2O4, Oxalic acid unloading, oxalic acid chain. Absolutely, C cut. The catalyst is preferred. The catalysts that work in combination with the titanyl oxalate catalyst and the metal oxalate enhancer include triacetate, sb (CH3c00) 3, glycerine oxide, sb2 (OCH2CH2〇) 3, antimony oxide (Sb203). An effective amount to enhance the catalytic activity of the titanyl oxalate catalyst is at least about i parts of the metal oxalate per part of the titanyl oxalate catalyst. Compared with I, it is based on titanium oxalate catalyst and even with the total weight of auxiliary catalyst, each part of the catalyst is enhanced by about 丨 to about ⑽ parts. A catalytically effective amount of titanium oxalate is added to the reactant forming the polyester. Preferably, it is based on the weight of titanium in the catalyst and the weight of the reactants forming the polyester, about 1 to about 40 parts per million catalyst, which is about the same as the weight based on the weight of titanium in the catalyst. 40 parts per million by weight of catalyst in polyester. The synergistic properties of a catalyst condensation agent in combination with one or more catalysts for the polycondensation reaction for manufacturing a pET resin are shown in the following examples. Example The catalyst evaluation was carried out with a 3/1/6 non-recording steel and a 1.5 l reactor at the bottom of the reactor. The container has 3 inlets and is stirred vertically by an electric motor with O: \ 68 \ 68625-9303I0 DOC -10- 1232775 with amperage monitoring. Laboratory experiments were performed using a polyester-forming reactant, BHET, and ordinary bottle resin thermostat prescriptions on a 40 Molar ruler. Add catalyst for experiment during BHET filling. The bis (2-hydroxyethyl) terephthalate (bhet) and the catalyst were added to the reactor, and the contents were shielded with nitrogen. The mixture was heated under reduced pressure and constantly stirred. Remove and retain EG produced during polymerization. When the torque of the stirrer reaches a level, it is indicated by the amperage to the stirrer motor, and when the polymer is usually IV ~ 〇6, the polymerization is stopped. Using the above procedure and the amounts of various catalysts and catalyst enhancers, M examples were performed. Example A Catalyst—240 Ppm Antimony Oxide (Sb203) Antimony—Reaction Time = 127 minutes Example B Catalyst 10 ppm from Oxygenate of Bell Oxalate _ Reaction Time = 100 minutes Example 1 Catalyst 1 1 〇 ppm self-fermenting > g force 丄 4 λ, the next day a lithium lice titanium + 146 ppm lithium oxalate (or about 5 equivalents)-reaction time = 53 minutes Example 2 catalyst-10 ppm self-oxalate oxygen Qin Zhong's Titanium + 735 Ppm Lithium Oxalate (or about 70 equivalents) _Reaction Time = 55 minutes 81 ^ 2〇3)-reaction time == 105 minutes of the example D catalyst-6 ppm from the oxalic acid g, Titanium Lithium Titanium + 150 ppm auto-oxidized antimony-reaction time = 110 Minutes β Example 3 catalyst—6 ppm of titanium lithium from oxalic acid lice of titanium + 75 ppm of self-oxidation, 367Ppm Qiange about 15 equivalents) _Reaction time ⑷minutes of Example 4 catalyst—3 ppm of oxalic acid Titanium clock + 38 ppm self-oxidized antimony + 184 ppm lithium oxalate (or Jordan, Tanari)-reaction time = 90 minutes
