TWI545145B - 以乳酸及異山梨醇共聚形成之聚酯樹脂及其製備方法 - Google Patents
以乳酸及異山梨醇共聚形成之聚酯樹脂及其製備方法 Download PDFInfo
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- TWI545145B TWI545145B TW101110868A TW101110868A TWI545145B TW I545145 B TWI545145 B TW I545145B TW 101110868 A TW101110868 A TW 101110868A TW 101110868 A TW101110868 A TW 101110868A TW I545145 B TWI545145 B TW I545145B
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- polyester resin
- lactic acid
- acid
- mol
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims description 86
- 229920001225 polyester resin Polymers 0.000 title claims description 77
- 239000004645 polyester resin Substances 0.000 title claims description 77
- 239000004310 lactic acid Substances 0.000 title claims description 43
- 235000014655 lactic acid Nutrition 0.000 title claims description 43
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 title claims description 28
- 229960002479 isosorbide Drugs 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 10
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 32
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- 150000001875 compounds Chemical class 0.000 claims description 21
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- 238000005886 esterification reaction Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 239000002253 acid Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229930182843 D-Lactic acid Natural products 0.000 claims description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
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- 229920000728 polyester Polymers 0.000 description 14
- 239000003086 colorant Substances 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 6
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- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Description
本申請案主張西元2011年3月29日申請的韓國專利申請案第10-2011-0028366號的優先權權益，該申請案全部內容以引用方式併入本文中。本發明係關於聚酯樹脂和製備聚酯樹脂的方法，且更特別係關於有較佳耐熱性與顏色和具高化合物含量的聚酯樹脂和製備聚酯樹脂的方法，化合物係源自乳酸共聚形成的生物質或源自乳酸與異山梨醇。
諸如聚酯、聚碳酸酯、聚苯乙烯、聚乙烯、聚丙烯、苯乙烯-丙烯酸共聚物等常用樹脂可取自化石資源，例如石油。近來正致力於減少化石資源的使用，以應付化石資源枯竭、大量消耗石油資源以致增加大氣中的二氧化碳含量及繼之的全球暖化問題。例如，使用源自植物的樹脂時，因植物成長伴隨排放二氧化碳至大氣中，故二氧化碳會經由環境循環，此可緩解全球暖化、石油資源枯竭等。
就環境循環樹脂(聚合物)而言，期望增加生物質資源含量(有機體總量)。生物質係指生物有機體，例如獲得太陽能的植物、微生物、菌體、動物體。生物質資源不僅包括源自植物的環境循環資源，例如澱粉資源(例
如穀物或馬鈴薯)、纖維素資源(例如藥材、林木、稻桿或稻殼)或蔗糖資源(例如甘蔗或甜菜)及包括源自動物的環境循環資源，例如腐土與牲畜屍體、微生物菌體，生物質資源還包括各種有機廢物，例如紙張和源自該等資源的食物廢料。生物質資源係環保的，因為不像化石資源，生物質資源可再生且取之不盡、用之不竭，燃燒釋放到大氣中的二氧化碳亦可在自然界循環。生物質資源可做為能源和各種合成材料成分，並結合生物與化學技術而取代傳統石化。
聚酯樹脂已泛用於封裝材料、成形產品與膜等領域，且為無內分泌干擾素的環保塑膠之一。近來在主要用作食物耐熱容器的聚碳酸酯方面，已發現雙酚A對人類的危害，是以對環保透明耐熱聚酯樹脂的需求更大。以只與對苯二甲酸和乙二醇聚合的同元聚酯為例，其物性和耐熱性可透過拉伸誘發結晶和熱固作用稍微提高。然在應用和耐熱性增強方面有所限制。因此，商業上已廣泛使用與二或更多二醇或二羧酸組分共聚的聚酯樹脂來改善成形性及去除結晶度。然對此共聚聚酯而言，難以藉由拉伸或結晶製程提高其耐熱性。
故近來已發展使用異山梨醇做為聚酯樹脂的共聚單體，以提高聚酯樹脂耐熱性的方法，異山梨醇係澱粉衍生的生物質化合物，且可以下列化學式1表示。
[化學式1]
已知異山梨醇做為二級醇有低反應性，故很難製備高黏度聚酯來製造片或瓶。然美國專利案第5,959,066號揭示使用對苯二甲酸與各種二醇(包括異山梨醇)進行熔融聚合，以製備本質黏度大於或等於0.35分升/克(dl/g)的聚酯的方法。本質黏度大於或等於0.35 dl/g的聚酯樹脂可用於光學產品和塗層，本質黏度大於或等於0.4 dl/g的聚酯樹脂可用於CD，本質黏度大於或等於0.5 dl/g的聚酯樹脂可用於瓶、膜、片和射出成型。再者，美國專利案第6,063,464號揭示使用二醇組分(包括異山梨醇)進行熔融聚合，以製備本質黏度大於或等於0.15 dl/g的聚酯的方法。在上述專利案中，即使以使用異山梨醇進行聚酯聚合之習知原料、方法和催化劑製備聚酯，源自生物質的化合物總量仍很少。
因此，本發明的一目的係提供利用異山梨醇與乳酸或乳酸衍生化合物而具高生物質含量的環保聚酯樹脂和製備聚酯樹脂的方法，異山梨醇與乳酸或乳酸衍生化合物為源自植物的環境循環型聚合資源。
本發明的另一目的係提供有較佳耐熱性與顏色的聚酯
樹脂和製備聚酯樹脂的方法。
為達上述目的，本發明提供由包括對苯二甲酸的二酸組分、相對總體二醇組分包括1至60莫耳%之異山梨醇與1至90莫耳%之乙二醇的二醇組分、和相對樹脂聚合用總反應物為1至50重量%之乳酸或乳酸衍生化合物共聚形成的聚酯樹脂，其中聚酯樹脂具有源自二酸組分之二酸基元、源自二醇組分之二醇基元和源自乳酸或乳酸衍生化合物之羥基單酸基元的重複結構。
本發明亦提供製備聚酯樹脂的方法，包含下列步驟：在0.1至3.0公斤力/平方公分(kgf/cm2)的壓力和200℃至300℃的溫度下，進行包括對苯二甲酸的二酸組分、相對總體二醇組分包括1至60莫耳%之異山梨醇與1至90莫耳%之乙二醇的二醇組分、和相對樹脂聚合用總反應物為1至50重量%之乳酸或乳酸衍生化合物的酯化反應或酯交換反應，計100分鐘至10小時的平均滯留時間；以及在400至0.1毫米汞柱的減壓環境和240℃至300℃的溫度下，進行反應產物的聚縮合反應，計1至10小時的平均滯留時間。
