(i) 200301273 玖、發明說明 (發明說明秦敘明:發明所屬之技術領域、先前技術、内容、 技術範圍 本發明係關於使用選擇的、熱穩定七 為催化劑，甚至於製程溫度高於225°C， 發明背景 已知可以使用有機锡作為g旨化及聚 劑，然而，現有的一種方法有其缺點 成，產生高色澤或終極產物性質不佳 新催化劑系統其會容許於高溫度，是 處理酯及聚酯而不產生上列之問題， 的單及二甲基錫化合物符合這些要求。 先前技藝概述 酯化及聚酯化反應需要極長的時間 的產物。在催化劑及熱之存在下該反 短。已使用多種具催化活性之含金屬 及聚酯製程之反應。例如銻，鈦，鋰石 在使用之有機錫化合物中，使用最廣 基錫化合物諸如氧化二丁基錫。也有 化合物作為酯化及聚酯化催化劑。美 錫化合物作為酯化，酯基轉移及聚酯 3,157,618 ； US 3,414,609 ； US 3,322,983 ； 4,0 18,708 ； US 4,973,737 ； US 4,28 1,175 ； 5,498,75 1 ； US 5,594,785 ；及US 5,606,103 °(i) 200301273 发明 Description of the invention (Explanation of the invention Qin Xuming: the technical field, prior art, content, technical scope of the invention belongs to the use of a selected, thermally stable seven as a catalyst, even if the process temperature is higher than 225 ° C, BACKGROUND OF THE INVENTION It is known that organotin can be used as a chelating agent and polymerization agent. However, one of the existing methods has the disadvantage of producing a new catalyst system with high color or poor final product properties. Polyesters do not cause the problems listed above. Mono- and dimethyltin compounds meet these requirements. Previous techniques outline products that require an extremely long time for esterification and polyesterification reactions. This reaction is short in the presence of catalysts and heat. .A variety of catalytically active metal-containing and polyester processes have been used. For example, antimony, titanium, and lithium are used in the organotin compounds used, and the broadest tin compounds such as dibutyltin oxide are used. There are also compounds for esterification and polymerization. Esterification catalyst. US tin compounds as esterification, transesterification and polyester 3,157,618; US 3,414,609; US 3,322,983; 4,0 18,7 08; US 4,973,737; US 4,28 1,175; 5,498,75 1; US 5,594,785; and US 5,606,103 °
實施方式及圖式簡單說明) .甲基錫化合物作 製造聚酯之方法。 酯化反應之催化 諸如多副產物形 。因此，對尋求 即約225 °C以上， 有所需要。選擇 以產生令人滿意 應時間是顯著縮 化合物以縮短酯 .有機錫化合物。 泛者是單及二丁 報告關於甲基錫 國專利列舉甲基 化催化劑包括US US 3,345,339 ； US US 4,473,702 ； US 200301273 r» *\ -1 士 2— ^ \ 發明說明績頁 (2) 以上引述之專利無一對應與於溫度高於225 °C處理酯或 聚酯相關連之問題。 晚近的專利公告關於使用甲基錫化合物於酯及聚酯製造 是日本專利申請 #61-68490，1986年 3 月 28 日（Turay Co.，Lta·， Tokyo， Japan) 〇 該公告揭示一種用於製造聚對酞酸丁二酯之方法藉避免 副產物四氫呋喃之形成。使用之催化劑是甲基錫酸。 另一晚近的專利申請，美國專利5,891，985，1999年4月6 日（E.D. DuPont de Nemours & Co.)描述一種可溶的單烷基錫 酸催化劑及一種方法供製備高分子量聚酯聚合物。揭示甲 基錫酸與一種二醇諸如1，4- 丁二醇之部分反應產物。酯化 溫度是220°C或低於220°C。 WO 99/28368，申請案描述一種製備酯及含二級羥基之聚 酯之方法。使用之催化劑可以是C 1至C3烷基錫酸，羧酸之 h至（：3烷基錫鹽，氧化或鹵化h至C3烷基錫或其混合物。 製程溫度可以達280°C。然而，在比較，例1中，氧化二丁 基錫，丁基錫酸及氧化二甲基錫於相等錫含量作比較，加 熱該反應混合物至225 °C及測定該三種有機錫催化劑之相 對活性。其數據，如所述，當該二醇僅含一級經基時示不 論那一種有機錫催化劑均未觀察到酯化率有所改進。 概要說明 本發明係關於使用甲基錫催化劑供自聚酯形成反應劑製 造聚酯。自該聚酯形成反應劑諸如低分子量醚（藉該反應 劑之多元醇成分之醚化作用），經由不受歡迎的副產物產 200301273 r» *\ -1 士 2— l* 办 \ | _丨丨· ............ '' (3) 發明說明續頁 量降低，達成極佳的聚酯性質，物理性質及化學性質兩者， 連同較快速的反應時間及所需之聚酯之較高產率。以本發 明之甲基錫催化劑與新穎及改進之高溫度方法也可以達成 更高反應溫度供製造聚酯。本發明提供一種用於製造聚酯 之改良方法，包括併合聚酯形成反應劑與催化劑上有效量 之一種甲基錫催化劑，及其中該反應劑包括一種多元醇及 低於50莫耳％之該多元醇是1,4-丁二醇及低於50莫耳％之該 多元醇是一種含二級羥基之多元醇。藉此方法製造之改進 之聚酯具低於約2之Gardner色值數值及含至少0.01莫耳％之 一種甲基錫催化劑。使用該催化劑獲致較短的反應時間， 尤其是在自該反應劑製造聚酯之反應之至少部分期間將該 反應劑與催化劑之組配之溫度提昇至高於240°C。本發明 限於反應在其中多元醇反應劑含低於50莫耳％之1，4-丁二 醇及低於5 0莫耳％之一種含二級羥基之二醇，三醇·或多 醇0 詳細說明 聚酯形成反應劑 用於製造聚酯之反應劑是此技藝所熟知者，及典型 上包括一種多元醇及多複酸。可以包括一些一元酸或 一元酸於反應劑中及通常發揮作為鏈終止劑之功能。 精於製造聚酯之技藝者通常根據所得之聚酯之所需之 性質及經濟考量選擇特定反應劑。