570955 A7 B7 五、發明説明（1 ) 發明詳述： 發明範圍 (請先閲讀背面之注意事項再填寫本頁) 本發明有關以該熔融方法製造之具有優良水解安定性 聚碳酸酯。本發明另外有關一種製備具有經改良水解安定 性之聚碳酸酯，以及由該具有經改良水解安定性之聚碳酸 酯製造的物件。 發明背景 習用工業設備係將二羥基化合物（例如雙酚- A )之 水溶液與一種包含碳醯鹵（例如碳醯氯）的有機溶劑混合 在一起，以合成聚碳酸酯。混合該不可互混有機相與水相 時，該二羥基化合物與該碳醯鹵於相界面處反應。通常， 於該水相添加一種相轉移催化劑，諸如一種三元胺，以加 強該反應。此種合成方法已知爲製備聚碳酸酯的“界面”合成 法。 經濟部智慧財產局員工消費合作社印製 該製造聚碳酸酯的界面合成法具有數個固有的缺點。 首先，因爲顯而易見的安全考量之故，進行一種需要碳醯 氯作爲反應物的方法是其缺點之一。其次，因爲必須採用 昂貴的預防措施，防止任何不良的環境影響，所以進行需 要大量有機溶劑之方法是其缺點之一。第三，該界面方法 需要相當大量的設備與資本投資。第四，已證實由該界面 方法製造的聚碳酸酯顏色不一致，微粒水準較高，而且氯 含量較高，其會造成腐飩。 某些新穎的市售聚碳酸酯設備係藉由轉酯化反應合成 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -4- 570955 A7 _ B7 五、發明説明（2 ) (請先閱讀背面之注意事項再填寫本頁) 聚碳酸酯，因而聚縮一種碳酸的二酯（例如二苯基碳酸酯 )與一種二羥基化合物（例如雙酚- A )。進行此反應不 需要溶劑，可以藉由在減壓而且高溫下混合反應物，同時 蒸餾該反應所產生的酚類而完成。該合成技術通常稱爲“熔 融”技術。因爲該熔融技術不使用碳醯氯、不需要溶劑，而 且使用較少設備之故，其優於該界面技術。此外，該熔融 方法所製造的聚碳酸酯不包含來自反應物的氯污染物，微 粒水準較低，而且具有更一致的顏色。因此，工業製造方 法中極需要使用該熔融技術。 以該熔融聚合方法製造聚碳酸酯過程當中，使用鹼金 屬氫氧化物類，特別是氫氧化鈉作爲聚合催化劑。雖然鹼 金屬氫氧化物類係適用之聚合催化劑，但是其也會影響造 成分支副反應產物的副反應。如此造成該聚碳酸酯熔融表 現的改變，其會導致處理困難度。 使用鹼性催化劑的其他缺點係，留在形成的聚碳酸酯 中之催化劑會對於該聚碳酸酯性質造成負面影響。特別是 ，該殘留催化劑會影響該聚碳酸酯的水解安定性。 經濟部智慧財產局員工消費合作社印製 針特定應用所需的水解安定性可能會改變。就特定應 用而言，例如，可用以製造雙壁薄板應用的薄板狀樹脂， 該聚碳酸酯的水解安定性要求變得更嚴格。 美國專利5，0 6 0，6 0 7揭示一種製備芳族聚碳 酸酯類之方法，其中存在一種含硫之酸組份添加一種環氧 化物。並未提及添加於該聚碳酸酯的添加劑對於該水解安 定性的影響。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 經濟部智慧財產局員工消費合作社印製 570955 A7 ____ B7 五、發明説明（3 ) 目前需要一種由該熔融方法製造，而且具有經改良水 解安定性的聚碳酸酯。特定言之，需要一種具有經改良水 解安定性之聚碳酸酯，其適於製造可用於雙壁應用的薄板 狀樹脂。 發明總論 一方面，本發明有關一種具有水解安定性的聚碳酸酯 組成物，該具有水解安定性的聚碳酸酯組成物約9 8莫耳 %以下之末端碳酸芳酯類，以及2莫耳％以上之末端經基 ，此係以該聚碳酸酯所有末端基團總莫耳數爲準，該具有 水解安定性的聚碳酸酯另外包括約3 · 6 p p m或以下的 催化劑抑制劑（quencher );約1，〇 〇 〇 p p m或以下 的亞磷酸酯組份，以及約2 0 0 p p m或以下的環.氧化物 水解安定劑。 本發明另外有關由該具有水解安定性的聚碳酸酯製造 的物件。在一具體實施例中，所形成物件係一種薄板，在 另外具體實施例中，該物件係一種雙壁薄板。 在其他方面，本發明有關一*種製備具有水解安定性之 聚碳酸酯組成物的方法，其具有約9 8莫耳％以下之末端 碳酸芳酯類，以及2莫耳％以上之末端羥基，此係以該聚 碳酸酯所有末端基團總莫耳數爲準，該方法包括在製備與 處理該具有水解安定性的聚碳酸酯期間，使催化劑抑制劑 水準在3 · 6 p p m或以下；使亞磷酸酯組份水準在約 1，〇 〇 〇 p p m或以下；以及使環氧化物水解安定劑水 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） - ---------裝----Ί—--訂 ^-------~ (請先閱讀背面之注意事項再填寫本頁) 570955 A7 B7 五、發明説明（4 ) 準在約2 0 0 P P m或以下等步驟。 在其他方面，本發明有關一種製備具有水解安定性的 聚碳酸酯之方法，該方法包括步驟： a )添加最多達約3 · 6 P P m之催化劑抑制劑，以 該熔融製備的聚碳酸酯爲基準； b )添加最多達約1 0 0 0 P P m之亞磷酸酯組份， 以該熔融製備的聚碳酸酯爲基準； c )添加最多達約2 0 0 P P m之環氧化物水解安定 劑，以該熔融製備的聚碳酸酯爲基準； 其中，組份a ) 、b )或c )當中至少一者的存在量 大於0 p p m，而且其中該具有水解安定性的聚碳酸酯在 1 2 0 t以及1 0 0 %相對濕度的蒸汽壓熱器當中，顯示 出分子量損失低於約3 0 %。 發明詳述 本發明提出此等有關內容並提供更令人意外的性質。 參考本發明下列較佳具體實施例詳細說明，以及其中 .包括的實施例，可以更容易暸解本發明。 揭示與說明本內容組成物以及方法之前，須暸解本發 明不受限於特定合成方法，或是受限於特定調配物，此等 方法與調配物當然有可能改變。亦必須暸解，本文所丨吏用 的術語僅供說明特定具體實施例用，不希望被其限制。 在下列說明書當中，參考資料係由許多下列意義界定 的用辭完成： 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 7 _ (請先閲讀背面之注意事項再填寫本頁) 裝----^---訂--- L--- 經濟部智慧財產局員工消費合作社印製 570955 經濟部智慧財產局員工消費合作社印製 A7 _____ B7 五、發明説明（5 ) 除非前後文另外指出，否則“一個，，與“該，，之單數形式包 括數個指示物。 “選擇性”或是“選擇地”意指其次\後所述事件或狀況可 能發生或不會發生，而且該說明包括該事件發生之情況以 及未發生之情況。 如本文所使用，“熔融聚碳酸酯”一群係指一種由碳酸二 酯與一種二羥基化合物轉酯化作用製得的聚碳酸酯。 本文之“BPA”定義爲雙酚A或2，2 -雙（4 一羥基 苯基）丙烷。 本文所使用之“聯苯”與“二羥酚”係同義字。 本文所使用之“酸物質”係一種在2 5 t水中，其p K a 値爲4 . 〇或以下的組份。 本文所使用之“水解安定性”意指該熔融製備之聚碳酸酯 在1 2 0 °C以及1 0 0 %相對濕度的蒸汽壓熱器當中 1 2 0小時期間，顯示出分子量損失低於約3 0 %。 本發明中，出乎意料地發現，添加於該熔融方法所製 備之聚碳酸酯的代表性添加劑水準會相互作用，產生熔融 聚碳酸酯的安定性問題，特別是水解安定性。該水解安定 性的臨界條件視該聚碳酸酯的預定用途而定。藉由使該熔 融聚碳酸酯中特定添加劑水準，特別是催化劑抑制劑、亞 磷酸酯組份以及過水解安定劑保持特定cnUcal範圍內，可 以戲劇性地改善該聚碳酸酯的水解安定性。該具有經改良 水解安定性的聚碳酸酯適用於薄板狀樹脂，其可用於雙壁 薄板應用。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------^^裝----Ί (請先閲讀背面之注意事項再填寫本頁} I--訂 570955 A7 B7 五、發明説明（6 ) 更明確地說，本發明提出具有水解安定性的聚碳酸酯 ，其可用於先前熔融製備之聚碳酸酯因水解安定性相關問 題而無法適用的應用。在一具體實施例中，例如，由該熔 融方法製備之具有水解安定性的聚碳酸酯可用於薄板應用 ，例如作爲溫室中之雙壁薄板。 界面製備之聚碳酸酯與熔融製備之聚碳酸酯，在製備 之後通常需要添加特定添加劑以安定留下的產物。不過， 界面製造的聚碳酸酯以及熔融製造的聚碳酸酯所需要的添 加劑差別在於，該熔融製造的聚碳酸酯需要添加一種催化 劑抑制劑，以中和殘留的鹼性材料，諸如殘留的鹼金屬或 鹼土金屬鹽類。針對此目的的代表性添加劑包括，例如硫 酸類（“ s ”酸類）或磷酸類（“ p ”酸類），以及其對應之酯 類。 由該界面方法製備之聚碳酸酯通常包含約9 8莫耳％ 以上之末端碳酸芳酯類，此係以該聚碳酸酯所有末端基團 總莫耳數爲準。由該熔融方法製備之聚碳酸酯包含約9 8 莫耳％以下之末端碳酸芳酯類，以及2莫耳％或以上之末 端羥基，此係以該聚碳酸酯所有末端基團總莫耳數爲準。 因此，在某些應用中造成性能問題，其部分原因係存在該 聚碳酸酯的末端羥基水解之故。此外，該熔融方法通常包 括添加磷酸，以免偶爾因該設備破裂所致之鐵污染，因而 抑制顏色形成。 一方面，本發明有關一種在熔融聚合系統中製造的具 有水解安定性聚碳酸酯，其中反應一種二羥酚與一種碳酸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9 _ (請先閲讀背面之注意事項再填寫本頁) 裝----Ί--訂 經濟部智慧財產局員工消費合作社印製 570955 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（7 ) 二酯。適於製備本發明聚碳酸酯的二羥酚可由下列通式表 示：570955 A7 B7 V. Description of the invention (1) Detailed description of the invention: Scope of the invention (please read the notes on the back before filling out this page) The present invention relates to polycarbonate with excellent hydrolytic stability manufactured by this melting method. The present invention further relates to a method for preparing a polycarbonate having improved hydrolytic stability, and an article made from the polycarbonate having improved hydrolytic stability. BACKGROUND OF THE INVENTION Conventional industrial equipment mixes an aqueous solution of a dihydroxy compound (such as bisphenol-A) with an organic solvent containing a carbohalide (such as carbochlorine) to synthesize polycarbonate. When the immiscible organic phase and the aqueous phase are mixed, the dihydroxy compound and the carbohalide react at the phase interface. Usually, a phase transfer catalyst, such as a triamine, is added to the aqueous phase to enhance the reaction. Such a synthesis method is known as an "interfacial" synthesis method for preparing polycarbonate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics This interfacial synthesis method for manufacturing polycarbonate has several inherent disadvantages. First, for obvious safety considerations, carrying out a method that requires carbochlorine as a reactant is one of its disadvantages. Second, because expensive precautions must be taken to prevent any adverse environmental effects, performing a method that requires a large amount of organic solvents is one of its disadvantages. Third, this interface method requires a considerable amount of equipment and capital investment. Fourth, it has been confirmed that the polycarbonate produced by this interface method is inconsistent in color, has a high level of particulates, and has a high chlorine content, which causes rot. Some novel commercially available polycarbonate equipment is synthesized by transesterification. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) -4- 570955 A7 _ B7 V. Description of the invention (2) (Please read the notes on the back before filling out this page) Polycarbonate, thus polycondensing a carbonic acid diester (such as diphenyl carbonate) and a dihydroxy compound (such as bisphenol-A). No solvent is required to perform this reaction, and it can be accomplished by mixing the reactants under reduced pressure and high temperature while distilling the phenols produced by the reaction. This synthesis technique is often referred to as "fusion" technology. This melting technology is superior to the interface technology because it does not use carbochlorine, requires no solvents, and uses less equipment. In addition, the polycarbonate produced by this melting method does not contain chlorine contaminants from the reactants, has a lower level of particulates, and has a more consistent color. Therefore, the use of this melting technology is highly required in industrial manufacturing methods. During the production of polycarbonate by this melt polymerization method, alkali metal hydroxides, particularly sodium hydroxide, are used as a polymerization catalyst. Although alkali metal hydroxides are suitable polymerization catalysts, they also affect the side reactions that cause branched side reaction products. This causes a change in the melting behavior of the polycarbonate, which can cause difficulty in handling. Another disadvantage of using a basic catalyst is that the catalyst remaining in the formed polycarbonate can negatively affect the properties of the polycarbonate. In particular, the residual catalyst may affect the hydrolysis stability of the polycarbonate. The hydrolytic stability required for specific applications printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs may change. For specific applications, for example, sheet-like resins that can be used to make double-walled sheet applications, the polycarbonate's hydrolytic stability requirements become more stringent. U.S. Patent No. 5,06,6,07 discloses a method for preparing aromatic polycarbonates in which a sulfur-containing acid component is added to an epoxy compound. The effect of the additives added to the polycarbonate on the hydrolytic stability is not mentioned. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 570955 A7 ____ B7 V. Description of the invention (3) Currently, a method is required to be manufactured by this melting method, and it has Polycarbonate with improved hydrolytic stability. In particular, there is a need for a polycarbonate having improved hydrolytic stability, which is suitable for making thin-plate resins that can be used in double-walled applications. SUMMARY OF THE INVENTION In one aspect, the present invention relates to a polycarbonate composition having hydrolytic stability, the polycarbonate composition having hydrolytic stability of about 98 mol% or less of terminal aryl carbonates, and 2 mol. % Or more of the terminal groups are based on the total moles of all the terminal groups of the polycarbonate. The polycarbonate with hydrolytic stability additionally includes a catalyst inhibitor (quencher) of about 3.6 ppm or less. ; About 1,000 ppm or less of a phosphite component, and about 200 ppm or less of an epoxide hydrolytic stabilizer. The invention further relates to articles made from the polycarbonate having hydrolytic stability. In one embodiment, the object formed is a thin plate. In another embodiment, the object is a double-walled plate. In other aspects, the present invention relates to a method for preparing a polycarbonate composition having hydrolytic stability, which has a terminal aryl carbonate of about 98 mol% or less, and a terminal hydroxyl group of 2 mol% or more, This is based on the total moles of all the terminal groups of the polycarbonate. The method includes making the catalyst inhibitor level at 3.6 ppm or less during the preparation and processing of the polycarbonate with hydrolytic stability; The level of the phosphite component is about 1,000 ppm or less; and the hydrolyzing stabilizer of the epoxide is suitable for the paper standard of China National Standard (CNS) A4 (210X297 mm)------- --- Installation ---- Ί --- Order ^ ------- ~ (Please read the precautions on the back before filling out this page) 570955 A7 B7 V. Description of the invention (4) The standard is about 2 0 0 PP m or less. In other aspects, the present invention relates to a method for preparing a polycarbonate having hydrolytic stability, which method comprises the steps of: a) adding a catalyst inhibitor of up to about 3.6 PP m, and using the melt-produced polycarbonate as Benchmark; b) adding up to about 1,000 PP m of phosphite component, based on the melt-produced polycarbonate; c) adding up to about 200 PP m of epoxide hydrolysis stabilizer , Based on the melt-prepared polycarbonate; wherein at least one of the components a), b) or c) is present in an amount greater than 0 ppm, and wherein the polycarbonate having hydrolytic stability