TW202321341A - 聚酯多元醇及其製備方法 - Google Patents
聚酯多元醇及其製備方法 Download PDFInfo
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- TW202321341A TW202321341A TW111121920A TW111121920A TW202321341A TW 202321341 A TW202321341 A TW 202321341A TW 111121920 A TW111121920 A TW 111121920A TW 111121920 A TW111121920 A TW 111121920A TW 202321341 A TW202321341 A TW 202321341A
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- polyester polyol
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Abstract
本發明係關於一種自反應混合物衍生之聚酯多元醇,該反應混合物包含:至少一種無水己糖醇、至少一種多官能羧酸及至少一種選自以下之非金屬無機酸性催化劑:具有呈+1氧化態之磷原子的非金屬無機酸性化合物、具有呈+3氧化態之磷原子的非金屬無機酸性化合物,及其混合物。此外,本發明係關於製造該聚酯多元醇之方法及其在聚胺基甲酸酯黏著劑組合物中之用途。
Description
本發明係關於一種聚酯多元醇,尤其生物基聚酯多元醇,及其製備方法。此外,本發明係關於一種包含該聚酯多元醇之聚胺基甲酸酯黏著劑組合物。
聚酯多元醇為用於產生聚胺基甲酸酯之原料中之一者,且通常為由多官能羧酸及多元醇之縮合聚合獲得之線性聚合物。縮合聚合為可逆反應,但隨著反應混合物之黏度在反應後期增加,作為反應產物之水不能輕易與反應混合物分離。因此,必須藉由加熱方式、增加攪拌速率等來維持反應的前進方向。然而,若反應時間過長,則成本將增加,且聚酯多元醇之特性可能劣化。為了縮短反應時間,已在聚酯多元醇之縮合聚合中廣泛使用適合催化劑。
另一方面,已成功地開發出可再生及生物基衍生之資源,且一系列生物基衍生之多元醇,諸如椰子油、天然橡膠、橡膠籽油、腰果油/腰果殼油、大豆油以及異山梨糖醇已用於聚酯多元醇。
其中,異山梨糖醇可經由山梨糖醇之催化脫水產生,該山梨糖醇為分佈廣泛的生物可再生葡萄糖之氫化產物。作為典型生物基化學物質,異山梨糖醇具有許多獨特特徵,諸如V形二醇分子之剛性結構、高熱穩定性、可生物降解性、可再生性、水溶性及無毒性,其可向具有異山梨糖醇作為單體的聚合物材料提供許多特點。近來,已使用異山梨糖醇來製備用於聚胺基甲酸酯黏著劑之聚酯多元醇。
舉例而言,US 20130109804 A1揭示聚碳酸酯二醇,其藉由使用金屬催化劑作為轉酯化催化劑,使選自異山梨糖醇、異甘露糖醇及異艾杜糖醇中之至少一種二醇,可能含有雜原子之具有1至15個碳之二醇及(iii)碳酸二酯反應獲得。
US 9309438 B2揭示一種可輻射固化組合物,其包含至少一種(甲基)丙烯酸化化合物(A);及至少一種惰性OH封端之聚酯(B),其由包含至少一種環醚多元醇之多元醇組分,且由多元酸組分,藉由使用強酸(如烷基磺酸及/或芳基磺酸)或有機金屬化合物作為催化劑製備。
US 20090253888 A1揭示一種藉由使用有機次膦酸化合物作為催化劑與金屬催化劑組合來製備聚酯之方法。
然而,由於異山梨糖醇之反應性,當藉由習知方法聚合含有大量異山梨糖醇建構嵌段之聚酯多元醇時,發現反應產物呈現深色,其表明在聚合期間,異山梨糖醇在習知催化劑存在下遇到副作用。因此,藉由使用有成本效益之催化劑以高轉化率產生含有高異山梨糖醇含量之聚酯多元醇將為合乎需要的。
本發明之第一目標為提供一種衍生自反應混合物之聚酯多元醇,該反應混合物包含
至少一種無水己糖醇,
至少一種多官能羧酸,及
至少一種非金屬無機酸性催化劑,其選自具有呈+1氧化態之磷原子的非金屬無機酸性化合物、具有呈+3氧化態之磷原子的非金屬無機酸性化合物,及其混合物。
本發明之另一目標為提供一種聚胺基甲酸酯黏著劑組合物,其包含多元醇組分及異氰酸酯組分,該多元醇組分包含至少一種根據本發明之聚酯多元醇,該異氰酸酯組分包含至少一種多官能異氰酸酯。
本發明之又一目標為提供一種聚胺基甲酸酯黏著劑組合物,其包含作為多元醇組分及異氰酸酯組分之反應產物的預聚物,該多元醇組分包含至少一種根據本發明之聚酯多元醇,該異氰酸酯組分包含至少一種多官能異氰酸酯。
