201144356 六、發明說明：201144356 VI. Description of the invention:
c發明所屬技術範圍：J 發明領域 本發明係關於碳酸酯聚合物，其具有一共聚合於其中 之有效量的磷化合物，較佳為三(4-羥基-2,2-雙二苯丙烷) 亞磷酸酯，以使該碳酸酯亞磷酸酯共聚物熱氧化性安定樹 脂具有低析出（plate-out)行為，以及製造該共聚物的方法。 發明背景 聚碳酸酯樹脂提供與透明度、韌度、空間穩定性及耐 熱度相關之性質間極佳的平衡。這些性質令聚碳酸酯成為 在製備許多類型之模製的、成型的或其他組裝元件的理想 選擇，尤其是包含電子儲存用途(CDs，DVDs等）、醫療用 途、壓片材或被使用於包覆(glazing)及其他戶外用途之其他 結構和部分。然而，如同多數有機聚合物，聚碳酸酯易於 氧化，尤其是熱氧化。聚碳酸酯熱氧化的典型表現為變黃、 耐衝擊強度的喪失和可造成透明度減低和對表面外觀非所 期望之影響例如破裂和光澤變化的延展。由於聚碳酸醋自 其極佳的光學性質衍生出許多其之價值和利用性，即，低 色度和高透明度及糾度，故抗熱氧化的保 多種方法已被嘗試用以安定聚碳酸醋之熱氧化反應， 包括⑴添加抗氧化化合物和(2)藉共聚合—抗氧化化合物 於其中而對碳酸酯骨架進行結構性修飾。 〇 使用在所有商用聚碳酸醋產品的習知方法係—抗氧化 201144356 穩定劑的添加，例如’添加劑方法。亞磷酸酯化合物已被 發現是對聚碳酸酯氧化安定性特別有效之一群化合物。亞 磷酸酯安定劑的例子見3,305,520 ; 4,066,611 ; 4,〇73,769 ; 4,088,709;4,427,813;和 4,254,014;或與其他穩定劑組合， 見 EP 825,226，JP 10-044,356 ; JP 10-044,357 ;和 JP 10-044,358; JP 04-103,626; JP 04-159,354 和 JP 1〇_138 435。 然而’於聚碳酸酯製造期間，抗氧化添加劑係傾向由 亞磷酸酯共聚物濾出或移出，且堆積於押出/成型設備及/ 或模具及/或模製元件上。此抗氧化劑的損失在射出成型或 發煙(fuming)期間係稱為壓汁(juicing)及/或模具渗汗、白霧 化及/或在片材擠壓中稱為析出（plate-0Ut)。析出（plate_〇ut) 是不好的，因為其係一於塑膠製程中逐漸形成在模具之金 屬表面上的塗層。該塗層是一或多種樹脂組分如潤滑油、 穩定劑、塑化劑和短鏈之聚碳酸酯寡聚物移動和沉積在具 模及/或製程設備的結果。由於種種原因，來自常用之抗氧 化添加劑的析出（plate-out)係難以去除的，尤其是低分子量 之亞磷酸酯，該等原因包括形成亞磷酸酯基之磷酸基團的 部分水解，其接著侵害或蝕刻模具之金屬表面且提供金屬 及部分水解亞填酸酯添加物間之機械結合位（sights)。這此 種類的沉積物係牢固地連接在金屬表面且難以去除。 這些影響有數個有害的影響：製造成本增加因為（1)因 頻繁、必需的設備清潔工作而降低的生產率，和(2)因在模 造或押出元件上抗氧化劑生成而造成之較高的廢品率。此 外，在聚碳酸酯中所減少之抗氧化劑的量增加了對變黃、 4 201144356 財衝擊度損失和模造/押出物之延展的敏感性。 藉共聚合亞鱗酸酯化合物於一碳酸酯聚合物之主鍵中 以降低壓汁(juicing)/析出（plate-out)問題的嘗試已達成有限 技術性成功和非商業性成功。作為後者的範例，US 3,578,634揭露藉溶液聚合製程，而將三氣化磷共聚合於聚 碳酸酯之主鏈中。於該專利中所揭露之小規模之下，此一 製程之產物顯示出有限之顏色安定性的改良。然而，用以 製造該聚碳酸酯之已揭露的溶液製程係僅對於如實驗室之 規模的製程為有用的；主要因為於一般商業界面之製程中 三氯化磷係被水解成磷酸，故其並未被推論至一可實行之 商業規模的聚碳酸酯製程。 用以克服非所期望之三氣化磷水解反應的方法已被擬 出’其中聚合以芳基取代之苯膦醯二氣或以芳基取代之二 氣化膦的嘗試已被揭露，見USP4,444,978。當低數量亞磷 被顯示用以令其進入碳酸酯共聚物之主鏈中，在熱老化 中，所得產物明顯地顯示較控制組多之初始顏色和後續顏 色的產生。USP 4,444,978進一步揭露了外來的具有超過 200單體單元之雙·或三_取代之亞磷酸酯募聚合物，其中碳 酸醋共聚物之顏色安定性係被改良。然而，’978專利完全 未提及這些外來之共聚單體對該所得之碳酸酯共聚物的其 他性質（即機械、熱學 '流變和物理的性質）有何影響。 期望具有可在商業性聚碳酸酿製程中被生產之碳酸醋 亞碌酸酯共聚物，該碳酸酯亞磷酸酯共聚物顯示良好的熱 氧化安定性而對其他重要性質無不利影響，同時進一步顯 201144356 示了對設備、模具和模製及/或押出之元件具一被降低之壓 汁(juicing)/析出（plate-out)程度之良好的黏性。 【發明内容】 發明概要 本發明係一用以製造熱氧化性安定之碳酸酯亞磷酸酯 共聚物的方法，其包括下列步驟： (a)於一具下式之有機亞磷酸酯存在下聚合一二羥酚 和一碳酸S旨前驅物： p-(o-z-oh)3 1 其中Z是苯二曱醇基、間苯二酚基、對苯二酚基、 鄰苯二酚基或具下式：C Technical Field of the Invention: J FIELD OF THE INVENTION The present invention relates to a carbonate polymer having an effective amount of a phosphorus compound copolymerized therein, preferably tris(4-hydroxy-2,2-bisdiphenylpropane) Phosphate ester, such that the carbonate phosphite copolymer thermal oxidative stabilizer has a low plate-out behavior, and a method of producing the copolymer. BACKGROUND OF THE INVENTION Polycarbonate resins provide an excellent balance of properties related to clarity, toughness, steric stability, and heat resistance. These properties make polycarbonate ideal for the preparation of many types of molded, formed or otherwise assembled components, especially for electronic storage applications (CDs, DVDs, etc.), medical applications, compressed sheets or used in packages. Other structures and parts of glazing and other outdoor uses. However, like most organic polymers, polycarbonates are susceptible to oxidation, especially thermal oxidation. Thermal oxidation of polycarbonate is typically characterized by yellowing, loss of impact strength, and elongation that can result in reduced transparency and undesired effects on surface appearance such as cracking and gloss changes. Since polycarbonate has derived many of its value and usability from its excellent optical properties, namely, low chroma and high transparency and correction, various methods of resisting thermal oxidation have been tried to stabilize polycarbonate. The thermal oxidation reaction comprises (1) adding an antioxidant compound and (2) structurally modifying the carbonate skeleton by a copolymerization-antioxidant compound therein.习 The conventional method used in all commercial polycarbonate products is the addition of antioxidants 201144356 stabilizers, such as the 'additive method'. Phosphinate compounds have been found to be a particularly effective group of compounds for the oxidation stability of polycarbonates. Examples of phosphite stabilizers are found in 3,305,520; 4,066,611; 4, 〇73,769; 4,088,709; 4,427,813; and 4,254,014; or in combination with other stabilizers, see EP 825,226, JP 10-044,356; JP 10-044,357; and JP 10-044,358 ; JP 04-103,626; JP 04-159,354 and JP 1〇_138 435. However, during the manufacture of polycarbonate, the antioxidant additive tends to be filtered out or removed from the phosphite copolymer and deposited on the extrusion/forming equipment and/or the mold and/or molded component. The loss of this antioxidant is referred to as juicing and/or mold perspiration, white atomization and/or precipitation (sheet-0Ut) in sheet extrusion during injection molding or fuming. . Precipitation (plate_〇ut) is not good because it is a coating that gradually forms on the metal surface of the mold during the plastic process. The coating is the result of movement and deposition of one or more resin components such as lubricating oils, stabilizers, plasticizers, and short chain polycarbonate oligomers in a mold and/or process equipment. For various reasons, plate-out from commonly used antioxidant additives is difficult to remove, especially low molecular weight phosphites, including partial hydrolysis of phosphate groups forming phosphite groups, which are followed by The metal surface of the mold is invaded or etched and provides mechanical bonding between the metal and the partially hydrolyzed ylide additive. This type of deposit is firmly attached to the metal surface and is difficult to remove. These effects have several detrimental effects: increased manufacturing costs due to (1) reduced productivity due to frequent, necessary equipment cleaning work, and (2) higher rejection rates due to antioxidant formation on molded or extruded components. . In addition, the reduced amount of antioxidants in the polycarbonate increases the sensitivity to yellowing, loss of 201144356 financial impact, and elongation of the molded/extracted material. Attempts to reduce the problem of juicing/plate-out by copolymerizing a sulphate compound in the primary bond of a monocarbonate polymer have met limited technical success and non-commercial success. As an example of the latter, U.S. Patent No. 3,578,634 discloses the use of a solution polymerization process to copolymerize tri-phosphorus phosphorus in the backbone of a polycarbonate. Under the small