TW200408660A

TW200408660A - Catalyst for polycondensation reaction and method for producing polyester using the same

Info

Publication number: TW200408660A
Application number: TW91134090A
Authority: TW
Inventors: Yosuke Iida; Toru Setoyama
Original assignee: Mitsubishi Chem Corp
Priority date: 2001-05-25
Filing date: 2002-11-22
Publication date: 2004-06-01
Also published as: JP2003040992A; JP4010872B2

Abstract

The present invention relates to a catalyst for polycondensation reaction and a method for producing polyester using the same.

Description

200408660 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（1 ) 本發明係有關縮聚反應用觸媒及使用其製造聚酯之方法。先行領域中，始於聚乙烯對苯二甲酸酯之聚酯其機械強度、化學安定性等良好性質被廣泛利用於各種領域，如 :衣料用、產業資材用纖維、包裝用、磁帶用等各種薄膜、薄片、木片、工程塑料等成型物，等各種廣範圍領域中。其中又以氣體隔離性、衛生性等良好，且較便宜、輕量下，做爲各種食品 '飮料包裝容器被廣範應用之，同時更積極擴展其應用領域。通常，聚酯係以二羧酸或其酯形成性衍生物，以及二醇做爲原料以多階段性進行製造者。首先，二羧酸與過剩之二醇相互酯化，或二羧酯酯與二醇相互酯交換後，製造由縮聚酯或縮聚酯與低聚酯之混合物所成之較低分子量聚酯預備縮合物。再將此聚酯預備縮合物於縮聚反應用觸媒之存在下，使副產之醇及/或水進行分離之同時進行縮聚後，做成目的之高分子量聚酯。做爲縮聚反應用觸媒者被提出極多報告，惟，幾乎所有商業過程中，其銻化合物或鍺化合物均做爲縮聚反應用觸媒之用者。先行技術中，銻化合物，其中又以Sb2〇3具有價廉，且良好活性之觸媒者，惟，利用Sb2〇3觸媒所製造之聚酯中所殘留之觸媒殘渣較易形成較大粒子狀者，降低聚酯之品質。做爲鍺化合物觸媒者有Ge〇2等爲公知者，相較於銻本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） —i.L---Μ---^ t衣------IT------ (請先閲讀背面之注意事項再填寫本頁) -5- 200408660 A7 ___ B7 五、發明説明（2 ) (請先閲讀背面之注意事項再填寫本頁) 觸媒較可製造出高品質之聚酯，環保面亦較少問題點。惟，鍺化合物價格昂貴，明顯提昇聚酯製造成本。因此，期待一種可取代銻化合物或鍺化合物之製造聚酯用觸媒者。爲提供取代銻化合物或鍺化合物之製造聚酯用觸媒的硏究如··被揭示於特公昭49 — 1 1474，特開昭55 - 23 1 36 中目前仍重覆進行之四丁基鈦酸酯類之烷基鈦酸酯觸媒。惟，鈦化合物之使用除出現聚酯強烈著色之外，亦出現取得聚酯之加熱成型時降低其熱安定性之問題點產生。控制聚酯之著色，提昇加熱成型時之熱安定之方法公知者有添加磷化合物之方法者，惟，添加磷化合物將造成降低鈦化合物觸媒之縮聚活性的缺點產生，導致鈦化合物觸媒之效果受限之問題點產生。經濟部智慧財產局員工消費合作社印製本發明者針對該課題進行精密硏討後結果發現，於有機矽氧烷化合物骨架中使用含特定金屬之觸媒做爲縮聚反應用觸媒之使用後，比使用先行公知之銻化合物，鍺化合物或鈦化合物更具極高之活性，對於聚酯成份之金屬使用量少量即可，且，以磷化合物做爲添加劑使用時，亦不會出現先行之降低鈦化合物類之活性者，進而完成本發明。亦即，本發明主旨係於有機矽氧烷化合物骨架中含有至少1種選自周期表第3〜1 5族之金屬Μ (惟，除Si之外 )之縮聚反應用觸媒及使用其之聚酯的製造方法者。 [發明實施之最佳形態] (縮聚反應用觸媒）本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6 - 200408660 A7 B7 五、發明説明（3 ) (請先閱讀背面之注意事項再填寫本頁) 本發明揭示之縮聚反應用觸媒之具體例係將有機矽氧烷化合物骨架中之至少1個矽以至少1種選自周期表（ IUPAC無機化學命名法1 990年規格）之第3〜15之矽以外的金屬Μ進行取代所成之化合物者。做爲金屬 Μ 者以 Sc、Ti、Zr、Hf、Α卜 Ga、Ge、Sn 、Sb等第3、4、13、14及15族之金屬者宜，其中又以 Ti及Ge爲特別理想，更佳者爲Ti者。本發明中，有機矽氧烷化合物係指針對1個Si至少 1個以上之有機基，如：氫原子，具有取代基亦可之烷基，具有取代基亦可之芳基，具有Si - Ο - Si結合之化合物者。本發明縮聚反應用觸媒較佳者係使下式（2·)所示有機矽氧烷化合物中之下記（A )所示至少1個部位被下記 (B )取代之化合物者。 (RxS i 〇0.5(4-x)) m' (2 ') 經濟部智慧財產局員工消費合作社印製 (式（21)中，R爲具有取代基亦可之烷基或具有取代基亦可之芳基（R爲複數時分別可爲相同，亦可爲相異者）者，X爲1〜2之數，m’2 2者）。又，式（2，）中理想之R爲與後述式（1 )中之R相同者。200408660 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) The present invention relates to a catalyst for polycondensation reaction and a method for producing polyester using the same. Among the leading fields, polyesters starting from polyethylene terephthalate have been widely used in various fields such as mechanical strength, chemical stability and other good properties, such as: clothing, fiber for industrial materials, packaging, tape, etc. Various films, sheets, wood chips, engineering plastics, and other molded articles, and a wide range of fields. Among them, it has good gas barrier properties and hygienic properties, and is relatively inexpensive and lightweight. It is widely used as a variety of food packaging materials, and it is also actively expanding its application fields. Generally, polyesters are manufactured in a multi-stage process using dicarboxylic acid or an ester-forming derivative thereof and glycol as raw materials. First, the dicarboxylic acid and excess diol are esterified with each other, or the dicarboxylate ester and diol are transesterified with each other to produce a lower molecular weight polyester made of a polycondensate or a mixture of a polycondensate and an oligoester. Prepare the condensate. This polyester precondensate is then subjected to polycondensation in the presence of a polycondensation catalyst to separate the by-produced alcohol and / or water, and then to obtain the desired high molecular weight polyester. Many reports have been made as catalysts for polycondensation reactions. However, in almost all commercial processes, antimony compounds or germanium compounds are used as catalysts for polycondensation reactions. In the prior art, antimony compounds, of which Sb203 has a low-cost and good activity catalyst, however, the catalyst residues remaining in the polyester produced by Sb203 catalyst are relatively easy to form larger Particles reduce the quality of polyester. As catalysts for germanium compounds, Ge02 and others are well known. Compared with antimony, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) —iL --- M --- ^ t-shirt- ----- IT ------ (Please read the notes on the back before filling out this page) -5- 200408660 A7 ___ B7 V. Description of the invention (2) (Please read the notes on the back before filling in this Page) The catalyst can produce high-quality polyester, and has less environmental issues. However, the germanium compound is expensive, which significantly increases the manufacturing cost of polyester. Therefore, a catalyst for manufacturing polyester which can replace antimony compounds or germanium compounds is expected. Research to provide catalysts for the production of polyesters instead of antimony compounds or germanium compounds is disclosed in Japanese Patent Publication No. 49-1147, Japanese Patent Publication No. 55-231-336. Alkali titanate catalysts. However, in addition to the occurrence of strong coloration of polyester, the use of titanium compounds also causes problems in reducing the thermal stability of the polyester obtained by heat molding. Methods for controlling the coloration of polyester and improving the thermal stability during thermoforming are known to add a phosphorus compound. However, the addition of a phosphorus compound will cause the disadvantage of reducing the polycondensation activity of the titanium compound catalyst, resulting in the titanium compound catalyst. Problems with limited effects arise. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on the subject of the present inventors, after careful discussion on the subject, it was found that after using a catalyst containing a specific metal in the organosiloxane compound skeleton as a catalyst for polycondensation reaction Higher activity than the previously known antimony compounds, germanium compounds or titanium compounds. A small amount of metal can be used for the polyester component, and the use of phosphorus compounds as additives will not lead to a decrease. Those who are active in titanium compounds have completed the present invention. That is, the present invention is directed to a polycondensation catalyst for a polycondensation reaction containing at least one metal M (except Si) selected from Groups 3 to 15 of the periodic table in the skeleton of the organosiloxane compound and the use thereof Manufacturer of polyester. [The best form of the invention implementation] (catalyst for polycondensation reaction) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -6-200408660 A7 B7 V. Description of the invention (3) (Please read the back first Please note this page to fill in this page) Specific examples of catalysts for polycondensation reactions disclosed in the present invention are selected from the periodic table (at least IUPAC inorganic chemical nomenclature 1 990) (Year specification), a compound formed by substitution of a metal M other than silicon 3 to 15 As the metal M, Sc, Ti, Zr, Hf, ΑGa, Ge, Sn, Sb and other metals of Groups 3, 4, 13, 14, and 15 are preferred, and Ti and Ge are particularly preferable. The better is Ti. In the present invention, the organosiloxane compound refers to an organic group having at least one Si group, such as a hydrogen atom, an alkyl group having a substituent, or an aryl group having a substituent, having Si-〇 -Si-bound compounds. The catalyst for the polycondensation reaction of the present invention is preferably a compound in which at least one site shown by the following formula (A) in the organosiloxane compound shown by the following formula (2 ·) is substituted with the following formula (B). (RxS i 〇0.5 (4-x)) m '(2') Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (In formula (21), R is an alkyl group which may have a substituent or a substituent may also be used Aryl groups (when R is plural, they may be the same or different), X is a number of 1 to 2, and m'2 2). In addition, the ideal R in the formula (2,) is the same as the R in the formula (1) described later.

I —Si-R (A) 202本紙張尺度適用中國國家標準（CNS ) A4規格（2l〇X297公釐） 200408660 經濟部智慧財產局員工消費合作社印製I —Si-R (A) 202 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 200408660 Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

