TWI719981B - 製備聚烯烴反應性遙爪預聚合物之方法 - Google Patents
製備聚烯烴反應性遙爪預聚合物之方法 Download PDFInfo
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- TWI719981B TWI719981B TW105113731A TW105113731A TWI719981B TW I719981 B TWI719981 B TW I719981B TW 105113731 A TW105113731 A TW 105113731A TW 105113731 A TW105113731 A TW 105113731A TW I719981 B TWI719981 B TW I719981B
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- Prior art keywords
- prepolymer
- telechelic
- polyolefin
- cyclooctene
- polymer
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 229920001730 Moisture cure polyurethane Polymers 0.000 title abstract 3
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- 125000006239 protecting group Chemical group 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 33
- 229920006395 saturated elastomer Polymers 0.000 claims description 17
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 229920006037 cross link polymer Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- -1 di-tert-butylbut-2-ene-1,4-diyl Chemical group 0.000 claims description 8
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- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 6
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Classifications
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract
提供一種製備聚烯烴反應性遙爪預聚合物之方法，包含使烷基-順-環辛烯及選擇性之順-環辛烯於擁有二或更多個胺基基團之一多官能性鏈轉移劑存在中，其中，此等二或更多個胺基基團係以一或多個保護基團保護，於開環移位聚合反應條件下反應形成一個二胺基甲酸酯遙爪不飽和聚烯烴預聚合物。
Description
本揭露係有關於一種製備聚烯烴反應性遙爪預聚合物之方法。
聚烯烴係作為高莫耳質量聚合物之有用材料。飽和聚烯烴材料結合具競爭性價格之高的耐化學性及耐氧化性使此等係塑料產業高度合意。已證實聚烯烴上之受控制地包括官能性基團能導致顯著性質增強。但是，儘管大量的自聚烯烴衍生之材料及應用，其等之預聚合物型式之製造係一未被充份探究的領域。聚烯烴之用於形成快速固化彈性體及高分子量聚合物之所需的精確且受控制之官能化係具挑戰性。用於使反應性基團併入聚烯烴內之大部份方法涉及後聚合反應，其對於官能化之位置及量一般具有差的控制，且導致減少之機械性質。形成固化及/或高分子量聚合物之可模製、可射出，及可以其它方式加工之反應性聚烯烴預聚合物的合成會係合意的，因為此等方法能於現今由諸如矽氧烷及胺甲酸酯彈性體之材料所支配之市場中
打開應用空間。
於一實施例，本揭露提供一種製備聚烯烴反應性遙爪預聚合物之方法，包含於開環移位聚合反應條件下，使烷基-順-環辛烯及選擇性之順-環辛烯於擁有二或更多個胺基基團之一多官能性鏈轉移劑存在中接觸，其中，此等二或更多個胺基基團係以一或多個保護基團保護，形成一個二胺基甲酸酯遙爪不飽和聚烯烴預聚合物。
圖1係例示交聯聚合物，XT-A-PH(3ECOE)-2，依據ASTM D1708於127mm/分鐘測量之應力應變曲線的圖。
圖2係例示交聯聚合物，XT-A-PH(3ECOE)-2之動態機械性熱分析的圖，以5℃/分鐘從-90至200℃之扭力測試，ω=6.28rad/s且γ=0.05%。