scale disclosed in this patent, the products of this process show a finite improvement in color stability. However, the disclosed solution process for making the polycarbonate is only useful for processes such as laboratory scale; primarily because the phosphorus trichloride is hydrolyzed to phosphoric acid during the general commercial interface process, It has not been inferred to a viable commercial scale polycarbonate process. A method for overcoming the undesired tri-phosphorus phosphorus hydrolysis reaction has been developed as an attempt to polymerize phenylphosphine disulfide substituted with an aryl group or a di-vaporated phosphine substituted with an aryl group, see USP 4 , 444, 978. When a low amount of phosphorous is shown to enter the backbone of the carbonate copolymer, the resulting product clearly shows more initial color and subsequent color generation than the control group during heat aging. Further, USP 4,444,978 discloses an external bis- or tri-substituted phosphite polymer having more than 200 monomer units, wherein the color stability of the carbonic acid vinegar copolymer is improved. However, the '978 patent does not mention at all the effect of these foreign comonomers on the other properties of the resulting carbonate copolymer (i.e., mechanical, thermal 'rheological and physical properties'). It is desirable to have a carbonated sulfonate copolymer which can be produced in a commercial polycarbonate process which exhibits good thermal oxidation stability without adversely affecting other important properties, while further 201144356 shows good adhesion to equipment, molds and molded and/or extruded components with a reduced degree of juicing/plate-out. SUMMARY OF THE INVENTION The present invention is a process for producing a thermally oxidatively stable carbonate phosphite copolymer comprising the steps of: (a) polymerizing in the presence of an organophosphite of the formula: Precursor of dihydric phenol and monocarbonic acid: p-(oz-oh)3 1 wherein Z is a benzophenanol group, a resorcinol group, a hydroquinone group, a catechol group or a formula :
於該處X係單鍵、一含1至15個碳原子之二價碳氫 化合物基或 0 0 0Here, the X-system single bond, a divalent hydrocarbon group having 1 to 15 carbon atoms or 0 0 0
II II IIII II II
-S-，一S-，-S-，—0-, or -C-， II Ο 且 Y係獨立地為氫、氣、漠、氣，或一價碳氫化合物 基，如1至4個碳之烷基，6至8個碳之芳香基(如， 苯基、曱苯基、二曱苯基）、1至4個碳之氧烷基或 6 201144356 一 6至個8碳之氧芳香基及 η是獨立地為自1至4之整數， 及 (b)回收較佳地具16,000g/莫耳至45,000g/莫耳重量平 均分子量之碳酸酯共聚物， 其中該碳酸酯共聚物具有一以共聚物之總重量為基準之自 5ppm至5000ppm之元素ί粦含量，更佳地為lOppm至 500ppm，且較佳地Z是一雙酌·Α基。 於揭露於此處之前之本發明之製程的不同具體實施例 中，在(a)步驟中之有機亞磷酸酯具有下列化學式： (R,-0)m-P-(0-Z-0H)n 6 其中在m加η等於3之條件下，m是1或2且η是1或2，R,係獨 立地為苯基、ρ-四級-丁基苯基、壬基-苯基或辛基苯基，較 佳地Ζ是一雙酚Α基，η等於1，m等於2，且心皆是ρ-四級-丁基苯基。 於本發明之製程的一具體實施例中，該有機亞磷酸酯 係一大於85重量百分比純度之被分離的固體。 於本發明之製程的另一具體實施例中，該有機亞磷酸 酯係一在反應過程中未自副產物之反應被分離之產物，且 係以所有反應產物之重量至少重量百分比為60之數量為基 準而在反應混合物中被呈現。 圖式簡單說明 第1圖顯示用於實施例1之反應產物的結構和重量百分 201144356 第2圖係—比較碳酸酯（共）聚合物烘箱老化顏色安定性 的圖表； 第3圖係一比較碳酸酯（共）聚合物黏性的圖表；以及 第4圖係—比較碳酸酯（共）聚合物之黏滯模數與彈性模 數（阻尼相）之比例的圖表。 I：實施方式3 詳細說明 使用於本發明之可用的二羥酚具有通式為 HO-M-OH，其中μ包括一直接與酚類氧原子連接之6至3〇 個碳原子的單-或多-芳香雙基。較佳地，於二羥酚η〇_μ 〇η 中的酚類羥基皆被排列在（多個）芳香環上之對位_位置。該 被使用在本發明之製程中的二羥酚包括二（芳香基-羥基-笨 基)烧叉基’該二（芳香基-經基-苯基)烧又基包括其被芳香族 和脂族所取代之衍生物，例如於USP 2,999,835 ; ; 3,334，154和4,299,928所揭露者；及如於USP3，169，121 中所 描述的芳香二元醇。本發明中適於聚碳酸酯之製造的最佳 二羥酚係二酚A、二酚A P、二酚F、四溴二酚a和四曱基二 酚A。最佳之二羥酚係二酚A。 適合用於本發明之合適的碳酸酯前驅物係幾基鹵化物 或醯基函化物，其中最佳為二氣化羰。二氯化幾係於水性 鹼溶液中與二羥酚化合物接觸，且可作為溶液而加入至水 不互溶之非反應性有機溶劑中，且完全地與水相混合，或 可被以氣體形式打入(bubbled)反應混合物中，且優先地溶 解和定位在有機相中。 8 201144356 本發明之碳酸酯共聚物包括一微小但有效量之共聚合 至碳酸酯共聚物主鏈中的亞磷酸酯化合物。較佳地該共聚 單體係一具下式之有機亞磷酸酯： ρ-(ο-ζ-οη)3 其中z係連接至亞磷酸和羥基之二價殘基（衍生自二羥 酚）。衍生出z之該二羥酚係挑選自此處之前所列出之二羥 酚。衍生出Z之該二羥酚可能與Μ相同（HO-Z-OH = M)或與 Μ不同（HO-Z-OH4M)。 Ζ包括酚類氧原子所直接連接之6至30個碳原子之單-或多•芳香基。Ζ可能為二羥基單核酚之雙基衍生物，較佳 為苯二甲醇基、間苯二紛基、對苯二盼基、鄰苯二盼基。 可替代的，Ζ可能為具下式之二羥基多核酚：-S-, an S-, -S-, -0-, or -C-, II Ο and the Y system is independently hydrogen, gas, desert, gas, or a monovalent hydrocarbon group, such as 1 to 4 Carbon alkyl, 6 to 8 carbon aryl (eg, phenyl, phenylphenyl, diphenyl), 1 to 4 carbon oxyalkyl or 6 201144356 6 to 8 carbon oxygen aromatic The base and η are independently an integer from 1 to 4, and (b) recovers a carbonate copolymer preferably having a weight average molecular weight of from 16,000 g/mol to 45,000 g/mol, wherein the carbonate copolymer has An element 粦 content of from 5 ppm to 5000 ppm, based on the total weight of the copolymer, more preferably from 10 ppm to 500 ppm, and preferably Z is a combination of fluorene groups. In various embodiments of the process of the invention disclosed herein before, the organophosphite in step (a) has the formula: (R,-0)mP-(0-Z-0H)n 6 Where m is 1 or 2 and η is 1 or 2, R is independently phenyl, ρ-quaternary-butylphenyl, fluorenyl-phenyl or octyl under the condition that m plus η is equal to 3. Phenyl, preferably hydrazine is a bisphenol fluorenyl group, η is equal to 1, m is equal to 2, and the core is ρ-quaternary-butylphenyl. In a specific embodiment of the process of the present invention, the organophosphite is a separated solid greater than 85 weight percent pure. In another embodiment of the process of the present invention, the organic phosphite is a product which is not separated from the by-product reaction during the reaction, and is at least 60% by weight of all reaction products. It is presented as a benchmark in the reaction mixture. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the structure and weight percentage of the reaction product used in Example 1 201144356 Fig. 2 is a graph comparing the color stability of carbonate (co)polymer oven aging; Fig. 3 is a comparison A graph of the viscosity of a carbonate (co)polymer; and a graph of a comparison of the ratio of the viscous modulus of the carbonate (co)polymer to the modulus of elasticity (damping phase). I: Embodiment 3 DETAILED DESCRIPTION The useful dihydric phenols used in the present invention have the formula HO-M-OH, wherein μ comprises a single- or 6- to 3 carbon atoms directly bonded to a phenolic oxygen atom. Multi-aromatic double base. Preferably, the phenolic hydroxyl groups in the dihydric phenol η〇_μ 〇η are arranged in the para-position on the aromatic ring(s). The dihydric phenol used in the process of the present invention includes a di(aryl-hydroxy-phenyl) pyridyl group. The bis(aryl-carbyl-phenyl)pyringyl group includes an aromatic group and a fat group. Derivatives substituted by the family, such as those disclosed in U.S. Patent Nos. 2,999,835; 3,334,154 and 4,299,928; and the aromatic diols as described in U.S. Patent 3,169,121. The most preferred dihydric phenols in the present invention for the production of polycarbonate are diphenol A, diphenol A P, diphenol F, tetrabromodiphenol a and tetradecyldiphenol A. The best dihydric phenol is diphenol A. Suitable carbonate precursors suitable for use in the present invention are a group of halides or sulfhydryl complexes, of which dicarbonylated carbonyl is most preferred. The dichlorobenzene is contacted with the dihydric phenol compound in an aqueous alkaline solution, and can be added as a solution to a water-immiscible non-reactive organic solvent, and completely mixed with the water, or can be used in the form of a gas. Bubled into the reaction mixture and preferentially dissolved and positioned in the organic phase. 