A7 __ ____B7五、發明説明（4 ) I 一丫-L (B) 特別理想者如下記一般式（1 )所示結構之觸媒者。 (RxS i O〇.5(4-x)) a ( Μ O 〇.5(p-qxy) L y) b ( 1 ) (式（1)中’ R代表氫原子，具有取代基亦可之烷基或具取代基亦可之芳基（R爲複數時，R分別爲相同或相異均可），Μ爲至少1種選自周期表之第3〜15族之金屬（惟，Si除外），L代表結合Μ之基（L爲複數時，L分別可爲相同或相異均可），x代表1〜2之數，y爲0以上之整數，P爲Μ價數之絕對値，q爲L價數之絕對値，（p 一 qx y ) g 1，a、b分別爲大於〇之數）。理想之R例爲氫原子，具有取代基亦可之碳數idO 鏈狀烷基，具有取代基亦可之碳數5〜8之環狀烷基，具有取代基亦可之苯基者。其中又以具取代基亦可之碳數5〜8之飽和環狀烷基者爲較佳，以碳數1〜5鏈狀烷基取代亦可之碳數5〜8之環狀院基者爲最佳者。 L之例者如：氫原子、鹵原子、烷基、芳基、脂烯基、或0W所示之取代基（R’爲氫原子，具有取代基亦可之烷基’具有取代基亦可之芳基，有機矽烷基）者宜。其中又以OR·所示之取代基爲較佳，R’爲氫原子，具有取代基亦可之碳數1〜20之鏈狀烷基，具有取代基亦可本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） Q (請先閱讀背面之注意事 1· •項再填· 裝-- :寫本頁) 訂 it 200408660 A7 B7五、發明説明（5 ) 之碳數5〜8之環狀烷基，具有取代基亦可之苯基者，以碳數1〜5烷基或對位被電子吸引性基取代之苯基爲更佳。該電子吸引性取代基係指哈曼特定數爲正取代基者，具體例如：硝基、鹵化院基、氰基、甲醯基、醯基、有機磺醯基、鹵原子等例，其中又以硝基、鹵化院基、或鹵原子爲較佳者，硝基、鹵化甲基或鹵原子爲最佳。做爲該鹵化烷基之鹵或鹵原子者以氟、氯爲宜。其中，做爲具有R及L亦可之取代基者只要不妨礙反應，於反應系中爲安定者即可，無特別限定，通常分子量爲200以下之取代基者，具體例如：碳數ido，較佳者爲碳數1〜10之烷基、苯基等例。本發明縮聚用觸媒中金屬Μ與矽相互之莫耳比（M:A7 __ ____ B7 V. Description of the invention (4) I Yaya-L (B) Those who are particularly desirable are catalysts with the structure shown in the general formula (1). (RxS i O0.5.4- (x)) a (M O 0.5 (p-qxy) L y) b (1) (In the formula (1), 'R represents a hydrogen atom, and a substituent may also be used. Alkyl or substituted aryl (R is plural, R may be the same or different), M is at least one metal selected from Groups 3 to 15 of the periodic table (except Si ), L represents the base bound to M (when L is plural, L may be the same or different), x represents a number of 1 to 2, y is an integer of 0 or more, and P is the absolute value of the valence of M, q is the absolute 値 of the valence of L, (p-qx y) g 1, a and b are numbers greater than 0, respectively). Ideal examples of R are a hydrogen atom, an idO chain alkyl group having a substituent and a cyclic alkyl group having 5 to 8 carbon atoms having a substituent, and a phenyl group having a substituent. Among them, a saturated cyclic alkyl group having 5 to 8 carbon atoms which may also have a substituent is preferable, and a cyclic courtyard having 5 to 8 carbon atoms which may also be substituted by a chain alkyl group having 1 to 5 carbon atoms. For the best. Examples of L are: a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, or a substituent represented by 0W (R ′ is a hydrogen atom, and the alkyl group having a substituent may have a substituent; Aryl, organosilyl) is preferred. Among them, the substituent represented by OR · is more preferable, R ′ is a hydrogen atom, and a substituted alkyl group having a carbon number of 1 to 20 may also be used. A substituted group is also applicable to Chinese national standards ( CNS) A4 specification (210 X 297 mm) Q (please read the notes on the back 1 · • fill in the items and fill in-: write this page) Order 200408660 A7 B7 5. The carbon number of the invention description (5) A cyclic alkyl group of 5 to 8 and a phenyl group which may have a substituent may be a phenyl group having 1 to 5 carbon atoms or a phenyl group substituted at the para position by an electron attracting group. The electron-attractive substituent refers to a specific Harman number that is a positive substituent. Specific examples include nitro, halogenated alkyl, cyano, methylamidino, fluorenyl, organic sulfonyl, and halogen atoms. Among them, Among them, a nitro group, a halogenated alkyl group, or a halogen atom is preferable, and a nitro group, a halogenated methyl group, or a halogen atom is most preferable. The halogen or halogen atom of the halogenated alkyl group is preferably fluorine or chlorine. Among them, those having substituents that can be R and L are not particularly limited as long as they do not hinder the reaction, and are stable in the reaction system. Generally, those having a molecular weight of 200 or less, such as carbon number ido, Examples of the alkyl group and the phenyl group having 1 to 10 carbon atoms are preferred. Molar ratio of metal M to silicon in the polycondensation catalyst of the present invention (M:

Si)( —般式（1)中，（b : a)示之）通常爲丄： :1'較佳者爲1: 99〜1: 1、更佳者爲者爲1· 7〜1: 1、最佳者爲1: 7。該一般式（1)中，a通常爲1〜99 數，更佳者爲7。 99 〜99 、特佳較佳者爲1〜20之 ---.1---r---^裝-- (請先閱讀背面之注意事項再填寫本頁) 、11 4 經濟部智慧財產局員工消費合作社印製爲1〜2之數，一般以1或2者爲較佳，最佳者爲 y爲Ml原子之L個數者，〇以上之整數者，依…之種類可變更〇〜7之値者。如：A1時爲〇〜2，較佳者爲〇， Ti’ Ge時爲1〜3，較佳者爲1。一般式（1 )中，最佳形態之a爲7時，本發明觸媒如下記結構式所示之立體結構（式（1 )中，1，p = 4，Si) (—in general formula (1), (b: a) is shown) is usually ::: 1 'is preferably 1: 99 ~ 1: 1, and more preferably is 1.7 ~ 1: 1. The best is 1: 7. In the general formula (1), a is usually a number from 1 to 99, and more preferably 7. 99 ~ 99, especially the best is 1 ~ 20 of ---. 1 --- r --- ^ pack-(Please read the precautions on the back before filling this page), 11 4 Intellectual Property of the Ministry of Economic Affairs The number of employees' cooperatives printed by the bureau is 1 ~ 2, generally 1 or 2 is better, the best one is the number of L of M1 atoms, and the integer is more than 0, which can be changed according to the type of ... ~ 7 of those who are. For example: 0 ~ 2 at A1, preferably 0, 1 ~ 3 at Ti 'Ge, and 1 is preferred. In general formula (1), when a is 7 in the best form, the catalyst of the present invention has a three-dimensional structure as shown in the following structural formula (in formula (1), 1, p = 4,

200408660 A7 B7 五、發明説明（6 ) q=l，y = l，b = l者）之形態者’做爲本發明之觸媒爲特別理想者。200408660 A7 B7 V. Description of the invention (6) Those in the form of q = l, y = l, b = l 'are particularly ideal as catalysts for this invention.

RR

Si——〇~ /〇i /〇i ^Si—〇rSi^R|Si——〇 ~ / 〇i / 〇i ^ Si—〇rSi ^ R |

II

l/° |/° R ,Si—〇——Si R〆 (請先閱讀背面之注意事項再填寫本頁) \r (縮聚反應用觸媒之調製方法）本發明縮聚反應用觸媒係使有機政氧院化合物與選自周期表第3〜1 5族之金屬Μ化合物反應後可進行製造之。經濟部智慧財產局員工消費合作社印製做爲共同反應之金屬Μ化合物例者如：蟻酸、醋酸、丙酸、草酸等之飽和脂肪族羧酸相互之鹽、丙烯酸、甲基丙烯酸等不飽和脂肪族羧酸相互之鹽、苯甲酸等芳香族羧酸之鹽、三氯醋酸等含鹵之羧酸鹽、乳酸、檸檬酸、水楊酸等之羥羧酸鹽、碳酸、硫酸、硝酸、磷酸、膦酸、碳酸氫、磷酸氫、硫酸氫、亞硫酸、硫代硫酸 '鹽酸、溴化氫酸、氯酸、溴酸等無機酸之鹽、甲磺酸、丙磺酸、對-甲苯磺酸等有機磺酸之鹽、甲氧基、乙氧基、正-丙氧基、異-丙氧基、正- 丁氧基、第三- 丁氧基等金屬醇鹽、乙醯醋酸酯等螯合化合物、氯化物、溴化物等金屬_化物例。其中又以飽和脂肪族羧酸之鹽、金屬醇鹽、金屬鹵化物爲較佳，特別以金屬醇鹽、金屬鹵化物爲更佳者。 10- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210x297公釐） 200408660 A7 _B7_ 五、發明説明（7 ) 做爲有機矽氧烷化合物者如：下記一般式（2 )所示之化合物者宜。 (請先閱讀背面之注意事項再填寫本頁) (RxS i 〇0.5(4x)) m (H2O) 0.5η (2) (式（2)中，R爲氫原子，具有取代基亦可之烷基或取代基亦可之芳基（R爲複數時，R分別可爲相同或相異均可），x爲1〜2之數，m^l、n爲2以上之整數者。）又，式（2)中理想R爲與上述式（1)之R爲相同者。添加縮聚反應用觸媒於縮聚反應之形態並未特別限定，預先使金屬Μ之化合物與式（2 )之有機矽氧烷化合物相互反應後，單離取得之化合物後，做成縮聚反應用觸媒添加於縮聚反應系者亦可，使金屬Μ化合物與有機矽氧烷化合物相互反應之反應液直接做成縮聚反應用觸媒溶液或漿料使用者亦可。經濟部智慧財產局員工消費合作社印製預先使金屬Μ化合物與有機矽氧烷化合物反應後，單離取得化合物時，使該有機矽氧烷化合物於溶解或分散之有機溶媒中混合該金屬Μ之化合物後，於室溫至溶媒之沸點溫度反應1〜24小時，較佳爲1〜10小時，更佳爲 1〜4小時後，由有機溶媒分離所取得化合物後可取得之。金屬Μ化合物與有機矽氧烷化合物相互反應之反應液直接做爲縮聚反應用觸媒溶液使用時，使該有機矽氧烷化合物於溶解或分散之有機溶媒中混合該金屬Μ化合物本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） y -11- 200408660 A7l / ° | / ° R, Si—〇——Si R〆 (Please read the notes on the back before filling this page) \ r (Method for preparing catalyst for polycondensation reaction) The catalyst for polycondensation reaction of the present invention uses The organic oxygen compound can be produced after reacting with a metal M compound selected from Groups 3 to 15 of the periodic table. Examples of metal M compounds printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs as common reactions are: formic acid, acetic acid, propionic acid, oxalic acid and other saturated aliphatic carboxylic acid mutual salts, acrylic acid, methacrylic acid and other unsaturated fats Mutual carboxylic acid salts, aromatic carboxylic acid salts such as benzoic acid, halogenated carboxylic acid salts such as trichloroacetic acid, hydroxycarboxylic acid salts such as lactic acid, citric acid, and salicylic acid, carbonic acid, sulfuric acid, nitric acid, and phosphoric acid , Phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfuric acid 'hydrochloric acid, hydrobromic acid, chloric acid, bromic acid and other inorganic acid salts, methanesulfonic acid, propanesulfonic acid, p-toluenesulfonic acid Salts of organic sulfonic acids such as acids, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy and other metal alkoxides, acetamyl acetate, etc. Examples of metal compounds such as chelate compounds, chlorides, and bromides. Among them, salts of saturated aliphatic carboxylic acids, metal alkoxides and metal halides are preferred, and metal alkoxides and metal halides are particularly preferred. 10- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210x297 mm) 200408660 A7 _B7_ V. Description of the invention (7) As an organosiloxane compound such as the compound shown by the following general formula (2) should. (Please read the precautions on the back before filling in this page) (RxS i 〇0.5 (4x)) m (H2O) 0.5η (2) (In formula (2), R is a hydrogen atom, and an alkane having a substituent may also be used. Group or substituent may be an aryl group (when R is plural, R may be the same or different), x is a number of 1 to 2, and m ^ l and n are integers of 2 or more.) Also, The ideal R in the formula (2) is the same as the R in the formula (1). The form of adding the polycondensation catalyst to the polycondensation reaction is not particularly limited. The compound of metal M and the organosiloxane compound of formula (2) are reacted with each other in advance, and the obtained compound is isolated to form a polycondensation reaction catalyst. It is also possible for the media to be added to the polycondensation reaction system, and the reaction solution for reacting the metal M compound and the organosiloxane compound with each other may be directly used as a catalyst solution or slurry for the polycondensation reaction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs after the metal M compound is reacted with the organosiloxane compound in advance, and the compound is obtained separately, the organosiloxane compound is mixed with the dissolved or dispersed organic solvent in the organic solvent. After the compound is reacted at room temperature to the boiling point of the solvent for 1 to 24 hours, preferably 1 to 10 hours, and more preferably 1 to 4 hours, the obtained compound can be obtained after being separated from the organic solvent. When the reaction solution of the metal M compound and the organosiloxane compound reacts directly as a catalyst solution for a polycondensation reaction, the organosiloxane compound is mixed with the organic M compound in a dissolved or dispersed organic solvent. This paper is suitable for this paper. China National Standard (CNS) Α4 Specification (210X 297mm) y -11- 200408660 A7