例如，當產製供用 於製造聚胺酯泡膠之聚酯時，該多羧酸反應劑時常包 括一種直鏈多羧酸諸如庚二酸。當產製聚酯供用於樹 200301273 r» *\ -1 士 2— ^ \ 發明說明績頁 (4) 脂尤其是供用於塗層或塗料時，時常包括異酞酸作為 該聚酯形成反應劑之一。適當多元醇反應劑可以是脂 族性，環脂性或芳族性及可以或可以不含不飽和及包 括新戊二醇，1，3 -丙二醇，1，4 -丁二醇，1，4 -環己基二 甲醇，1,6 -己二醇，2 -甲基-1，3 -丙二醇，1，2 -丙二醇， 三羥甲基丙烷，三羥甲基乙烷，2，2，4 -三甲基-1，3 -戊二 醇，季戊四醇。適當多羧酸包括異酞酸，對酞酸，苯-1，2，4 -三羧酸酐，酞酸酐，順-丁烯二酸酐，癸二酸， 六氫酞酸酐，十二二酸，己二酸，1,4-環己烷二酸。也 可以使用對等的酸Sf。 該多元醇與多羧基化合物之莫耳比可以在寬廣的範 圍變動。可取的莫耳比是自0.5至約1.5，以0.8至1.2為更 可取。 丁基錫催化劑已商業上廣用於製造聚酯。丁基錫催化劑 之例是：丁基錫酸，三（2 -乙基己酸酯）丁基錫，二氫氧化 丁基氧錫，及氧化二丁基錫。 適合用於催化酯及聚酯形成反應劑以製造酯及聚酯之催 化劑包括此式MenSnXy之化合物，其中X是選自h至（：16羧 酸，氯化物，溴化物，氧化物，氫氧化物，或硫醇化物、 及X可以是相同或不同，n=l或2，及y = 4-n。可取者是此式 (Me)nSnX(4.n)之催化劑其中X是選自q至Cl6羧酸及η是選自 一個1至2之值。可以使用不同的甲基錫催化劑之混合物以 施行本發明。也可以使用甲基錫催化劑與其他有機錫催化 劑諸如丁基錫催化劑之混合物。 -9- (5) 發明說明續頁 特定可取的甲基錫催化劑是三乙酸單甲基錫 (CH3Sn(OAc)3)，雙（新十二酸）二甲基錫（(CH3)2Sn(neo-dec)7)， 三（2-乙基己酸）單甲基錫（CH3Sn(2-EHA)3)，及甲基錫酸 (MeSn(0)(0H))或 Sf [(MeSnC^ 5)x]。 自該聚酯形成反應劑之不受歡迎的副產物包括醛類及醚 類其是自多元醇分解作用或自多元醇諸如二醇之醚化反應 之結果。為補償多元醇成為不受歡迎的副產物之損失，加 入過量的多元醇至該反應器。送入至該反應器之過量多元 醇之典型範圍是該多元醇反應劑之1至4重量°/。。由本發明 提供之一項重大利點是自減低加入至該反應器之多元醇所 得之節省同時仍產生一種聚酯具所需的經基值。使用三（2_ 乙基己酸）丁基錫作為催化劑於260°C在聚醋化反應期間損 失之多元醇是4.6重量％之新戊二醇β以三乙基己酸）甲 基錫多元醇之損失降低至3·9%。此是在該反應期間槓失之 多元醇之1 5 %減低。 反應溫度 根據吾人之發現甲基錫催化劑比其丁基錫同系物類 穩定，可以使用較高溫度於該聚酯形成反應中。在該 反應期間該聚酯形成反應劑之溫度至少在部分之反應 期間可以提昇至高於240°C供自該反應劑製造聚醋。可以 使用高達260°C之溫度。 會例說明 在以次之例中，使用不同型之聚酯樹醋配方以潑明甲基 錫催化劑比丁基錫催化劑自多種聚酯-形成反應劑製造聚 200301273 r» *\ -1 士 2— 办 \ 發明說明讀頁 (6) 酯之優點。在例中使用之份，除另行聲明者外，全部是重 量份。 例A，B，1及2 在例A，B，1及2中使用聚酯形成反應劑供製作一種 類型之聚酯樹脂用於塗料工業供製作溶劑型塗層。這 些塗層包括溶劑型聚酯聚胺酯塗層及溶劑型聚酯三聚 氰胺塗層。以此配方，較諸丁基錫催化劑重大的主要 利點是低色澤。塗料製造廠商不能用一種聚酯其具色 值高於Gardner 2者（較黃），因其會影響該塗層之最終色 澤。於260°C進行這些聚酯化反應。通常不在如此高的溫 度進行聚酯-形成反應劑之丁基錫催化之反應，因為在一 種丁基錫催化劑之存在下產生過多顏色於所得之聚酯中及 大量反應劑轉化成為不受歡迎的副產物。該甲基錫催化之 聚酯具Gardner色值等於2 ;而該三（2 -乙基己酸）丁基錫系統 者具Gardner色值等於6。該反應溫度260 °C接近該甲基錫催 化劑之上限，但其確展示甲基錫與丁基錫催化劑間之重大 差異。表1列該聚酯-形成反應劑及產製之聚酯之資據。該 聚酯之目標酸值是3-4 mg KOH/g聚酯。聚酯化反應於溫度 超過225 °C之第二項爭論點是副反應所造成之產生不受歡 迎的副產物。自以下之數據，顯然可見使用一種丁基錫催 化劑於260°C比該甲基錫催化劑促進更多的醚化作用。反 應率是非常相似。於此極端溫度難以看出反應率差異由於 於260°C甚至弱催化劑能是有效。 200301273 r» *\ -1 士 2— ^ \ 發明說明續頁 (7) 表1 例 例A 例1 例2 例B 原料 重量 重量 重量 重量 己二酸 50.23 克 50.208 50.21 克 50.21 克 異酞酸 228.41 克 228.302 228.40 克 228.39 克 新戊二醇 178.98 克 178.909 179.03 克 179.12 克 三羥甲基丙烷 23.08 克 23.052 23.14克 23.09 克 催化劑 0.5504 克 0.5571 克 0.1597 克 0.356 克 催化劑濃度 0.025莫耳％ 0.027莫耳％ 0.026 莫耳。/〇 0.016莫耳％ 反應溫度°c 260 260 260 235 反應時間 160分 150分 150分 240分 聚酯性質 色澤 黃 淡黃 淡黃 無色 酸值 3.4 mgKOH/g 3.6 mgKOH/g 3.5 mgKOH/g 3.3 mgKOH/g OH值 48.8 mgKOH/g 53.4 mgKOH/g 51.6 mgKOH/g 53.3 mgKOH/g Mw 12,000 12,000 13,000 12,000 Μη 3,200 3,000 3,000 3,000 聚分散性 3.7 4.0 4.2 3.9 Gardner 色值 6 2 2 <1 APHA色值 >500 170 200 20 熔體黏度於220 °C 4.23 泊 3.67 泊 4.21 泊 4.04 泊 Tg 藉 DSC 25.4〇C 26.2〇C 25.9〇C 26.5〇C 催化劑 BuSn(2-EHA), MeSn(2-EHA), MeSnO(OH) BuSn(2-EHA)3 •12- 200301273 Γ» 士 A- ΙΛ 办、 _________ (8) I發明說明續頁 用於七匕處，MeSn(2-EHA)3代表三（2·乙基己酸）單甲基 錫，BuSn(2-EHA)3代表三（2-乙基己酸）及MeSn(OH)是甲基 錫酸。Mw，Μη分別是重量平均及數目平均分子量單位 =g(克）mole(莫耳）。PD=聚分散性（Mw/Mn)。設計用於例 A，B，1及2之聚酯組成是以產製一種聚酯具物理性質 其是基於工業中所知之公佈數值。 在表1中，除例B外，是於2601製備全部聚酯。例B是 作為一個比較例，自該相同的聚酯-形成反應劑在三（2 -乙基己酸）丁基錫之存在下於2 3 5 °C製備聚酯。注意反應 時間是遠較長，240分鐘較諸甲基錫催化劑於260°C之150分 鐘。在該最終聚酯中該羥基值，當使用BuSn(2-EHA)3於235 °C進行反應是高於於260°C者。例a及B之酸值指示在兩者 中發生相同的反應程度。此支持於較高溫度發生較多的醚 化作用造成一種聚酯具較低基值及較高的二醇淨損失之 觀念。於235°C以BuSn(2-EHA)3製備之聚酯具53·3 mg KOH/g 之羥基值，但當使用BuSn(2-EHA)J> 260°C該值降至48·8 mg KOH/g。該MeSn(2-EHA)3於260 °C催化之聚醋之經基值與 BuSn(2-EHA)3於235°C者相似。於不相上下之反應程度該較 高羥基值是該最終樹脂中所企求者。 