is at 1 2 0 The vapor autoclave at t and 100% relative humidity showed a molecular weight loss of less than about 30%. DETAILED DESCRIPTION OF THE INVENTION The present invention addresses these concerns and provides more surprising properties. The present invention can be more easily understood by referring to the following detailed description of the preferred embodiments of the present invention and the embodiments included therein. Before revealing and explaining the composition and method of this content, it must be understood that the present invention is not limited to a specific synthetic method, or is restricted to a specific formulation. Such methods and formulations may of course change. It must also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. In the following descriptions, the reference materials are completed by many terms defined in the following meanings: This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 7 _ (Please read the precautions on the back before filling this page ) Install ---- ^ --- Order --- L --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 570955 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____ B7 V. Description of Invention (5) Unless The context also states otherwise that the singular form of "an," and "the," includes several indicators. "Selective" or "optionally" means that the event or condition described below may or may not occur, and that the description includes what happened and what didn't happen. As used herein, the "melt polycarbonate" group refers to a polycarbonate made by transesterification of a carbonic acid diester with a dihydroxy compound. "BPA" is defined herein as bisphenol A or 2,2-bis (4-hydroxyphenyl) propane. As used herein, "biphenyl" and "dihydroxyphenol" are synonyms. As used herein, an "acid substance" is a component whose p K a 値 is 4.0 or less in 25 t of water. As used herein, "hydrolytic stability" means that the melt prepared polycarbonate exhibits a molecular weight loss of less than about 120 hours at 120 ° C and 100% relative humidity in a steam autoclave. 30%. In the present invention, it has been unexpectedly discovered that the level of representative additives added to the polycarbonate prepared by the melting method can interact with each other, causing problems with the stability of the molten polycarbonate, particularly hydrolysis stability. The critical condition for the hydrolytic stability depends on the intended use of the polycarbonate. By keeping the level of specific additives in the molten polycarbonate, especially catalyst inhibitors, phosphite components and perhydrolytic stabilizers within a specific range of cnUcal, the polycarbonate's hydrolysis stability can be dramatically improved. This polycarbonate with improved hydrolytic stability is suitable for thin-plate resins and can be used for double-walled thin-plate applications. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -------- ^^ 装 ---- Ί (Please read the precautions on the back before filling this page} I--Order 570955 A7 B7 5. Description of the invention (6) More specifically, the present invention proposes a polycarbonate with hydrolytic stability, which can be used in applications where previously melt-produced polycarbonates cannot be applied due to issues related to hydrolytic stability. In a specific embodiment, for example, the polycarbonate having hydrolytic stability prepared by the melting method can be used in sheet applications, for example, as a double-walled sheet in a greenhouse. The polycarbonate produced at the interface and the polycarbonate produced by melting, After the preparation, it is usually necessary to add specific additives to stabilize the remaining product. However, the difference between the additive produced by the interfacial polycarbonate and the melt produced polycarbonate is that the melt produced polycarbonate needs a catalyst inhibitor. To neutralize residual alkaline materials, such as residual alkali or alkaline earth metal salts. Representative additives for this purpose include, for example, sulfuric acids ("s Acid) or phosphoric acid ("p" acid) and their corresponding esters. Polycarbonates prepared by this interfacial method usually contain about 98 mole% or more of terminal aryl carbonates, which is based on the polycarbonate The total moles of all the terminal groups of the esters shall prevail. The polycarbonate prepared by this melting method contains terminal aryl carbonates of less than 98 mole% and terminal hydroxyl groups of 2 mole% or more. The total moles of all the terminal groups of the polycarbonate shall prevail. Therefore, the performance problems in some applications are partly due to the hydrolysis of the terminal hydroxyl groups of the polycarbonate. In addition, the melting method usually includes the addition of Phosphoric acid to prevent occasional iron contamination due to cracking of the equipment, thereby inhibiting color formation. In one aspect, the present invention relates to a polycarbonate having hydrolytic stability manufactured in a melt polymerization system, in which a dihydric phenol and a carbonic acid are reacted. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -9 _ (Please read the precautions on the back before filling this page) Installation ---- Ί--Order the Ministry of Economic Affairs wisdom Property Office employee consumer cooperative printed 570955 A7 B7 economic Intellectual Property Office employee consumer cooperative printed V. invention is described in (7) diester of the present invention suitable for preparation of polycarbonates dihydric phenol by the following general formula represents:
其中： R分別選自鹵素、一價烴以及一價含氧烴基； R 1分別選自鹵素、一價烴以及一價含氧烴基； W選自二價烴基，Wherein: R is selected from halogen, monovalent hydrocarbon and monovalent oxygen-containing hydrocarbon group; R 1 is selected from halogen, monovalent hydrocarbon and monovalent oxygen-containing hydrocarbon group; W is selected from divalent hydrocarbon group,
η與η 1分別選自數値自〇至4 ( 〇與4包括在內） 的整數；以及 b係零或一。 由R與R 1表示的一價烴基包括烷基、環烷基、芳基、 芳烷基以及烷芳基。較佳烷基係包含自1至約1 2個碳原 子者。該較佳環烷基係包含自4至8個環形碳原子者。較 佳芳基係包含自6至1 2個環形碳原子者，即苯基、蔡基 與聯苯基。較佳烷芳基與芳烷基係包含自7至約1 4個碳 原子者。 由R與R 1表示的較佳鹵素基係氯與溴。 由W表示的二價烴基包括伸烷基、亞烷基、環伸院基 與環亞院基。較佳伸院基係包含自2至3 0個碳原子者。 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐）-10 - —--------^-裝----Ί (請先閱讀背面之注意事項再填寫本頁) I I * . If 經濟部智慧財產局員工消費合作社印製 570955 A7 B7 五、發明説明（8 ) 較佳亞烷基係包含自1至約3 0個碳原子者。較佳環伸烷 基與環亞烷基係包含自6至約1 6個環形碳原子者。 由R與R 1表示的一價含氧烴基可由通式——〇R2表 示，其中R 2係上述種類的一價烴基。較佳之一價含氧烴基 係烷氧基與芳氧基。 適用之二羥酚類包括但不受限於：B P A ; 2，2 — 雙（3，5 —二溴—4 —羥基苯基）丙烷；2，2 —雙（ 3， 5 —二甲基一 4 一羥基苯基）丙烷；1， 1 一雙（4 —羥基苯基）環己烷；1， 1 —雙（3，5 —二甲基—4 一羥基苯基）環己烷；1，1 一雙（4 一羥基苯基）癸烷 ;1， 1 一雙（4 一羥基苯基）己烷；1， 1 一雙（4 一 HH. - - ϋϋ mu ml —ϋ - 士^^ 11— --. (請先閱讀背面之注意事項再填寫本頁) -n mi 訂...... ' ·ι _ 羥 基 苯 基 ) ϊ四 癸 烷 ； 1 1 — 雙 ( 3 y 5 — 二 甲 基 — 4 — 羥 基 苯 基 ) 環 癸 院 7 4 y 4 — 二 羥 基 苯 醚 f 4 5 4 — 硫 代 聯 苯 j 4 4 — 二 羥 基 — 3 3 — 一 氯 一 苯 醚 y 4 4 — 硫 代 聯 苯 ， 4 4 — 二 羥 基 — 3 3 — 二 氯 二 苯 醚 ， 4 4 — 二 羥 基 — 2 5 — 一 羥 基 二 苯 醚 ·， B P I 1 1 — 雙 ( 4 — 羥 基 苯 基 ) — 1 — 苯 醚 ， 1 1 — 雙 ( 3 — 甲 基 — 4 — 羥 基 苯 基 ) — 1 — 苯 基 乙 院 5 及 其 混 合 物 〇 在 —* 具 體 實 施 例 中 該 聚 碳 酸 酯 中 之 二 羥 酚 殘 留 物 包括 1 〇 〇 r r * 旲 耳 % 衍 生 白 B P A 之 殘 留 物 〇 視 情 況 而 要 可 以 使 用 多 官 能 化 合 物 〇 該 分 支 聚 碳 酸 酯 聚 合 作 用 中 所 使 用 的 多 官 能 化合 物 包括但 不 受 限 於 ： 1 1 1 — 三 ( 4 — 羥 基 苯 基 ) 乙 院 4 5 [ 4 — [ 1 1 — 雙 ( 4 — 羥 基 苯 基 ) — 乙 基 ) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ ^ 570955 A7 B7 五、發明説明（9) 一二甲基苄基.〕， 苯偏三酸酐， (請先閱讀背面之注意事項再填寫本頁) 苯偏三酸，或其酸氯化物衍生物。 可以使用各種化合物作爲碳酸的二酯，包括但不受限 於：碳酸二芳酯化合物、碳酸二烷酯化合物以及碳酸烷基 芳酯化合物。適用之碳酸的二酯類包括但不受限於：碳酸 二苯酯·，雙（4 一第三一丁基苯基）碳酸酯；雙（2，4 一二氯苯基）碳酸酯；雙（2，4，6 -三氯苯基）碳酸 酯；雙（氰基苯基）碳酸酯；雙（鄰-硝基苯基）碳酸酯 ;碳酸二甲苯酯；碳酸間一甲酚酯；碳酸二萘酯；雙（二 苯基）碳酸酯；碳酸二乙酯；碳酸二甲酯；碳酸二丁酯； 碳酸二環己酯；以及其混合物。其中，以碳酸二苯酯爲佳 。若使用兩種以上此等化合物，較佳情況係其中一者爲碳 酸二苯酯。 經濟部智慧財產局員工消費合作社印製 本發明方法中，可視需要使用一種封端劑。適用之封 端劑包括一價芳族羥基化合物、一價芳族羥基化合物之鹵 仿化物衍生物、一價羧酸類、一價羧酸類的鹵化物衍生物 ，以及其混合物。 適用之封端劑包括但不受限於酚、對-第三丁基酚； 對-枯基酚；對枯基酚碳酸醋；十一酸、月桂酸、硬脂酸 ;氯甲酸苯酯、氯甲酸第三丁基苯酯、氯甲酸對枯基酯、 氯甲酸色滿酯、氯甲酸辛基苯酯、氯甲酸壬基苯酸或其混 合物。 若存在該封端劑，其存在數量係每1莫耳該二羥酚使 本紙張尺度適财關家縣(_CNS ) A视格（210X297公釐) " -- -12- 570955 A7 B7 五、發明説明（10) 用約〇.〇1至約〇· 2〇莫耳，約〇· 〇 2至約 〇· 1 5莫耳爲佳，約〇 · 〇 2至約〇 · 1 〇莫耳更佳。 (請先閱讀背面之注意事項再填寫本頁) 本發明方法中，該催化劑系統包括至少一種鹼金屬及 /或鹼土金屬化合物。此等化合物係以鹼金屬與鹼土金屬 衍生物形式使用爲佳，諸如其有機酸鹽；無機酸鹽；氧化 物；氫氧化物；氫化物；醇化物或其混合物。 可作爲催化劑的適用鹼金屬化合物包括但不受限於： 氫氧化鈉、氫氧化鉀、氫氧化鋰、碳酸氫鈉、碳酸氫鉀、 碳酸氫鋰、碳酸鈉、碳酸鉀、碳酸鋰、醋酸鈉、醋酸鉀、 醋酸鋰、硬脂酸鈉、硬脂酸鉀、硬脂酸鋰及其混合物。 可作爲催化劑的適用鹼土金屬化合物包括但不受限於 :氫氧化鈣、氫氧化鋇、氫氧化鎂、氫氧化緦、碳酸氫鈣 、碳酸氫鋇、碳酸氫鎂、碳酸氫緦、碳酸鈣、碳酸鋇、碳 酸鎂、碳酸緦、醋酸鈣、醋酸鋇、醋酸鎂、醋酸緦、硬脂 酸鈣、硬脂酸鋇、硬脂酸鎂、硬脂酸緦及其混合物。 該催化劑的較佳用量係每1莫耳二羥酚化合物使用自 1〇8至1 0 — 3莫耳催化劑，每1莫耳二羥酚化合物使用 自1 0 7至1 0 — 5莫耳催化劑更佳。當該數量少於 經濟部智慧財產局員工消費合作社印製 1 0 8莫耳時，有可能無法顯示該催化劑活性。當該數量 大於每1莫耳二羥酚使用1 0 — 5莫耳時，可能會負面影響 該最終聚碳酸酯產物的性質。 除了上述催化劑之外，該催化劑系統可視需要包括一 種四元銨鹽及/或一種鳞催化劑。適用之四元銨鹽實例包 括但不受限於：具有院基、芳基與院芳基之錢的氨氧化物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 570955 A7 B7 五、發明説明（12) (請先閲讀背面之注意事項再填寫本頁) 示出分子量損失低於約3 0 % ;在1 2 0 °C以及1 0 0 % 相對濕度的蒸汽壓熱器當中1 2 0小時期間，顯示出的分 子量損失低於約2 0 %更佳；在1 2 0 °C以及1 0 0 %相 對濕度的蒸汽壓熱器當中1 2 0小時期間，顯示出的分子 量損失低於約1 〇 %更佳。 經濟部智慧財產局員工消費合作社印製 本發明中，小心控制該催化劑抑制劑、亞磷酸酯組份 以及環氧化物水解安定劑之水準。出乎意料地發現，該熔 融製造之聚碳酸酯中存在的亞磷酸酯組份與酸物質交互反 應，因此降低熔融聚碳酸酯的水解安定性。酸物質可能是 由通常作爲熔融轉酯化所製造之聚碳酸酯中的添加劑催化 劑抑制劑產生的，該催化劑抑制劑可能爲一種酸物質，或 者因爲其他目的添加該酸物質。甲苯磺酸丁酯——一種常見 催化劑抑制劑--一可能在聚碳酸酯中水解形成甲苯磺酸，該 甲苯磺酸丁酯於聚碳酸酯中作爲一種催化劑抑制劑。磷酸 或其衍生物亦可作爲催化劑抑制劑。已發現，小心控制該 亞磷酸酯組份與該聚碳酸酯中之催化劑抑制劑水準，可以 製備具有較高水解安定性之聚碳酸酯。此外，該聚碳酸酯 中之其他酸物質濃度最好保持最低水準。特別是，該聚碳 酸酯樹脂中之酸物質（其係作爲該催化劑抑制劑或是基於 其他目的而添加）總數量，最好保持約3 · 6 p p m或以 下。另外發現，添加適用之環氧化物水解安定劑可以進一 步增加該熔融製備聚碳酸酯的水解安定性。 可用以製備具有水解安定性之聚碳酸酯的適用催化劑 抑制劑包括但不受限於：硫酸與磷酸及其酯類；以硫酸與 本紙張尺度適用中國國家標準·（ CNS ) A4規格（210x297公釐） 570955 A7 B7 五、發明説明（ ---------扯衣II (請先閱讀背面之注意事項再填寫本頁} 磷酸之烷基酯類爲佳，以甲苯磺酸烷基酯更佳，諸如甲苯 磺酸丁酯與甲苯磺酸正丁酯。可用以製備具有水解安定性 的聚碳酸酯之適用亞磷酸酯包括但不受限於：亞磷酸三苯 酯；亞磷酸2，4 -二一第三丁酯；亞磷酸參（壬基苯） 酯；亞磷酸參異癸酯；及其混合物；以亞磷酸三苯酯爲佳 。可用以製備具有水解安定性的聚碳酸酯之適用環氧化物 水解安定劑包括但不受限於含環氧基脂肪類與油類；縮水 甘油化合物，諸如苯基縮水甘油醚；環氧基環己烷化合物 ;四苯基環氧乙烷。 需要使用之酸物質、亞磷酸酯組份與環氧化物水解安 定劑之總數量必須足以安定該聚碳酸酯使其不會褪色，以 及改善用於預定應用之水解安定性，同時保持良好性質。 線 經濟部智慧財產局員工消費合作社印製 該具有水解安定性的聚碳酸酯中的催化劑抑制劑組份 存在量自約0至約3 . 6 p p m ;自約〇 . 5至約2 . 0 P p m爲佳；自約〇至約1 · 〇 p p m更佳，此係以該聚 碳酸酯爲基準。該亞磷酸酯組份存在量佔該聚碳酸酯重量 自約0 p P m至約1， 0 0〇p p m ;約5 0至7 0 0 p P m更佳；自約1〇〇至5 0〇p p m更佳。該環氧化 物水解安定劑存在量佔該聚碳酸酯重量自約〇至約2 0 0 p p m，自約1 〇 〇至2 0 0 p p m更佳。如上述，此等 添加數量視該聚碳酸酯預定用途而定。 某些應用中，諸如室內應用，例如在光碟中，該催化 劑抑制劑、亞磷酸酯與環氧化物水解安定劑的濃度低。其 烛應周中，例如會曝於水與陽光的薄板材料，此等濃度必 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 570955 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（14 ) 須較高。在一具體實施例中，將該熔融聚碳酸酯形成溫室 用的雙壁薄板。 在一具體實施例中，本發明之水解安定性薄板等級材 料包含自〇·5至3·6ppm(〇·5至2·〇ppm 更佳）之催化劑抑制劑；自約5 0至約7 0 〇 P p m (自 5〇至500??1^更佳，自50至25〇？？111更佳） 之亞磷酸酯組份；以及自約1 0 0至2 0 0 P P m之水解 安定性。該水解安定性薄板等級材料中的酸物質（作爲該 催化劑抑制劑或因其他目的而添加者）總數量保持約 3 . 6 ppm或以下爲佳。 該催化劑抑制劑、亞磷酸酯組份與環氧化物水解安定 劑可以在該聚縮反應之後添加於該反應器或擠出機內呈熔 融狀態的聚碳酸酯，然後捏合或進行習知將添加劑導入聚 碳酸酯材料的任何其他技術。亦可以粉末濃縮物形式將此 等添加劑加入相同或不同聚碳酸酯。該聚碳酸酯的平均分 子量自約1， 000至約300， 000。較介之分子量 視該聚碳酸酯的預定用途而定。例如，就薄板應用而言， 較佳之分子量在約1 0，0 0 0至約8 0，0 0 0範圍內 ，約1 8，〇〇〇至約5 0，〇〇〇更佳。 如上述，在本發明一具體實施例中，該可以將包括該 樹脂抑制組成物的聚碳酸酯形成薄板。在一特定應用中， 該聚碳酸酯可形成溫室建築用的雙壁薄板。該聚碳酸酯可 由聚合熔體直接形成薄板，或者，由該熔體形成容易處理 的形狀，諸如九粒，然後形成薄板。可以本技藝中習知之 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） 裝----Ί (請先閱讀背面之注意事項再填寫本頁) I--訂----L---- 570955 A7 B7 五、發明説明（15) 各種方法形成本發明薄板，其包括但不受限於擠出、溶液 鑄造或是射出模製。 只要不會對該聚碳酸酯產物性質造成不良影響，亦可 於其中添加另外添加劑。此等添加劑包括以往基於各種用 途而添加於該聚碳酸酯之廣泛範圍物質。