五、發明説明（8 ) 後，於室溫〜溶媒之沸點溫度下反應卜以小時，較佳爲卜10小時，更佳者爲Μ小時後，所取得反應液可^接做爲縮聚反應用觸媒使用之。此時，做爲有機溶媒者以烴類、醚類、醇類爲理想例者，較佳者如：戊烷、己烷、庚烷、苯、甲苯、二甲苯、二***、四氫呋喃、二氧陸圜、甲醇、乙醇、丙醇、乙醇、1，2 醇、1，3 —丙二醇、1，2 — 二醇，等例，特別理想者如：己烷、甲苯、呋喃、二氧陸圜等例。醇、1，4— 丁 ***、四氫 (請先閲讀背面之注意事項再填寫本頁) (縮聚反應方法）經濟部智慧財產局員工消費合作社印製本發明縮聚反應用觸媒可用於製造聚酯、聚碳酸酯、聚醯胺、聚亞胺、苯酣樹脂及蜜胺樹脂之縮聚反應者。其中又以用於製造聚酯及聚碳酸酯之縮聚反應爲較佳，更佳者可用於聚酯之製造的縮聚反應者。製造聚酯縮聚反應係於該有機矽氧烷化合物骨架中含有至少1種選自周期表第 3〜1 5族之金屬Μ (惟，S i除外）之觸媒存在下，使二羧酸成份與二醇成份進行縮聚反應者。以下，具體說明聚酯製造步驟。本發明觸媒可於聚酯製造步驟之任意階段進行添加，惟，較佳者以製造由二羧酸成份與二醇成份之聚酯預備縮合物後，縮聚反應前或縮聚反應初期之階段者爲較佳。本發明所使用之該縮聚用觸媒使用量以金屬Μ換算一般爲總生成聚酯總重量之〇·卜5000ppm者宜，較佳爲 -12- yM氏張尺度逍用中國國家標準（CNS ) A4規格（210><297公釐 200408660 A7 ___B7_ 五、發明説明（9 ) 〇·5〜500ppm、更佳爲0.5〜lOOppm使用之。 (請先閱讀背面之注意事項再填寫本頁) 做爲二羧酸成份者如：芳香族二羧酸、脂肪族二羧酸 '或其酯形成性衍生物等例。做爲芳香族二羧酸或其酯形成性衍生物者其具體例如··對苯二甲酸、酞酸、異酞酸、二溴化異酞酸、磺異酞酸鈉、苯二氧二羧酸、4,4· 一二苯基二羧酸、4,4’一二苯醚二羧酸、4,4, 一二苯酮二羧酸、 4,4’一二苯氧基乙烷二羧酸、4,4’ —二苯磺二羧酸、2,6 -萘二羧酸，以及對苯二甲酸二甲酯、2,6 —萘二羧酸二甲酯等，該芳香族二羧酸之碳數1〜4烷酯等鹵化物例者。做爲脂肪族二羧酸或其酯形成性衍生物例者其具體例如：環己烷二羧酸等脂環式二羧酸、琥珀酸、戊二酸、己二辛、庚二酸、辛二酸、壬二酸、癸二酸、十一基二羧酸、月桂二羧酸等脂肪族二羧酸，以及此等脂環式二羧酸、脂肪族二羧酸之碳數1〜4烷酯等，鹵化物等例。其中又以對苯二甲酸、異酞酸、2,6 -萘二羧酸，以及對苯二甲酸二甲酯、2,6 —萘二羧酸二甲酯爲較佳者，更佳者爲對苯二甲酸、對苯二甲酸二甲酯者。經濟部智慧財產局員工消費合作社印製做爲二醇或其酯形成性衍生物例者如：乙二醇、三亞甲基二醇、四亞甲基二醇、五亞甲基二醇、六亞甲基二醇、辛亞甲基二醇、癸亞甲基二醇、新戊二醇、2-乙基—2 一丁基一 1，3 —丙二醇、二乙二醇、聚乙二醇、聚四亞甲基醚二醇等脂肪族二醇例者。又，如：1，2-環己二醇、1，4 —環己二醇、1，1一環己二羥甲基、1，4 一環己烷二羥甲基、2,5 —原菠烷二羥甲基 13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） 200408660 A7 B7 五、發明説明（1〇 ) 等脂環式二醇、以及二甲苯二醇、4,4’ 一二羥基聯苯基、 (請先閱讀背面之注意事項再填寫本頁) 2,2 —雙（4· 一羥基苯基）丙烷、2,2 —雙（4，— /3 -羥基乙氧基苯基）丙烷、雙（4 一羥基苯基）碼、雙（4 一 /3 -羥基乙氧基苯基）磺酸等芳香族二醇，以及2,2-雙（4’ -羥基苯基）丙烷之環氧乙烷附加物或環氧丙烷附加物等例。其中又以乙二醇、三亞甲基二醇、四亞甲基二醇、五亞甲基二醇、六亞甲基二醇等脂肪族二醇、1，4 一環己烷二羥甲基爲較佳，更佳者爲乙二醇、三亞甲基二醇、四亞甲基二醇。經濟部智慧財產局員工消費合作社印製本發明更可於未超出本發明效果範圍下含少量單官能成份、多官能成份者。具體例如：二醇酸、對-羥基苯曱酸、對- /3 -羥基乙氧基苯曱酸等羥基羧酸、烷氧基羧酸、以及硬脂醇、苄醇、硬酯酸、苯甲酸、第三-苯甲酸丁酯、苯甲酸苯甲酯等單官能成份、丙三羧酸、偏苯三酸、均苯三酸 '均苯四甲酸、沒食子酸、三羥甲基乙烷、三羥曱基丙烷、甘油、季戊四醇等三官能以上之多官能成份例者。爲提昇所生成聚酯之色調，加熱成型時之熱安定性等目的下，亦可添加磷化合物於縮聚反應系中。所添加磷化合物並未特別限定，具例例如：正燐酸、聚燐酸、三曱基磷鹽、三乙基磷酸、三-正-丁基磷鹽、三辛基磷鹽、二苯基磷鹽、三甲酚磷鹽、三（三乙二醇）磷鹽、乙基一乙基磷乙酸酯、甲基酸性磷鹽，、乙基酸性磷鹽、異丙基酸性紙張尺度適用中國國家標準（CNS ) A4規格（2!〇X297公釐） 200408660 A7 B7 五、發明説明（n) (請先閱讀背面之注意事項再填寫本頁) 磷鹽、丁基酸性磷鹽、單丁基磷鹽、二丁基磷鹽、二辛基磷鹽、三乙二醇酸性磷鹽等5價燐化合物、亞燐酸、次亞燐酸、二乙基磷酸鹽、三月桂磷酸鹽、三壬癸磷酸鹽、三苯基磷酸鹽等3價燐化合物例。其中又以正燐酸、三（三乙二醇）磷鹽、乙基二乙磷乙酸酯、乙基酸性磷鹽、三乙二醇酸性磷鹽、亞燐酸爲較佳，特別以三（三乙二醇）磷鹽、乙基二乙磷乙酸酯、乙基酸性磷鹽、三乙二醇酸性磷鹽爲更佳。本發明縮聚反應方法並未特別限制，一般做爲以2階段進行反應之方法者如：於第1階段製造聚酯預備縮合物、於第2階段進行該聚酯預備縮合物之縮聚反應之以下方法例者。經濟部智慧財產局員工消費合作社印製以酯化反應進行第1階段聚酯預備縮合物時，通常使二羧酸與過剩之二醇以1.02〜2.0之比率，較佳者爲1.03 〜1.7之比率於23 0°C〜28(TC下，較佳於250〜270°C之溫度下，以0〜0.3MPa，較佳爲0〜0.2MPa之壓力下，無觸媒，或驗金屬化合物、驗土類金屬化合物、鋅化合物、猛化合物等酯化觸媒之存在下藉由酯化反應達成之。又，以酯交換反應進行聚酯預備縮合物製造時，通常使二羧酸酯與二醇以1.02〜2·0，較佳爲1.03〜1.7之比率，230°C〜280°C下，較佳者25 0〜270°C之溫度下，以0〜〇.3MPa，較佳爲0〜 0.2 MPa之壓力下，鹼金屬化合物、鹼土類金屬化合物、鋅化合物、錳化合物等酯交換觸媒之存在下，藉由酯交換反應後達成之。無論使用酯化反應，酯交換反應之任意方杰紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~~ -15- 200408660 A7 B7 五、發明説明（12 ) 法做爲第2階段之縮聚反應原料均不成問題，可取得聚酯預備縮合物者。 (請先閲讀背面之注意事項再填寫本頁) 第2階段之縮聚反應係於本發明聚合觸媒之存在下，使聚酯預備縮合物進行分離副產物之醇及/或水之同時進行縮聚後，做成目的之高分子量聚酯。縮聚反應通常於 250〜30(TC，較佳爲260〜295 °C下，由常壓至漸次減壓後，最後於1500〜10Pa ’較佳者爲650Pa〜50Pa之減壓下’進行 1〜20小時之熔融縮聚後達成之。此等以連續式，或分批式進行之。一般藉由熔融縮聚取得之聚酯係設於縮聚槽之底部由取出口呈單絲狀取出後，進行水冷之同時，或水冷後以切割刀切成顆粒狀，小片狀等粒狀體（通常固有粘度爲 0.4〜1.5dl/g ) 〇經濟部智慧財產局員工消費合作社印製如此取得之聚酯亦可依所期待者更進行固相縮聚亦可。固相縮聚係於不熔融供於固相縮聚反應之聚酯樹脂高溫下，較佳者於190〜250°C，特別以195〜240°C之溫度條件下，於氮、氬、二氧化碳等不活性氣體氣氛下進行反應時，常壓，或針對常壓以O.IMPa以下，較佳者爲〇.〇2MPa 以下之微加壓下，或於減壓氣氛下進行反應時，於l〇Pa 〜7000Pa，較佳者65Pa〜1300Pa之減壓下藉由加熱進行之。固相縮聚之溫度、壓力、反應時間、不活性氣體流量等其聚酯生成物可適當選擇具所期待物性者，而使用本發明所揭示之聚酯製造用觸媒後，即使於固相縮聚反應中仍具高活性者，因此，相較於先行既知觸媒，較具可縮短反應 2 U本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）經濟部智慧財產局員工消費合作社印製 200408660 A7 _B7 _________ 五、發明説明（13) 時間之有利點者。如上述，本發明縮聚反應用觸媒於熔融縮聚，固相縮聚均具有高活性者，又，爲提昇所取得聚酯之色調、熱安定性，進行添加磷化合物時仍不引起先行酞化合物之活性降低之不利點，可適用於木板成型所使用高分子量聚酯呈高品質且有效之製造。 [實施例] 以下，藉由下記實施例進行本發明更詳細之說明，惟，本發明在不超越該主旨下不受限於該實施例者。又，固有粘度之測定依下記進行之。 (固有粘度之測定）將0.5g樹脂試料於苯酚/1，1，2,2-四氯乙烷（重量比 1/1 )混合溶媒中使濃度（C )做成1.0g/dl，於110°C下進行溶解30分鐘。針對此溶液利用Ubbelohde型毛細粘度管於30°C下進行測定相對粘度（C rel )。針對此相對粘度所求取比粘度（々sp )求出與濃度（c)相互之比（7? sp/c )。同樣的針對濃度（c)做成 0.5g/dl、0.2dl/g、0.1dl/g 之溶液求出與分別濃度相互之比（々s P /c ) ’由此等値’ 當濃度（c )外插於〇時之比（C s p / c )做成固有粘度[] (d 1 / g )求取之。 [實施例1] I—Γ--------裝----^---訂------- (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（210X297公釐） -17- 200408660 A7 B7 五、發明説明（14 ) (觸媒溶液之調製）將0.63g四異丙基酞酸酯（2.2mM)及2.15g之下記結構式1 (式（3)中，πι = 7、n = 3)所不之庚環己二環庚矽氧烷三醇（環己基倍半矽氧烷三醇）（2· 2mM )溶於 5 0ml之四氫呋喃後，室溫下進行攪拌3小時。由取得溶液於減壓下餾去溶媒後，取得2·4〇g由鈦與環己基倍半矽氧院所成之觸媒。藉由紫外線可視吸光光譜、EXAFS、 NMR進行分析所取得觸媒之結構，確定下記結構式2所示之觸媒（Ti/Si=l/7 )者。將取得觸媒溶於甲苯後’做成 1重量％觸媒溶液。V. Description of the invention After (8), the reaction is performed at room temperature to the boiling point of the solvent in hours, preferably 10 hours, and more preferably M hours. The obtained reaction solution can be used as a polycondensation reaction. The catalyst is used. At this time, as the organic solvent, hydrocarbons, ethers, and alcohols are the ideal examples. Preferable examples are: pentane, hexane, heptane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, and dioxygen. Lupin, methanol, ethanol, propanol, ethanol, 1,2 alcohol, 1,3-propanediol, 1,2-diol, etc., particularly preferred are: hexane, toluene, furan, dioxolane, etc. example. Alcohol, 1,4-diethyl ether, tetrahydro Polyester, polycarbonate, polyamine, polyimide, phenylene resin and melamine resin polycondensation reaction. Among them, the polycondensation reaction for producing polyester and polycarbonate is more preferable, and the polycondensation reaction for producing polyester is more preferable. The production of polyester polycondensation reaction is to make the dicarboxylic acid component in the presence of a catalyst containing at least one metal M (except S i) selected from Groups 3 to 15 of the periodic table in the organosiloxane compound skeleton. Condensation reaction with diol components. Hereinafter, the polyester production process will be specifically described. The catalyst of the present invention can be added at any stage of the polyester manufacturing step. However, it is preferred to prepare the polycondensate prepared from a dicarboxylic acid component and a diol component before the polycondensation reaction or the initial stage of the polycondensation reaction. Is better. The amount of the polycondensation catalyst used in the present invention in terms of metal M is generally equal to 5,000 ppm of the total weight of the total polyester produced, preferably -12-yM scale standard Chinese National Standard (CNS) A4 specification (210 > < 297 mm 200408660 A7 ___B7_ V. Description of the invention (9) 0.5 ~ 500ppm, more preferably 0.5 ~ 100ppm. (Please read the precautions on the back before filling this page) as Examples of the dicarboxylic acid component are: aromatic dicarboxylic acid, aliphatic dicarboxylic acid 'or an ester-forming derivative thereof. Specific examples of the aromatic dicarboxylic acid or an ester-forming derivative thereof are: Phthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, benzenedioxydicarboxylic acid, 4,4 · diphenyldicarboxylic acid, 4,4'-diphenylbenzene Ether dicarboxylic acid, 4,4, benzophenone dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonic dicarboxylic acid, 2,6-naphthalene dicarboxylic acid Examples of halides such as carboxylic acids, dimethyl terephthalate, dimethyl 2,6-naphthalene dicarboxylate, and the like, and aromatic alkyl carboxylic acids having 1 to 4 alkyl esters. Carboxylic acid or its ester formation Examples of sexual derivatives include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Examples of aliphatic dicarboxylic acids such as undecyl dicarboxylic acid and lauric dicarboxylic acid, and alicyclic dicarboxylic acids and aliphatic dicarboxylic acids having 1 to 4 carbon esters, and halides are examples. Among them, Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylic acid are preferred, and the more preferred is terephthalic acid. Dicarboxylic acid and dimethyl terephthalate. Examples of glycol or ester-forming derivatives printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as ethylene glycol, trimethylene glycol, and tetramethylene Based glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, 2-ethyl-2 monobutyl-1, 3-propanediol Examples of aliphatic diols such as diethylene glycol, diethylene glycol, polyethylene glycol, and polytetramethylene ether glycol. Also, such as: 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1 , 1-cyclohexanedimethylol, 1 4,4-cyclohexane dimethylol, 2,5-ortho- spinane dimethylol 13- This paper size applies to Chinese National Standard (CNS) A4 (210x297 mm) 200408660 A7 B7 V. Description of the invention (1〇 ) And other alicyclic diols, as well as xylene glycol, 4,4'-dihydroxybiphenyl, (Please read the precautions on the back before filling this page) 2,2 —bis (4 · monohydroxyphenyl ) Propane, 2,2-bis (4, — / 3-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) code, bis (4-1 / 3 / 3-hydroxyethoxyphenyl) sulfonic acid Examples include aromatic diols, and ethylene oxide or propylene oxide additions to 2,2-bis (4'-hydroxyphenyl) propane. Among them, aliphatic glycols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, and hexamethylene glycol, and 1,4-cyclohexanedimethylol are Preferred, more preferred are ethylene glycol, trimethylene glycol, and tetramethylene glycol. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention can further contain a small amount of monofunctional and multifunctional components without exceeding the scope of the present invention. Specific examples: glycolic acid, p-hydroxybenzoic acid, p- / 3-hydroxyethoxybenzoic acid, hydroxycarboxylic acids, alkoxycarboxylic acids, and stearyl alcohol, benzyl alcohol, stearic acid, benzene Monofunctional components such as formic acid, tert-butyl benzoate, benzyl benzoate, glycerol, trimellitic acid, pyromellitic acid 'pyromellitic acid, gallic acid, trimethylolethyl Examples of trifunctional or higher polyfunctional components such as alkane, trihydroxymethylpropane, glycerol, pentaerythritol and the like. Phosphorus compounds can also be added to the polycondensation reaction system for the purpose of improving the color tone of the resulting polyester and thermal stability during heat molding. The phosphorus compound to be added is not particularly limited, and examples include, for example, orthophosphoric acid, polyphosphoric acid, trimethylphosphonium salt, triethylphosphoric acid, tri-n-butylphosphonium salt, trioctylphosphonium salt, and diphenylphosphonium salt. , Tricresyl phosphate, tris (triethylene glycol) phosphate, ethyl monoethyl phosphoric acid acetate, methyl acid phosphoric acid salt, ethyl acid phosphoric acid salt, isopropyl acid paper scales are applicable to Chinese national standards ( CNS) A4 specification (2.0 × 297 mm) 200408660 A7 B7 V. Description of invention (n) (Please read the notes on the back before filling this page) Phosphate, butyl acid phosphate, monobutyl phosphate, Divalent phosphonium compounds such as dibutyl phosphorus salt, dioctyl phosphorus salt, and triethylene glycol acid phosphorus salt, arsonic acid, hypoarsinic acid, diethyl phosphate, trilauric acid phosphate, trinonanodecyl phosphate, Examples of trivalent europium compounds such as phenyl phosphate. Among them, orthophosphoric acid, tris (triethylene glycol) phosphoric acid salt, ethyl diethyl phosphoric acid acetate, ethyl acidic phosphoric acid salt, triethylene glycol acidic phosphoric acid salt, and arsenic acid are particularly preferred, and particularly Ethylene glycol) phosphorus salts, ethyl diethyl phosphoric acid acetate, ethyl acid phosphorus salts, and triethylene glycol acid phosphorus salts are more preferred. The polycondensation reaction method of the present invention is not particularly limited. Generally, as a method for performing the reaction in two stages, for example, a polyester precondensate is produced in the first stage, and a polycondensation reaction of the polyester precondensate is carried out in the second stage. Method example. When the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the first stage polyester precondensation by esterification reaction, the ratio of dicarboxylic acid and excess diol is usually 1.02 ~ 2.0, preferably 1.03 ~ 1.7 The ratio is at 23 0 ° C ~ 28 (at TC, preferably at a temperature of 250 to 270 ° C, at a pressure of 0 to 0.3 MPa, preferably 0 to 0.2 MPa, without catalyst, or metal test compounds, It can be achieved by esterification reaction in the presence of soil metal compounds, zinc compounds, fibrous compounds and other esterification catalysts. In addition, when the polyester precondensation is produced by transesterification, the dicarboxylic acid ester and The alcohol is at a ratio of 1.02 to 2.0, preferably 1.03 to 1.7, at 230 ° C to 280 ° C, preferably at 25 0 to 270 ° C, at 0 to 0.3MPa, preferably 0. Under the pressure of ~ 0.2 MPa, it can be achieved after the transesterification reaction in the presence of transesterification catalysts such as alkali metal compounds, alkaline earth metal compounds, zinc compounds, and manganese compounds. Regardless of the esterification reaction, the transesterification reaction is arbitrary. Fang Jie paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ~~ -15- 200408660 A7 B7 V. Explanation of the invention (12) The method used as the raw material for the second stage of the polycondensation reaction is not a problem, and those who can obtain the polyester precondensate. (Please read the precautions on the back before filling this page) The two-stage polycondensation reaction is performed in the presence of the polymerization catalyst of the present invention, and the polyester preliminary condensation product is subjected to polycondensation while separating by-product alcohol and / or water, and then the target high molecular weight polyester is made. The polycondensation reaction is usually After 250 ~ 30 (TC, preferably 260 ~ 295 ° C, gradually decompressing from normal pressure to gradually, finally at 1500 ~ 10Pa 'preferably under a reduced pressure of 650Pa ~ 50Pa' for 1 ~ 20 hours This can be achieved after melt polycondensation. These can be carried out continuously or in batches. Generally, polyester obtained by melt polycondensation is set at the bottom of the polycondensation tank and taken out in a monofilament form from the take-out port. Or water-cooled and cut into granules, flakes and other granules (usually with an inherent viscosity of 0.4 to 1.5 dl / g) with a cutter. 〇 The polyester printed in this way can be printed according to the requirements of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives. Expectants can also perform solid phase polycondensation The solid phase polycondensation is a polyester resin which is not melted for the solid phase polycondensation reaction at a high temperature, preferably at 190 ~ 250 ° C, especially at a temperature of 195 ~ 240 ° C, under nitrogen, argon, carbon dioxide, etc. When the reaction is carried out in an active gas atmosphere, at normal pressure, or under a slight pressure of at most 0.1 MPa, preferably at most 0.02 MPa, or at a pressure of 10 Pa when the reaction is performed in a reduced pressure atmosphere, under normal pressure. ~ 7000Pa, preferably 65Pa ~ 1300Pa under reduced pressure by heating. Polyester products such as temperature, pressure, reaction time, and flow rate of inert gas of solid phase polycondensation can be appropriately selected to have desired physical properties, and After using the catalyst for polyester manufacturing disclosed in the present invention, it has high activity even in the solid-phase polycondensation reaction. Therefore, it can shorten the reaction 2 U compared with the prior known catalyst. This paper size is applicable to China Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 200408660 A7 _B7 _________ 5. Description of the invention (13) Those who have the advantage of time. As mentioned above, the catalyst for the polycondensation reaction of the present invention has high activity in melt polycondensation and solid phase polycondensation. In addition, in order to improve the color tone and thermal stability of the obtained polyester, the addition of a phosphorus compound does not cause the leading phthalic compound. The disadvantage of reduced activity can be applied to the high-quality and efficient production of high-molecular-weight polyester used in wood board molding. [Examples] Hereinafter, the present invention will be described in more detail through the following examples. However, the present invention is not limited to the examples without exceeding the gist thereof. The measurement of the intrinsic viscosity was performed as follows. (Measurement of Intrinsic Viscosity) 0.5 g of a resin sample was prepared in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1) to a concentration (C) of 1.0 g / dl at 110 Dissolve at ° C for 30 minutes. The relative viscosity (C rel) of this solution was measured using a Ubbelohde-type capillary viscosity tube at 30 ° C. For this relative viscosity, the specific viscosity (々sp) is obtained to obtain the ratio (7? Sp / c) to the concentration (c). Similarly, for the concentration (c) of 0.5g / dl, 0.2dl / g, and 0.1dl / g, find the ratio to the respective concentrations (々s P / c) 'and so on.' When the concentration (c ) The ratio (C sp / c) extrapolated at 0 is made into the intrinsic viscosity [] (d 1 / g) and calculated. [Example 1] I—Γ -------- Installation ---- ^ --- Order ------- (Please read the precautions on the back before filling in this page) This paper size is applicable China National Standard (CNS) A4 specification (210X297 mm) -17- 200408660 A7 B7 V. Description of the invention (14) (Catalyst solution preparation) 0.63g of tetraisopropylphthalate (2.2mM) and 2.15g is given below in structural formula 1 (where in the formula (3), π = 7, n = 3) that heptylcyclohexanedicycloheptylsiloxanetriol (cyclohexylsilsesquioxanetriol) (2 · 2 mM) was dissolved in 50 ml of tetrahydrofuran, and then stirred at room temperature for 3 hours. From the obtained solution, the solvent was distilled off under reduced pressure, and 2.40 g of a catalyst made of titanium and cyclohexylsilsesquioxane was obtained. The structure of the catalyst obtained by analysis by ultraviolet visible absorption spectrum, EXAFS, and NMR was determined, and the catalyst (Ti / Si = 1/7) shown in the following structural formula 2 was determined. The obtained catalyst was dissolved in toluene 'to make a 1% by weight catalyst solution.