於製備聚烯烴反應性遙爪預聚合物之本發明方法，使用烷基-順-環辛烯及/或芳基-順-環辛烯。可用於本發明實施例之烷基-順-環辛烯係此項擇藝已知。例示之烷基-順-環辛烯包括3-取代-順-環辛烯類，諸如，3-甲基-順-環辛烯、3-乙基-順-環辛烯，及3-己基-順-環辛烯。例示之芳基-順-環辛烯類包括3-苯基-順-環辛烯類。
烷基-順-環辛烯及選擇性之順-環辛烯係於擁有二或更多個胺基基團之一多官能性鏈轉移劑存在中接觸，其中，此等二或更多個胺基基團係受一或多個保護基團保護。例示之保護基團包括下列種類之化合物：胺基甲酸酯類(胺基-酯類)、醯胺類(胺基-酮)、苯甲基-胺類，及磺酸酯類。可用於本發明之例示的特別保護基團包括胺基甲酸第三丁酯(“BOC胺”)；胺基甲酸9-芴基甲酯(“FMOC胺”)；胺基甲酸苯甲酯；三氟乙醯胺；酞醯亞胺；苯甲胺；及對-甲苯磺醯胺(“甲苯磺醯胺”)。例示之受保護的鏈轉移劑包括二第三丁基丁-2-烯-1,4-二基(E)-二胺基甲酸酯；N,N'-(丁-2-烯-1,4-二基)雙(2,2,2-三氟乙醯胺)；及2,2'-(丁-2-烯-1,4-二基)雙(異吲哚啉-1,3-二酮)。
接觸係於開環移位聚合反應(ROMP)條件下發生，此等條件係此項技藝已知且係描述於，例如，“3-取代環辛烯類之區域及立體選擇性開環移位聚合反應”(“Regio-and Stereoselective Ring-Opening Methathesis Polymerization of 3-Substituted Cyclooctenes”)，Shingo Kobayashi等人，J.Am.Chem.Soc.2011，133，5794-5797及“藉由ROMP使用馬來酸作為鏈轉移劑之羧基遙爪聚烯烴”(“Carboxy-Telechelic Polyolefins by ROMP Using Maleic Acid as a Chain Transfer Agent”)，Pitet及Hillmyer，Macromolecules 2011，44,2378-2381。廣泛之各種催化劑係已知可用於ROMP，包括以簡單金屬為主之化合物，諸如，RuCl3/醇之混合物，及多種錯合Grubbs催化劑，其包括第一及第二代Grubbs催化劑
及Hoveyda-Grubbs催化劑。第一代Grubbs催化劑係具有如下通式之一過渡金屬碳烯錯合物：
第二代Grubbs催化劑具有通式：
Hoyveda-Grubbs催化劑具有通式：
熟習此項技藝者會瞭解適於ROMP之任何催化劑可被使用。本發明不限於前述催化劑結構，亦不限於使用釕作為用於此等催化劑之金屬。
於烷基-順-環辛烯及選擇性之順-環辛烯於擁有二或更多個受保護之胺基基團的一多官能性鏈轉移劑存在中，於開環移位聚合反應條件下接觸後，形成一個二胺基甲酸酯遙爪不飽和聚烯烴預聚合物。形成之預聚合物的分子量及特性係依烷基-順-環辛烯之烷基官能性而定。
本揭露進一步揭露此處所述方法，其進一步包含
使二胺基甲酸酯遙爪不飽和聚烯烴預聚合物部份氫化製備一飽和聚烯烴二胺基甲酸酯遙爪預聚合物。於一特別實施例，部份氫化係藉由使二胺基甲酸酯遙爪不飽和聚烯烴預聚合物於對-甲苯磺醯肼存在中迴流而完成。以下之反應流程係概略說明一個二胺基遙爪飽和聚烯烴預聚合物之形成：
於一特別實施例，氫化提供至少90%飽和度，且造成每一預聚合物鏈具有至少1.7個官能性的一飽和聚烯烴二胺基甲酸酯遙爪預聚合物。從每一預聚合物鏈為1.7個官能性之下限的所有個別數值及子範圍係於此處被包含且於此處被揭露。例如，官能性可為從每一預聚合物鏈為1.7、1.8、1.9，或2.0個官能性之下限。於一另外實施例，一經氫化之聚烯烴反應性遙爪預聚合物係每一預聚合物鏈為等於或少於10個官能性，或另外，係每一預聚合物鏈為從等於或少於7個官能性，或另外，係每一預聚合物鏈為從等於或少於4個官能性。
於一另外實施例，除了於氫化後保留至少60%之
官能性外，本發明提供依據此處揭露的任何實施例之一種製備飽和聚烯烴二胺基甲酸酯遙爪預聚合物之方法。從至少60%之所有個別數值及子範圍係於此處被包含且於此處被揭露。例如，氫化後保留之官能性百分率範圍可為從60、70、80、90或95之下限。
於一另外實施例，除了氫化造成存在於預聚合物中之至少90%的不飽和被氫化外，本發明係提供一種依據此處揭露之任何實施例之製備飽和聚烯烴二胺基甲酸酯遙爪預聚合物之方法。從至少90%之所有個別數值及子範圍係於此處被包含且於此處被揭露；例如，氫化程度可為從90、92.5、95，或97%之下限。