8 201144356 The carbonate copolymer of the present invention comprises a small but effective amount of a phosphite compound copolymerized into the backbone of the carbonate copolymer. Preferably, the comonomer system has an organophosphite of the formula: ρ-(ο-ζ-οη)3 wherein z is attached to a divalent residue of a phosphorous acid and a hydroxyl group (derived from a dihydric phenol). The dihydric phenol derived from z was selected from the dihydric phenols listed previously herein. The dihydric phenol from which Z is derived may be the same as hydrazine (HO-Z-OH = M) or different from hydrazine (HO-Z-OH4M). Ζ includes mono- or poly-aryl groups of 6 to 30 carbon atoms to which a phenolic oxygen atom is directly bonded. The hydrazine may be a diradical derivative of a dihydroxy mononuclear phenol, preferably a benzenedimethanol group, a m-benzoic acid group, a p-phenylene diphenyl group or an o-phenylene diphenyl group. Alternatively, the ruthenium may be a dihydroxy polynuclear phenol having the following formula:
於該處X係單鍵、含1至15個碳原子之二價碳氫化合物基， 或 —S—, —S—, —S —, —Ο—, or —C一, 〇 Υ係獨立地為氫、氣、溴、氟，或一價碳氫化合物基，如1 至4個碳之烷基、6至8個碳之芳香基(如，苯基、甲苯基、 二曱苯基）、1至4個碳之氧烷基或一 6至8個碳之氧芳香基， 9 201144356 及η是獨立地為自1至4之整數。 較佳地Ζ是二紛Α基且有機亞碟酸酯是三(4·經基_2，2-雙·一本-丙院）亞鱗酸醋：Here, the X-system single bond, a divalent hydrocarbon group having 1 to 15 carbon atoms, or -S-, -S-, -S-, -Ο-, or -C-, is independently Is hydrogen, gas, bromine, fluorine, or a monovalent hydrocarbon group, such as an alkyl group of 1 to 4 carbons, an aromatic group of 6 to 8 carbons (eg, phenyl, tolyl, diphenyl), 1 to 4 carbon oxyalkyl groups or 6 to 8 carbon oxyaryl groups, 9 201144356 and η are independently an integer from 1 to 4. Preferably, the oxime is a disulfide group and the organic sulfonate ester is a tris(4. thiol-2,2-bis-one-propyl) linoleic acid vinegar:
3 本發明之碳酸酯亞磷酸酯共聚物具下式： P-(0-Z-R)3 4 其中Z係如此處之前所定義且R是衍生自前述之二經紛和 兔酸醋前驅物的聚碳酸醋主鏈’較佳為二盼A和二氣化幾。 於本發明之一較佳的具體實施例中，有機亞填酸酯（z) 之二羥酚雙基係衍生自包括碳酸酯聚合物R(即ho-z-oh — Μ)主鏈之相同的二經盼(μ)，且碳酸酯亞磷酸酯共聚物可 被呈現為下式： p-(o-r)3 5 於本發明之一較佳的碳酸酯亞磷酸酯共聚物包括二氣 化羰存在時來自二酚A和三(4-羥基-2, 2-雙二苯-丙烷）亞磷 酸酯聚合反應之碳酸酯共聚物。 於另一具體實施例中，該共聚單體係一具下式之有機 亞磷酸酯： (Rr〇)m-P-(〇-Z-〇H)„ 6 其中在m加η等於3之條件下，m是1或2且11是1或2且 心(獨立地假若m等於2時)係為酚基，較佳為笨基、壬基苯 基或辛基苯基。這些具混和之苯基的亞磷酸酯可利用雙官 10 201144356 能基和單官能基酚之混合物而被製備，例如，酚、p-四級_ 丁基紛、丁盼、壬紛或辛齡。 該亞磷酸酯共聚單體被聚合在本發明之碳酸酯共聚物 中以長:供在共聚物構架中等於或大於lppm之基本含碟化合 物的數量，較佳為5ppm，較佳為10ppm，更佳為⑼卯爪，其 中ppm係以碳酸酯共聚物之總重量為基準。該亞磷酸酯共聚 單體係被聚合在本發明之碳酸酯共聚物中以提供在共聚物 構架中等於或小於1〇,〇〇〇ppm之基本含磷化合物的數量較 佳為5,0〇〇ppm ,較佳為1〇〇〇ppm，較佳為5〇〇卯爪，較佳為 lOOppm’更佳為5〇ppm’其中ppm係以碳酸酯共聚物之總重 量為基準。 任何用以製造使用於本發明之有機亞碌酸酯的製程係 可接受的，且該製程係未被特別限制的。該有機亞磷酸酯 可月b於非連續（批次)之製程或連續之製程中被製成。該有機 亞磷酸酯可能被分離為相對較純之組分（即，自其之合成反 應的/谷劑、未反應的反應物及/或反應副產物所分離的固體 形式，且包括大於85重量百分比之所期望的亞磷酸酯，較 佳為大於90%，較佳為大於95%，更佳為大於99重量百分比 之所期望的亞磷酸酯），或以中間原位產物使用。一原位產 物未自其之典型反應之副產物（尤其為單_、雙_、環-及/或募 聚物-亞磷酸酯及/或磷酸酯）被分離，當其共聚合至碳酸酯 共聚物主鏈中時，其亦將對共聚物提供熱氧化安定性，且 由於其結合至聚合物之主鏈中，故為抗壓汁析出 (plate-out)。較佳地，若亞磷酸酯係以原位產物般被加入， 11 201144356 所期望之亞磷酸酯以等於或大於約60重量百分比的數量存 在於反應混合物中，較佳為等於或大於約70重量百分比， 較佳為等於或大於約75重量百分比，較佳為等於或大於約 80重量百分比，較佳為等於或大於約85重量百分比，較佳 為等於或大於約90重量百分比，較佳為等於或大於約95重 量百分比，更佳為等於或大於約98重量百分比，其中重量 百分比係以反應產物之總重量為基準。 於一具體實施例中，用於本發明之有機亞磷酸酯係以 使用雙酚A和三氣化磷之一非連續性批次方法所製備。雙酚 -A(bis A)被添加至二氣曱烷(MeCl2)和三乙胺(TEA)之溶液 中。溶於二氣甲烷之三氣化磷的混合物被加入在此溶液 中。此混合物典型地於至多120分鐘内進行反應，但更佳地 於至多30分鐘内，且所期望之有機亞磷酸酯可能被分離或 可能以未與任何副產物分離之反應混合物形式而被使用。 在大氣壓力下反應期間的溫度係介於〇°C至40°C，較佳為 25°C至35°C。加壓時，該溫度可能亦增加至高達l〇〇°C。 TEA: PC13之適合的莫耳比係介於1 : 10,較佳為自2.5 : 4，且更佳為自3.5 : 4.0。雙酚A : PC13之適合的莫耳比係自 1 : 50，較佳為自3 : 10，且更佳為自2·5 : 6。MeCl2 :雙酚 A之適合的重量比係自1 : 100，較佳為自5 : 30，且更佳為 自10 : 15。TEA :雙酚A之適合的莫耳比係自0.1 : 5，更佳 為 0.5 : 1.5 。 例如，適合用於自雙酚A製造有機亞磷酸酯混合物的原 料係20.2毫莫耳之雙酚A、24.7毫莫耳之TEA和6.85毫莫耳 12 201144356 之PC13，該等原料造成下列莫耳比（莫耳/莫耳）：雙酚A: PC13 為2.95、TEA :雙紛A為 1.22和TEA/PC13為3.61。 於本發明之製程的一具體實施例中，該有機亞磷酸酯 係藉一連續製程所製成，該製程為藉由在一攪拌反應器 中，使用前文所述之原料的比例而連續地將雙酚A加入至 MeCl2和TEA之混合物中，此混合物接著被連續地抽注至含 有溶於MeCl2之PC13(或可選擇性地為純PC13)的第二反應器 (槽或管）’且此混合物被給予一適當的反應時間以形成所期 望的亞鱗酸酯中間產物，接著反應混和物被饋送至碳酸酯 的聚合製程中。 於本發明之製程的另一具體實施例中，該有機亞磷酸 酯係藉一連續製程所製成，該製程為藉由在一攪拌反應器 中，使用前文所述之原料的比例而連續地將TEA加入一溶 於MeCl2之bis A溶液或漿體中。此混合物被連續地抽注至含 有溶於MeCb中之PCI3(或可選擇性地為純pCi3)的第二反應 器（槽或管），且此混合物被給予一適當的反應時間以形成所 期望的亞麟酸酯中間產物，接著反應混和物被饋送至碳酸 酯的聚合製程中。 於本發明之製程的又一具體實施例中，該有機亞磷酸 酯係藉由一連續製程所製成，該製程為使用前文所述之原 料的比例，連續地將來自第一攪拌槽之溶於MeCl22bis A 之溶液或漿體加入至一第二槽或一管路系統，於此，純TEa 或較佳為一TEA/MeCl2溶液係被加入以溶解bis a。該溶液 被抽注至一第二槐拌槽或一管路，於此，溶於MeCl2之 13 201144356 PCl3(或可選擇性地為純PC13)係被加入。於一用以形成所期 望之亞碟酸酯中間產物之適當的反應時間後，接著反應混 合物被饋送至碳酸酯的聚合製程中。 有機亞磷酸酯之反應混合物可能利用一與質譜儀(MS) 結合之尚效液相層析儀(HPLC)的組合進行分析。該MS分析 界定了與HPLC訊號峰/滞留時間有關之亞磷酸酯續酸酯的 結構。一旦滯留時間對結構之校正被完成，反應混合物可 能以一在相似條件下操作且裝設有一 uv偵測器之第二 HPLC進行分析。各種類的定量分析係以訊號的大小為基 準。 用於本發明製程之鏈終止劑之適合的種類和數量可被 使用以獲得於碳酸酯共聚物中所期望的分子量和分枝程 度°有助於本發明之碳酸酯共聚物生產之較佳的鏈終止劑 係為酚和其衍生物，例如酚、對三級丁苯酚(pTBp)、對茴 香基盼和對+辛苯酚（4-(1,1，2,2，-四曱基丁基）-苯酚或 PTOP) 〇 除聚合磷酸至碳酸酯共聚物之主鏈中外，有機亞磷酸 醋共聚單體作為一分枝劑。若一較高分枝程度是被期望 的’選擇性的分枝劑，如藤黃酸；間苯三酚；三（4_ 羥苯基）乙烷；1，2,4-笨三曱酸；偏笨三酸曱氣(trimelHtic trichloride);焦蜜石酸；二苯酮四甲酸和其之酸氣化物；2,6_ 双[(2-經基-5-甲基笨基）曱基]_4_甲基苯酚和13 5•三(4•羥基 苯基)苯可被使用。若本發明之碳酸酯共聚物被使用，這些 分枝劑可能被使用在於每莫耳二羥基化合物中含約〇 〇〇〇5 14 201144356 至約ο·ι莫耳之分枝劑的範圍中，較佳為約〇.001至約〇 〇ι 更佳為於每莫耳二羥基化合物中含約0.002至0 〇〇5莫耳之 分枝劑。 用於本發明之碳酸酯共聚物之適合的耦合催 三級胺’包括三曱胺、三丁胺、4-N，N-二甲胺基„比咬，以一 甲胺為最佳，例子見USP 6,225,436、5 321 ", ’ 1，丄16、和 5,412,064，其之全部於此處係整體地被納入。 用於本發明之碳酸酯共聚物之適合的耦合催化^係^ 三級胺，包括三曱胺、三丁胺、4-N，N-二甲胺基。比 一 甲胺為最佳，例子見USP 6,225,436、5 321 ,,, ，以，116、和 5,412,0644，其之全部於此處係整體地被納人。 聚碳酸酯樹脂可能藉轉酯反應製程或藉界面聚人反應 製程被製造。本發明之碳酸酯共聚物係較佳藉—禪準界@ 製程而製造，該製程係可以批次或連續進行。如同已知 用於碳酸芳基酯共聚物聚合反應之一標準界面製程（亦稱 為相界面法）包括二經紛(如雙盼A)和碳酸酯前驅物（如_氣 化羰）的反應。界面方法之初始階段係為單體的製備。雔盼 A係至少部分地於一水性驗溶液中被溶解且去質子化以开< 成雙酚鹽A (酚鹽）。選擇性地溶解在一惰性有機溶劑中之二 氣化羰被供予至該製程’該惰性有機溶劑係形成最初作為 一乳化幾通過之溶劑之二相中之第二相’但反應過程中亦 作為氣碳酸芳基醋和於寡聚反應製程中被形成之寡碳酸I旨 的媒介物。 水性鹼溶液可於水中藉添加鹼，如苛性鈉NaOH，而形 15 201144356 成。鹼係典型地被使用在界面聚合反應的整個過程中，且 進一步被添加在反應混合物中，於此適於維持合適的pH。 該苛性鈉被加入在反應混合物中以調整混合物之pH至二經 酚化合物係至少部分被轉化為二陰離子形式的程度。如亞 硫酸鈉或二硫亞磺酸鈉之還原劑亦可有益地被加入至反應 混合物。 二相混合物之另一相係一不與水溶混且典型地為碳酸 酯前驅物和聚碳酸酯產物可溶解於其中之非反應性有機溶 劑。具代表性的溶劑包括以二氣曱烷、1，2_二氣乙烷、四氣 乙烷、氣苯和較佳三氯曱烷氣化的碳氫化合物。 