RR

RR

R R =環己基經濟部智慧財產局員工消費合作社印製R R = Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy

RR

X 0X 0

Si——0—Ti XSi—Oj-Si^Lp^I 07.>—〇〇—〆〆 xr (結構式2 )Si——0—Ti XSi—Oj-Si ^ Lp ^ I 07. > —〇〇—〆〆 xr (Structure formula 2)

R R =環己基，L = i-丙氧基 7 Π本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 200408660 A7 B7 五、發明説明（15 ) (請先閱讀背面之注意事項再填寫本頁) 於分批式反應槽內置入100g之藉由無觸媒直接與另外調製之對苯二甲酸與乙二醇之酯化反應取得之聚酯預備縮合物（數平均聚合度=7 )，氮取代反應槽內之同時昇溫至26(TC。常壓下進行約1小時之熔融後，針對聚酯低聚物進行添加換算P原子呈13ppm之正磷酸1.64重量％乙二醇溶液後，更於5分鐘後，進行添加換算Ti金屬呈 20ppm之該觸媒溶液。再使系內進行加熱20分鐘至280°C之同時，以400Pa 進行減壓20分鐘後，於285 °C，400Pa之條件下以lOOrpm 進行攪拌。到達285 °C，400Pa之條件後，於89分鐘後呈攪拌轉矩0.45Nm時完成縮聚。由反應器底部之取出口以單絲狀取出聚酯生成物後，水冷之後，以切割刀切成小片狀。取得聚酯之固有粘度爲 0.60dl/g 者。 [實施例2] 經濟部智慧財產局員工消費合作社印製針對聚酯低聚物進行添加換算P原子呈6· 5ppm之正磷酸1.64重量％乙二醇溶液，更於5分鐘後，進行添加換算Ti金屬呈20ppm之該觸媒溶液除外，與實施例1同法維持28 5 °C，400Pa之條件下，以lOOrpm進行攪拌之。達到285 °C、400Pa之條件後，、69分鐘後’呈攪拌轉矩0.4 5Nm時完成縮聚。由反應器底部取出口呈單絲狀取出後，水冷之後，以切割刀切取小片狀，取得聚酯之固有 -19- 2i4本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 200408660 A7 __ B7 _ 五、發明説明（16 ) 粘度爲0.56dl/g者。 (請先閱讀背面之注意事項再填寫本頁) [實施例3] 針對聚酯低聚物進行添加換算P原子呈66ppm之正磷酸1.64重量％乙二醇溶液，更於5分鐘後，進行添加換算Ti金屬呈20ppm之該觸媒溶液除外，與實施例1同法維持於285 °C、400pa之條件後，以lOOrpm進行攪拌之。由達到28CTC、400Pa之條件後，190分鐘後，呈攪拌轉矩0.45Nm時完成縮聚後，由反應器底部之取出口呈單絲狀取出，水冷後以切割刀切成小片。取得聚酯固有粘度爲 0.57dl/g 者。 [實施例4] 將2g實施例1取得之聚酯小片塡入附玻璃內筒之管型反應器中，反應器內以流量20ml/分鐘進行流通He之同時，於21(TC下進行加熱4小時後，進行固相縮聚反應。藉由固相縮聚反應取得之聚酯固有粘度爲〇.64dl/g者。經濟部智慧財產局員工消費合作社印製 [比較例1] 針對聚酯低聚物進行添加換算P原子呈1 3ppm之正磷酸1 · 64重量％乙二醇溶液後，更於5分鐘後，進行添加換算Ti金屬呈20ppm之做爲觸媒溶液使用之四丁基鈦酸酯之1重量％甲苯溶液使用之外，與實施例1同法維持於 2 80°C，400Pa之條件下，以l〇〇rpm進行攪拌之。達到 20- 2 ί 5本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 200408660 A7 B7 五、發明説明（17 ) (請先閲讀背面之注意事項再填寫本頁) 285 °C，400Pa之條件後，23 8分鐘後，呈攪拌轉矩0.45 Nm時，完成縮聚。由反應器底部之取出口以單絲狀進行取出後，水冷之後，以切割刀切取小片狀者。取得聚酯固有粘度爲〇.56dl/g者。 [比較例2] 針對聚酯低聚物進行添加換算P原子呈6.5ppm之正磷酸1.64重量％乙二醇溶液後，更於5分鐘後，換算Ti 金屬呈20ppm之四丁基酞酸酯之1重量％甲苯溶液進行添加之外，與實施例2同法維持285 °C，400Pa之條件下，以lOOrpm進行攪拌。達到285 °C，400Pa之條件後，持續攪撐180分鐘時之攪拌轉矩〇.33Nm者，無法達到目標之 0 · 4 5 N m，因此止於此結束縮聚之。 [比較例3 ] 經濟部智慧財產局員工消費合作社印製針對聚酯低聚物進行添加換算P原子呈66ppm之正磷酸1.64重量％乙二醇溶液後，更於5分鐘後，進行添加換算Ti金屬呈20ppm之四丁基酞酸酯之1重量％甲苯溶液之外，與實施例3同法維持於2 8 5 °C，4OOPa之條件下，lOOrpm進行攪拌。達到285 °C，400Pa之條件後，持續攪拌240分鐘時攪拌轉矩爲0.34Nm，未達目標之0.45Nm ，於此時點結束縮聚。 [比較例4 ] 2 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 200408660 B7 五、發明説明（18 ) (請先閲讀背面之注意事項再填寫本頁) 實施例1取得之聚酯小片（2g )塡入附玻璃內筒之管型反應器後，反應器內以流量20ml/分鐘進行流通He之同時，210°C下加熱4小時後，進行固相縮聚反應。藉由固相縮聚反應取得之聚酯固有粘度爲0.57dl/g者。實施例1、2、3及比較例1、2、3之結果如表-1所示，實施例4及比較例4之結果示於表-2。表-1 攪拌轉矩達到〇.45Nm之所需時間 (分）實施例1 89 (P 濃度：13ppm) 比較例1 238 (P 濃度：13ppm) 實施例2 69 (P 濃度·· 6.5ppm) 比較例2 1 80分反應後仍無法達到攪拌轉矩爲 (P 濃度：6.5ppm) 0.45Nm 者實施例3 190 (P 濃度：66ppm) 比較例3 240分反應後仍無法達到攪拌轉矩爲 (P 濃度：66ppm) 0.45Nm 者經濟部智慧財產局員工消費合作社印製 -22 体紙張尺度適用中國國家標準（CNS)A4規格（210X297公釐） 200408660 A7 B7 五、發明説明（19 ) 表-2 固相縮聚前固有粘度 (dl/g) 固相縮聚後固有粘度 (dl/g) 實施例4 0.60 0.64 比較例4 0.56 0.57 (請先閱讀背面之注意事項再填寫本頁) 由表-1證明，相較於先行公知之烷基酞酸酯觸媒，本發明特定觸媒之使用可明顯提昇縮聚反應之活性。更針對使用鍺、銑、鋁、鋅取代鈦做爲金屬Μ仍進行實施縮聚反應。 [實施例5 ] (觸媒溶液之調製）經濟部智慧財產局員工消費合作社印製於7ml四氫呋喃中溶解〇.〇7g ( 0.24mM )之鍺四乙醇鹽及該結構式1 (惟，R =環戊基）（式（2)中，m = 7， n = 3 )所示之0.21g ( 0.24mM )之庚環戊基三環戊矽氧烷三醇（環戊基倍半矽氧烷三醇）後，於60°C下攪拌3小時。於取得溶液添加30ml乙腈後，析出白色固體。於冰箱進行60小時取得混合物之熟化後，回收固體後，以乙腈進行洗淨後，50°C下進行4小時減壓乾燥後，取得 0.23g之白色固體。藉由NMR分析取得白色固體之結構後，確定由鍺與環戊倍半矽氧烷所成下記結構式3所示之觸媒（Ge/Si=l/7 )者。將取得觸媒溶於甲苯後，做成1重量％之觸媒溶液。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23 200408660 A7 B7 五、發明説明（2〇 ) R,RR = cyclohexyl, L = i-propoxy 7 Π This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 200408660 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before (Fill in this page) Into a batch reaction tank, 100 g of a polyester preliminary condensate obtained by the esterification reaction of terephthalic acid and ethylene glycol directly prepared without a catalyst (number average degree of polymerization = 7), the temperature in the reaction tank was increased to 26 ° C while nitrogen was substituted. After melting for about 1 hour at normal pressure, a 1.64% by weight orthophosphoric acid solution of 13 ppm P orthophosphoric acid was added to the polyester oligomer. After 5 minutes, the catalyst solution containing 20 ppm of Ti metal was added. While heating the system for 20 minutes to 280 ° C, the pressure was reduced at 400 Pa for 20 minutes, and then at 285 ° C, Stirring at 100 rpm at 400 Pa. After reaching 285 ° C and 400 Pa, the polycondensation was completed at a stirring torque of 0.45 Nm after 89 minutes. After the polyester product was taken out in a monofilament form from the outlet at the bottom of the reactor After water cooling, cut into small pieces with a cutter. Those with an inherent viscosity of 0.60 dl / g are obtained. [Example 2] Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and added to the polyester oligomer. P atom is 6.5 ppm orthophosphoric acid 1.64% by weight. The diol solution was added after 5 minutes, except that the catalyst solution converted to Ti metal at 20 ppm was added. The same solution as in Example 1 was maintained at 28 5 ° C and 400 Pa, and stirred at 100 rpm. 285 ° After the conditions of C and 400Pa, after 69 minutes, the polycondensation was completed at a stirring torque of 0.4 5Nm. After taking out the filament in a monofilament form from the bottom of the reactor, after water cooling, cut it into small pieces with a cutter to obtain polyester. Inherent-19- 2i4 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 200408660 A7 __ B7 _ V. Description of the invention (16) Those with a viscosity of 0.56dl / g. (Please read the precautions on the back first (Refill this page) [Example 3] For polyester oligomers, 1.64% by weight of ethylene glycol solution of orthophosphoric acid with 66 ppm of P atoms was added, and after 5 minutes, the conversion of Ti metal with 20 ppm was added. Except vehicle solutions, and implementation 1 After maintaining the conditions of 285 ° C and 400pa in the same way, stir at 100rpm. After reaching the conditions of 28CTC and 400Pa, after 190 minutes, the condensation polymerization was completed at a stirring torque of 0.45Nm, and then taken from the bottom of the reactor. The outlet is taken out in the form of a monofilament, and cut into small pieces with a cutter after water cooling. Obtain a polyester with an inherent viscosity of 0.57 dl / g. [Example 4] 2 g of the polyester flakes obtained in Example 1 were poured into a tube-type reactor with a glass inner tube, and the reactor was heated at a flow rate of 20 ml / min while heating at 21 ° C. 4 Hours later, the solid-phase polycondensation reaction was carried out. The intrinsic viscosity of the polyester obtained by the solid-phase polycondensation reaction was 0.64 dl / g. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Comparative Example 1] For polyester oligomers After adding a 1.64 wt% ethylene glycol solution of orthophosphoric acid with a P atom of 13 ppm, 5 minutes later, the addition of tetrabutyl titanate with a Ti metal content of 20 ppm as a catalyst solution was added. Except 1% by weight toluene solution, it was maintained at 2 80 ° C and 400 Pa in the same manner as in Example 1 and stirred at 100 rpm. It reached 20-2. 5 This paper size applies Chinese national standards ( CNS) A4 specification (210X297 mm) 200408660 A7 B7 V. Description of the invention (17) (Please read the precautions on the back before filling this page) 285 ° C, 400Pa, after 23 8 minutes, stirring torque is displayed At 0.45 Nm, the polycondensation is completed. After taking out the monofilament, water-cooled, the small pieces were cut with a cutter. Those with a polyester intrinsic viscosity of 0.56 dl / g were obtained. [Comparative Example 2] Polyester oligomer was added and converted into a P atom of 6.5. After adding 1.64% by weight of ethylene glycol solution of orthophosphoric acid in ppm, more than 5 minutes later, the Ti metal was added as a 1% by weight solution of tetrabutyl phthalate in toluene at 20 ppm, and was maintained in the same manner as in Example 2 except that 285 was maintained. Stirring at 100 rpm under ° C and 400 Pa. After reaching 285 ° C and 400 Pa, the stirring torque 0.33 Nm when continuously agitated for 180 minutes cannot reach the target 0.45 N m, so [Comparative Example 3] After printing, a 1.64% by weight ethylene glycol solution of orthophosphoric acid with 66 ppm of P atom added to the polyester oligomer was printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and more than 5 Minutes later, except that a 1% by weight toluene solution of tetrabutylphthalate having a Ti metal content of 20 ppm was added, and maintained at 285 ° C and 4OOPa in the same manner as in Example 3, stirring was performed at 100 rpm. After 285 ° C and 400Pa, continue to stir for 240 The stirring torque at the hour is 0.34Nm, and 0.45Nm which has not reached the target, and the polycondensation ends at this point. [Comparative Example 4] 2 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 200408660 B7 V. Invention Explanation (18) (Please read the precautions on the back before filling this page) The polyester flakes (2g) obtained in Example 1 were inserted into a tube reactor with a glass inner tube, and the flow rate in the reactor was 20ml / min. While flowing He, it was heated at 210 ° C for 4 hours, and then a solid phase polycondensation reaction was performed. The polyester obtained by the solid-phase polycondensation reaction has an intrinsic viscosity of 0.57 dl / g. The results of Examples 1, 2, 3 and Comparative Examples 1, 2, and 3 are shown in Table-1, and the results of Example 4 and Comparative Example 4 are shown in Table-2. Table-1 Time required for stirring torque to reach 0.45 Nm (minutes) Example 1 89 (P concentration: 13 ppm) Comparative example 1 238 (P concentration: 13 ppm) Example 2 69 (P concentration · 6.5 ppm) Comparison Example 2 After 80 minutes of reaction, the stirring torque could not be reached (P concentration: 6.5ppm) 0.45Nm Example 3 190 (P concentration: 66ppm) Comparative Example 3 After 240 minutes of reaction, the stirring torque could not be reached (P (Concentration: 66ppm) 0.45Nm Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -22 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 200408660 A7 B7 V. Description of the invention (19) Intrinsic viscosity before polycondensation (dl / g) Intrinsic viscosity after solid-phase polycondensation (dl / g) Example 4 0.60 0.64 Comparative Example 4 0.56 0.57 (Please read the precautions on the back before filling this page) Proof from Table-1, Compared with the previously known alkyl phthalate catalyst, the use of the specific catalyst of the present invention can significantly improve the activity of the polycondensation reaction. The polycondensation reaction is performed even when germanium, milling, aluminum, and zinc are used instead of titanium as the metal M. [Example 5] (Preparation of catalyst solution) Printed by dissolving 0.07 g (0.24 mM) of germanium tetraethanol salt in 7 ml of tetrahydrofuran and the structural formula 1 (however, R = Cyclopentyl) (in formula (2), m = 7, n = 3) 0.21 g (0.24 mM) of heptylcyclopentyltricyclopentylsiloxanetriol (cyclopentylsilsesquioxane) Triol), and then stirred at 60 ° C for 3 hours. After 30 ml of acetonitrile was added to the obtained solution, a white solid was precipitated. After ripening the mixture for 60 hours in the freezer, the solids were recovered, washed with acetonitrile, and dried under reduced pressure at 50 ° C for 4 hours to obtain 0.23 g of a white solid. After obtaining the structure of the white solid by NMR analysis, it was confirmed that the catalyst (Ge / Si = 1/7) shown by the following structural formula 3 was formed from germanium and cyclopentasilsesquioxane. The obtained catalyst was dissolved in toluene to prepare a catalyst solution of 1% by weight. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -23 200408660 A7 B7 V. Description of the invention (2) R,