本發明之又一目標為提供一種單部分、兩部分或多部分黏著劑系統,其包含根據本發明之反應性黏著劑組合物。
本發明之又一目標為提供一種將材料黏合在一起之方法,其包含塗覆根據本發明之一部分、兩部分或多部分黏著劑系統。
本發明更詳細地描述於以下段落中。除非相反地清楚指示,否則如此描述之各態樣可與任何其他態樣組合。特定言之,任何指示為較佳或有利之特徵可與任何其他指示為較佳或有利之特徵組合。
除非另外定義,否則用於揭示本發明之所有術語(包括技術性及科學性術語)具有如一般熟習本發明所屬技術者通常所瞭解之含義。藉助於進一步引導,包括術語定義以充分理解本發明之教示內容。
除非上下文另外清楚地規定,否則如本文所使用之單數形式「一(a/an)」及「該」包括單數個及複數個提及參照物。
如本文所使用之術語「包含(comprising/comprises/comprised of)」與「包括(including/includes)」或「含有(containing/contains)」同義,且為包括性或開放性的,且不排除其他未敍述成員、要素或方法步驟。
術語「生物基」係指至少部分來源於生質(諸如植物、樹木或動物)之材料或產物,其可經物理、化學或生物處理。術語「完全生物基」係指完全衍生自生質(諸如植物、樹木或動物)之材料或產物,其可經物理、化學或生物處理。
數值端點之列舉包括包含於各別範圍內之所有數字及分數,以及所敍述端點。
在本說明書中所引用之所有參考文獻以全文引用之方式併入本文中。
除非另外說明,否則若在本文中提及聚合物之分子量,則此提及係指數目平均重量M
n。聚合物之數目平均分子量M
n可例如藉由凝膠滲透層析法(GPC)用THF作為溶離劑來測定。若並未另外陳述,則所有給出之分子量為藉由GPC測定、使用聚苯乙烯標準物校準之彼等分子量。平均分子量M
w亦可藉由GPC測定,如關於M
n所描述。
本發明之聚酯多元醇係衍生/獲自反應混合物,該反應混合物包含至少一種無水己糖醇、至少一種多官能羧酸及至少一種選自以下之非金屬無機酸性催化劑:具有呈+1氧化態之磷原子的非金屬無機酸性化合物、具有呈+3氧化態之磷原子的非金屬無機酸性化合物,及其混合物。
藉由使己糖醇,如山梨糖醇(葡萄糖醇)、甘露糖醇、艾杜糖醇脫水來獲得無水己糖醇,該等己醣醇藉由還原己糖,如葡萄糖、甘露糖、艾杜糖(其通常源自如小麥、玉米、纖維素之若干生物原料)之羰基來產生。
雙重脫水產生二脫水己糖醇。通常,無水己糖醇為二脫水己糖醇,如二脫水甘露糖醇、二脫水山梨糖醇、二脫水艾杜糖醇及其混合物。二脫水己糖醇較佳為二脫水山梨糖醇,諸如異山梨糖醇、異甘露糖醇及異艾杜糖醇,且更尤其為異山梨糖醇。有幾家公司已專門從事生產異山梨糖醇、異甘露糖醇及異艾杜糖醇。
較佳地,以聚酯多元醇之反應物的總莫耳數計,至少一種無水己糖醇之量為20 mol%至60 mol%。
除無水己糖醇以外,聚酯多元醇之反應物可視情況包含至少一種除無水己糖醇以外之多元醇以與多官能羧酸反應。
此類多元醇之實例包括單乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇(包括R-形式、S-形式及外消旋體)、1,4-丁二醇、1,4-戊二醇、3-甲基戊烷-1,5-二醇、新戊二醇(2,2-二甲基-1,3-丙二醇)、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、環己烷二甲醇、2-甲基丙烷-1,3-二醇、二乙二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇及聚丁二醇。
較佳地,除無水己糖醇以外之多元醇為完全生物基的。此類多元醇之實例包括但不限於丙三醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇(包括R-形式、S-形式及外消旋體)、1,4-丁二醇、1,4-戊二醇、1,5-戊二醇、乙二醇、二乙二醇及三乙二醇。此等多元醇係單獨或組合使用。
在一個實施例中,聚酯多元醇之反應物包含至少一種除無水己糖醇以外之多元醇。若存在,則以聚酯多元醇之反應物的總莫耳數計,除無水己糖醇以外之多元醇的量為1 mol%至35 mol%。
在另一實施例中,聚酯多元醇之反應物僅包含無水己糖醇作為用於製備根據本發明之聚酯多元醇的多元醇來源。