O:\68\68625-930310.DOC !232775 實例5觸媒一2·6 ppm自草酸氧鈦鋰之鈦+33 ppm自氧化銻 之銻+160 ppm草酸鋰-反應時間=1 1〇分鐘 實例6觸媒一3 ppm自草酸氧鈦鋰之鈦+38 ppm自氧化銻 之銻+185 ppm草酸鋰-反應時間=95分鐘 實例7觸媒一3.3 ppm自草酸氧鈦鋰之鈦+41 ρρπ^氧化銻 之銻+1 46 ppm草酸鋰-反應時間=7〇分鐘 實例8觸媒一2.0 ppm自草酸氧鈦鋰之鈦+25 ppm自氧化銻 之銻+90 ppm草酸鋰-反應時間:^20分鐘 實例9觸媒一4.7 ppm自草酸氧鈦鋰之鈦+59 ppm自氧化銻 之銻+118??111草酸鋰_反應時間=1〇〇分鐘 實例10觸媒一2.0 ppm自草酸氧鈦鋰之鈦+25 ppm自氧化 銻之銻+5〇 ppm草酸鋰·反應時間=125分鐘 貫例11觸媒一2.0 ppm自草酸氧鈦鉀之鈦+25 ppm自氧化 銻之銻+90 ppm草酸鉀_反應時間=115分鐘 實例12觸媒―2·0 PPm自草酸氧鈦鉀之鈦+25 ppm自氧化 錦之銻+5 0 ppm草酸鋰·反應時間=165分鐘 貫例E觸媒—240 ppm自氧化銻之銻，包括商用顏色調整_ 反應時間=1 1 0分鐘 實例結果及討論 頃發現具有增強劑之觸媒提供改良生產力、較高亮度、 較高黃色、在大部份情況下，聚合物内減少之乙醛（AA)位 準。 比較實例B與實例丨，草酸鋰之加入草酸氧鈦鋰提供僅用 草酸鋰達成之雙倍聚合速率。形成之聚合物具有類似顏O: \ 68 \ 68625-930310.DOC! 232775 Example 5 Catalyst-2.6 ppm titanium from lithium titanyl oxalate + 33 ppm antimony from antimony oxide + 160 ppm lithium oxalate-reaction time = 1 10 minutes Example 6 Catalyst-3 ppm titanium from lithium titanyl oxalate + 38 ppm antimony from antimony oxide + 185 ppm lithium oxalate-reaction time = 95 minutes Example 7 catalyst-3.3 ppm titanium from lithium titanyl oxalate + 41 ρρπ ^ Antimony antimony oxide + 46 ppm lithium oxalate-reaction time = 70 minutes Example 8 catalyst-2.0 ppm titanium from lithium titanyl oxalate + 25 ppm antimony from antimony oxide + 90 ppm lithium oxalate-reaction time: ^ 20 Example 9 Catalyst-4.7 ppm of titanium from lithium titanyl oxalate + 59 ppm of antimony from antimony oxide + 118 ?? 111 lithium oxalate_Reaction time = 100 minutes Example 10 Catalyst-2.0 ppm from lithium titanyl oxalate Titanium + 25 ppm antimony from antimony oxide + 50 ppm lithium oxalate · Reaction time = 125 minutes Example 11 Catalyst-2.0 ppm titanium from potassium titanyl oxalate + 25 ppm antimony from antimony oxide + 90 ppm potassium oxalate _Reaction time = 115 minutes Example 12 catalyst ―2. 0 PPm from titanium titanyl oxalate + 25 ppm antimony from oxidized bromide + 5 0 ppm lithium oxalate • Reaction time = 165 minutes Example E catalyst-240 ppm Antimony from antimony oxide Including commercial color adjustments_ Reaction time = 1 10 minutes Example results and discussions found that catalysts with enhancers provide improved productivity, higher brightness, higher yellow, and in most cases reduced acetaldehyde in polymers (AA) level. In Comparative Example B and Example 丨, the addition of lithium oxalate to lithium titanyl oxalate provided a double polymerization rate achieved only with lithium oxalate. The polymer formed has a similar appearance