二相皆以足以使含碳酸酯前驅物之滴狀物分散或懸浮 於水性驗混合物中或足以使該前驅物與水性驗混合物接觸 的方式混合。水相中之碳酸酯前驅物和酚鹽反應物間的反 應主要產生了碳酸醋前驅物與和二經驗化合物之雙醋，該 雙酯可進一步與更多二羥酚單元反應以形成更長鏈的寡聚 物。 藉耦合催化劑之添加，耦合反應係發生在酯的部分之 間，以將寡聚物耦合/共聚至碳酸酯共聚物中。典型地，催 化劑在二氣化羰反應期間或在二氣化羰反應之後的某一時 點被加入。所欲之聚ί厌酸醋的分子量藉單體對键終止劑之 比例而被支配。 鏈終止劑係典型地被使用且可在單體製備時或之後被 加入，於二氣化羰反應期間或之後加入，或聚合反應及/或 縮合步驟期間或之後加入。 201144356 界面製程的最後階段包括取得完成之碳酸酯共聚物。於 聚合反應完成時，有機相和水相被分離以容許有機相之純 化和自其回收聚碳酸酯產物。有機相依需求以稀釋之酸、 水及/或稀釋之鹼清洗直到沒有未反應單體、殘餘之製程化 學藥品，如耦合催化劑及/或其他電解質。碳酸酯共聚物產 物的回收受噴霧乾燥法、蒸氣去揮發作用、於一排氣型押 出機之直接去揮發作用'使用反溶劑之沉澱法所影響。本 發明之已完成的碳酸酯共聚物可以片狀或丸粒狀之形式回 收。 一般而言，無論是藉任何生產技術製備，及無論其為 何種型式，本發明之碳酸酯共聚物應具有一分子量，其可 依據於加工特徵(熔態流動率、熔融強度 '切變敏感性及其他） 和物理性質（韌度 '表面性質及其他）間之已知的取捨而提供 加工特徵與物理性質之間的理想平衡。 一般而& ,本發明之碳酸酯共聚物所欲之重量平均分 子量為等於或大於約每莫耳10,000克(g/莫耳），較佳為等於 或大於約16,000g/莫耳，更佳為等於或大於約18,〇〇〇g/莫 耳，更佳為等於或大於約2〇,〇〇〇g/莫耳，更佳為等於或大於 約22,000g/莫耳，及再更佳為等於或大於約25,000g/莫耳。 為了取得具有最小化之膠體程度和其他有益效果的聚合 物’已發現聚合物之重量平均分子量應等於或小於1〇〇,〇〇〇 g/莫耳，較佳為等於或小於80,000 g/莫耳，較佳為等於或小 於60,000 g/莫耳，較佳為等於或小於45 〇〇〇g/莫耳，較佳為 等於或小於40,000 g/莫耳，更佳為等於或小於35,〇〇〇 g/莫 17 201144356 耳。除非另有註明，當提及分子量時，其意指重量平岣分 子量。 已發現，於此範圍中，本發明之碳酸酯共聚物應具有 依ASTM D 1238 ’ 於300。(：和 1.2公斤重（300°C/1.2kg)之情況 下所測定之一等於或大於每10分鐘約1.5克（g/10min)的炫 態流動率(MFR)，，較佳為等於或大於約2g/10min，較佳為 等於或大於約2.5g/10min，及最佳為等於或大於約 3g/10min。已發現本發明之碳酸酯共聚物應具有一熔態流 動率，該熔態流動率較佳等於或小於約l〇〇g/l〇min，較佳 為等於或小於約80g/10min，較佳為等於或小於約 45g/10min，較佳為等於或小於約3〇g/i〇min，較佳為等於或 小於約22g/l Omin，較佳為等於或小於約i 5g/〖〇min，及更佳 為等於或小於約12g/l〇min。 若一額外的分枝劑被使用在本發明之製程中，一般來 說，在該碳酸酯共聚物中是否有一足夠的分枝度，可藉由 測量將分枝化碳酸酯聚合物納入於碳酸酯聚合物混合物之 組成中所造成之剪切敏感性的變化而被間接性地決定。該 剪切敏感性之測量可藉具有動態機械光譜(D M s)或毛細管 流變測定法的標準技術來完成。 已被了解的是，對本發明之碳酸酯共聚物而言，該碳 酸酯共聚物包括一分枝化碳酸酯共聚物組分（來自有機亞 磷酸酯之聚合反應）和非分枝化線性同元聚合物組分（不含 有機亞雜S旨）。進-步被了解的是，本發明之碳酸酿共聚 物可為直接由-聚合反應製料取得的―單組分碳酸能共 18 201144356 聚物。其亦可能與一或多碳酸酯同元聚合物（非前迷之含非 有機亞磷酸酯組份）、分枝化碳酸酯同元聚合物或其等之 組合混合。另一方面，碳酸酯共聚物亦可為基於具不同分 子里和熔態流動率及/或元素磷含量之相同種類碳酸酯共 聚物之二組分的組合，該二組份係被混合以取得所欲之中 間炼態流動率/璃含量的產物。 本發明之碳酸酯共聚物可更進一步包括通常被使用在 此種類之碳酸酯聚合物組成之含量的其他已知添加物及/ 或穩定劑，例如色素、染劑、uv穩定劑、x射線穩定劑、 光穩定劑、脫模劑、炭化劑、滞焰劑或加工穩定劑，其等 係如於USP 5,288,778中所述者。 欲被包括在本發明之碳酸酯共聚物中之添加劑之種類 和數量將隨著所欲之性質和成本之組合的平衡而改變。一 般而言’為提供重要的穩定效果和利益，該添加劑應在以 該化合物將被混入之碳酸酯共聚物之重量為基準之最少約 5ppm數量下被使用’較佳為最少約25ppm，更佳為最少約 50ppm，及最佳為最少約l〇〇ppm。通常於高濃度程度下， 利益是被減少的’且這些化合物之數量應不大於約 5000ppm，較佳為不大於約3000ppm，及最佳為不大於約 2000ppm。 [實施例] 實施例1係為用於製備三(4-羥基-2, 2-二苯-丙烷）亞碟 酸酯的製程’該亞磷酸酯係為被用於下列實施例之本發明 之有機亞磷酸酯。該三(4-羥基-2, 2-二苯-丙炫）亞鱗酸酯之 19 201144356 有機亞磷酸酯係藉使用雙酚A和三氯化磷以一批次方法所 製備，且作為一未分離之中間產物。4 6g(2〇 2毫莫耳)雙酚 A被加入一 200ml圓底燒瓶中之溶於6〇mi二氣曱烧之 2.5g/3.42ml(24.2毫莫耳）的三乙胺溶液中。溶於1〇m丨二氣甲 烷之0.94g/0.6ml(6_8毫莫耳）三氣化磷之混合物被加入至該 溶液中。該混合物在始於-2。(：且溫熱至24。(：下進行反應30 分鐘。三(4-羥基-2, 2-二笨-丙烷）亞磷酸酯未被分離，而是 與任何反應副產物一起溶於二氣曱烷，以溶液形式加至碳 酸酯聚合反應過程中。典型地，當以HpLC/MS分析決定時， 三(4-羥基-2, 2-二苯-丙烷）亞磷酸酯（C45H45〇7p)係以約75重 ΐ百分比存在於反應混合物中（見第一圖）。 貫施例2和3及比較例Α和Β係在一受控制之溫度、擭 拌、15升、夾套玻璃反應器中進行聚合反應。水、苛性鈉、 一孔曱炫*、二級-丁基-本盼溶液和三乙胺溶液之供應係與一 CAMILE控制系統連接以提供適當進給速率，且該供應被 以氮氣所填充以避免所述原料氧化。一反應器中之pH電極 允許在光氣化反應期間在一控制之pH值下之添加物的加 入。就下述之聚合反應，使用下列原料之數量和條件： 雙酚A(BPA) : 0.700kg(3莫耳）； 水：3.870kg ; 苛性鈉溶液(溶於水之30重量百分比的NaOH) : 0.9kg ; 二氣曱烷：2.000kg ; 二氯化羰流：0.06g/s(0.6毫莫耳/s); 總二氣化羰進給量：405g(4.1莫耳）； 20 201144356 反應溫度：介於20°C至40°C，通常為25°C 攪拌器速度：250rpm ; 三級-丁基-苯酚(PTBP):200毫莫耳，溶於55〇克二氯甲 烷；及 三乙胺（TEA) : 6.6gTEA(65毫莫耳TEA)，溶於80ml二 氣曱烷。 β亥雙酌·Α(0. 70kg/3莫耳)係在真空下於一玻璃燒瓶中進 行去氧化10分鐘。接著其被保存在氮氣中以去除微量的 氧。§亥去氧之雙紛A被加入至被以氮氣清潔之不斷地授拌之 20升雙層玻璃反應器中。為了溶解雙酚a，經氬清潔的水 (3_87kg)和苛性鈉（〇.9kg之30重量百分比的氫氧化鈉）被加 入。在溶解期間，氮氣被覆蓋在混合物之上以逐出氧。在 所有雙酚A被溶解之後，2.0kg二氣甲烷被加入，該反應器 被封閉且在氬氣氛圍下攪拌20分鐘，接著光氣化反應被啟 動。於光氣化反應和所有其餘聚合反應期間，反應混合物 被不斷地攪拌。 光氣化反應後，就貫施例2和3而言，實施例1之反應產 物係被加入以在最終的碳酸酯共聚物中達到一特定之磷含 量，而就比較例A而言，則無亞磷酸酯單體或添加物被加 入。對實施例2而言，5.45ml之實施例丨之肀間亞磷酸酯混 合物被加入至聚合反應中。對實施例3而言，95ml中間亞 磷酸酯混合物被加入。接著一溶於Meci2之TEA溶液被加入 至5^合反應中。20分鐘後聚合反應完成。包括聚合物之有 機相係與水相分離。該聚合物溶液以1〇重量百分比之鹽酸 21 201144356 π洗-次’接著以純水作四次清洗。對比較例B而言，一亞 -/、'加物（非共聚單體)被加人至聚合物減且被渡合 以在俩㈣合物中達到—特定之嶙含量。之後，該二氯 甲烧溶劑係藉蒸氣沉殿法去除，且（共）聚合物以片狀形式被 獲得。各(共)聚合物具有—約4()，_§/莫耳之目標重量平均 分子量。 浔之反g文S曰（共）聚合物片在真空中8〇〇c被乾燥％小 夺被擠壓且改變成丸粒狀。該擠壓過程係在具一螺检壓 縮比例為1:3、對全部五個加熱區之擠壓溫度為·。c的一 阶—加之19/25單螺栓押出機進行。該螺栓速度被限制在 40-45rpm。在表丨中，實施例2和3及比較例八和8之磷的來 源和數量係被提供。 實施例 比較例 A B 2 3 m, ppm 源自P 168 30 源自實施例1 19 33 用於性質分析，各碳酸酯（共）聚合物被壓縮成型成具 4 0 m m直徑和3 m m厚度之盤狀物。該壓縮成型測試樣本利用 一熱迷你喷射壓縮成型機自粒狀被塑形。約7g丸粒狀物被 填充入已加熱的桶中且於320oC下鑄型7分鐘。7分鐘後，該 熔融之聚合物在1200巴壓力下被鑄形3〇秒。铸型後之回壓 為600巴、30秒。所產生之盤狀物具一4〇mm直徑和一3mm 厚度。 [熱老化測試] 22 201144356 在一Hereaus 6060烘箱中，經壓縮成型之樣本於14〇〇〇 下進行烘箱老化高達500小時。黃化指數(γι)係在進行老化 前和定期地至多500小時而被決定。ΥΙ係依aST]V[D 1925， 以一 Hunterlab顏色調查機決定。該結果藉下方之方程式被 正規化。 YI(於[X小時]當時） 正規化之YI=------ Υΐ(於初始時[〇小時]) 該結果被繪製並顯示在第2圖。如同所見，本發明之碳酸酯 共聚物，實施例2和3顯示相對於不具任何含磷化合物或具 含構化合物的比較例Α或包括源自亞磷酸酯添加物之含磷 的比較例B之增加的YI和被降低的熱氧化分解。本發明之碳 酸醋亞填酸醋共聚物所示之資料展示了與添加之亞礙酸醋 相比較之相同或更佳的熱氧化行為。 [析出] 含磷組份的移動，或析出，係藉由利用一 Shimadzu GC-MS機器之PY-2020iD單元之GC_mS/高溫分解（WEB EDMS方法A020708)而進行。測試係藉在高溫分解單元中 放置重約0.5mg的粒狀物’以氮氣清潔，接著在325C>C、35〇〇c 和375°C溫度下加熱60分鐘而進行，且被移動之產物接著係 以氣相層析法-質譜儀(GC-MS)被分析。 下列莫耳重量被識別為P-168 : 57g/莫耳、191g/莫耳和 206g/莫耳。P-168在低於325°C開始自碳酸酯共聚物中昇華 而出。 23 201144356 下列莫耳重量係為實施例1 : 65g/莫耳、165 g/莫耳和 231g/莫耳。本發明之碳酸酯共聚物組成之磷化合物的移 動’在375°C之前未被發現’ 375γ係比包括P-168穩定性物 質之碳酸酯聚合物高5〇。(：。定性之析出結果係總結於表2 中’無=沒有可測得之析出，低=極微且可接受數量之析出， 高=過量且非可接受程度之析出。 表2 實施例 比較例 A B 2 3 析出 325°C 益 $ »»\ 尚 無 350°C 無 高 無 無 375°C 無 低 低 [流變特徵] 碳酸酯（共）聚合物之黏性係以一 Physica MCR 300動態 摯 機械光譜儀決定。具0.M00i/S角頻率之一頻率掃描在— 300 C之測試溫度下被進行。被表示為Pa*s之複合黏度(η) 的總量係被計算且被顯示於第3圖中。黏滯模數(G，，)和彈性 模數(G’)和結果之比例（阻尼相s，G，/G”)被計算且被顯示於 第4圖。 、 【圖式簡單說明】 第1圖顯示實施例1之反應產物的結構和重量百分比； 第2圖係一比較碳酸酯（共）聚合物烘箱老化顏色安定性 的圖表； 第3圖係一比較碳酸酯（共）聚合物黏性的圖表；以及 第4圆係一比較碳酸酯（共）聚合物之黏滯模數與彈性模 24 201144356 數（阻尼相）之比例的圖表。 【主要元件符號說明】 (無）3 The carbonate phosphite copolymer of the present invention has the formula: P-(0-ZR)3 4 wherein Z is as defined hereinbefore and R is a polymer derived from the aforementioned bismuth and vinegar precursors The carbonated vinegar backbone is preferably a second gas and a second gasification. In a preferred embodiment of the invention, the dihydric phenolic diradical of the organic sub-filler (z) is derived from the same backbone comprising the carbonate polymer R (ie ho-z-oh- Μ) The second expectation (μ), and the carbonate phosphite copolymer can be presented as: p-(or) 3 5 . One of the preferred carbonate phosphite copolymers of the present invention includes di-vaporized carbonyl. A carbonate copolymer derived from the polymerization of diphenol A and tris(4-hydroxy-2,2-bisdiphenyl-propane) phosphite in the presence. In another embodiment, the copolymer system has an organic phosphite of the formula: (Rr〇)mP-(〇-Z-〇H) „ 6 wherein m is η equal to 3, m is 1 or 2 and 11 is 1 or 2 and the core (independently, if m is equal to 2) is a phenol group, preferably a strepyl, a nonylphenyl or an octylphenyl group. These are mixed phenyl groups. Phosphite esters can be prepared using a mixture of diastere 10 201144356 energy groups and monofunctional phenols, for