R R\ . /L Si—〇——Ge/i /iηί—o—Si^R| ,Si—o—Si nr (結構式3 ) 經濟部智慧財產局員工消費合作社印製 R =環戊基，L=乙氧基 (縮聚反應）置入100g聚酯低聚物於縮聚反應器，於常壓’ 26〇°C 熔融中針對聚酯低聚物進行添加換算Ge金屬呈20ppm之該觸媒溶液。系內加熱20分鐘至285°C爲止同時，以400Pa進行減壓20分鐘後，以285 °C，400Pa之條件下’ l〇〇rpm進行攪拌之。到達285 °C，400Pa之條件後，169分鐘後攪拌轉矩呈0.4 8 N m時，結束縮聚。由反應器底部取出口使聚酯生成物呈單絲狀取出後’ 水冷後的切割刀切取小片狀。取得聚酯固有粘度爲 0.58dl/g 者。RR \. / L Si—〇——Ge / i / iηί—o—Si ^ R |, Si—o—Si nr (Structural Formula 3) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R = cyclopentyl, L = ethoxy group (polycondensation reaction) Put 100g of polyester oligomer in the polycondensation reactor, and add it to the polyester oligomer during melting at normal pressure '26 °° C. This catalyst solution is converted into Ge metal at 20ppm. . While heating in the system for 20 minutes to 285 ° C, the pressure was reduced at 400 Pa for 20 minutes, and then the mixture was stirred at 285 ° C and 400 Pa at 100 rpm. After reaching the conditions of 285 ° C and 400 Pa, the polycondensation was completed when the stirring torque was 0.4 8 N m after 169 minutes. After taking out the polyester product in the form of a monofilament through the outlet at the bottom of the reactor, the water-cooled cutting blade cut out small pieces. A polyester with an inherent viscosity of 0.58 dl / g was obtained.

[比較例5] (縮聚反應）縮聚反應器中置入1 0 0 g之聚酯低聚物，於2 6 0 °C 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） … -24 - (請先閲讀背面之注意事項再填寫本頁) 200408660 A7 B7 五、發明説明（21) (請先閱讀背面之注意事項再填寫本頁) 常壓下熔融中針對聚酯低聚物進行添加換算Ge金屬呈 20ppm之二氧化鍺之乙二醇溶液（Ge金屬換算〇·51重量 % )。使系內加熱20分鐘至285 °C之同時，於400Pa下進行減壓20分鐘後，於285 °C，400Pa之條件下以l〇〇rpm 進行攪拌。達到285°C，400Pa之條件後持續攪拌180分鐘時，攪拌轉矩爲0.30Nm，未達目標之0.45Nm，於此時點結束縮聚反應。 [實施例6] (觸媒溶液之調製）該結構式1 (惟，R =環戊基）（式（2 )中，m = 7， n = 3)所示之庚環戊基三環庚矽氧烷三醇（環戊倍半矽氧烷三醇）0.35g(0_40mM)溶於5ml之二氧陸圜中，進行添加0.19g鍩三（正-丙氧基）之70重量％正-丙醇溶液（鉻三（正-丙氧基）換算0.41 mM)後，取得溶液進行3小時加熱逐流。經濟部智慧財產局員工消費合作社印製取得溶液放冷至室溫後，加入30ml乙腈後，析出白色固體。所取得混合物於冰箱內進行熟化1 5小時，回收固體，以乙腈洗淨後，50°C下進行減壓乾燥4小時後，取得〇.41g白色.固體。藉由NMR分析取得之白色固體結構後，確定由锆與環戊倍半矽氧烷所成之下記結構式4所示之觸媒（Zr/Si=l/7 )者。所取得觸媒溶於甲苯後，做成1 重量％觸媒溶液。 -25- 22杳紙張尺度適用中國國家標準（匸奶）八4規格（21〇父297公釐） 200408660 A7 B7 五、發明説明（22)[Comparative Example 5] (Polycondensation reaction) 100 g of polyester oligomer was placed in a polycondensation reactor at a temperature of 2600 ° C. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) ... -24-(Please read the precautions on the back before filling this page) 200408660 A7 B7 V. Description of the invention (21) (Please read the precautions on the back before filling this page) For polyester oligomers under melting at normal pressure An ethylene glycol solution (Ge metal conversion: 0.51 wt%) in which Ge metal was converted to 20 ppm of Ge metal was added. While heating the inside of the system for 20 minutes to 285 ° C, the pressure was reduced at 400 Pa for 20 minutes, and then the mixture was stirred at 100 rpm at 285 ° C and 400 Pa. When the conditions of 285 ° C and 400 Pa were reached for 180 minutes, the stirring torque was 0.30 Nm, which was less than the target of 0.45 Nm. At this point, the polycondensation reaction was terminated. [Example 6] (Preparation of catalyst solution) The heptylcyclopentyl tricycloheptyl represented by the structural formula 1 (however, R = cyclopentyl) (in the formula (2), m = 7, n = 3) Siloxatriol (cyclopentasilsesquioxanetriol) 0.35 g (0-40 mM) was dissolved in 5 ml of dioxotriol, and 0.19 g of tris (tri-n-propoxy) 70% by weight of n- After the propanol solution (chromium tris (n-propoxy) conversion was 0.41 mM), the solution was obtained and heated for 3 hours to flow. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. After the solution was cooled to room temperature, 30 ml of acetonitrile was added, and a white solid precipitated. The obtained mixture was aged in a refrigerator for 15 hours, and the solid was recovered, washed with acetonitrile, and dried under reduced pressure at 50 ° C for 4 hours to obtain 0.41 g of a white solid. After the white solid structure obtained by NMR analysis, the catalyst (Zr / Si = 1/7) shown in the following structural formula 4 formed by zirconium and cyclopentasilsesquioxane was determined. The obtained catalyst was dissolved in toluene to prepare a 1% by weight catalyst solution. -25- 22 杳 Paper size applies to Chinese National Standard (匸奶) 44 size (21〇 father 297 mm) 200408660 A7 B7 V. Description of invention (22)