O:\68\68625-930310.DOC •12- 1232775 色、乙醛濃度及CEG數。加入額外量之草酸鋰，如實例2之 It况，相對於實例i呈現者，不會進一步增加聚合速率。顯 示在草酸氧鈦鋰與草酸鋰間之增效關係之存在。在比較實 例B、1及2與實例A時，在較實例A更低金屬負荷下可看見 月者之較高聚合速率，及類似聚合物IV、CEG數、乙醛濃 度及對前者之較高L*及b*值。 匕較灵例C與貫例3，草酸鐘之加入草酸氧鈦鐘與氧化録 之混合物實質上增加聚合速率。提供聚合物類似ceg數及 乙醛濃度。然而，實例3提供聚合物較實例c所製成者更高 L*及更低b*值。 比較實例C與實例4，當鋰與銻之位準被減半時，實例4 中草酸鋰之加入在鈦/銻負荷之5〇%下提供較高聚合速率， 提供氧化鋰能力之直接證據，以增強鈦與銻觸媒混合物之 催化活性。又，用實例4製成之聚合物内乙醛之濃度較實例 C者低得多。顏色亦改良，如值之改變所標示。 比較實例5至12(其係由草酸氧鈦、金屬草酸鹽及氧化録 之混合物所組成）與實例E(其為氧化銻），加入商用調整物。 可看到所有實例之類似聚合速率。然而，實例5至12之3成 份觸媒混合物皆具較低金屬負荷。又，用實例5至丨2製成之 聚合物濃度較實例E對照所看者更低（最多5〇%)，所得聚合 物具有良好顏色。 商用顏色調整物之加入實例E之氧化銻對照物内具有減 少所得聚合物之L*及b*值（即，亮度及泛黃度）之影響。若 商用顏色調整物未加入此對照物内時，所得聚合物之L*及 O:\68\68625-930310 DOC -13- 1232775 b:會具有類似於實例5至12所得者之值。 b*)、相觸等11例丨〇之觸媒混合物。其提供良好顏色㈣ “日，μ對對照物及在低觸媒位準下於PET内減 )相當之A A。O: \ 68 \ 68625-930310.DOC • 12-1232775 color, acetaldehyde concentration and CEG number. Adding an additional amount of lithium oxalate, as in the case of It in Example 2, does not further increase the polymerization rate relative to the presenter of Example i. The existence of a synergistic relationship between lithium titanyl oxalate and lithium oxalate is shown. When comparing Examples B, 1 and 2 and Example A, the higher polymerization rate of the month can be seen under the lower metal load than Example A, and the similar polymers IV, CEG number, acetaldehyde concentration and the higher of the former L * and b * values. Compared to the examples C and 3, the addition of a mixture of oxotitanium oxalate and oxidized clock to the oxalate clock substantially increased the polymerization rate. Provide polymer similar ceg number and acetaldehyde concentration. However, Example 3 provides polymers with higher L * and lower b * values than those made in Example c. Comparing Example C and Example 4, when the level of lithium and antimony is halved, the addition of lithium oxalate in Example 4 provides a higher polymerization rate at 50% of the titanium / antimony load, and provides direct evidence of the ability of lithium oxide. To enhance the catalytic activity of titanium and antimony catalyst mixtures. Further, the concentration of acetaldehyde in the polymer prepared in Example 4 was much lower than that in Example C. Colors have also improved, as indicated by changes in value. Comparative Examples 5 to 12 (comprising a mixture of titanyl oxalate, metal oxalate, and oxidizer) and Example E (which is antimony oxide) were added with commercial modifiers. Similar polymerization rates can be seen for all instances. However, 3 parts of the catalyst mixtures of Examples 5 to 12 all had a lower metal load. In addition, the polymers prepared using Examples 5 to 2 had a lower concentration (up to 50%) than the viewer of Example E, and the resulting polymers had good color. The addition of a commercial color adjuster has the effect of reducing the L * and b * values (i.e., brightness and yellowness) of the resulting polymer in the antimony oxide control of Example E. If a commercial color adjuster is not added to this control, the L * and O: \ 68 \ 68625-930310 DOC -13-1232775 b: of the obtained polymer will have values similar to those obtained in Examples 5 to 12. b *), 11 cases and other catalyst mixtures. It provides good color: "A, μ is equivalent to the control and subtracted from PET at low catalyst levels).