聚酯多元醇可藉由在根據本發明之催化劑的存在下,使無水己糖醇及視情況選用之至少一種除無水己糖醇以外之多元醇以及一種亞化學計算量之量的多官能羧酸聚縮合來製備。較佳地,多官能羧酸具有2至36個碳原子,諸如二羧酸及/或三羧酸,或其反應性衍生物,諸如羧酸酐、羧酸氯及羧酸酯。
二羧酸之實例包括己二酸、丁二酸、壬二酸、癸二酸、十二烷二酸、十四烷二酸、十六烷二酸、十八烷二酸、衣康酸(itaconic acid)、呋喃二甲酸、間苯二甲酸、對苯二甲酸、鄰苯二甲酸、二聚脂肪酸、三聚脂肪酸及其類似者。此等二羧酸係單獨或組合使用。羧酸酐之實例包括己二酸酐、丁二酸酐及其類似者。此等二羧酸酐係單獨或組合使用。在一個實施例中,多官能羧酸係選自丁二酸、壬二酸、癸二酸、二聚脂肪酸、三聚脂肪酸及其混合物。
二聚脂肪酸為單不飽和或多不飽和酸及/或其酯之二聚產物。較佳二聚脂肪酸為C10-至C36-,更佳C12-至C24-,尤其C14-至C22-烷基鏈之二聚物。適合之二聚脂肪酸包括油酸、亞麻油酸、次亞麻油酸、棕櫚油酸及反油酸之二聚產物。亦可使用在天然脂肪及油(例如葵花籽油、大豆油、橄欖油、菜籽油、棉籽油及松油)之水解中獲得之不飽和脂肪酸混合物之二聚產物。二聚(二聚物)脂肪酸之實例為可購自Croda之Pripol 1019、1013、1017、1006。
根據本發明,以聚酯多元醇之反應物的總莫耳數計,至少一種多官能羧酸之量不大於50 mol%,且較佳40 mol%至50 mol%。
無水己糖醇及視情況選用之多元醇以及多官能羧酸之聚縮合在至少一種催化劑存在下進行。催化劑為非金屬無機酸性催化劑,其選自具有呈+1氧化態之磷原子的非金屬無機酸性化合物、具有呈+3氧化態之磷原子的非金屬無機酸性化合物,及其混合物。在一個較佳實施例中,至少一種非金屬無機酸性催化劑係選自次膦酸、膦酸及其混合物。在一個更佳實施例中,非金屬無機酸性催化劑為次膦酸。
用於製備聚酯多元醇之反應混合物可進一步包含至少一種溶劑,諸如水。若存在,則溶劑係以反應物總重量之0.01至1重量%之量,且更特定言之以0.1至0.5重量%之量包含在內。非金屬無機酸性催化劑可首先以5:1至1:5且較佳1:1之重量比溶解於水中,且隨後與其他反應物混合以形成反應混合物。
本發明人已出人意料地發現,根據本發明之非金屬無機酸性催化劑可在高溫下在聚縮合反應期間防止無水己糖醇分解(例如在聚合反應器之局部區域),且相較於習知使用之催化劑(諸如金屬催化劑及有機磷酸,該等催化劑相當昂貴),降低此類聚酯多元醇之大規模生產的成本。另外,藉由使用根據本發明之非金屬無機酸性催化劑,基於無水己糖醇之聚酯多元醇的製造不產生不符合化學品登記及法規之有害副產物。因此,可克服在製造含有高異山梨糖醇含量以及有機磷化合物之聚酯多元醇中之成本及技術難題,諸如所需產品規格、產品顏色淡、反應時間較短及副反應較少。
聚縮合反應中所用之非金屬無機酸性催化劑的量較佳在反應物總重量之0.001至5重量%範圍內,且更特定言之在0.02至1重量%範圍內。
另外,聚酯多元醇之反應混合物基本上不包含其他催化劑,諸如有機磷酸、金屬催化劑、胺催化劑或具有呈+5氧化態之磷原子的無機磷酸。較佳地,以反應混合物之總重量計,其包含小於0.05重量%,特定言之小於0.02重量%之此類催化劑。在一個較佳實施例中,聚酯多元醇之反應混合物不含其他催化劑。
金屬催化劑之實例為鋁醇鹽、鈦醇鹽、鎂醇鹽及鋯醇鹽、錫化合物,更特定言之,有機錫羧酸鹽,諸如二月桂酸二丁基錫、二乙酸二丁基錫、雙(2-乙基己酸)二丁基錫或其他有機錫化合物,諸如氧化二丁基錫、二甲醇二丁基錫、二溴二丁基錫、二氯二丁基錫、二氯二三級丁基錫,二溴二甲基錫、二氯二甲基錫、二氯二苯基錫或辛酸錫、乙酸鐵、苯甲酸鐵、環烷酸鐵;乙醯基丙酮酸鐵、乙酸錳、環烷酸錳及乙醯基丙酮酸錳。
根據本發明,含有較高量之無水己糖醇建構嵌段之聚酯多元醇較佳藉由包含以下步驟之方法製備:(1)提供包含至少一種無水己糖醇、至少一種多官能羧酸、至少一種非金屬無機酸性催化劑及視情況至少一種直鏈或分支鏈脂族多元醇之反應混合物以形成混合物,(2)逐步將混合物加熱至200℃至220℃且在氮氣流下維持20至40小時,(3)逐步將壓力降低至1至300 mbar以完成反應,及(4)當反應混合物之酸值不超過5時冷卻反應混合物,且獲得聚酯多元醇。
在本發明中,藉由如上文所描述之方法製備之聚酯多元醇的物理特性不存在限制。較佳地,聚酯多元醇為完全生物基的,且在室溫下呈非晶形液體、結晶固體或非晶形固體形式。
一般而言,黏著劑組合物中所使用之聚酯多元醇之分子量不存在限制,只要其對黏著劑組合物及固化黏著劑之特性不具有負面影響即可。較佳地,聚酯多元醇之分子量M