因根據本發明的聚酯樹脂係利用異山梨醇與乳酸或乳酸衍生化合物製備，異山梨醇與乳酸或乳酸衍生化合物為源自生物質的化合物，故該聚酯樹脂很環保且有較佳耐熱性與顏色。
在參閱實施方式詳細說明後，將對本發明和許多伴隨優點有更完整的了解。
根據本發明的聚酯樹脂係藉由二酸組分、二醇組分和乳酸或乳酸衍生化合物共聚製得，且具有源自二酸組分之二酸基元、源自二醇組分之二醇基元和源自乳酸或乳酸衍生化合物之羥基單酸基元的重複結構。
用於製造根據本發明共聚聚酯樹脂的二酸組分包括(i)對苯二甲酸做為主要組分，及若有需要，包括(ii)二羧酸組分做為共聚單體，以改善製得聚酯樹脂的性質，二羧酸組分選自由碳數為8至14的芳香族二羧酸組分和碳數為4至12的脂族二羧酸組分所組成的群組。碳數為8至14的芳香族二羧酸組分包括製造聚酯樹脂習用的各種芳香族二羧酸組分，芳香族二羧酸組分實例除對苯二甲酸外包括間苯二甲酸、奈系二羧酸(例如2,6-奈系二羧酸)、聯苯二羧酸等。碳數為4至12的脂族二羧酸組分包括製造聚酯樹脂習用的各種直鏈、支鏈或環狀脂族二羧酸組分，脂族二羧酸組分實例包括環己二羧酸(例如1,4-環己二羧酸與1,3-環己二羧酸)、鄰苯二甲酸、癸二酸、丁二酸、異癸丁二酸、順丁烯二酸、反丁烯二酸、己二酸、戊二酸、壬二酸等。在本發明中，二羧酸組分可單獨或混合使用。二羧酸組分量相對總體二酸組分為80至100莫耳%，較佳為90至100莫耳%，更佳為95至100莫耳%，總體二酸組分的剩餘組分為除對苯二甲酸外的芳香族或脂族二羧酸組分。其中若對苯二甲酸組
分量太少，則製得聚酯樹脂無足夠的耐熱性而不能用於成型應用。
在本說明書中，「對苯二甲酸或對苯二甲酸組分」一詞係指對苯二甲酸、其烷基酯(低級烷基(碳數為1至4)酯，例如單甲基、單乙基、二甲基、二乙基、二丁基酯等)及/或酸酯形成衍生物，例如其酸酐，該衍生物與二醇組分反應時會產生對苯二甲醯基基元。又在本說明書中，二酸基元、二醇基元和羥基單酸基元代表酸組分、二醇組分與乳酸或乳酸衍生化合物聚合反應而移除氫、羥基或烷氧基後所留下的殘基。
用於本發明的二醇組分相對總體二醇組分包括(i)1至60莫耳%的異山梨醇(雙無水己醣醇)，較佳為5至50莫耳%，更佳為10至30莫耳%，(ii)1至90莫耳%的乙二醇，較佳為10至85莫耳%，更佳為50至80莫耳%，且最佳為70至80莫耳%，及若有需要，包括(iii)0至20莫耳%的二醇做為共聚單體，以改善製得聚酯樹脂的性質，二醇較佳為1至10莫耳%，且選自由二伸乙甘醇、三伸乙甘醇、丙二醇(1,2-丙二醇、1,3-丙二醇等)、1,4-丁二醇、戊二醇、己二醇(1,6-己二醇等)、新戊二醇(2,2-二甲基-1,3-丙二醇)、1,2-環己二醇、1,4-環己二醇、1,2-環己二甲醇、1,3-環己二甲醇、1,4-環己二甲醇、四甲基環丁二醇和上述物質的混合物所組成的群組。
用於本發明的乳酸或乳酸衍生化合物係兼具酸與醇性質的化合物，且包括從乳酸產生的D-乳酸、L-乳酸、D-
乳酸交酯或L-乳酸交酯。乳酸或乳酸衍生化合物量相對總體樹脂聚合反應物為1至50重量%，較佳為10至40重量%，更佳為20至30重量%。乳酸或乳酸衍生化合物的用量越多，除非受到影響，否則製得聚酯樹脂的耐熱性和顏色越佳。然若用量太多，則會惡化聚酯樹脂的耐熱性。在根據本發明的聚酯樹脂中，相對總體聚酯樹脂聚合反應物，包括異山梨醇與乳酸或乳酸衍生化合物的生物質資源組分量較佳為5至70重量%，更佳為20至60重量%，最佳為30至50重量%，包括二酸組分與二醇組分的石油資源衍生化合物量為30至95重量%，較佳為40至80重量%。當生物質資源組分量少於5重量%時，使用生物質資源組分毫無意義；當生物質資源組分量多於70重量%時，可能會惡化製得聚酯樹脂的耐熱性和顏色。
以下將描述製備本發明聚酯樹脂的方法。首先，(a)在0.1至3.0公斤/平方公分(kg/cm2)的升壓環境和200℃至300℃的溫度下，使聚合反應物經歷酯化反應或交酯化反應，計100分鐘至10小時的平均滯留時間，聚合反應物相對總體樹脂聚合反應物包括(i)包括對苯二甲酸及若有需要包括芳香族或脂族二羧酸組分的二酸組分、(ii)包括1至60莫耳%之異山梨醇、1至90莫耳%之乙二醇及若有需要包括其他二醇組分的二醇組分、和(iii)1至50重量%之乳酸或乳酸衍生化合物。接著，(b)在400至0.1毫米汞柱的減壓環境和240℃至300℃的溫度下，使