S承口生產率、乙醛在包裝樹脂内之減少及銻與全部 胃媒之成本有效降低為本發明之若干優點，如實例所示。 J7個實例之結果示於下表。所有觸媒(除了實例12)皆證 κ比李乂於實例A及E之標準録觸媒在BHE丁聚合中改良之生 產力。所得較亮但更黃產品及對所有批之咖3範圍為17± 内其對本纟a月實驗室熱麼器進行為典型$。對含欽聚 合物之乙難通常高於對含銻聚合物者。但須知，觸媒實 例4至12製成之聚合物，比較於在極低觸媒位準（當比較於 對物％，25%或以下金屬含量）達成之銻對照物時，其具 有顯著減少之乙酸：。 實例分成二組。實例A-D及1-4係關於草酸氧鈦鋰與草酸 鐘、草酸氧鈦鐘及草酸鋰與銻之增效作用，其導致改良極 大之聚合速率。實例E及5-12顯示，當3種成份之量被最適 化時’其產生一在減少相當多之金屬負荷下具有相等於對 照物速率之觸媒，所得聚合物具有良好顏色及減少之Aa含 量。 」^媒 量 聚合時間 IV CEG AA L* b* A .292公克 127分鐘 0.679 16 99 ppm 68.1 7.8 B .063公克 100分鐘 0.674 16 95 ppm 78.4 26.1 1 .212公克 53分鐘 0.666 18 112 ppm 75.9 28.3 2 .810公克 55分鐘 0.683 18 136 ppm 72.9 31.2 C .128公克 105分鐘 0.644 17 126 ppm 75.9 28.1 ~ O:\68\68625-9303 10.DOC -14- 1232775 D .220公克 110分鐘 0.694 18 128 ppm 72.8 22.5 3 .501公克 65分鐘 0.68 14 106 ppm 79.8 21.1 4 .250公克 90分鐘 0.628 24 47 ppm 80.46 20.1 5 .220公克 110分鐘 0.599 11 38 ppm 53.7 39.4 6 .253公克 95分鐘 0.590 13 37 ppm 48.3 39.8 7 .220公克 70分鐘 0.576 10 29 ppm 54.7 39.8 8 .135公克 120分鐘 0.603 13 43 ppm 48.4 41.9 9 .220公克 100分鐘 0.597 12 41 ppm 51.5 43.6 10 .094公克 125分鐘 0.602 13 26 ppm 48.9 38.3 11 .137公克 115分鐘 0.598 13 28 ppm 43.4 53.9 12 .096公克 165分鐘 0.581 16 19 ppm 45.4 49.3 E .292公克 110分鐘 0.599 14 48 ppm 29.9 -4.2 L*係關於亮度，愈接近100之值，聚合物愈亮。比較3成 份觸媒之L*為80.5(實例4)對在68.1下對氧化銻者（實 例A) 〇 b*測定係關係聚合物黃色之程度，b*值愈低，聚合物愈 不黃。比較3成份觸媒（實例4)b*值為20.1對在7.8下之 氧化銻（實例A)。 乙醛之濃度：AA為不宜聚合副產物。比較3成份觸媒（實 例10)AA位準為26 ppm對氧化銻對照物（實例E)所看見者， 48 ppm 〇 聚合速率：在反應時IV增加之速率，當IV約為0.6時，在 此情況下採取之測定。比較3成份觸媒（實例4)產生聚合物， 具有IV>0.6，反應時間為90分鐘。氧化銻（實例A)產生聚合 物，具有IV>0.6，反應時間為127分鐘。 固有黏度（IV):在反應時發生之聚合程度之標示。IV為 0.6示出數目平均分子量為〜19,000。 CEG :羧端基，每單位重量聚合物酸端基數之標示。比 較3成份觸媒（實例10)產生聚合物，具有CEG位準為13，氧 O:\68\68625-930310 DOC -15 - 1232775 化銻具有CEG位準有14。顯示用二系統製成之聚合物結構 上極類似。 觸媒濃度：實例10之3成份觸媒製成之聚合物含有34 ppm 自觸媒衍生之金屬，比較於自氧化銻製成之聚合物含有240 ppm自觸媒衍生之金屬。 O:\68\68625-930310.DOC -16-S mouthpiece productivity, reduction of acetaldehyde in packaging resin, and effective reduction of the cost of antimony and total gastric media are several advantages of the present invention, as shown in the examples. The results of J7 examples are shown in the table below. All catalysts (except Example 12) demonstrate the improved productivity of Kappa compared with Li's standard recorded catalysts in Examples A and E in BHE polymerization. The resulting brighter but yellower product and a range of 17 ± 3 for all batches are typical for a laboratory thermostat in this month. Difficulty with chitin-containing polymers is usually higher than with antimony-containing polymers. However, it should be noted that the polymers made from catalyst examples 4 to 12 have a significant reduction when compared to the antimony control achieved at a very low catalyst level (when compared to the antimony%, 25% or less metal content). Acetic acid :. The examples are divided into two groups. Examples A-D and 1-4 relate to the synergistic effects of lithium titanyl oxalate and bell oxalate, lithium titanyl oxalate, and lithium oxalate with antimony, which