n為500至20,000 g/mol,尤其1,000至10,000 g/mol。
在本發明中,聚酯多元醇較佳具有0.1至5,且較佳1至3 mg KOH/g之酸值。假設所有包括於1 g樹脂中之酸基為游離酸,根據本發明之聚酯多元醇的「酸值」藉由中和酸所需的一定毫克之氫氧化鉀的計算值來表示。因此,即使酸基以鹼形式存在於實際系統中,但仍假定其為游離酸。根據DIN 51558,藉由將聚酯多元醇溶解於溶劑中,添加酚酞作為指示劑,且用0.1 mol/l氫氧化鉀-乙醇溶液滴定來測定根據本發明之「酸值」。
在本發明中,聚酯多元醇之羥基值可為5至150 mg KOH/g、較佳10至120 mg KOH/g且尤其15至100 mg KOH/g。如本文所用,羥基值意謂當1 g樹脂乙醯化時,中和與羥基結合之乙酸所需的一定毫克之氫氧化鉀。
根據DIN 51558,藉由將乙醯化試劑添加至聚酯多元醇,用甘油溶液加熱,使其冷卻,接著添加酚酞作為指示劑,並用氫氧化鉀-乙醇溶液滴定來測定根據本發明之「羥基值」。
在本發明中,聚酯多元醇之玻璃轉移溫度可為-100℃至100℃。使用差示掃描量熱計來量測聚酯多元醇之玻璃轉移溫度。關於適當量之樣品,藉由差示掃描熱量測定在10℃/分鐘之升溫率下量測DSC曲線,且將所獲得之DSC曲線的拐點的溫度視為玻璃轉移溫度。
在一個實施例中,聚酯多元醇,較佳完全生物基衍生之聚酯多元醇為非晶形液體。較佳地,此類聚酯多元醇之酸值為0.1至3 mg KOH/g。較佳地,此類聚酯多元醇之羥基值為30至120 mg KOH/g,更佳50至100 mg KOH/g。較佳地,此類聚酯多元醇之Tg為-70至-20℃,且更佳為-30至-60℃。
在另一實施例中,聚酯多元醇,較佳完全生物基衍生之聚酯多元醇為結晶固體。較佳地,此類聚酯多元醇之酸值為0.1至3 mg KOH/g。較佳地,此類聚酯多元醇之羥基值為20至100 mg KOH/g、更佳30至60 mg KOH/g。較佳地,此類聚酯多元醇之熔融溫度為30至100℃且較佳40至70℃。
在又一實施例中,聚酯多元醇,較佳完全生物衍生之聚酯多元醇為非晶形固體。較佳地,此類聚酯多元醇之酸值為0.1至3 mg KOH/g。較佳地,此類聚酯多元醇之羥基值為20至100 mg KOH/g,且更佳30至80 mg KOH/g。較佳地,此類聚酯多元醇之Tg為-15至80℃,且更佳為-10至60℃。
本發明之另一目標為提供一種反應性黏著劑組合物,其包含多元醇組分及異氰酸酯組分,該多元醇組分包含至少一種根據本發明之聚酯多元醇,該異氰酸酯組分包含至少一種多官能異氰酸酯。
根據本發明,以反應性黏著劑組合物之總重量計,反應性黏著劑組合物包含5重量%至80重量%、較佳10重量%至50重量%之量的聚酯多元醇。
本發明之又一目標為提供一種聚胺基甲酸酯黏著劑組合物,其包含預聚物,該預聚物為由包含多元醇組分及異氰酸酯組分之反應混合物獲得的反應產物,該多元醇組分包含至少一種根據本發明之聚酯多元醇,該異氰酸酯組分包含至少一種多官能異氰酸酯。
根據本發明,以反應物之總重量計,預聚物之反應物包含5重量%至80重量%、較佳10重量%至50重量%之量的聚酯多元醇。
可用於實踐本發明之多官能異氰酸酯包括伸烷基二異氰酸酯、伸環烷基二異氰酸酯、芳族二異氰酸酯及脂族-芳族二異氰酸酯。適合的含異氰酸酯化合物之特定實例包括但不限於乙烯二異氰酸酯、伸乙基二異氰酸酯、丙烯二異氰酸酯、丁烯二異氰酸酯、二異氰酸三亞甲酯、二異氰酸六亞甲酯、二異氰酸甲苯酯、伸環戊基-1,3-二異氰酸酯、環-己烯-1,4-二異氰酸酯、伸環己基-1,2-二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,2-二苯基丙烷-4,4'-二異氰酸酯、苯二甲基二異氰酸酯、1,4-伸萘基二異氰酸酯、1,5-伸萘基二異氰酸酯、間伸苯基二異氰酸酯、對伸苯基二異氰酸酯、二苯基4,4'-二異氰酸酯、偶氮苯4,4'-二異氰酸酯、二苯碸-4,4'-二異氰酸酯、2,4-甲苯烯二異氰酸酯、二氯六亞甲基二異氰酸酯、呋喃亞甲基二異氰酸酯、1-氯苯-2,4-二異氰酸酯、4,4',4''-三苯基甲烷三異氰酸酯、1,3,5-三異氰酸基-苯、2,4,6-三異氰酸基-甲苯、4,4'-二甲基二苯基-2,2',5,5-四異氰酸酯及其類似者。在本發明之一個實施例中,第一多元醇係選自聚酯多元醇、聚醚多元醇及其混合物。亦可在本發明中利用上述單體異氰酸酯之寡聚物,諸如二聚物或三聚物。較佳地,多官能異氰酸酯為4,4'-二苯基甲烷二異氰酸酯(MDI)。