特定實例包括熱 安定劑、環氧化合物、紫外線吸收劑、脫模劑、著色劑、 抗靜電劑、助滑劑劑、防黏劑、潤滑劑、防霧劑、中性油 類、合成油類、鱲類、有機塡料、阻燃劑、無機塡料與任 何其他習知之添加劑種類。 該反應可以分批或連續方法進行。只要該反應器具有 原有的攪拌能力，本發明中所使用的材料與反應器結構並 無特別限制。當該反應後面階段中，該反應系統的黏度提 高時，該反應器可以在高黏度條件下攪拌爲佳。 本發明具有水解安定性的聚碳酸酯組成物可與習用添 加劑混合，諸如增塑劑、顏料、潤滑劑、脫模劑、安定劑 以及有機塡料。脫模劑係較佳添加劑。另外發現，脫模劑 (諸如肆硬脂酸季戊四醇酯）不會對本發明具有水解安定 性的聚碳酸酯之水解安定性造成不良影響。 除了上述用途之外，本發明具有水解安定性的聚碳酸 酯可用於室外用途，諸如汽車零件、用於各種儀器罩，以 及用於光學物件，諸如鏡片或光碟。如上述，在一具體實 施例中，使用該具有水解安定性的聚碳酸酯製備溫室用的 雙壁薄板。 亦可摻合該聚碳酸酯與其他聚合物，包括但不受限於 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I -- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -18- 570955 A7 B7 五、發明説明（16) 聚烯烴類、聚苯乙烯類、聚磺酸酯類、聚醯胺類與聚苯醚 類。 實施例 提出下列實施例，對習知本技藝者完整說明如何製造 與評估本文主張權利之內容組成物與方法，但是不希望限 制本發明人認定的發明範圍。已經盡力確保數値（例如數 量、濫度等）之精確度，但是仍然必須將某些誤差與偏差 考慮在內。徐了另有指明，不然份數係以重量計，溫度係 以°c計。 分子量係數量平均分子量（Mw)，並且使用聚苯乙 烯標準，G P C分析熔融製備之聚碳酸酯所測得。 下列實施例中，顯示由界面與熔融方法製備的聚碳酸 酯。所使用之界面製備聚碳酸酯係G e n e r a 1 E1 e c t r i c Company所售的LEX AN LF 100等級樹脂。該熔融製備聚碳 酸酯係 General Electric Company 所售的 LEXAN LX 140 等級 樹脂。 使用1 0 0等級LEXAN LF作爲該添加劑的濃縮原料混 合該聚碳酸酯，摻合比例係整體執料對濃縮原料比例爲 9 5 : 5 ( w : w )。使用1加畜H e n s c h e 1混合機摻合此 等添加劑與該粉末濃縮物。然後，使用一種雙螺旋擠壓器 混合材料，該擠壓器的桶溫度設爲2 8 0 °C，送料速率爲 2 5磅/小時，螺旋速度介於每分鐘3 5 0與4 0 0轉（ r p m s )。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 項再填办 經濟部智慧財產局員工消費合作社印製 570955 A7 B7 五、發明説明（j 在該壓熱器步驟中，在一 NlsseiFE160射出模製機上 模製dynatup碟片，並於1 2 0 C及1 5 p s i之蒸h下壓 熱五天◦每天處理樣本（一至五），先將該壓熱器冷卻至 室溫，然後移出該碟片，並且切下該模製碟片一部分，以 測量分子量。剩餘的碟片放回爐中。五天當中，每天以這 種方式進行測量。 然後使用這段時間內分子量所產生的曲線斜度測重5亥 樣本的相對水解安定性。表1中，顯不結果，其中此等斜 度表示爲“一（1 〇 g M w / ( τ 1 0 〇 〇 ) ”或是“K斜 度”。本發明樣本的Κ斜度低於約1 · 6 1 5爲佳。 所使用的亞磷酸酯係Ciba-Geigy所製造的IRGAPHOS 1 68，所使用的催化劑抑制劑係甲苯磺酸正丁酯，所使用的 環氧化物水解安定劑係Uniob Carbide所製造的e r 1 -4 2 2 1。該脫模劑係肆硬脂酸季戊四醇酯，而U V安定 劑係Ciba-Gelgy所製造的CYAS0RB 5411。表1所示之濃度 爲每百萬份之份數（p p m )。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ297公釐） -20- 570955η and η 1 are each selected from integers ranging from 0 to 4 (including 0 and 4); and b is zero or one. The monovalent hydrocarbon group represented by R and R 1 includes an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkaryl group. Preferred alkyl systems include from 1 to about 12 carbon atoms. The preferred cycloalkyl system contains from 4 to 8 ring carbon atoms. More preferred aryl groups are those containing from 6 to 12 ring carbon atoms, i.e. phenyl, Czeki and biphenyl. Preferred alkaryl and aralkyl systems contain from 7 to about 14 carbon atoms. Preferred halogen groups represented by R and R 1 are chlorine and bromine. The divalent hydrocarbon group represented by W includes an alkylene group, an alkylene group, a cycloalkylene group, and a cycloalkylene group. The preferred extension system contains from 2 to 30 carbon atoms. This paper size applies to Chinese National Standard (CNS) A4 specification (210x297 mm) -10----------- ^-packing ---- Ί (Please read the precautions on the back before filling this page) II *. If printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 570955 A7 B7 V. Description of the invention (8) Preferred alkylenes contain from 1 to about 30 carbon atoms. Preferred cycloalkylene and cycloalkylene systems contain from 6 to about 16 ring carbon atoms. The monovalent oxygen-containing hydrocarbon group represented by R and R 1 can be represented by the general formula-OR2, where R 2 is a monovalent hydrocarbon group of the above-mentioned kind. Preferred monovalent oxygen-containing hydrocarbon groups are alkoxy and aryloxy. Suitable dihydric phenols include but are not limited to: BPA; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-1 4 monohydroxyphenyl) propane; 1, 1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4 4-hydroxyphenyl) cyclohexane; 1, 1 bis (4-hydroxyphenyl) decane; 1,1 bis (4-hydroxyphenyl) hexane; 1,1 bis (4-HH.--Ϋϋ mu ml —ϋ-士 ^^ 11 —-. (Please read the notes on the back before filling out this page) -n mi Order ... '· _ hydroxyphenyl) tetradecane; 1 1 — bis (3 y 5 — two (Methyl — 4 — hydroxyphenyl) cyclodecane 7 4 y 4 — dihydroxyphenyl ether f 4 5 4 — thiobiphenyl j 4 4 — dihydroxy — 3 3 — monochloromonophenyl ether y 4 4 — sulfur Substituted biphenyl, 4 4 —dihydroxy — 3 3 —dichlorodiphenyl ether, 4 4 —dihydroxy — 2 5 — monohydroxydiphenyl ether ·, BPI 1 1 —bis (4 —hydroxyphenyl) — 1 — Phenyl ether, 1 1 — bis ( 3 —methyl — 4 —hydroxyphenyl) — 1 —phenylethane 5 and mixtures thereof. In the specific embodiment, the dihydroxyphenol residue in the polycarbonate includes 100 rr * mole%. Residues derived from white BPA. Polyfunctional compounds may be used as appropriate. Polyfunctional compounds used in the polymerization of this branched polycarbonate include, but are not limited to: 1 1 1-tris (4-hydroxyphenyl) Yiyuan 4 5 [4 — [1 1 — bis (4-hydroxyphenyl) — ethyl) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 570955 A7 B7 V. Description of the invention ( 9) Monodimethylbenzyl.], Trimellitic anhydride, (Please read the notes on the back before filling out this page) trimellitic acid, or its acid chloride derivative. Various compounds can be used as the diester of carbonic acid, including but not limited to: diaryl carbonate compounds, dialkyl carbonate compounds, and alkyl aryl carbonate compounds. Suitable carbonic acid diesters include, but are not limited to: diphenyl carbonate, bis (4-tris-butylphenyl) carbonate; bis (2,4-dichlorophenyl) carbonate; bis (2,4,6-trichlorophenyl) carbonate; bis (cyanophenyl) carbonate; bis (o-nitrophenyl) carbonate; xylyl carbonate; m-cresol carbonate; carbonic acid Dinaphthyl ester; bis (diphenyl) carbonate; diethyl carbonate; dimethyl carbonate; dibutyl carbonate; dicyclohexyl carbonate; and mixtures thereof. Among them, diphenyl