酯化反應或交酯化反應的產物經歷聚縮合反應，計1至10小時的平均滯留時間，以製造本發明的聚酯樹脂。較佳地，聚縮合反應的壓力最終達小於2.0毫米汞柱，酯化反應或交酯化反應和聚縮合反應可在鈍氣大氣中進行。
製備本發明聚酯樹脂的聚合條件將詳述於後。為製備具二酸組分(例如對苯二甲酸等)、二醇組分(例如異山梨醇等)與乳酸的共聚聚酯樹脂，按控制在1.05至3.0的二醇組分與二酸組分莫耳比加入二酸組分和二醇組分，及加入相對總體樹脂聚合反應物為1至50重量%的乳酸或乳酸衍生化合物，接著在200℃至300℃的溫度(較佳為240℃至260℃，更佳為245℃至255℃)和0.1至3.0 kgf/cm2的升壓環境(較佳為0.2至2.0 kgf/cm2)下進行酯化反應。當二醇組分與二酸組分的莫耳比小於1.05時，聚合反應後仍有未反應的二酸組分，故會惡化樹脂透明度；當莫耳比大於3.0時，聚合反應速率會下降，以致樹脂生產率不如人意。酯化反應的反應時間(平均滯留時間)通常為100分鐘至10小時，較佳為2小時至500分鐘，反應時間可視反應溫度、反應壓力和二醇組分與二酸組分的莫耳比而定。製備聚酯樹脂的製程可分成酯化反應(步驟1)和聚縮合反應(步驟2)。酯化反應不需催化劑，但催化劑可用來縮短反應時間。可以批次或連續方式進行酯化反應(步驟1)。各反應物可個別引入反應器，但最好引入包括二醇組分與二羧酸組分的
漿料至反應器內。
酯化反應完成後，進行聚縮合反應。開始聚縮合反應前，可將聚縮合催化劑、穩定劑、著色劑和其他添加劑加入酯化反應的產物中。聚縮合催化劑實例包括習知鈦基催化劑、鍺基催化劑、銻基催化劑、鋁基催化劑、錫基催化劑和上述物質的混合物。其中，以鍺基催化劑製得的聚酯樹脂顏色優於使用銻基催化劑和鈦基催化劑製得的聚酯樹脂顏色。習知各種磷質基穩定劑可做為聚縮合反應的穩定劑，例如磷酸、磷酸三甲酯、磷酸三乙酯等。較佳地，穩定劑乃引入使穩定劑的磷質量相對最終製得聚酯樹脂總重量為10至100 ppm。當穩定劑的磷質量少於10 ppm時，聚酯樹脂不夠穩定，且聚合物(聚酯樹脂)的顏色會變黃。當穩定劑的磷質量超過100 ppm時，聚合物的聚合程度不足。加入著色劑，以改善聚酯樹脂的顏色性質。著色劑實例包括習知著色劑，例如乙酸鈷、丙酸鈷。若有需要，可使用有機著色劑做為著色劑。著色劑的較佳用量相對聚酯樹脂總重量為0至100 ppm。通常，聚縮合反應係在240℃至300℃的溫度(較佳為250℃至290℃，更佳為260℃至280℃)和400至0.1毫米汞柱的減壓環境下進行。維持400至0.1毫米汞柱的減壓環境，以移除聚縮合反應的副產物或過量二醇。聚縮合反應可進行直到獲得預定聚酯樹脂本質黏度為止，例如可進行1至10小時的平均滯留時間。若有需要，在根據本發明的聚酯聚合中，除二酸組分、二醇組
分和乳酸或乳酸衍生化合物外，可額外使用少量(例如佔總反應物的0.1至10莫耳%)的三酸及/或三醇組分。當本發明聚酯樹脂經鄰氯苯酚(OCP)溶解成1.2克/分升(g/dl)的濃度時，聚酯樹脂在35℃下的本質黏度為0.5 dl/g或以上，較佳為0.6 dl/g或以上，更佳為0.7 dl/g。由於本發明的聚酯樹脂有較佳的耐熱性和顏色，故聚酯樹脂適於製造選自由膜、片、飲料瓶、奶瓶、光纖、光學產品等所組成群組的聚酯樹脂物件。
以下將提供較佳實例，以對本發明有更深入的理解。然本發明不限於下述實例。在以下實例和比較實例中，除非特別提及，否則「份」或「%」係指「重量份(按重量計份)」或「重量%(按重量計%)」，TPA代表對苯二甲酸，IPA代表間苯二甲酸，ISB代表異山梨醇(1,4：3,6-二脫水山梨醇)，EG代表乙二醇，1,3-PDO代表1,3-丙二醇，乳酸交酯代表L-乳酸交酯，且依下列方法評估聚合物的性能。
(1)本質黏度(IV)：在150℃下，以鄰氯苯酚將聚合物溶解成0.12%的濃度後，利用烏氏黏度計，在35℃恆溫器中測量聚合物的IV。
(2)耐熱性(玻璃-橡膠轉化溫度(Tg))：在加熱速率為10℃/分鐘的第二次掃描期間，測量聚酯樹脂的Tg。
(3)顏色：利用Pacific Scientific公司的Colorgard系統，測量聚酯樹脂的顏色。
(4)生物含量(%)：利用600兆赫(MHz)的核磁共振
(NMR)光譜儀，測量樹脂中各生物質資源組分量。