多官能異氰酸酯亦包括封閉型多異氰酸酯,諸如單醇或單羥基酚化合物與有機多異氰酸酯之反應產物。此包括含有至少兩個異氰酸基之有機化合物,及包括烴二異氰酸酯(例如,伸烷基二異氰酸酯及伸芳基二異氰酸酯),以及已知之三異氰酸酯及聚亞甲基聚(伸苯基異氰酸酯)。
用於製備封閉型異氰酸酯之說明性多異氰酸酯為:2,4'-二異氰酸基甲苯、2,6-二異氰酸基甲苯、亞甲基雙(4-異氰酸環己酯)、1,2-二異氰酸基乙烷、1,3-二異氰酸基丙烷、1,2-二異氰酸基丙烷、1,4-二異氰酸基丁烷、1,5-二異氰酸基戊烷、1,6-二異氰酸基己烷、雙(3-異氰酸基丙基)醚、雙(3-異氰酸丙基)硫醚、1,7-二異氰酸基庚烷、1,5-二異氰酸基-2,2-二甲基戊烷、1,6-二異氰酸基-3-甲氧基己烷、1,8-二異氰酸基辛烷、1,5-二異氰酸基-2,2,4-三甲基戊烷、1,9-二異氰酸基壬烷、1,4-丁二醇之1,10-二異氰酸丙基)醚、1,11-二異氰酸基十一烷、1,12-二異氰酸基十二烷、雙(異氰酸己基)硫醚、1,4-二異氰酸苯酯、2,4-二異氰酸甲苯酯、2,6-二異氰酸甲苯酯、1,3-二異氰酸基-鄰二甲苯、1,3-二異氰酸基-間二甲苯、1,3-二異氰酸基-對二甲苯、2,4-二異氰酸基-l-氯苯、2,4-二異氰酸基-l-硝基苯、2,5-二異氰酸基-l-硝基苯、4,4-二苯基亞甲基二異氰酸酯、3,3-二苯基-亞甲基二異氰酸酯、聚亞甲基聚(亞苯基二異氰酸酯)、異佛爾酮二異氰酸酯(isophorone diisocyanate)及其混合物。
根據本發明,以反應性黏著劑組合物或反應物之總重量計,反應性黏著劑組合物或預聚物之反應物包含5重量%至50重量%、較佳10重量%至30重量%之量的多官能異氰酸酯。
反應性黏著劑組合物之多元醇組分或預聚物之反應物可包含其他聚合物多元醇以進一步改良黏著劑之特性。此類其他聚合物多元醇可為生物基衍生的或基於化石。較佳地,此類聚合物多元醇亦為生物基衍生的,以便增加黏著劑組合物中生質之含量。在一個較佳實施例中,多元醇組分進一步包含其他生物基聚合物多元醇。在另一較佳實施例中,以反應性黏著劑組合物之總重量計,完全生物基衍生之聚酯多元醇及其他生物基聚合物多元醇(若存在)之量為50重量%至85重量%。
若存在,則以黏著劑組合物之總重量計,其他聚合物多元醇以1至50重量%之量存在於黏著劑組合物中。
在一較佳實施例中,至少一種多官能異氰酸酯與至少一種根據本發明之聚酯多元醇及其他聚合物多元醇(若存在)之莫耳比(表示為NCO/OH)為5:1至1:1、較佳2.5:1至1.05:1。
催化劑可包含於反應性黏著劑組合物中。在雙組分黏著劑組合物之情況下,其可含有於異氰酸酯組分或多元醇組分中。當使用催化劑時,促進羥基與多官能異氰酸酯之異氰酸酯基之間的交聯反應。催化劑之實例包括三級胺化合物及有機金屬化合物。
三級胺化合物之實例包括三乙胺、三伸乙基二胺、N,N-二甲基苯甲胺、N-甲基𠰌啉、二氮雜雙環十一烯(亦稱為DBU)及其類似者。
有機金屬化合物之實例包括錫化合物及非錫化合物。
錫化合物之實例包括二氯二丁基錫、氧化二丁基錫、二溴二丁基錫、二順丁烯二酸二丁基錫、二月桂酸二丁基錫(亦稱為DBTDL)、二乙酸二丁基錫、硫化二丁基錫、硫化三丁基錫、氧化三丁基錫。實例包括乙酸三丁基錫、乙醇三乙基錫、乙醇三丁基錫、氧化二辛基錫、氯化三丁基錫、三氯乙酸三丁基錫及2-乙基己酸錫。
非錫化合物之實例包括鈦化合物,諸如二氯二丁基鈦、鈦酸四丁脂及三氯丁氧基鈦;鉛化合物,諸如油酸鉛、2-乙基己酸鉛、苯甲酸鉛及環烷酸鉛。鐵化合物,諸如乙基己酸鐵及2,4-乙醯丙酮鐵;鈷化合物,諸如苯甲酸鈷及2-乙基己酸鈷;鋅化合物,諸如環烷酸鋅及2-乙基己酸鋅;及環烷酸鋯。
其中,在反應性及衛生方面,二氮雜雙環十一烯(DBU)、二月桂酸二丁基錫(DBTDL)、2-乙基己酸鋅及其類似者為較佳的。
黏著劑組合物之催化劑可單獨或以兩者或更多者之組合形式使用。
根據本發明之黏著劑組合物可含有或不含有機溶劑。有機溶劑之實例將包括雜環、脂族或芳族烴,諸如甲苯、異佛爾酮、二甲苯、一元醇或多元醇(諸如乙基己醇、丁氧基丙醇、異丙醇、丁基乙二醇、甲醇、乙醇、丙醇及丁醇)、醚(諸如二乙二醇二甲醚及二丙二醇甲醚、乙二醇單乙醚及乙二醇丁醚)、酯(諸如乙酸乙酯、乙酸丁酯、乙酸戊酯或乙氧基丙酸乙酯)、酮(諸如環己酮、甲基乙基酮(MEK)、甲基戊基酮、甲基異丁基酮(MIBK)及丙酮)及醯胺(諸如N-甲基吡咯啶酮、N-乙基吡咯啶酮、甲氧基乙酸丙酯及二甲基甲醯胺)。