本揭露進一步提供此處揭露之方法，其進一步包含自飽和二胺基甲酸酯遙爪聚烯烴預聚合物移除此一或多個保護基團製備一飽和聚烯烴二胺基遙爪預聚合物。與保護基團反應及使其等移除之任何適合方法(例如，與一酸接觸)可被使用。於一特別實施例，保護基團可藉由使飽和二胺基甲酸酯遙爪聚烯烴預聚合物與三氟乙酸於室溫接觸而移除。於一另外實施例，保護基團係藉由於100℃，於吡啶或三甲胺溶劑中使飽和二胺基甲酸酯遙爪聚烯烴預聚合物與使得pH<1之一酸接觸數分鐘至數小時反應時間而移除。
於另一實施例，本揭露提供依據此處所述之方法製備之一種二胺基甲酸酯遙爪聚烯烴預聚合物。
於另一實施例，本揭露提供一種用於製備經交聯聚合物之方法，此方法包含於選擇性缺乏催化劑，使一個
二胺基遙爪聚烯烴預聚合物與一或多種與此預聚合物具反應性之多官能性化合物接觸，形成一經交聯及/或鏈延長之聚合物。於此處使用時，術語多官能性化合物係指具有多於一個與預聚合物之胺官能基具反應性之官能性基團的一化合物。依多官能性化合物中之官能性基團而定，預聚合物可作為一個二官能性預聚合物或一四官能性預聚合物。例如，每一胺基團可與二環氧基團反應係意指此預聚合物係四官能性。可被使用之例示多官能性化合物包括多官能性環氧化物類，諸如，二官能性環氧化物類、多元異氰酸酯類、多元羧酸類、多元醯基氯化物類，及多元環氧化物類。
本揭露進一步提供一種用於製備高分子量聚合物之方法，此方法包含於選擇性缺乏一催化劑中，使二胺基遙爪聚烯烴預聚合物與一或多個與遙爪預聚合物具反應性之二官能性化合物接觸，形成一高分子量聚合物。於此處使用時，高分子量聚合物意指具有聚烯烴反應性遙爪預聚合物的分子量之至少二倍的分子量之一聚合物。從至少二倍的所有個別數值及子範圍係於此處被包含且於此處被揭露。例如，高分子量聚合物之分子量可為從聚烯烴反應性遙爪預聚合物之分子量的二倍之下限，或另外，高分子量聚合物之分子量可為從聚烯烴反應性遙爪預聚合物之分子量的五倍之下限，或另外，高分子量聚合物之分子量可為從聚烯烴反應性遙爪預聚合物之分子量的十倍之下限，或另外，高分子量聚合物之分子量可為從聚烯烴反應性遙
爪預聚合物之分子量的十五倍之下限。
於一另外實施例，本揭露提供一種依據此處揭露之任何實施例之方法，除了此方法進一步包含選擇性於缺乏一催化劑中，同時使經氫化之聚烯烴反應性遙爪預聚合物以二官能性化合物之混合物鏈延長，及使經鏈延長之氫化聚烯烴反應性遙爪預聚合物以一多官能性化合物熱交聯，二者係與遙爪預聚合物具反應性，形成一經鏈延長、交聯之聚合物。例示之鏈延長多官能性化合物包括雙異氰酸酯類(諸如，4,4'-伸甲基雙(苯基異氰酸酯)及伸甲苯基-2,4-二異氰酸酯)、二醯基氯化物類(諸如，癸二醯基氯化物)，及雙環氧化物類(諸如，1,4-丁二醇二縮水甘油醚，及雙酚A二縮水甘油醚)。例示之交聯多官能性化合物包括三環氧化物類(諸如，三(2,3-環氧基丙基)異氰脲酸酯，及三羥甲基丙烷三縮水甘油醚)，及雙環氧化物類(諸如，1,4-丁二醇二縮水甘油醚，及雙酚A二縮水甘油醚)。
鏈延長反應係以如下之反應流程概略顯示：
交聯反應係以如下反應流程概略描述：
於另一實施例，本揭露提供如此處所述般製備之一經交聯及/或鏈延長之聚合物。
於另一實施例，除了不飽和及/或經氫化之聚烯烴反應性遙爪預聚合物具有從1至20公斤/莫耳之莫耳質量外，本揭露提供一種依據此處揭露之任何實施例製備聚烯烴反應性遙爪預聚合物、不飽和聚烯烴反應性遙爪預聚合物、經氫化之聚烯烴反應性遙爪預聚合物、經交聯之聚合物及高分子量聚合物之方法。從1至20公斤/莫耳之莫耳質量的所有個別數值及子範圍係於此處被包含且於此處被揭露；例如，不飽和聚烯烴反應性遙爪預聚合物之莫耳質量可為從1、3、6、9、12、15，或18公斤/莫耳之下限至2、5、8、11、14、17或20公斤/莫耳之上限。
於一另外實施例，除了多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例係從
1：2至2：1外，本揭露係提供一種依據此處揭露之任何實施例之製備聚烯烴反應性遙爪預聚合物、不飽和聚烯烴反應性遙爪預聚合物、經氫化之聚烯烴反應性遙爪預聚合物、經交聯之聚合物，及高分子量聚合物之方法。從1：2至2：1之所有個別數值及子範圍係於此處被包含且於此處被揭露；例如，多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1：2，或另外，多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為2：1，或另外，多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1.5：2，或另外，多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為2：1.5，或另外，多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1：1.05，或另外，多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1：0.95。於一特別實施例，多官能性化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例係從1：0.94至1：1.06。