根據表1所列用量，將反應物加到容量7公升的反應器中，及加入200 ppm的鍺基催化劑、70 ppm的磷酸鹽基穩定劑和50 ppm的鈷基著色劑，接著加熱反應器達240℃至300℃，以進行酯化反應。當為副產物的水有70%至99%排出系統時，開始進行聚縮合反應，並在達目標黏度時終止反應。按催化劑、穩定劑和著色劑的中心元素原子數計分別加入ppm單位的催化劑、穩定劑和著色劑至總體資源(反應物)中。測量製得聚酯樹脂的生物含量(%)、本質黏度、耐熱性(Tg)、顏色L和顏色b，且列於表1。
除使用表1所列反應物用量外，以和比較實例所述一樣的方式製備聚酯樹脂。測量製得聚酯樹脂的生物含量(%)、本質黏度、耐熱性(Tg)、顏色L和顏色b，且列於表1。
表1列出用於製備聚酯的所有二酸組分與二醇組分輸入量。如表1所示，相較於習知聚酯樹脂，本發明包括乳酸或乳酸衍生化合物的聚酯樹脂具有高生物含量，同時本發明聚酯樹脂具有相同或更佳的耐熱性。具體而言，比較實例1至3的聚酯樹脂係以異山梨醇製備的高耐熱性聚酯樹脂，該聚酯樹脂的Tg和生物含量很高，且顏色L和顏色b比習知聚酯樹脂淺一點，IV則類似習知聚酯樹脂。然為得高生物含量而增加做為生物資源的異山梨醇輸入量，儘管製得聚酯的Tg很高，卻易惡化顏色。若Tg高於所需，則因高溫下的熔融黏度增加而難以合成高分子量聚酯，又因反應性降低，導致顏色惡化。比較實例4和5的聚酯樹脂製備係以1,3-PDO做為生物資源，該聚酯樹脂的IV和Tg類似比較實例1，但生物含量較高。然1,3-PDO會大幅降低Tg，故需增加異山梨醇輸入量。若增加異山梨醇輸入量，則會惡化製得聚酯
的顏色，1,3-PDO亦不利於提高製得聚合物的顯色強度。在實例1至6中，另加入乳酸交酯至比較實例的相同資源中，該等實例的聚酯樹脂在類似Tg與IV下有較高生物含量和較佳顏色。
Claims (7)
- 一種聚酯樹脂，該聚酯樹脂由包括對苯二甲酸的一二酸組分、相對一總體二醇組分包括10至60莫耳%之異山梨醇與1至90莫耳%之乙二醇的一二醇組分、和相對樹脂聚合用總反應物為1至50重量%之乳酸或一乳酸衍生化合物共聚反應形成，其中該聚酯樹脂具有源自該二酸組分之二酸基元、源自該二醇組分之二醇基元和源自該乳酸或該乳酸衍生化合物之羥基單酸基元的重複結構。
- 如請求項1之聚酯樹脂，其中相對一總體聚酯樹脂聚合反應物，包括該異山梨醇與該乳酸或該乳酸衍生化合物的一生物質資源組分量為5重量%至70重量%，包括該二酸組分與該二醇組分的一石油資源衍生組分量為30重量%至95重量%。
- 如請求項1之聚酯樹脂，其中該乳酸或該乳酸衍生化合物係選自由D-乳酸、L-乳酸、D-乳酸交酯和L-乳酸交酯所組成的群組。
- 如請求項1之聚酯樹脂，其中該二酸組分相對該總體二酸組分包括80至100莫耳%之對苯二甲酸，剩餘組分則為一二羧酸組分，該二羧酸組分選自由碳數為8至14 的芳香族二羧酸組分和碳數為4至12的脂族二羧酸組分所組成的群組。
- 如請求項1之聚酯樹脂，其中相對該總體二醇組分，該異山梨醇量為10至50莫耳%，該乙二醇量為50至80莫耳%。
- 如請求項1之聚酯樹脂，其中該聚酯樹脂的一本質黏度為0.5分升/克(dl/g)或以上，該本質黏度係在35℃下測量，同時該聚酯樹脂以鄰氯苯酚溶解成1.2克/分升的濃度。
- 一種製備聚酯樹脂的方法，該方法包含下列步驟：在0.1至3.0公斤力/平方公分(kgf/cm2)的一壓力和200℃至300℃的一溫度下，進行包括對苯二甲酸的二酸組分、相對總體二醇組分包括10至60莫耳%之異山梨醇與1至90莫耳%之乙二醇的二醇組分、和相對樹脂聚合用總反應物為1至50重量%之乳酸或一乳酸衍生化合物的一酯化反應或一酯交換反應，計100分鐘至10小時的一平均滯留時間；及在400至0.1毫米汞柱的一減壓環境和240℃至300℃的一溫度下，進行反應產物的一聚縮合反應，計1至10小時的一平均滯留時間。
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| CN105440268B (zh) * | 2014-08-29 | 2018-02-13 | 中国科学院长春应用化学研究所 | 一种脂肪族‑芳香族‑聚乳酸多嵌段共聚物 |
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