例C，3及4 使用於例C，3及4中之聚酯-形成反應劑之配方’是 典型的反應劑類型用於製作一種聚酯多元醇’可用於 製作聚胺酯粉末塗層者，不同於以上之例之溶劑型塗 層。其結果摘錄於表2中。這些例證明以該甲基錫催化 200301273 r» #\ -i 士 L t* 扣、 發明說明續頁 (9) 劑較諸該對等的丁基錫催化劑獲得之其他利點。在該 使用之反應條件下色澤改進不像先前之例那麼重大’ 然而，反應率及羥基值較諸該丁基錫催化劑顯著改進。 反應率該甲基錫催化劑於245 °C及255 °C兩者均比該丁基 錫催化劑快速。出乎意料，該甲基錫催化劑於255°C比於245 。(：，反應率沒有快多少。以該甲基錫催化劑，完成該聚酯 化反應之反應時間是210-225分鐘。以BuSn(2-EHA)3該反應 時間是300分鐘於245 °C及260分鐘於255 °C。就算225分鐘 甲基錫催化劑比BuSn(2-EHA)^> 245 °C快速25%。注意’以 BuSn(2-EHA)3製備之聚酯其酸值4.4較諸甲基錫催化劑者 <3。因此，此反應尚未達完成及其必須比300分鐘更長 久才能完成。未以這些反應劑進行260°C之反應由於出乎 意料地著色（Gardner=>2)。表2中之數據示以該甲基錫催化 劑反應率重大增加（較短的反應時間）及以丁基錫催化劑較 多的副反應。以該甲基錫催化劑於255 °C該羥基值是3 5 ’ 以BuSn(2-EHA)3催化劑其降至24至29。以該相同的聚酯· 形成反應劑以相同比例產製之聚酯之較低羥基值，證 明以丁基錫催化劑較多二醇反應劑損失由於形成不受 歡迎。一般上揮發性、醚化作用之副產物較諸該甲基 錫催化劑。在例C中，其中該聚酯是以BuSn(2-EHA)3於255 °C產製，多元醇反應劑損失，基於多元醇反應劑之重量， 是4.4% ;然而，在比較例3中，其中該聚酯是以MeSn(2-EHA)3 於255°C催化，該多元醇反應劑損失只是多元醇之2·4重量 %。使用該MeSn(2-EHA)3作為催化劑有降低該多元醇損 -14- 200301273 r» -1 士 L id：办 \ 發明說明續頁 (10) 失之約5 Ο %之利點。 能在較高溫度進行該反應之一項優點在於反應時間 是大為縮短，容許該反應器進行更多的製造周期。然 而，倘若不需要較高的生產率，該甲基錫催化劑於與 一種丁基錫催化劑之反應相同的溫度進行反應，可以 實現較高的品質聚酯。當脂族性多羧酸是包括於該聚 画旨-形成反應劑中，如以庚二酸示於例中，以根據本發 明之甲基錫催化劑產製從色澤的角度極佳的聚酯。The embodiment and the diagram are briefly explained). A methyl tin compound is used as a method for manufacturing a polyester. Catalysis of esterification reactions such as multiple byproducts. Therefore, there is a need for seeking above about 225 ° C. Choosing to produce a satisfactory response time is a significant shrinking compound to shorten the ester. Organotin compounds. Ubiquitous mono- and di-butyl reports on methyl tin country patents include methylation catalysts including US US 3,345,339; US US 4,473,702; US 200301273 r »* \ -1 士 2— ^ \ Summary page of the invention (2) Above quote None of the patents correspond to problems associated with the treatment of esters or polyesters at temperatures above 225 ° C. A recent patent publication on the use of methyltin compounds in the manufacture of esters and polyesters is Japanese Patent Application # 61-68490, March 28, 1986 (Turay Co., Lta., Tokyo, Japan). This publication discloses a The method of making polybutylene terephthalate avoids the formation of by-product tetrahydrofuran. The catalyst used is methylstannic acid. Another recent patent application, U.S. Patent 5,891,985, April 6, 1999 (ED DuPont de Nemours & Co.) describes a soluble monoalkylstannic acid catalyst and a method for preparing high molecular weight polyester polymerization Thing. Partial reaction products of methylstannic acid with a diol such as 1,4-butanediol are disclosed. The esterification temperature is 220 ° C or below. WO 99/28368, the application describes a method for preparing esters and polyesters containing secondary hydroxyl groups. The catalyst used may be C 1 to C 3 alkyltin acid, carboxylic acid h to (3 alkyl tin salt, oxidized or halogenated h to C 3 alkyl tin or mixture thereof. The process temperature may reach 280 ° C. However, In comparison, Example 1, dibutyltin oxide, butyltin acid and dimethyltin oxide were compared for equivalent tin content, the reaction mixture was heated to 225 ° C and the relative activities of the three organotin catalysts were measured. The data are as shown It is stated that when the diol contains only a single warp group, no improvement in the esterification rate is observed regardless of which organic tin catalyst. An overview of the present invention relates to the use of a methyl tin catalyst for the production of a polymer from a polyester-forming reaction agent. Esters. Reagents such as low-molecular-weight ethers (by the etherification of the polyol component of the reactants) are formed from the polyester through the undesirable by-products 200301273 r »* \ -1 士 2— l * Office \ _ 丨 丨 · ............ '' (3) Description of the invention The amount of continuation is reduced to achieve excellent polyester properties, both physical and chemical properties, together with a faster reaction Time and the higher yield of the polyester required. Catalysts and novel and improved high-temperature methods can also achieve higher reaction temperatures for the manufacture of polyesters. The present invention provides an improved method for the manufacture of polyesters, which comprises combining a polyester to form an effective amount of a methyl group on a reactant and a catalyst A tin catalyst, and the reactant therein comprises a polyol and less than 50 mole% of the polyol is 1,4-butanediol and less than 50 mole% of the polyol is a polyhydric alcohol containing a secondary hydroxyl group. An improved polyester produced by this method has a Gardner color value of less than about 2 and a methyltin catalyst containing at least 0.01 mole%. The use of this catalyst results in a shorter reaction time, especially since The temperature of the combination of the reactant and the catalyst is raised above 240 ° C during at least part of the reaction of the reactant to produce the polyester. The present invention is limited to reactions in which the polyol reactant contains less than 50 mol% of 1,4 -Butanediol and a secondary hydroxyl-containing diol, triol or polyhydric alcohol below 50 mole%. Detailed description of polyester-forming reagents. Reagents used in the manufacture of polyesters are well known in the art. , And typically Includes a polyhydric alcohol and polybasic acid. May include some monoacids or monoacids in the reactant and usually functions as a chain terminator. Skilled artisans in polyester manufacturing usually rely on the desired properties of the resulting polyester And economic considerations to select specific reactants. For example, when producing polyesters for use in polyurethane foam, the polycarboxylic acid reactant often includes a linear polycarboxylic acid such as pimelic acid. When producing polyesters for use in Tree 200301273 r »* \ -1 士 2— ^ \ Summary sheet (4) Fats, especially when used in coatings or coatings, often include isophthalic acid as one of the polyester-forming reactants. Appropriate polyol reactions Agents may be aliphatic, cycloaliphatic or aromatic and may or may not be unsaturated and include neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexyldimethanol , 1,6-hexanediol, 2-methyl-1,3-propanediol, 1,2-propanediol, trimethylolpropane, trimethylolethane, 2,2,4-trimethyl-1 , 3-pentanediol, pentaerythritol. Suitable polycarboxylic acids include isophthalic acid, terephthalic acid, benzene-1,2,4-tricarboxylic anhydride, phthalic anhydride, maleic anhydride, sebacic acid, hexahydrophthalic anhydride, dodecanedioic acid, hexane Diacid, 1,4-cyclohexanedioic