雖然反應性黏著劑組合物可如上文所描述直接使用,但必要時本發明之黏著劑組合物亦可與習知添加劑一起調配,該等添加劑與組合物相容。添加劑可包含於多元醇組分及/或異氰酸酯組分中,只要其對諸如多元醇及/或異氰酸酯之其他成分為惰性的即可。此類添加劑包括黏著促進劑、消泡劑、光學增亮劑、分散劑、顏料、黏度調節劑及其混合物。
用於本發明之黏著劑組合物中之適合黏著促進劑為例如矽烷化合物,諸如巰基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷,及3-丙烯醯氧基丙基三甲氧基矽烷,N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、雙-(γ-三甲氧基矽烷基丙基)胺、N-β-(胺基乙基)-γ胺基丙基甲基二甲氧基矽烷、參-(γ-三甲氧基矽烷基)異氰尿酸酯及其混合物。
用作添加劑之適合消泡劑為例如丙烯酸酯共聚物。
用作添加劑之適合光學增亮劑為例如2,5-噻吩二基雙(5-三級丁基-1,3-苯并㗁唑)。
待使用之適合的分散劑為例如高分子量烷胺基醯胺、羥基官能性羧酸酯及結構化丙烯酸酯共聚物。
待使用之適合顏料為例如顏料漿及色漿。
待使用之適合黏度調節劑為例如煙霧狀二氧化矽。
本發明之黏著劑組合物/系統可藉由混合組分/部分/預聚物及視情況選用之添加劑來產生。混合方法不存在特定限制,只要可獲得本發明之目標黏著劑即可。混合組分之次序亦不存在特定限制。根據本發明之黏著劑組合物/系統可在不需要特殊混合方法及特殊混合順序之情況下製備。
本發明亦提供一種將製品黏合在一起之方法,其包含:將呈液體形式之本發明之黏著劑系統塗覆至第一製品,使第二製品與塗覆至第一製品之系統接觸,及使塗覆之系統經歷將使得系統固化且黏合基板之條件。組合物通常以其液體或固體形式儲存及分佈,且在沒有水分之情況下儲存。亦提供一種製品,其包含根據本發明之黏著劑組合物的固化產物。
本發明將藉助於以下實例更詳細地說明,該等實例不應理解為限制本發明之概念。
實例在實例中使用以下材料。
來自Sigma Aldrich之癸二酸。
來自Sigma Aldrich之丁二酸。
來自Roquette,商品名為Polysorb PA之異山梨糖醇。
來自Godavari Biorefineries之1,3-丁二醇。
來自Sigma Aldrich之1,2-丙二醇。
來自Sigma Aldrich之乙二醇。
來自Croda,商品名為Pripol之二聚物脂肪酸。
來自Sigma Aldrich之次膦酸。
來自Sigma Aldrich之正磷酸。
來自Sigma Aldrich之(2-甲氧基苯基)苯基次膦酸。
來自Sigma Aldrich之異丙醇鈦(IV)。
來自Covestro之2,4'-MDI。
聚酯多元醇之製備聚酯多元醇之本發明實例(Ex. 1至Ex. 6)係根據表1中之配方製備。聚酯多元醇之比較實例(CEx. 1至CEx. 5)係根據表2中之配方製備。
向配備有氮氣充氣管、熱電偶、頂置式攪拌器及蒸餾臂之1或5公升,4頸燒瓶中饋入多元酸及多元醇。混合物在氮氣流下逐步加熱至最大220℃。視反應組合物(單體及催化劑)而定,完全反應進行大約20小時至40小時。自聚縮合反應開始時或在聚縮合反應過程期間直接添加1:1重量比之催化劑水溶液。隨後,將系統之壓力逐步地降低至10至300 mbar以達成完全轉化。一旦酸值達到5 mg KOH/g或更小值,則冷卻反應物。根據GPC方法,聚酯多元醇係藉由其酸值(mg KOH/g)、羥基值(mg KOH/g)、在特定溫度下黏度(Pa·s)以及Mn (g/mol)表徵。進行DSC量測以便測定最終聚酯多元醇之Tg及熔點Tm (以℃計)。
表1.本發明聚酯多元醇之反應物及特性
1AS:非晶形固體;
2CS:結晶固體;
3AL:非晶形液體
表2.非根據本發明之聚酯多元醇的反應物及特性
1AS:非晶形固體;
2CS:結晶固體;
3AL:非晶形液體
反應物 | Ex. 1 | Ex. 2 | Ex. 3 | Ex. 4 | Ex. 5 | Ex. 6 |
癸二酸 (重量(g)) | - | 129.47 | 129.5 | 254.48 | 245.58 | 238.02 |
癸二酸 (mol%) | - | 18.6 | 19.1 | 45.9 | 45.3 | 45.2 |
丁二酸 (重量(g)) | 86.58 | 113.33 | 113.35 | - | - | - |