example, phenol, p-quaternary butyl butyl, butyl phthalate, hydrazine or sulphur. The body is polymerized in the carbonate copolymer of the present invention to be long: the amount of the basic disc-containing compound to be equal to or more than 1 ppm in the copolymer framework, preferably 5 ppm, preferably 10 ppm, more preferably (9) paw. Wherein ppm is based on the total weight of the carbonate copolymer. The phosphite copolymer mono-system is polymerized in the carbonate copolymer of the present invention to provide equal to or less than 1 〇, 〇〇〇 ppm in the copolymer framework. The amount of the basic phosphorus-containing compound is preferably 5,0 〇〇ppm, preferably 1 〇〇〇ppm, preferably 5 〇〇卯, preferably 100 ppm. It is 5 〇 ppm' where ppm is based on the total weight of the carbonate copolymer. Any process for producing the organic linoleic acid ester used in the present invention is acceptable, and the process is not particularly limited. The organic phosphite can be prepared in a discontinuous (batch) process or a continuous process. The organic phosphite may be separated into relatively pure components (ie, synthesized from it). a solid form separated from the colostrum, unreacted reactants and/or reaction by-products, and comprising greater than 85 weight percent of the desired phosphite, preferably greater than 90%, preferably greater than 95%, more Preferably, it is greater than 99% by weight of the desired phosphite), or used as an intermediate in situ product. An in situ product is not a by-product of its typical reaction (especially mono-, double-, ring- and/or The polymer-phosphite and/or phosphate ester is isolated and, when copolymerized into the carbonate copolymer backbone, it will also provide thermal oxidation stability to the copolymer and due to its incorporation into the polymer In the main chain, it is plate-out for pressure-resistant juice. Wherein, if the phosphite is added as an in situ product, the desired phosphite of 11 201144356 is present in the reaction mixture in an amount equal to or greater than about 60 weight percent, preferably equal to or greater than about 70 weight percent, It is preferably equal to or greater than about 75 weight percent, preferably equal to or greater than about 80 weight percent, preferably equal to or greater than about 85 weight percent, preferably equal to or greater than about 90 weight percent, preferably equal to or greater than About 95 weight percent, more preferably equal to or greater than about 98 weight percent, wherein the weight percent is based on the total weight of the reaction product. In one embodiment, the organic phosphite used in the present invention is bisphenol. A non-continuous batch process of A and tri-phosphorus phosphorus was prepared. Bisphenol-A (bis A) was added to a solution of dioxane (MeCl2) and triethylamine (TEA). A mixture of tri-phosphorus phosphorus dissolved in di-methane is added to the solution. This mixture is typically reacted in up to 120 minutes, but more preferably in up to 30 minutes, and the desired organic phosphite may be isolated or may be used in the form of a reaction mixture that is not separated from any by-products. The temperature during the reaction at atmospheric pressure is from 〇 ° C to 40 ° C, preferably from 25 ° C to 35 ° C. This temperature may also increase up to 10 °C when pressurized. TEA: A suitable molar ratio of PC13 is between 1:10, preferably from 2.5:4, and more preferably from 3.5:4.0. A suitable molar ratio of bisphenol A: PC13 is from 1:50, preferably from 3:10, and more preferably from 2:5:6. A suitable weight ratio of MeCl2: bisphenol A is from 1:100, preferably from 5:30, and more preferably from 10:15. TEA: The suitable molar ratio of bisphenol A is from 0.1:5, more preferably 0.5:1.5. For example, a suitable starting material for the manufacture of an organic phosphite mixture from bisphenol A is 20.2 millimolar bisphenol A, 24.7 millimoles TEA and 6.85 millimoles 12 201144356 PC13, which result in the following moles Ratio (mole/mole): bisphenol A: PC13 is 2.95, TEA: double A is 1.22 and TEA/PC13 is 3.61. In a specific embodiment of the process of the present invention, the organophosphite is produced by a continuous process which is continuously carried out by using a ratio of the raw materials described above in a stirred reactor. Bisphenol A is added to a mixture of MeCl2 and TEA, which mixture is then continuously pumped to a second reactor (tank or tube) containing PC13 (or optionally PC13) dissolved in MeCl2 and this The mixture is given a suitable reaction time to form the desired avermitate intermediate, which is then fed to the polymerization process of the carbonate. In another embodiment of the process of the present invention, the organophosphite is produced by a continuous process which is continuously carried out by using a ratio of the raw materials described above in a stirred reactor. The TEA is added to a solution or slurry of bis A dissolved in MeCl2. This mixture is continuously pumped to a second reactor (tank or tube) containing PCI3 (or optionally pure pCi3) dissolved in MeCb, and the mixture is given an appropriate reaction time to form the desired The linoleate intermediate is then fed to the carbonate polymerization process. In still another embodiment of the process of the present invention, the organophosphite is produced by a continuous process which continuously dissolves the solvent from the first agitation tank using a ratio of the raw materials described hereinbefore. The solution or slurry of MeCl22bis A is added to a second tank or a piping system where pure TEa or preferably a TEA/MeCl2 solution is added to dissolve the bis a. The solution is pumped to a second mixing tank or a line where it is added to MeCl2 13 201144356 PCl3 (or optionally pure PC13). After a suitable reaction time to form the desired sub-plate acid ester intermediate, the reaction mixture is then fed to a polymerization process of the carbonate. The reaction mixture of the organic phosphite may be analyzed using a combination of a mass spectrometer (MS) combined with a liquid chromatography (HPLC). This MS analysis defines the structure of the phosphite retorate associated with the peak/detention time of the HPLC signal. Once the calibration of the structure is completed, the reaction mixture may be analyzed by a second HPLC operating under similar conditions and equipped with a uv detector. Quantitative analysis of various classes is based on the size of the signal. Suitable