Si——〇——SiSi——〇——Si

R〆、R (請先閲讀背面之注意事項再填寫本頁) R =環戊基，L = n-丙氧基 (縮聚反應）縮聚反應器內置入l〇〇g之聚酯低聚物，260°C，常壓下熔融中針對聚酯低聚物進行添加換算Ζι*金屬之lOOppm 該觸媒溶液。系內加熱20分鐘至285°C之同時於400Pa下進行減壓20分鐘後，於285 °C，400Pa之條件下以lOOrpm進行攪拌之。達到285°C，400Pa之條件後，235分鐘後攪拌轉矩呈0.46Mm時，結束縮合。經濟部智慧財產局員工消費合作社印製由反應器底部取出口以單絲狀取出聚酯生成物，水冷之後，以切割刀切成小片狀。取得聚酯之固有粘度爲 0.55dl/g 者。 [實施例7] (觸媒漿料之調製）於7ml四氫呋喃中溶解〇.3 5g ( 〇.40mM)之該結構式 )体紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） … ,26 - 200408660 A7 _ B7 五、發明説明（23) (請先閱讀背面之注意事項再填寫本頁) 1 (惟，R =環戊基）（式（2)中，m = 7，N = 3 )所示之庚環戊基三環庚砂氧院三醇（環戊倍半砂氧院三醇）後，添加0.4ml之三乙鋁之己烷溶液（鋁金屬濃度1.0M/1)後，產生氣泡之同時進行反應後，生成白色沈澱。所取得溶液於室溫下進行攪拌後，減壓下餾去溶媒後，取得0.36g之鋁與環戊矽倍半噁所成之觸媒。取得觸媒分散於甲苯中做成1重量％之觸媒漿料。 (縮聚反應）於縮聚反應器中置入100g之聚酯低聚物，260°C，常壓下熔融中針對聚酯低聚物進行添加換算A1金屬呈50 ppm之該觸媒溶液。系內加熱20分鐘至285 °C之同時，於400Pa進行減壓20分鐘後，於285 °C，400Pa之條件下以lOOrpm進行攪拌。達到285°C，400Pa之條件後，263分鐘後，呈攪拌轉矩爲0.47Nm時，結束縮聚。經濟部智慧財產局員工消費合作社印製由反應器底部之取出口呈單絲狀取出聚酯生成物，水冷後以切割器切成小片狀。取得聚酯固有粘度爲0.57dl/g [比較例6] 縮聚反應器中置入100g之聚酯低聚物，260°C，常壓下熔融中針對聚酯低聚物進行添加換算A1金屬呈20ppm 之三異丙鋁之甲苯溶液。系內加熱20分鐘至285 °C，同 !冬紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^ -27- 200408660 A7 _ _ B7_ 五、發明説明（24) (請先閱讀背面之注意事項再填寫本頁) 時於400Pa下減壓20分鐘後，於285 °C，400Pa之條件下，以lOOrpm進行攪拌。達到285 °C，400Pa之條件持續攪拌40分鐘時，攪拌轉矩爲0.17Nm，未達目標之〇.45Nm ，結束縮聚反應。 [實施例8] (觸媒溶液之調製）於5ml四氫呋喃中溶解〇.21g ( 0.24mM )之該結構式 1 (惟，R =環戊基）（式（2)中m = 7，n = 3)所示之庚環戊基三環庚矽氧烷三醇（環戊倍半矽氧烷三醇）後，添加〇·25ιη1二乙鋅之己烷溶液（鋅金屬濃度1.0M/1 )。取得溶液於室溫下進行攪拌3小時後，添加30ml乙腈後析出白色固體。取得混合物於冰箱進行熟化1 5小時，回收固體後，以乙腈洗淨之後，減壓下50°C進行乾燥4 小時，取得0.2 2 g之鋅與環戊砂倍半噁所成之觸媒，甲苯中溶解所取得觸媒後，做成1重量％觸媒溶液。經濟部智慧財產局員工消費合作社印製 (縮聚反應）縮聚反應器中置入100g聚酯低聚物，260°C，常壓下熔融中針對聚酯低聚物進行添加換算Zn金屬呈30ppm之該觸媒溶液。. 系內加熱20分鐘至285 °C之同時於400Pa下減壓20 分鐘後，於285°C，400Pa之條件下以1⑼rpm進行攪拌。達到285°C，400Pa之條件140分鐘後，攪拌轉矩爲〇·46 ;_紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） _ 28 200408660 A7 _ B7 _ 五、發明説明（25 )R〆, R (Please read the notes on the back before filling this page) R = cyclopentyl, L = n-propoxy (polycondensation reaction) 100 g of polyester oligomer is built into the polycondensation reactor, At 260 ° C, 100ppm of this catalyst solution is added to the polyester oligomer during melting under normal pressure. After heating in the system for 20 minutes to 285 ° C and depressurizing at 400 Pa for 20 minutes, the mixture was stirred at 100 rpm at 285 ° C and 400 Pa. After the conditions of 285 ° C and 400 Pa were reached, the condensation was terminated when the stirring torque was 0.46 Mm after 235 minutes. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Take out the polyester product in a monofilament form from the outlet of the bottom of the reactor, and cut it into small pieces with a cutter after water cooling. Obtain the intrinsic viscosity of polyester is 0.55dl / g. [Example 7] (Preparation of catalyst slurry) Dissolve 0.35g (0.40mM) of this structural formula in 7ml of tetrahydrofuran) The paper size of the paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ... , 26-200408660 A7 _ B7 V. Description of the invention (23) (Please read the notes on the back before filling out this page) 1 (However, R = cyclopentyl) (in formula (2), m = 7, N = 3) After the heptylcyclopentyltricycloheptaerythritol triol (cyclopentasyloxasyltriol) shown in the figure, add 0.4ml of triethylaluminum in hexane solution (aluminum metal concentration 1.0M / 1) After the reaction was performed while generating bubbles, a white precipitate was formed. After the obtained solution was stirred at room temperature, the solvent was distilled off under reduced pressure, and 0.36 g of a catalyst composed of aluminum and cyclopentasilyl sesquioxane was obtained. The catalyst was dispersed in toluene to make a catalyst slurry of 1% by weight. (Polycondensation reaction) 100 g of a polyester oligomer was placed in a polycondensation reactor at 260 ° C, and the catalyst solution was added to the polyester oligomer at 50 ppm in conversion to A1 metal at normal pressure. While heating the system for 20 minutes to 285 ° C, the pressure was reduced at 400 Pa for 20 minutes, and then the mixture was stirred at 100 rpm at 285 ° C and 400 Pa. After the conditions of 285 ° C and 400 Pa were reached, after 263 minutes, when the stirring torque was 0.47 Nm, the polycondensation was terminated. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The polyester product is taken out in a monofilament from the outlet at the bottom of the reactor, and cut into small pieces with a cutter after water cooling. Obtained a polyester intrinsic viscosity of 0.57 dl / g. [Comparative Example 6] 100 g of polyester oligomer was placed in a polycondensation reactor at 260 ° C, and the polyester oligomer was added and converted during melting at normal pressure. 20ppm triisopropylaluminum in toluene solution. Heating in the system for 20 minutes to 285 ° C, the same! Winter paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ -27- 200408660 A7 _ _ B7_ V. Description of the invention (24) (Please read the back first Note: Please fill in this page again.) After depressurizing at 400Pa for 20 minutes, stir at 100rpm at 285 ° C and 400Pa. When the temperature reached 285 ° C and 400 Pa was continuously stirred for 40 minutes, the stirring torque was 0.17 Nm, which was less than the target of 0.45 Nm, and the polycondensation reaction was terminated. [Example 8] (Preparation of catalyst solution) 0.25 g (0.24 mM) of the structural formula 1 (but R = cyclopentyl) was dissolved in 5 ml of tetrahydrofuran (m = 7, n = in formula (2) 3) After the heptylcyclopentyltricycloheptasiloxanetriol (cyclopentasilsesquioxanetriol) shown in the figure, a hexane solution of diethylzinc 0.25 (Zn metal concentration 1.0M / 1) was added. . The obtained solution was stirred at room temperature for 3 hours, and 30 ml of acetonitrile was added to precipitate a white solid. Obtain the mixture and mature in the refrigerator for 15 hours. After recovering the solid, wash it with acetonitrile, and dry it at 50 ° C for 4 hours under reduced pressure to obtain 0.2 2 g of the catalyst formed by zinc and cyclopentasil. After the obtained catalyst was dissolved in toluene, a 1% by weight catalyst solution was prepared. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (polycondensation reaction) 100g of polyester oligomer is placed in the polycondensation reactor at 260 ° C. Polyester oligomer is added and converted under normal pressure. Zn metal is 30ppm. The catalyst solution. After heating in the system for 20 minutes to 285 ° C while decompressing at 400 Pa for 20 minutes, the mixture was stirred at 285 ° C and 400 Pa at 1⑼rpm. After 140 minutes at 285 ° C and 400Pa, the stirring torque is 0.46; _Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 28 200408660 A7 _ B7 _ V. Description of the invention (25)

Nm時，結束縮聚。由反應器底部之取出口將聚酯生成物呈單絲狀取出後，冰冷後以切割刀切取小片狀。取得聚酯之固有粘度爲 0.58dl/g 0 [產業上可利用性] 藉由本發明特定觸媒之聚合反應後，相較於先行公知觸媒，明顯提局活性。又’添加隣化合物於聚合反應系時，仍不致出現如先行鈦化合物之降低活性狀況，具有安定觸媒結構之良好保存安定性，爲工業上利用價値極高者。 (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 -29- 2 2夺紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）At Nm, the polycondensation is terminated. After the polyester product was taken out in a monofilament form through the take-out port at the bottom of the reactor, it was cut into small pieces with a cutter after cooling in ice. Obtaining the inherent viscosity of the polyester is 0.58 dl / g 0 [Industrial Applicability] After the polymerization reaction of the specific catalyst of the present invention, the activity is obviously improved compared with the prior known catalyst. In addition, when an adjacent compound is added to the polymerization reaction system, it does not appear to reduce the activity status of the previous titanium compound, and it has a good catalyst structure with good storage stability, which is extremely high in industrial utilization. (Please read the precautions on the back before filling out this page} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -29- 2 2The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims

200408660 8 888 ABCD 經濟部智慧財產局員工消費合作社印製六、申請專利範圍 1 1_ 一種縮聚反應用觸媒，其特徵係於有機矽氧烷化合物骨架中含有至少1.種選自周期表第3〜15族之金屬M( 惟Si除外）者。 2·如申請專利範圍第丨項之縮聚反應用觸媒，其中該觸媒以下記一*般式（1)不之， (Rx S ί Ο〇.5(4·χ)) a ( Μ O 〇.5(p-q xy) L y) b ( 1 ) (式（1)中，R代表氫原子，具有取代基亦可之烷基或具有取代基亦可之芳基（R爲複數時R分別可爲相同或相異者均可），Μ代表至少1種選自周期表第3〜15族之金屬（惟S i除外），L代表與Μ結合之基（L爲複數時，L 分別爲相同或相異均可），入爲1〜2之數，：/爲〇以上之整數，Ρ爲Μ之價數的絕對値，q爲L價數之絕對値’（ p-qx y ) - 1，a、b分別代表大於0者）。 3·如申請專利範圍第1項或第2項之縮聚反應用觸媒，其中該金屬Μ與矽之比率爲1: 99〜99 : 1者。 4·如申請專利範圍第3項之縮聚反應用觸媒’其中_ 金屬Μ與矽之比率爲1: 99〜1: 1者。 5.如申請專利範圍第2項至第4項中任一項之縮聚反應用觸媒，其中該縮聚反應用觸媒於式（1 )中，.係a = 7 所代表觸媒者。 6·如申請專利範圍第1項至第5項中任一項·之縮聚反應用觸媒，其中該縮聚反應用觸媒具有下記結構式所示$ 22沐紙張尺度適用中國國家橾準（(：灿）八4規格（21〇><297公嫠） —裝訂 (請先閲讀背面之注意事項再填寫本頁) 200408660 Α8 Β8 C8 D8 、申請專利範圍 2 體結構之觸媒者，200408660 8 888 ABCD Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs VI. Application for patents 1 1_ A catalyst for polycondensation reaction, characterized in that the skeleton of the organosiloxane compound contains at least 1. Species selected from the third table ~ Group 15 metals M (except Si). 2. The catalyst for polycondensation reaction according to item 丨 in the scope of application for patent, wherein the catalyst is described by the following general formula (1): (Rx S ί 〇〇.5 (4 · χ)) a (Μ O 0.5 (pq xy) L y) b (1) (In the formula (1), R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may also have a substituent (where R is plural, R is respectively It may be the same or different), M represents at least one metal selected from Groups 3 to 15 of the periodic table (except S i), and L represents a group bonded to M (when L is plural, L is respectively It can be the same or different), the number is 1 ~ 2, / is an integer of 0 or more, P is the absolute value of the valence of M, q is the absolute value of the valence of L '(p-qx y)- 1, a, b respectively represent greater than 0). 3. If the catalyst for polycondensation reaction of item 1 or item 2 of the scope of patent application, wherein the ratio of the metal M to silicon is 1: 99 ~ 99: 1. 4. The catalyst for polycondensation reaction according to item 3 of the patent application, where _ the ratio of metal M to silicon is 1: 99 ~ 1: 1. 5. The polycondensation reverse application catalyst according to any one of items 2 to 4 of the scope of patent application, wherein the catalyst for the polycondensation reaction is in formula (1), where a = 7 represents the catalyst. 6. The catalyst for polycondensation reaction as in any of the items 1 to 5 of the scope of patent application, wherein the catalyst for polycondensation reaction has the structural formula shown in the following formula: $ 22mu The paper size is applicable to Chinese national standards (( : Can) 8 size 4 (21〇 > < 297 cm) — Binding (please read the precautions on the back before filling out this page) 200408660 Α8 Β8 C8 D8, catalyst for patent application scope 2 body structure,