丁二酸 (mol%) | 38.2 | 27.9 | 28.6 | - | - | - |
1,3-丁二醇 (重量(g)) | - | - | - | - | - | 75.31 |
1,3-丁二醇 (mol%) | - | - | - | - | - | 30.1 |
二聚物脂肪酸 (重量(g)) | 83.25 | - | - | - | - | - |
二聚物脂肪酸 (mol%) | 7.5 | - | - | - | - | - |
乙二醇 (重量(g)) | - | - | - | 52.63 | - | - |
乙二醇 (mol%) | - | - | - | 30.9 | - | - |
1,2-丙二醇 (重量(g)) | - | - | - | - | 65.03 | - |
1,2-丙二醇 (mol%) | - | - | - | - | 31.9 | - |
異山梨糖醇 (重量(g)) | 152.22 | 268.9 | 256.33 | 92.88 | 89.43 | 86.73 |
異山梨糖醇 (mol%) | 54.3 | 53.5 | 52.3 | 23.2 | 22.8 | 22.8 |
次膦酸 (重量(g)) | 0.61 | 0.96 | 0.94 | 0.75 | 0.75 | 0.75 |
次膦酸 (重量%) | 0.19 | 0.19 | 0.19 | 0.19 | 0.19 | 0.19 |
特性 | ||||||
酸值(mg KOH/g) | 1.6 | 2.1 | 2.8 | 0.2 | 1.0 | 2.2 |
OH值(mg KOH/g) | 61 | 60 | 41 | 55 | 62 | 60 |
黏度@80℃ (Pa·s) | 363 | 105 | 283.5 | 0.6 | 1.0 | 0.9 |
分子量 (Mn, g/mol) | 2644 | 2900 | 2223 | 3364 | 2554 | 2618 |
Tg (℃) | 21 | 25 | 29 | - | -37.5 | -44 |
Tm (℃) | - | - | - | 46 | - | - |
物理狀態 | AS 1 | AS 1 | AS 1 | CS 2 | AL 3 | AL 3 |
顏色 | 淡黃色至微黃色 | 無色至淡黃色 | 無色至淡黃色 | 白色至淡黃色 | 無色至淡黃色 | 無色至淡黃色 |
反應物 | CEx. 1 | CEx. 2 | CEx. 3 | CEx. 4 | CEx. 5 |
癸二酸 (重量(g)) | - | 787.3 | 1794.9 | 1782.2 | - |
癸二酸 (mol%) | - | 19.3 | 46.1 | 45.8 | - |
丁二酸 (重量(g)) | 86.69 | 689.6 | - | - | 53.81 |
丁二酸 (mol%) | 38.3 | 29.0 | - | - | 38.2 |
1,3-丁二醇 (重量(g)) | - | - | - | 540 | - |
1,3-丁二醇 (mol%) | - | - | - | 31.1 | - |
1,4-丁二醇 (重量(g)) | - | - | 531 | - | - |
1,4-丁二醇 (mol%) | - | - | 30.6 | - | - |
二聚物脂肪酸 (重量(g)) | 83.25 | - | - | - | 51.73 |
二聚物脂肪酸 (mol%) | 7.4 | - | - | - | 7.5 |
異山梨糖醇 (重量(g)) | 152.1 | 1523.1 | 654.9 | 650.3 | 94.52 |
異山梨糖醇 (mol%) | 54.3 | 51.7 | 23.3 | 23.1 | 54.3 |
異丙醇鈦(IV) (重量(g)) | 0.07 | 0.9 | 0.6 | 0.59 | - |
異丙醇鈦(IV) (重量%) | 0.02 | 0.02 | 0.02 | 0.02 | - |
正磷酸 (重量(g)) | 0.11 | 1.02 | 0.76 | 0.76 | - |
正磷酸 (重量%) | 0.03 | 0.03 | 0.03 | 0.03 | - |
(2-甲氧基苯基)苯基次膦酸 (重量(g)) | - | - | - | - | 0.2 |
(2-甲氧基苯基)苯基次膦酸 (重量%) | - | - | - | - | 0.1 |
特性 | |||||