carbonate is preferred. If two or more of these compounds are used, it is preferable that one of them is diphenyl carbonate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the method of the present invention, a capping agent may be used as needed. Suitable end-capping agents include monovalent aromatic hydroxy compounds, haloformide derivatives of monovalent aromatic hydroxy compounds, monovalent carboxylic acids, monovalent carboxylic acid halide derivatives, and mixtures thereof. Suitable capping agents include, but are not limited to, phenol, p-tertiary butyl phenol; p-cumyl phenol; p-cumyl phenol carbonate; undecanoic acid, lauric acid, stearic acid; phenyl chloroformate, Third butyl phenyl chloroformate, p-cumyl chloroformate, chroman chloroformate, octyl phenyl chloroformate, nonyl benzoic acid chloroformate, or mixtures thereof. If the end-capping agent is present, the amount of the dihydroxyphenol per 1 mole of this dihydroxyphenol makes this paper suitable for Guanjia County (_CNS) A sight (210X297 mm) "--12- 570955 A7 B7 5 2. Description of the invention (10) About 0.001 to about 0.2 Moore, preferably about 0.02 to about 0.1 Moore, and about 0.002 to about 0.1 Moore Better. (Please read the notes on the back before filling this page) In the method of the present invention, the catalyst system includes at least one alkali metal and / or alkaline earth metal compound. These compounds are preferably used in the form of alkali metal and alkaline earth metal derivatives, such as their organic acid salts; inorganic acid salts; oxides; hydroxides; hydrides; alcoholates or mixtures thereof. Suitable alkali metal compounds that can be used as catalysts include, but are not limited to: sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate , Potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, and mixtures thereof. Suitable alkaline earth metal compounds that can be used as catalysts include, but are not limited to: calcium hydroxide, barium hydroxide, magnesium hydroxide, thorium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, thorium bicarbonate, calcium carbonate, Barium carbonate, magnesium carbonate, scandium carbonate, calcium acetate, barium acetate, magnesium acetate, scandium acetate, calcium stearate, barium stearate, magnesium stearate, scandium stearate, and mixtures thereof. The preferred amount of the catalyst is from 108 to 10-3 moles per 1 mole of dihydroxyphenol compound, and from 107 to 10-5 moles per 1 mole of dihydroxyphenol compound. Better. When the amount is less than 108 moles printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the catalyst activity may not be displayed. When the amount is more than 10 to 5 moles per 1 mole of dihydroxyphenol, the properties of the final polycarbonate product may be negatively affected. In addition to the above catalyst, the catalyst system may optionally include a quaternary ammonium salt and / or a scale catalyst. Examples of suitable quaternary ammonium salts include, but are not limited to: ammonia oxides with the base, aryl, and aryl bases. This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) 570955 A7 B7 V. Description of the invention (12) (Please read the notes on the back before filling in this page) It shows that the molecular weight loss is less than about 30%; in a steam autoclave at 120 ° C and 100% relative humidity During 120 hours, it is better to show a molecular weight loss of less than about 20%; in a steam autoclave at 120 ° C and 100% relative humidity, the molecular weight loss is shown to be 120 hours It is more preferably less than about 10%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the present invention, the levels of the catalyst inhibitor, the phosphite component, and the epoxide hydrolytic stabilizer are carefully controlled. It was unexpectedly found that the phosphite component present in the melt-produced polycarbonate interacts with an acid substance, thereby reducing the hydrolytic stability of the melted polycarbonate. The acid substance may be produced as an additive catalyst inhibitor commonly used in polycarbonates produced by melt transesterification. The catalyst inhibitor may be an acid substance, or the acid substance may be added for other purposes. Butyl tosylate, a common catalyst inhibitor, may be hydrolyzed to form tosylate in polycarbonate. The butyl tosylate acts as a catalyst inhibitor in polycarbonate. Phosphoric acid or its derivatives can also be used as catalyst inhibitors. It has been found that by carefully controlling the levels of the phosphite component and the catalyst inhibitor in the polycarbonate, polycarbonates having higher hydrolytic stability can be prepared. In addition, the concentration of other acids in the polycarbonate is preferably kept to a minimum. In particular, the total amount of the acid substance in the polycarbonate resin (whether it is added as the catalyst inhibitor or for other purposes) is preferably maintained at about 3.6 p p m or less. In addition, it has been found that the addition of a suitable epoxide hydrolytic stabilizer can further increase the hydrolytic stability of the melt-produced polycarbonate. Suitable catalyst inhibitors that can be used to prepare polycarbonates with hydrolytic stability include, but are not limited to: sulfuric acid and phosphoric acid and their esters; Chinese sulfur standard and (CNS) A4 size (210x297) ) 570955 A7 B7 V. Description of the invention (--------- Pull clothes II (Please read the precautions on the back before filling in this page) The alkyl