L R (請先閲讀背面之注意事項再填寫本頁) 7 ·如申請專利範圍第2項至第6項中任一項之縮聚反應用觸媒，其中該R爲具有取代基亦可之碳數5〜8之飽和環狀烷基者。 8·如申請專利範圍第2項至第7項中任一項之縮聚反應用觸媒，其中該L爲氧原子、鹵原子、烷基、芳基、脂烯基，或OR’所示之取代基CR’爲氫原子，具有取代基亦可之烷基，具有取代基亦可之芳基、有機矽氧烷基）者〇 9.如申請專利範圍第2項至第8項中任一項之縮聚用觸媒，其中該L爲OR’所示取代基者，R’爲碳數1〜5之烷經濟部智慧財產局員工消費合作社印製基者。 1 0.如申請專利範圍第1項至第9項中任一項之縮聚反應用觸媒，其中該觸媒係藉由下記一般式2 )所示有機矽氧烷化合物與金屬Μ化合物相互反應後取得f (RxS i 〇0.5(4 x)) m (Η2Ο) 0.5η ( 2 ) 22法紙張尺度適用中國國家梂準（CNS ) A4規格（210X297公嫠） 200408660 A8 B8 C8 D8 六、申請專利範圍 3 (請先閱'tl背面之注意事項再填寫本頁) (式（2)中，R代表氫原子，具有取代基亦可之烷基或具有取代基亦可之芳.基（R爲複數時R分別可爲相同或相異者均可），X代表1〜2之數，m2 1，η爲2以上之整數者）。 11·一種聚酯之製造方法，其特徵係使二羧酸或其烷酯與二醇進行酯化或酯交換反應後製造聚酯預備縮合物，再1使該預備縮合物於縮聚用觸媒存在下反應後製造聚酯之方法中’以含有至少1種選自周期表第3〜15族之金屬Μ (惟’ Si除外）於有機矽氧烷化合物骨架中之觸媒做爲縮聚用觸媒使用者。 12·如申請專利範圍第11項之聚酯製造方法，其中該方法係使用藉由下記一般式（2)所示矽氧烷化合物與至少1種選自周期表第3〜15族之金屬Μ (惟，Si除外）之化合物相互反應後取得之觸媒者 (RxS i 〇0.5(4-x)) m (H2〇) 0.5n ( 2 ) 經濟部智慧財產局員工消費合作社印製 (式（2)中’ R代表氫原子，具有取代基亦可之烷基或具有取代基亦可之芳基（R爲複數時，R分別爲相同或相異者均可），x爲1〜2之數，m^l，n爲2以上之整數）〇 .1 3 .如申請專利範圍第11項或第1 2項之聚酯製造方法，其中該方法係使用下記一般式（1 )所示之觸媒者 72沐紙張尺度逋用中國國家梂準（（：阳）八4規格（21(^297公釐） -32 - 200408660 A8 B8 C8 D8 六、申請專利範圍 4 (RxS i 〇0.5(4x)) a ( Μ O 0.5(p-qxy) L y) b ( 1 ) (請先閱讀背面之注意事項再填寫本頁) (式（1)中，R爲氫原子，具有取代基亦可之烷基，或具有取代基亦可之芳基（R爲複數時，R分別爲相同或相異者均可），Μ爲至少1種選自周期表第3〜15族之金屬 (惟，Si除外），L爲與Μ結合之基（L爲複數時L分別爲相同或相異者均可），义爲1〜2之數，¥爲0以上之整數，Ρ爲Μ之價數，q爲L之價數絕對値，（p-qx y ) - 1 ，a、b分別代表大於0者）。 14. 如申請專利範圍第11項至第13項中任一項之聚酯製造方法，其中使用該金屬Μ與矽之比率爲1 : 99〜1 : 1之觸媒者。 15. 如申請專利範圍第13項或第14項之聚酯製造方法，其中該聚酯製造用觸媒係於式（1 )中，a = 7所示之觸媒者。經濟部智慧財產局員工消費合作社印製 16·如申請專利範圍第11項至第15項中任一項之聚酯製造方法，其中該縮聚反應用觸媒係具有下記結構式所示立體結構之觸媒者 R , \ . /L /Si—〇一Μ i r0?H°^s'\ Ι·/〇 I/0 R Si—〇——Si 〆、R 17·如申請專利範圍第12項至第16項中任一項之聚 22沐紙張尺度適用中國國家標準（CNS ) M規格（210X297公釐） -33- 200408660 A8 B8 C8 D8 六、申請專利範圍 5 酯製造方法，其中該R爲具有取代基亦可之碳數5〜8之飽和環狀烷基者。 18. 如申請專利範圍第丨3項至第17項中任一項之聚酯製造方法，其中該L爲氧原子、鹵原子、院基、芳基 '脂烯基，或OR·所示之取代基（R’爲氫原子，具取代基亦可之烷基，具取代基亦可之芳基、有機矽氧烷基）者。 19. 如申請專利範圍第Π項至第18項中任一項之聚酯製造方法，其中該L爲OR’所代表之取代基者，R’爲碳數1〜5之烷基者。 20·—種聚酯組成物，其特徵係含有以有機矽氧烷化合物骨架中含有至少1種周期表第3〜15族之金屬Μ (惟，Si除外）之觸媒做爲殘渣者。 2 1 ·如申請專利範圍第1 6項之聚酯組成物，其中該聚酯組成物中觸媒殘渣之含量以金屬Μ原子換算爲0.001〜 5000ppm 者。裝訂 (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 229本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）LR (Please read the notes on the back before filling out this page) 7 · If the catalyst for polycondensation reaction in any of the items 2 to 6 of the scope of patent application, where R is the number of carbons that can also have a substituent 5 ~ 8 saturated cyclic alkyl. 8. The catalyst for polycondensation reaction according to any one of items 2 to 7 in the scope of the patent application, wherein the L is an oxygen atom, a halogen atom, an alkyl group, an aryl group, an alimentyl group, or an OR ' The substituent CR ′ is a hydrogen atom, an alkyl group having a substituent, an aryl group having an substituent, or an organosiloxy group) 9. If any one of the items 2 to 8 of the scope of patent application is applied The catalyst for the polycondensation of the item, where L is the substituent shown by OR ′, and R ′ is the base printed by the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the carbon number of 1 to 5. 10. The catalyst for polycondensation reaction according to any one of the items 1 to 9 of the scope of the patent application, wherein the catalyst is reacted with an organic siloxane compound and a metal M compound by the following general formula 2) F (RxS i 〇0.5 (4 x)) m (Η2Ο) 0.5η (2) 22 method paper size applicable to China National Standard (CNS) A4 specification (210X297) 嫠 200408660 A8 B8 C8 D8 Range 3 (Please read the precautions on the back of 'tl before filling out this page) (In formula (2), R represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic group which may have a substituent. The group (R is In the plural, R may be the same or different), X represents a number of 1 to 2, m2 1, and η is an integer of 2 or more). 11. A method for producing a polyester, characterized in that a polyester precondensate is produced after an esterification or transesterification reaction of a dicarboxylic acid or an alkyl ester thereof with a diol, and further 1 that the precondensate is used in a polycondensation catalyst In the method for producing polyester after reacting in the presence of 'condensation catalyst, a catalyst containing at least one metal M selected from Groups 3 to 15 of the periodic table (except' Si) in the organosiloxane compound skeleton is used. Media users. 12. The method for producing a polyester according to item 11 of the scope of patent application, wherein the method uses a siloxane compound represented by the following general formula (2) and at least one metal M selected from Groups 3 to 15 of the periodic table (RxS i 〇0.5 (4-x)) m (H2〇) 0.5n (2) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (except Si) 2) In the formula, R represents a hydrogen atom, an alkyl group having a substituent or an aryl group having a substituent (when R is plural, R may be the same or different, respectively), and x is 1 to 2 Number, m ^ l, n is an integer of 2 or more) 〇. 1 3. As the method of manufacturing polyester for the 11th or 12th of the scope of the patent application, wherein this method uses the following general formula (1) The catalyst 72mu paper standard uses the Chinese national standard ((: Yang) 8 4 size (21 (^ 297 mm) -32-200408660 A8 B8 C8 D8 6. Application for patent scope 4 (RxS i 〇0.5 (4x )) a (Μ O 0.5 (p-qxy) L y) b (1) (Please read the notes on the back before filling out this page) (In the formula (1), R is a hydrogen atom and a substituent is also An alkyl group or an aryl group having a substituent (when R is plural, R may be the same or different), and M is at least one metal selected from Groups 3 to 15 of the periodic table (but, Except for Si), L is the base combined with M (L is the same or different when L is plural), meaning 1 to 2; ¥ is an integer of 0 or more; P is the valence of M, q is the absolute valence of L, (p-qx y)-1, and a and b respectively represent greater than 0. 14. For example, a method for manufacturing a polyester according to any one of claims 11 to 13 Among them, the catalyst using the ratio of the metal M to silicon is 1: 99 ~ 1: 1. 15. For example, the polyester manufacturing method of the 13th or 14th in the scope of patent application, wherein the polyester manufacturing catalyst It is the catalyst shown in formula (1), a = 7. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 16. If the patent application method is any one of the 11th to the 15th, the polyester manufacturing method Where the catalyst for the polycondensation reaction is a catalyst R having a three-dimensional structure as shown in the following structural formula, \. / L / Si—〇一 Μ i r0? H ° ^ s' \ Ι · / 〇I / 0 R Si—〇——S i 〆, R 17 · If the size of the 22nd paper in any of the 12th to 16th of the scope of the patent application is applied, the Chinese paper standard (CNS) M specification (210X297 mm) -33- 200408660 A8 B8 C8 D8 Six 5. Patent application 5 The method for producing an ester, wherein the R is a saturated cyclic alkyl group having 5 to 8 carbon atoms which may have a substituent. 18. The method for producing a polyester according to any one of claims 3 to 17 in the scope of application for a patent, wherein the L is an oxygen atom, a halogen atom, a courtyard group, an aryl 'aliphatic alkenyl group, or OR · Substituents (R 'is a hydrogen atom, an alkyl group having a substituent group, an aryl group having a substituent group, or an organosiloxy group). 19. The method for producing a polyester according to any one of claims Π to 18, wherein L is a substituent represented by OR ′, and R ′ is an alkyl group having 1 to 5 carbon atoms. 20 · —A polyester composition characterized by containing a catalyst containing at least one metal M (except Si) of group 3 to 15 of the periodic table in the organosilicon compound skeleton as a residue. 2 1 · The polyester composition according to item 16 of the patent application range, wherein the content of the catalyst residue in the polyester composition is 0.001 to 5000 ppm in terms of metal M atoms. Binding (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 229 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)

200408660 (一) 、本案指定代表圖爲：無 (二）、本代表圖之元件代表符號簡單說明：無200408660 (1) The designated representative picture in this case is: None (II) The component representative symbols in this representative picture are simply explained: None

本案若有化學式時，請掲不最能顯不發明特徵的化學式： (RxS i O 0.5(4*x)) a ( Μ O 0.5(p*q xy) L y) b ( 1 ) -3-If there is a chemical formula in this case, please do not show the chemical formula that can best reveal the features of the invention: (RxS i O 0.5 (4 * x)) a (Μ O 0.5 (p * q xy) L y) b (1) -3-