acid. Equivalent acid Sf can also be used. The molar ratio of the polyhydric alcohol to the polycarboxyl compound can be varied over a wide range. The molar ratio is preferably from 0.5 to about 1.5, and more preferably from 0.8 to 1.2. Butyltin catalysts have been widely used commercially for the manufacture of polyesters. Examples of butyltin catalysts are: butyltin acid, tris (2-ethylhexanoate) butyltin, butyltin dihydroxide, and dibutyltin oxide. Suitable catalysts for catalyzing esters and polyesters to form reactants to make esters and polyesters include compounds of the formula MenSnXy, where X is selected from the group consisting of h to (16 carboxylic acids, chlorides, bromides, oxides, hydroxides The compounds, or thiolates, and X may be the same or different, n = 1 or 2, and y = 4-n. The preferable is a catalyst of the formula (Me) nSnX (4.n) where X is selected from q The Cl6 carboxylic acid and η are selected from a value of 1 to 2. A mixture of different methyl tin catalysts may be used to carry out the present invention. A mixture of a methyl tin catalyst and other organic tin catalysts such as a butyl tin catalyst may also be used. 9- (5) Description of the invention The specific preferred methyl tin catalysts on the following pages are monomethyltin triacetate (CH3Sn (OAc) 3), bis (neododecanoic acid) dimethyltin ((CH3) 2Sn (neo- dec) 7), tris (2-ethylhexanoic acid) monomethyltin (CH3Sn (2-EHA) 3), and methyltin acid (MeSn (0) (0H)) or Sf [(MeSnC ^ 5) x]. Undesirable by-products that form a reactant from the polyester include aldehydes and ethers which are the result of the decomposition of polyols or the etherification of polyols such as glycols. Loss of alcohol as an undesirable by-product, excess polyol is added to the reactor. A typical range of excess polyol fed to the reactor is from 1 to 4 weight ° of the polyol reactant. A major benefit provided by the invention is the savings from reducing the polyol added to the reactor while still producing a polyester with the required base value. Tris (2-ethylhexanoate) butyltin was used as a catalyst at 260 The polyol lost during the polyacetation reaction at ° C was 4.6% by weight of neopentyl glycol β to triethylhexanoate) methyltin polyol and the loss was reduced to 3.9%. This is a 15% reduction in polyols lost during the reaction. Reaction temperature According to our findings, methyl tin catalysts are more stable than their butyl tin homologs, and higher temperatures can be used in the polyester formation reaction. The temperature of the polyester-forming reactant during the reaction can be raised to above 240 ° C for the manufacture of polyacetate from the reactant at least in part of the reaction period. Can use temperatures up to 260 ° C. The example shows that in the following example, different types of polyester resin vinegar formulations were used to produce poly200301273 from a variety of polyester-forming reactants using predminyl methyl tin catalyst over butyl tin catalyst. The invention explains the advantages of reading page (6) esters. All parts used in the examples are weight parts unless otherwise stated. Examples A, B, 1 and 2 In Examples A, B, 1 and 2, polyester-forming reactants were used to make one type of polyester resin for the