esters of phosphoric acid are preferred. More preferred are esters such as butyl tosylate and n-butyl tosylate. Suitable phosphites that can be used to prepare polycarbonates with hydrolytic stability include, but are not limited to: triphenyl phosphite; phosphorous acid 2 4,4-bis-tert-butyl ester; ginseng (nonylbenzene) phosphite; ginseng isodecyl phosphite; and mixtures thereof; triphenyl phosphite is preferred. It can be used to prepare polycarbonate with hydrolytic stability. Suitable epoxide hydrolytic stabilizers for esters include, but are not limited to, epoxy-containing fats and oils; glycidyl compounds such as phenyl glycidyl ether; epoxy cyclohexane compounds; tetraphenylethylene oxide Alkane, acid substance and phosphite group The total amount of water and epoxide hydrolytic stabilizer must be sufficient to stabilize the polycarbonate so that it does not fade, and to improve the hydrolytic stability for the intended application while maintaining good properties. The catalyst inhibitor component in the polycarbonate having the hydrolytic stability is present in an amount of from about 0 to about 3.6 ppm; preferably from about 0.5 to about 2.0 P pm; from about 0 to about 1 · 0ppm is better, which is based on the polycarbonate. The phosphite component is present in an amount of from about 0 p P m to about 1,000 ppm; about 50 to 7 0 0 p P m is more preferred; more preferably from about 100 to 500 ppm. The epoxide hydrolytic stabilizer is present in an amount of from about 0 to about 200 ppm, and from about 100% by weight of the polycarbonate. 0 to 200 ppm is better. As mentioned above, the amount of these additions depends on the intended use of the polycarbonate. In some applications, such as indoor applications, such as in optical discs, the catalyst inhibitor, phosphite and ring The concentration of the oxide hydrolytic stabilizer is low. The candle should be exposed to water and yang during the week, for example The thickness of the sheet material must be in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). -16- 570955 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (14) Higher. In a specific embodiment, the molten polycarbonate is formed into a double-walled sheet for a greenhouse. In a specific embodiment, the hydrolytically stable sheet-grade material of the present invention contains from 0.5 to 3.6 ppm ( 0.5 to 2.0 ppm is more preferred) as a catalyst inhibitor; from about 50 to about 700 pm (more preferably from 50 to 500 ??, from 50 to 25? ? 111 is more preferred), a phosphite component; and hydrolytic stability from about 100 to 200 P P m. The total amount of acid substances in the hydrolytically stable sheet-grade material (as the catalyst inhibitor or added for other purposes) is preferably kept at about 3.6 ppm or less. The catalyst inhibitor, the phosphite component, and the epoxide hydrolysis stabilizer can be added to the polycarbonate in the reactor or the extruder in a molten state after the polycondensation reaction, and then kneaded or conventionally added additives Any other technology that introduces polycarbonate materials. These additives can also be added to the same or different polycarbonates as a powder concentrate. The average molecular weight of the polycarbonate is from about 1,000 to about 300,000. The specific molecular weight depends on the intended use of the polycarbonate. For example, for thin plate applications, the preferred molecular weight is in the range of about 10,000 to about 80,000, and more preferably about 18,000 to about 50,000. As described above, in a specific embodiment of the present invention, the polycarbonate including the resin suppressing composition can be formed into a sheet. In one particular application, the polycarbonate can form a double-walled sheet for greenhouse construction. The polycarbonate may be formed into a sheet directly from a polymer melt, or it may be formed into a shape that is easy to handle, such as nine pellets, and then formed into a sheet. The paper size that is known in the art can be applied to the Chinese National Standard (CNS) A4 specification (210x297 mm). Loading Ί Ί (Please read the precautions on the back before filling this page) I--Order ---- L ---- 570955 A7 B7 V. Description of the invention (15) Various methods for forming the sheet of the present invention include, but are not limited to, extrusion, solution casting, or injection molding. As long as it does not adversely affect the properties of the polycarbonate product, additional additives may be added thereto. These additives include a wide range of substances conventionally added to the polycarbonate for various purposes. Specific examples include heat stabilizers, epoxy compounds, ultraviolet absorbers, mold release agents, colorants, antistatic agents, slip agents, anti-sticking agents, lubricants, anti-fog agents, neutral oils, and synthetic oils. , Concrete, organic materials, flame retardants, inorganic materials and any other known additives. The reaction can be carried out in a batch or continuous process. As long as the reactor has the original stirring ability, the materials and reactor structure used in the present invention are not particularly limited. When the viscosity of the reaction system increases in the later stages of the reaction, the reactor can be stirred under high viscosity conditions. The polycarbonate composition having hydrolytic stability of the present invention can be mixed with conventional additives such as plasticizers, pigments, lubricants, mold release agents, stabilizers, and