types and amounts of chain terminators useful in the process of the present invention can be used to achieve the desired molecular weight and degree of branching in the carbonate copolymer, which contributes to the preferred production of the carbonate copolymer of the present invention. Chain terminators are phenols and their derivatives, such as phenol, p-tert-butylphenol (pTBp), p-anisine and p-octylphenol (4-(1,1,2,2,-tetradecylbutyl) )-Phenol or PTOP) The organic phosphite comonomer is used as a branching agent in addition to the main chain of the polymerized phosphoric acid to carbonate copolymer. If a higher degree of branching is the desired 'selective branching agent, such as gambogic acid; phloroglucinol; tris(4-hydroxyphenyl)ethane; 1,2,4-stupoleic acid; TrimelHtic trichloride; pyromic acid; benzophenone tetracarboxylic acid and its acid vapor; 2,6_bis[(2-carbazhen-5-methylphenyl)indenyl]_4 _Methylphenol and 13 5•tris(4•hydroxyphenyl)benzene can be used. If the carbonate copolymer of the present invention is used, these branching agents may be used in a range of from about 145 14 201144356 to about ο·m mole of branching agent per mole of dihydroxy compound. More preferably, from about 〇.001 to about 〇〇ι, it is preferably from about 0.002 to 0 〇〇 5 moles of branching agent per mole of dihydroxy compound. Suitable coupling tertiary amines for use in the carbonate copolymers of the present invention include tridecylamine, tributylamine, 4-N,N-dimethylamine groups, and monomethylamine is preferred. See USP 6,225,436, 5 321 ", 1, 1, 16, and 5, 412, 064, all of which are incorporated herein in their entirety. Suitable Coupling Catalysts for Carbonate Copolymers of the Invention , including tridecylamine, tributylamine, 4-N,N-dimethylamino group. It is the best than monomethylamine. See USP 6,225,436, 5 321 , , , , 116 , and 5,412,0644 for examples. All of them are generally incorporated herein. Polycarbonate resins may be manufactured by a transesterification process or by an interfacial polymerization process. The carbonate copolymer of the present invention is preferably by the Zen Quasi @process Manufacture, the process can be carried out batchwise or continuously. As is known for the polymerization of aryl carbonate copolymers, a standard interface process (also known as phase interface method) includes two processes (such as double-prepared A) and carbonic acid. The reaction of the ester precursor (such as _ gasification carbonyl). The initial stage of the interface process is the preparation of the monomer. Partially dissolved and deprotonated in an aqueous assay solution to form a bisphenolate A (phenolate). The di-vaporized carbonyl selectively dissolved in an inert organic solvent is supplied to the process. 'The inert organic solvent forms the second phase of the two phases which are initially used as a solvent for emulsification, but the oligocarbonate is also formed as a gas carbonate aryl vinegar and in the oligomerization reaction process. The aqueous alkaline solution can be added to the water by adding a base such as caustic soda NaOH, and is formed in the form of a polymer. The base system is typically used throughout the interfacial polymerization reaction and is further added to the reaction mixture. Suitable to maintain a suitable pH. The caustic soda is added to the reaction mixture to adjust the pH of the mixture to the extent that the phenolic compound is at least partially converted to the dianion form. For example, sodium sulfite or sodium disulfoxide sodium reducing agent It may also be beneficial to be added to the reaction mixture. The other phase of the two phase mixture is not miscible with water and is typically non-reactive in which the carbonate precursor and polycarbonate product are soluble. Organic solvent. Representative solvents include hydrocarbons vaporized with dioxane, 1,2 dioxaethane, tetraethane, benzene and preferably trichlorodecane. Sufficient to mix the suspension of the carbonate-containing precursor in the aqueous test mixture or to mix the precursor with the aqueous test mixture. The reaction between the carbonate precursor and the phenate reactant in the aqueous phase The double vinegar of the carbonated acetal precursor and the second empirical compound is mainly produced, and the bisester can be further reacted with more dihydric phenol units to form a longer chain oligomer. By the addition of the coupling catalyst, the coupling reaction occurs in the Between the ester moieties to couple/copolymerize the oligomer into the carbonate copolymer. Typically, the catalyst is added during the second gasification carbonylation reaction or at some point after the second gasification carbonylation reaction. The molecular weight of the desired vinegar is governed by the ratio of monomer to bond terminator. Chain terminators are typically employed and may be added during or after monomer preparation, during or after the second gasification carbonylation reaction, or during or after the polymerization and/or condensation steps. The final stage of the 201144356 interface process includes the completion of the carbonate copolymer. Upon completion of the polymerization, the organic and aqueous phases are separated to allow purification of the organic phase and recovery of the polycarbonate product therefrom. The organic phase is washed with diluted acid, water and/or a dilute base until there are no unreacted monomers, residual process chemicals, such as coupling catalysts and/or other electrolytes. The recovery of the carbonate copolymer product is affected by the spray drying method, the vapor devolatization, and the direct devolatization of a venting extruder, using an anti-solvent precipitation method. The completed carbonate copolymer of the present invention can be recovered in the form of flakes or pellets. In general, the carbonate copolymer of the present invention should have a molecular weight, whether by any production technique, and regardless of its type, which can be based on processing characteristics (melt flow rate, melt strength, shear sensitivity). And other) and the known trade-offs between physical properties (toughness 'surface properties and others) provide an ideal balance between processing and physical properties. Generally, the carbonate copolymer of the present invention has a weight average molecular weight of equal to or greater than about 10,000 grams per gram (g/mole), preferably equal to or greater than about 16,000 