coatings industry for solvent-based coatings. These coatings include solvent-based polyester polyurethane coatings and solvent-based polyester melamine coatings. With this formulation, the main advantage over butyltin catalysts is the low color. Coating manufacturers cannot use a polyester with a higher color value than Gardner 2 (yellower) because it will affect the final color of the coating. These polyesterification reactions were performed at 260 ° C. Polyester-reactant-forming butyltin-catalyzed reactions are generally not carried out at such high temperatures, because too much color is produced in the resulting polyester in the presence of a butyltin catalyst and a large amount of the reactant is converted into an undesirable by-product. The methyltin-catalyzed polyester has a Gardner color value of 2; and the tris (2-ethylhexanoate) butyltin system has a Gardner color value of 6. The reaction temperature of 260 ° C is close to the upper limit of the methyl tin catalyst, but it does show a significant difference between methyl tin and butyl tin catalysts. Table 1 lists the data of the polyester-forming reactant and the polyester produced. The target acid value of this polyester is 3-4 mg KOH / g polyester. The second issue of polyesterification at temperatures above 225 ° C is the undesired by-products of side reactions. From the data below, it is clear that the use of a butyltin catalyst at 260 ° C promotes more etherification than the methyltin catalyst. The response rates are very similar. It is difficult to see the difference in reaction rate at this extreme temperature because even weak catalysts are effective at 260 ° C. 200301273 r »* \ -1 士 2— ^ \ Description of the invention continued (7) Table 1 Example A Example 1 Example 2 Example B Raw material weight weight weight adipic acid 50.23 g 50.208 50.21 g 50.21 g isophthalic acid 228.41 g 228.302 228.40 grams 228.39 grams neopentyl glycol 178.98 grams 178.909 179.03 grams 179.12 grams trimethylolpropane 23.08 grams 23.052 23.14 grams 23.09 grams catalyst 0.5504 grams 0.5571 grams 0.1597 grams 0.356 grams catalyst concentration 0.025 mole% 0.027 mole% 0.026 mole . /〇0.016 mole% reaction temperature ° c 260 260 260 235 reaction time 160 minutes 150 minutes 150 minutes 240 minutes polyester properties yellowish yellowish yellowish colorless acid value 3.4 mgKOH / g 3.6 mgKOH / g 3.5 mgKOH / g 3.3 mgKOH / g OH number 48.8 mgKOH / g 53.4 mgKOH / g 51.6 mgKOH / g 53.3 mgKOH / g Mw 12,000 12,000 13,000 12,000 Mn 3,200 3,000 3,000 3,000 Polydispersity 3.7 4.0 4.2 3.9 Gardner color value 6 2 2 < 1 APHA color value> 500 170 200 20 Melt viscosity at 220 ° C 4.23 poise 3.67 poise 4.21 poise 4.04 poise Tg DSC 25.4〇C 26.2〇C 25.9〇C 26.5〇C Catalyst BuSn (2-EHA), MeSn (2-EHA), MeSnO (OH) BuSn (2-EHA) 3 • 12- 200301273 Γ »Shi A- ΙΛ Office, _________ (8) I Description of the invention The continuation page is used for seven daggers, MeSn (2-EHA) 3 represents three (2 · Ethylhexanoic acid) monomethyltin, BuSn (2-EHA) 3 stands for tris (2-ethylhexanoic acid) and MeSn (OH) is methylstannic acid. Mw, Mη are weight average and number average molecular weight unit = g (gram) mole. PD = polydispersity (Mw / Mn). The polyester composition designed for use in Examples A, B, 1 and 2 was