organic additives. The release agent is a preferred additive. It has also been found that release agents such as pentaerythritol stearate do not adversely affect the hydrolytic stability of the polycarbonate having hydrolytic stability of the present invention. In addition to the above-mentioned uses, the hydrolytically stable polycarbonate of the present invention can be used in outdoor applications such as automobile parts, in various instrument covers, and in optical articles such as lenses or optical discs. As described above, in a specific embodiment, a double-walled sheet for a greenhouse is prepared using the polycarbonate having hydrolytic stability. Can also be blended with this polycarbonate and other polymers, including but not limited to this paper size applicable Chinese National Standard (CNS) A4 specification (210X297 mm) I-(Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-18- 570955 A7 B7 V. Description of the invention (16) Polyolefins, polystyrenes, polysulfonates, polyamines and polyphenylene ethers . EXAMPLES The following examples are presented to fully explain to those skilled in the art how to make and evaluate the claimed content composition and methods, but it is not intended to limit the scope of the invention identified by the inventors. Every effort has been made to ensure the accuracy of numbers (such as numbers, profusion, etc.), but certain errors and deviations must still be taken into account. Xu Le stated otherwise, otherwise parts are by weight and temperature is in ° C. The molecular weight coefficient is an average molecular weight (Mw) and is measured by analyzing a polycarbonate prepared by melting using a polystyrene standard and GPC analysis. The following examples show polycarbonates prepared by the interfacial and melting method. The interface used to prepare the polycarbonate is a LEX AN LF 100 grade resin sold by the Genaer a 1 E1 e c t r c c Company. This melt-produced polycarbonate is a LEXAN LX 140 grade resin sold by General Electric Company. The polycarbonate was blended using 100 grade LEXAN LF as a concentrated raw material for the additive, and the blending ratio was 95: 5 (w: w). These additives were blended with the powder concentrate using a 1-plus animal H en s c h e 1 mixer. Then, a twin-screw extruder was used to mix the materials. The barrel temperature of the extruder was set to 280 ° C, the feed rate was 25 lbs / hour, and the screw speed was between 350 and 400 revolutions per minute. (Rpms). This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page), then fill in the printing by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 570955 A7 B7 V. Description of the invention (j In this autoclave step, a dynatup disc is molded on an NlsseiFE160 injection molding machine, and autoclaved for five days at a steaming temperature of 120 ° C and 15 psi for 5 days. 5) First, cool the autoclave to room temperature, then remove the disc, and cut a part of the molded disc to measure the molecular weight. The remaining disc is returned to the oven. For five days, use this The measurement was then carried out. The relative hydrolytic stability of the sample was measured using the slope of the molecular weight generated during this time. The results are shown in Table 1. The slopes are expressed as "一 (1 0 g). M w / (τ 1 00 〇) ”or“ K slope ”. The K slope of the sample of the present invention is preferably less than about 1.615. The phosphite used is manufactured by Ciba-Geigy IRGAPHOS 1 68, the catalyst inhibitor used is tosylate Butyl ester, the epoxide hydrolysis stabilizer used is er 1 -4 2 2 1 manufactured by Uniob Carbide. The release agent is pentaerythritol stearate, and the UV stabilizer is CYAS0RB manufactured by Ciba-Gelgy. 5411. The concentration shown in Table 1 is parts per million (ppm). (Please read the precautions on the back before filling out this page.) Printed on the paper scales applicable to Chinese national standards (CNS) A4 specification (21 × 297 mm) -20-570955
A B 經濟部智慧財產局員工消費合作社印製 五、發明説明（18 ) 表1 樣 本 亞磷 酸酯 脫模 劑 UV安 定齊fj 催化劑 抑制劑 HsPOa 環氧化 物安定 劑 -Κ斜 度 120小 時後 的Mw LF樹脂 1 純樹脂 0.54 42950 2 500 1000 700 Μ ^ττΓ ΜΙΓ j\\\ Μ j\\\ 1.55 3 500 1000 700 3.6 2.0 Μ j \ \\ 2.20 27255 LX樹脂 4 純樹脂 1.12 3669 1 5 500 1000 700 3.6 2.0 Μ j \\\ 7.63 6072 6 250 1000 1500 1.0 1111 J \ \\ Μ y\\\ 2.04 28455 7 250 1000 1500 1.0 4ττΤ. itrr J \ w 200 1.24 35495 8 500 1000 1500 1.0 -fnT- ΊΊΤΓ y、 Μ 川、、 2.46 25 3 37 9 500 1000 2000 1.0 ntr j\\\ 200 1.13 36590 1 0 250 1000 2000 1.0 Mil: J \ w 200 1.27 35202 雖然已特別參考較佳具體實施例詳細說明本發明，但 是須明白，本發明精神與範圍內可以進行許多變化與修正 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐）Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (18) Table 1 Sample Phosphite Release Agent UV Stabilizer fj Catalyst Inhibitor HsPOa Epoxide Stabilizer-K Mw LF after 120 hours Resin 1 Pure resin 0.54 42950 2 500 1000 700 Μ ττΓ ΜΙΓ j \\\ Μ j \\\ 1.55 3 500 1000 700 3.6 2.0 Μ j \ \\ 2.20 27255 LX resin 4 Pure resin 1.12 3669 1 5 500 1000 700 3.6 2.0 Μ j \\\ 7.63 6072 6 250 1000 1500 1.0 1111 J \ \\ Μ y \\\ 2.04 28455 7 250 1000 1500 1.0 4ττΤ. Itrr J \ w 200 1.24 35495 8 500 1000 1500 1.0 -fnT- ΊΊΤΓ y, M, 2.46 25 3 37 9 500 1000 2000 1.0 ntr j \\\ 200 1.13 36590 1 0 250 1000 2000 1.0 Mil: J \ w 200 1.27 35202 Although the present invention has been described in detail with particular reference to preferred embodiments, It must be understood that many changes and corrections can be made within the spirit and scope of the present invention (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (21 OX 297 mm)