g/mole, more preferably Is equal to or greater than about 18, 〇〇〇g/mole, more preferably equal to or greater than about 2 〇, 〇〇〇g/mole, more preferably equal to or greater than about 22,000 g/mole, and even better It is equal to or greater than about 25,000 g/mole. In order to obtain a polymer having a minimized colloidal degree and other beneficial effects, it has been found that the weight average molecular weight of the polymer should be equal to or less than 1 〇〇, 〇〇〇g/mole, preferably equal to or less than 80,000 g/m. The ear, preferably equal to or less than 60,000 g/mole, preferably equal to or less than 45 〇〇〇g/mole, preferably equal to or less than 40,000 g/mole, more preferably equal to or less than 35, 〇 〇〇g/莫17 201144356 ear. Unless otherwise stated, when referring to molecular weight, it is meant to refer to the weight of the molecular weight. It has been found that in this range, the carbonate copolymer of the present invention should have an ASTM D 1238 ' at 300. (: and one of the measures measured in the case of 1.2 kg weight (300 ° C / 1.2 kg) is equal to or greater than about 1.5 g (g/10 min) of illusive flow rate (MFR) per 10 minutes, preferably equal to or It is greater than about 2 g/10 min, preferably equal to or greater than about 2.5 g/10 min, and most preferably equal to or greater than about 3 g/10 min. It has been found that the carbonate copolymer of the present invention should have a melt flow rate, the molten state. The flow rate is preferably equal to or less than about 10 g/l min, preferably equal to or less than about 80 g/10 min, preferably equal to or less than about 45 g/10 min, preferably equal to or less than about 3 g/g. i 〇 min, preferably equal to or less than about 22 g / l Omin, preferably equal to or less than about i 5 g / 〇 min, and more preferably equal to or less than about 12 g / l 〇 min. If an additional branch The agent is used in the process of the present invention. Generally, whether there is sufficient branching in the carbonate copolymer can be determined by incorporating the branched carbonate polymer into the carbonate polymer mixture. The change in shear sensitivity caused by it is indirectly determined. The measurement of shear sensitivity can be obtained by dynamic mechanical spectroscopy (D M s) or standard techniques for capillary rheometry. It is understood that for the carbonate copolymer of the present invention, the carbonate copolymer comprises a branched carbonate copolymer component (from organic Polymerization of phosphites) and non-branched linear homopolymer components (excluding organic hydrazines). It is understood that the carbonated copolymers of the present invention can be directly polymerized by-polymerization. The one-component carbonic acid obtained by the reaction preparation can be a total of 18 201144356 polymer. It may also be combined with a mono- or multi-carbonate homopolymer (non-previous non-organophosphite component), branched carbonate. Mixing with a homopolymer or a combination thereof, etc. On the other hand, the carbonate copolymer may also be a two component based on the same type of carbonate copolymer having different molecular and molten flow rates and/or elemental phosphorus contents. In combination, the two components are mixed to obtain a product of the desired intermediate refining flow rate/glass content. The carbonate copolymer of the present invention may further comprise a content of a carbonate polymer generally used in this type. Other known additions Additives and/or stabilizers, such as pigments, dyes, uv stabilizers, x-ray stabilizers, light stabilizers, mold release agents, carbonizers, flame retardants or processing stabilizers, are as described in USP 5,288,778. The type and amount of the additive to be included in the carbonate copolymer of the present invention will vary with the balance of the desired properties and cost combination. Generally speaking, 'to provide important stabilizing effects and benefits The additive should be used at a minimum of about 5 ppm based on the weight of the carbonate copolymer to which the compound will be incorporated, preferably at least about 25 ppm, more preferably at least about 50 ppm, and most preferably at least about 1 〇〇ppm. Generally at high concentrations, the benefit is reduced' and the amount of these compounds should be no greater than about 5000 ppm, preferably no greater than about 3000 ppm, and most preferably no greater than about 2000 ppm. [Examples] Example 1 is a process for preparing tris(4-hydroxy-2,2-diphenyl-propane) sulfite esters. The phosphite is the invention used in the following examples. Organic phosphite. The tris(4-hydroxy-2,2-diphenyl-propanyl) sulphite 19 201144356 organic phosphite is prepared by a batch process using bisphenol A and phosphorus trichloride, and as a Unseparated intermediate product. 4 6 g (2 Torr 2 mmol) of bisphenol A was added to a 200 ml round bottom flask in a solution of 2.5 g / 3.42 ml (24.2 mmol) of triethylamine dissolved in 6 〇mi. A mixture of 0.94 g / 0.6 ml (6 - 8 mmol) of tri-phosphorus phosphorus dissolved in 1 〇 m 丨 dioxane was added to the solution. The mixture starts at -2. (: and warm to 24. (: The reaction is carried out for 30 minutes. The tris(4-hydroxy-2,2-di-p-propane) phosphite is not separated, but is dissolved in two gases together with any reaction by-products. Decane is added as a solution to the polymerization of the carbonate. Typically, tris(4-hydroxy-2,2-diphenyl-propane) phosphite (C45H45〇7p) when determined by HpLC/MS analysis It is present in the reaction mixture at a concentration of about 75 hydrazine (see Figure 1). Examples 2 and 3 and Comparative Examples Β and Β are at a controlled temperature, mash, 15 liter, jacketed glass reactor The polymerization is carried out. The supply of water, caustic soda, porphyrin*, sec-butyl-pretentium solution and triethylamine solution is connected to a CAMILE control system to provide a suitable feed rate, and the supply is Filled with nitrogen to avoid oxidation of the feedstock. The pH electrode in a reactor allows for the addition of additives at a controlled pH during the phosgenation reaction. The following materials are used in the polymerization described below. And conditions: Bisphenol A (BPA): 0.700kg (3 moles); Water: 3.770kg; Caustic soda solution (soluble in water 30% by weight of NaOH): 0.9kg; dioxane: 2.000kg; dicarbonyl chloride stream: 0.06g/s (0.6mmol/s); total two gasification carbonyl feed: 405g (4.1 mo Ear); 20 201144356 Reaction temperature: between 20 ° C and 40 ° C, usually 25 ° C stirrer speed: 250 rpm; tertiary - butyl - phenol (PTBP): 200 millimoles, soluble in 55 grams Dichloromethane; and triethylamine (TEA): 6.6 g TEA (65 mmol MoA), dissolved in 80 ml of dioxane. β海双酌·Α (0. 