produced to produce a polyester with physical properties based on published values known in the industry. In Table 1, except for Example B, all polyesters were prepared at 2601. Example B is As a comparative example, a polyester was prepared from this same polyester-forming reagent in the presence of tris (2-ethylhexanoate) butyltin at 2 3 5 ° C. Note that the reaction time is much longer, 240 minutes compared to 150 minutes at 260 ° C for methyltin catalysts. In the final polyester, the hydroxyl value is higher than 260 ° C when the reaction is performed at 235 ° C using BuSn (2-EHA) 3. The acid values of Examples a and B indicate that the same degree of reaction occurred in both. This supports the idea that more etherification at higher temperatures results in a polyester with a lower base value and a higher net diol loss. Polyester prepared with BuSn (2-EHA) 3 at 235 ° C has a hydroxyl value of 53.3 mg KOH / g, but when using BuSn (2-EHA) J > 260 ° C this value drops to 48 · 8 mg KOH / g. The mesn (2-EHA) 3 catalyzed polyacetic acid at 260 ° C has a base value similar to that of BuSn (2-EHA) 3 at 235 ° C. This relatively high hydroxyl value is what is desired in the final resin at comparable levels of reaction. Examples C, 3, and 4 The polyester-reactant formulations used in Examples C, 3, and 4 'are typical reactant types used to make a polyester polyol' and can be used to make polyurethane powder coatings, different Solvent-based coatings in the above examples. The results are summarized in Table 2. These examples show that the methyl tin catalyzed 200301273 r »# \ -i 士 L t * buckle, description of the invention continued (9) The agent has other advantages over the equivalent butyl tin catalyst. Under the reaction conditions used, the color improvement is not as significant as the previous example. However, the reaction rate and the hydroxyl value are significantly improved compared to the butyltin catalyst. Reaction rate The methyl tin catalyst is faster than the butyl tin catalyst at both 245 ° C and 255 ° C. Unexpectedly, the methyltin catalyst was better than 245 ° C at 255 ° C. (:, The reaction rate is not much faster. With the methyl tin catalyst, the reaction time to complete the polyesterification reaction is 210-225 minutes. With BuSn (2-EHA) 3, the reaction time is 300 minutes at 245 ° C and 260 minutes at 255 ° C. Even 225 minutes methyl tin catalyst is 25% faster than BuSn (2-EHA) ^ > 245 ° C. Note that polyesters prepared with BuSn (2-EHA) 3 have an acid value of 4.4. Those methyl tin catalysts are <3. Therefore, this reaction has not been completed and it must take longer than 300 minutes to complete. The reaction at 260 ° C without these reactants was unexpectedly colored (Gardner = > 2). The data in Table 2 show that the methyl tin catalyst has a significant increase in the reaction rate (shorter reaction time) and more side reactions with the butyl tin catalyst. With the methyl tin catalyst at 255 ° C, the hydroxyl value is 3 5 'With BuSn (2-EHA) 3 catalyst, it is reduced to 24 to 29. The lower hydroxyl value of the polyester produced with the same polyester and reactant at the same ratio proves that more butyl tin catalyst is used. The loss of alcohol reactants is undesirable due to the formation. Generally, the