酸值(mg KOH/g) | 1.4 | 2.7 | 1.0 | 1.0 | 2.5 |
OH值(mg KOH/g) | 59 | 38 | 62 | 68 | 69 |
黏度@80℃ (Pa·s) | 231 | 333 | 1.65 | 1.0 | 146.5 |
分子量 (Mn, g/mol) | 2681 | 4206 | 2555 | 2605 | 未偵測 |
Tg (℃) | 19.5 | 26 | - | -43 | 19 |
Tm (℃) | - | - | 36 | - | - |
物理狀態 | AS 1 | AS 1 | CS 2 | AL 3 | AS 1 |
顏色 | 深橙色至棕色 | 深棕色至黑色 | 深棕色 | 深棕色 | 深黃色 |
如自表1及2可見,根據本發明所製備之聚酯多元醇呈現無色至淡黃色或微黃色,而並非根據本發明所製備之聚酯多元醇呈現深色或甚至黑色,其表明在聚合反應製程中異山梨糖醇發生分解。另外,比較實例5中聚酯多元醇之製備需要26小時(包括在真空條件下16小時),而實例1中聚酯多元醇之製備僅需要21小時(包括在真空條件下13.5小時)。
Claims (15)
- 一種衍生自反應混合物之聚酯多元醇,該反應混合物包含 至少一種無水己糖醇, 至少一種多官能羧酸,及 至少一種非金屬無機酸性催化劑,其選自具有呈+1氧化態之磷原子的非金屬無機酸性化合物、具有呈+3氧化態之磷原子的非金屬無機酸性化合物,及其混合物。
- 如請求項1之聚酯多元醇,其中該無水己糖醇為異山梨糖醇。
- 如請求項1或2之聚酯多元醇,其中該多官能羧酸係生物基的,且較佳選自己二酸、丁二酸、壬二酸、癸二酸、十二烷二酸、十四烷二酸、十六烷二酸、十八烷二酸、衣康酸(itaconic acid)、呋喃二甲酸、間苯二甲酸、對苯二甲酸、鄰苯二甲酸、二聚脂肪酸、三聚脂肪酸,及其混合物。
- 如請求項1至3中任一項之聚酯多元醇,其中該至少一種非金屬無機酸性催化劑選自次膦酸、膦酸及其混合物。
- 如請求項1至4中任一項之聚酯多元醇,其中以該等反應物之總莫耳數計,該至少一種無水己糖醇之量為20 mol%至60 mol%。
- 如請求項1至5中任一項之聚酯多元醇,其中以該等反應物之總莫耳數計,該至少一種多官能羧酸之量不大於60 mol%,較佳20 mol%至50 mol%。
- 如請求項1至6中任一項之聚酯多元醇,其中該反應混合物進一步包含至少一種除無水己糖醇以外之多元醇,較佳生物基的,且更佳選自甘油、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,4-戊二醇、1,5-戊二醇、乙二醇、二乙二醇、三乙二醇及其混合物。
- 如請求項7之聚酯多元醇,其中以該等反應物之總莫耳數計,該至少一種除無水己糖醇以外之多元醇之量為1 mol%至50 mol%,較佳10 mol%至40 mol%。
- 如請求項1至8中任一項之聚酯多元醇,其中該聚酯多元醇為非晶形液體、結晶固體或非晶形固體。
- 如請求項1至9中任一項之聚酯多元醇,其中該反應混合物基本上不包含金屬催化劑,較佳包含以該反應混合物之總重量計,小於0.02重量%之金屬催化劑。
- 如請求項1至9中任一項之聚酯多元醇,以聚酯多元醇之重量計,其包含量為小於0.002重量%、較佳小於0.001重量%之金屬元素。
- 一種製備如請求項1至11中任一項之聚酯多元醇之方法,其包含以下步驟: 1) 提供反應混合物,其包含至少一種無水己糖醇、至少一種多官能羧酸、至少一種非金屬無機酸性催化劑及視情況至少一種直鏈或分支鏈脂族多元醇, 2) 將該反應混合物逐步加熱至200℃至220℃且在氮氣流下維持20至40小時, 3) 逐步地將該壓力降低至1至300 mbar以完成該反應且獲得反應產物,及 4) 當該反應產物之酸值不超過5時冷卻該反應產物,且獲得聚酯多元醇。
- 一種聚胺基甲酸酯黏著劑組合物,其包含多元醇組分及異氰酸酯組分,該多元醇組分包含至少一種如請求項1至10中任一項之聚酯多元醇,該異氰酸酯組分包含至少一種多官能異氰酸酯。
- 一種聚胺基甲酸酯黏著劑組合物,其包含預聚物,該預聚物為由包含多元醇組分及異氰酸酯組分之反應混合物獲得的反應產物,該多元醇組分包含至少一種根據本發明之聚酯多元醇,該異氰酸酯組分包含至少一種多官能異氰酸酯。
- 一種製品,其包含如請求項13或14之聚胺基甲酸酯黏著劑組合物的固化產物。
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