70kg/3 mol) is under vacuum Deoxidation was carried out for 10 minutes in a glass flask. It was then stored in nitrogen to remove traces of oxygen. § The deoxygenated A was added to a 20 liter double-layer glass reaction which was continuously purged with nitrogen. In order to dissolve bisphenol a, argon-cleaned water (3_87 kg) and caustic soda (〇9 kg of 30% by weight of sodium hydroxide) were added. During the dissolution, nitrogen was overlaid on the mixture to eject. After all the bisphenol A was dissolved, 2.0 kg of di-methane was added, the reactor was closed and stirred under an argon atmosphere for 20 minutes, and then the phosgenation reaction was initiated. During the gasification reaction and all remaining polymerizations, the reaction mixture was continuously stirred. After the phosgenation reaction, the reaction product of Example 1 was added to the final carbonate copolymer for the purposes of Examples 2 and 3. A specific phosphorus content was reached, and in the case of Comparative Example A, no phosphite monomer or additive was added. For Example 2, 5.45 ml of the Example 肀 肀 亚 phosphite mixture was Add to the polymerization reaction. For Example 3, a 95 ml intermediate phosphite mixture was added. Next, a TEA solution dissolved in Meci2 was added to the reaction. The polymerization was completed after 20 minutes. The organic phase including the polymer is separated from the aqueous phase. The polymer solution was washed once with 1% by weight of hydrochloric acid 21 201144356 π followed by four washes with pure water. For Comparative Example B, a sub-/, 'additive (non-comonomer) was added to the polymer minus and was blended to achieve a specific hydrazine content in the two (tetra) complexes. Thereafter, the methylene chloride solvent was removed by a vapor deposition method, and the (co)polymer was obtained in the form of a sheet. Each (co)polymer has a target weight average molecular weight of about 4 (), _§ / mole. The 聚合物 反 文 文 曰 曰 共 共 共 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物The extrusion process has a screwing ratio of 1:3 and an extrusion temperature of all five heating zones. The first step of c—in addition to the 19/25 single-bolt extruder. The bolt speed is limited to 40-45 rpm. In the tables, the sources and amounts of phosphorus of Examples 2 and 3 and Comparative Examples 8 and 8 are provided. EXAMPLES Comparative Example AB 2 3 m, ppm from P 168 30 From Example 1 19 33 For property analysis, each carbonate (co)polymer was compression molded into a disk having a diameter of 40 mm and a thickness of 3 mm. Shape. The compression molded test specimen was shaped from a granular shape using a hot mini jet compression molding machine. Approximately 7 g of pellets were filled into a heated bucket and cast for 7 minutes at 320 °C. After 7 minutes, the molten polymer was cast at a pressure of 1200 bar for 3 seconds. The back pressure after casting is 600 bar and 30 seconds. The resulting disc has a diameter of 4 mm and a thickness of 3 mm. [Heat aging test] 22 201144356 In a Hereaus 6060 oven, the compression-molded samples were oven-aged at 14 Torr for up to 500 hours. The yellowing index (γι) is determined before aging and up to 500 hours on a regular basis. The ΥΙ is based on aST]V[D 1925, determined by a Hunterlab color survey machine. The result is normalized by the equation below. YI (at the time of [X hours]) Normalized YI=------ Υΐ (at the beginning [〇 hours]) The result is plotted and shown in Figure 2. As can be seen, the carbonate copolymers of the present invention, Examples 2 and 3, show Comparative Example B with respect to a phosphorus-free compound or a compound containing a compound containing compound or containing phosphorus derived from a phosphite additive. Increased YI and reduced thermal oxidative decomposition. The data shown in the carbonic acid acetal copolymer of the present invention shows the same or better thermal oxidation behavior as compared to the added sulfite. [Precipitation] The movement or precipitation of the phosphorus-containing component was carried out by GC_mS/pyrolysis (WEB EDMS method A020708) of a PY-2020iD unit of a Shimadzu GC-MS machine. The test was carried out by placing a pellet of about 0.5 mg in a pyrolysis unit, purged with nitrogen, followed by heating at 325 C > C, 35 ° C and 375 ° C for 60 minutes, and the product to be moved was It was analyzed by gas chromatography-mass spectrometry (GC-MS). The following molar weights were identified as P-168: 57 g/mole, 191 g/mole and 206 g/mole. P-168 begins to sublime from the carbonate copolymer starting below 325 °C. 23 201144356 The following molar weights are Example 1: 65 g/mole, 165 g/mole and 231 g/mole. The movement of the phosphorus compound composed of the carbonate copolymer of the present invention was not found before 375 ° C. The 375 γ system was 5 Å higher than the carbonate polymer including the P-168 stable substance. (: Qualitative precipitation results are summarized in Table 2 'no = no measurable precipitation, low = very small and acceptable amount of precipitation, high = excess and unacceptable precipitation. Table 2 Example Comparative Example AB 2 3 Precipitation 325°C Benefits $ »»\ No 350°C No height and no 375°C No low [Rheological characteristics] The viscosity of carbonate (co)polymer is dynamically mediated by a Physica MCR 300 Determined by a mechanical spectrometer. A frequency sweep with a frequency of 0.M00i/S is performed at a test temperature of -300 C. The total viscosity (η) expressed as Pa*s is calculated and displayed in the first In Fig. 3, the viscous modulus (G,,) and the ratio of the elastic modulus (G') to the result (damping phase s, G, /G") are calculated and shown in Fig. 4. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the structure and weight percentage of the reaction product of Example 1; Fig. 2 is a graph comparing the color stability of carbonate (co)polymer oven aging; Fig. 3 is a comparison of carbonates (total a graph of the viscosity of the polymer; and a viscous mode of the fourth round system compared to the carbonate (co)polymer Chart elastic 24201144356 number (damping phase) mode of the scale. The main element REFERENCE NUMERALS (None)