by-products of volatility and etherification are compared Tin catalyst. In Example C, where the polyester was produced at 255 ° C with BuSn (2-EHA) 3, the polyol reactant was lost, based on the weight of the polyol reactant, it was 4.4%; however, in comparison In Example 3, where the polyester was catalyzed by MeSn (2-EHA) 3 at 255 ° C, the polyol reactant loss was only 2.4% by weight of the polyol. The MeSn (2-EHA) 3 was used as a catalyst There is a point of reducing the loss of the polyol -14- 200301273 r »-1 L L id: Office \ Description of the invention (10) The loss of about 50%. One advantage of being able to carry out the reaction at a higher temperature is that The reaction time is greatly shortened, allowing the reactor to carry out more manufacturing cycles. However, if higher productivity is not required, the methyl tin catalyst can be reacted at the same temperature as the reaction of a butyl tin catalyst, which can achieve higher The quality of polyester. When aliphatic polycarboxylic acid is included in the polyimide-forming reaction agent, as shown in the example of pimelic acid, produced with methyl tin catalyst according to the present invention from the perspective of color Excellent polyester.
-15- 200301273 r» *\ -1 士 2— ^ \ 發曰·明績頁 (11) 表2 例號 例C 例3 例4 例D 例5 原料 重量 重量 重量 重量 重量 異酞酸 285.99 285.95 286.13 286.11 285.97 新戊二醇 183.11 183.01 183.14 183.12 183.13 三經甲基丙烷 12.18 12.31 12.19 12.21 12.17 催化劑 0.5545 0.5099 0.5390 0.5485 0.5120 催化劑濃度 0.026莫耳％ 0.026莫耳％ 0.027莫耳％ 0.026莫耳％ 0.026莫耳％ 反應時間 260分 225分 210分 300分 225分 反應溫度°0 255〇C 255〇C 255〇C 245〇C 245〇C 色澤 無色 無色 無色 無色 無色 酸值 4.4 mgKOH/g 2.1 mgKOH/g 1.7 mgKOH/g 4.4 mgKOH/g 3.6 mgKOH/g OH值 24.4 mgKOH/g 34.8 mgKOH/g 35.4 mgKOH/g 28.9 mgKOH/g 31.05 Mw 11,000 12,000 11,000 13,000 10,000 Μη 3,200 3,600 3,100 3,500 3,300 聚分散性 3.4 3.4 3.5 3.6 3.0 Gardner 色值 <1 <1 <1 <1 <1 APHA色值 50 50 40-50 30-40 40 熔體黏度於 200°C 12.1 泊 12.4 泊 14·0 泊 15.5 泊 Tg 藉 DSC 54.4〇C 56.4〇C 56.5〇C 54.9 56.1 催化劑 BuSn(2-EHA)3 MeSn(2- EHA), BuSn(2-EHA)3 BuSn(2-EHA)3 MeSn(2- EHA), 見表1之說明 -16--15- 200301273 r »* \ -1 士 2— ^ \ FaYu · Achievement Page (11) Table 2 Example No. Example C Example 3 Example 4 Example D Example 5 Raw Material Weight Weight Weight Weight Isophthalic Acid 285.99 285.95 286.13 286.11 285.97 neopentyl glycol 183.11 183.01 183.14 183.12 183.13 trimethylolpropane 12.18 12.31 12.19 12.21 12.17 catalyst 0.5545 0.5099 0.5390 0.5485 0.5120 catalyst concentration 0.026 mole% 0.026 mole% 0.027 mole% 0.026 mole% 0.026 mole% reaction time 260 minutes 225 minutes 210 minutes 300 minutes 225 minutes Reaction temperature ° 0 255 ° C 255 ° C 255 ° C 245 ° C 245 ° C Colorless colorless colorless colorless colorless colorless acid value 4.4 mgKOH / g 2.1 mgKOH / g 1.7 mgKOH / g 4.4 mgKOH / g 3.6 mgKOH / g OH value 24.4 mgKOH / g 34.8 mgKOH / g 35.4 mgKOH / g 28.9 mgKOH / g 31.05 Mw 11,000 12,000 11,000 13,000 10,000 Μη 3,200 3,600 3,100 3,500 3,300 Polydispersity 3.4 3.4 3.5 3.6 3.0 Gardner Color value < 1 < 1 < 1 < 1 < 1 APHA color value 50 50 40-50 30-40 40 Melt viscosity at 200 ° C 12.1 poise 12.4 poise 14.0 poise 15.5 poise Tg Borrow DSC 54.4〇C 56.4 〇C 56.5〇C 54.9 56.1 Catalyst BuSn (2-EHA) 3 MeSn (2- EHA), BuSn (2-EHA) 3 BuSn (2-EHA) 3 MeSn (2- EHA), see the description in Table 1 -16-