lead to improved extremely large polymerization rates. Examples E and 5-12 show that when the amounts of the three ingredients are optimized, it produces a catalyst with a rate equivalent to that of the control under a considerable reduction in metal load, and the resulting polymer has good color and reduced Aa content. ^ Vehicle polymerization time IV CEG AA L * b * A .292 g 127 minutes 0.679 16 99 ppm 68.1 7.8 B .063 g 100 minutes 0.674 16 95 ppm 78.4 26.1 1.212 g 53 minutes 0.666 18 112 ppm 75.9 28.3 2 .810 grams 55 minutes 0.683 18 136 ppm 72.9 31.2 C. 128 grams 105 minutes 0.644 17 126 ppm 75.9 28.1 ~ O: \ 68 \ 68625-9303 10.DOC -14-1232775 D .220 grams 110 minutes 0.694 18 128 ppm 72.8 22.5 3 .501 g 65 minutes 0.68 14 106 ppm 79.8 21.1 4 .250 g 90 minutes 0.628 24 47 ppm 80.46 20.1 5 .220 g 110 minutes 0.599 11 38 ppm 53.7 39.4 6 .253 g 95 minutes 0.590 13 37 ppm 48.3 39.8 7 .220 g 70 minutes 0.576 10 29 ppm 54.7 39.8 8 .135 g 120 minutes 0.603 13 43 ppm 48.4 41.9 9 .220 g 100 minutes 0.597 12 41 ppm 51.5 43.6 10 .094 g 125 minutes 0.602 13 26 ppm 48.9 38.3 11 .137 115 minutes 0.598 13 28 ppm 43.4 53.9 12 .096 grams 165 minutes 0.581 16 19 ppm 45.4 49.3 E .292 grams 110 minutes 0.599 14 48 ppm 29.9 -4.2 L * is about brightness, the closer the value is to 100, the brighter the polymer . Compare the 3 part catalyst with L * of 80.5 (Example 4) to 68.1 for antimony oxide (Example A). B * Determine the degree of yellowness of the polymer. The lower the b * value, the less yellow the polymer. The 3-component catalyst (example 4) was compared with a b * value of 20.1 versus antimony oxide at 7.8 (example A). Concentration of acetaldehyde: AA is not suitable for polymerization by-products. Compare the three-component catalyst (Example 10) with an AA level of 26 ppm to the antimony oxide control (Example E), 48 ppm. Polymerization rate: The rate of IV increase during the reaction. When the IV is about 0.6, the The measurement taken in this case. Comparative 3 component catalyst (Example 4) produced a polymer with IV > 0.6 and a reaction time of 90 minutes. Antimony oxide (Example A) produced a polymer with an IV > 0.6 and a reaction time of 127 minutes. Intrinsic viscosity (IV): The indication of the degree of polymerization that occurs during the reaction. An IV of 0.6 shows a number average molecular weight of ~ 19,000. CEG: carboxyl end group, indicating the number of acid end groups per unit weight of polymer. Comparing the three-component catalyst (Example 10) to produce a polymer with a CEG level of 13, and oxygen O: \ 68 \ 68625-930310 DOC -15-1232775 antimony chemical has a CEG level of 14. It is shown that the polymer structures made with the two systems are very similar. Catalyst concentration: The polymer made from the 3-component catalyst of Example 10 contains 34 ppm of metal derived from the catalyst, compared to 240 ppm of metal derived from catalyst from the polymer made from antimony oxide. O: \ 68 \ 68625-930310.DOC -16-