於一另外實施例，除了二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例係從1：2至2：1外，本揭露提供一種依據此處揭露之任何實施例之製備聚烯烴反應性遙爪預聚合物、不飽和聚烯烴反應性遙爪預聚合物、經氫化之聚烯烴反應性遙爪預聚合物、經交聯之聚合物，及高分子量聚合物之方法。從
1：2至2：1之所有個別數值及子範圍係於此處被包含且於此處被揭露；例如，二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1：2，或另外，二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為2：1，或另外，二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1.5：2，或另外，二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為2：1.5，或另外，二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1：1.05，或另外，二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例可為1：0.95。於一特別實施例，二官能性及多官能性之化合物上之官能性對聚烯烴反應性遙爪預聚合物之官能性的莫耳比例係從1：0.94至1：1.06。
於一另外實施例，除了此方法進一步包含使一填料添加至反應產物外，本揭露提供依據此處揭露之任何實施例的方法之一反應產物。填料可為一強化或非強化之填填料。適合填料之非限制性範例包含滑石、碳酸鈣、白堊、硫酸鈣、黏土、高嶺土、二氧化矽、玻璃、煅製二氧化矽、雲母、矽灰石、長石、矽酸鋁、矽酸鈣、氧化鋁、諸如氧化鋁三水合物之水合氧化鋁、玻璃微球、陶瓷微球、熱塑性微球、重晶石、木粉、玻璃纖維、碳纖維、大理石粉塵、
水泥粉塵、氧化鎂、氫氧化鎂、氧化銻、氧化鋅、硫酸鋇、二氧化鈦，及鈦酸鹽類。於另一實施例，本方法進一步包含使一或多種前述填料添加至反應產物。一或多種填料之添加可用以增強反應產物之機械性質，例如，抗拉及撕裂性質、模量，及耐熱性。
下列範例係例示本發明，但不打算限制本發明之範圍。
受第三丁氧基羰基保護之胺基鏈轉移劑係使用於Biochimica et Biophysica Acta(BBA)；He et al，1995，第1253冊，第117頁，及Macromolecules Nagarkar，et al 2012，第45冊，第4447頁中所述且於以下之反應流程1所示般之方法製備：
特別地，1,4-二溴-2-丁烯中之溴係於藉由酞醯亞胺之親核性攻擊被置換，產生化合物1；於酸性條件下移除此基團產生化合物2，二胺基化合物之二氫氯酸鹽。然後，
二胺基化合物之此衍生物以一第三丁氧基羰基基團保護獲得化合物3，二第三丁基丁-2-烯-1,4-二基(E)-二胺基甲酸酯。
然後，作為鏈轉移劑(CTA)之此二第三丁基丁-2-烯-1,4-二基(E)-二胺基甲酸酯係如下之流程2中例示般與3-乙基環辛烯接觸，製備一個二胺基甲酸酯遙爪不飽和聚烯烴預聚合物，P(3ECOE)：
其中，G2係一第二代Grubbs催化劑，特別地係(1,3-雙(2,4,6-三甲基苯基)-2-偏咪唑啶基)二氯(苯基伸甲基)(三環己基膦)釕(“(IMesH2)-(Cy3P)RuCl2(CHPh)”)。
二第三丁基丁-2-烯-1,4-二基-二胺基甲酸酯(CTA)被置於一單頸20毫升燒瓶內，其具有一以鐵弗隆塗覆之磁性攪半棒。燒瓶以一橡膠隔片關閉。使用一針，燒瓶及其內容物被置於高壓下10分鐘，然後，以氬氣回填；此抽空-填充之週期被進行三次。無水氯仿及3-乙基-順-環辛烯經由注射器添加至燒瓶。此系統以氬氣沖洗20分鐘，然後，浸於40℃之油浴。G2催化劑以於1毫升之無水經脫氣的氯仿中的一溶液經由注射器添加。20小時後，溶液以0.1毫升之乙基乙烯醚淬息，且另外攪拌10分鐘。預聚合物藉由沉澱於室溫之甲醇中而隔離。溶液被攪拌1小時，然後，甲醇被傾析留下一高黏稠性液體預聚合物。此預聚合物被
溶於8毫升之CH2Cl2內，然後，添加2毫克之經丁基化之羥基甲苯(BHT)。溶劑被移除，且預聚合物於40℃高度真空下乾燥。
1H NMR(500MHz，CDCl3)：δ=5.32(m，1H，=C(1)H)，5.07(m，1H，=C(2)H)，4.45(b，NH)，3.65(m，C(11)H)，1.98(m，2H，-C(8)H2)，1.76(m，1H，-C(3)H)，1.45(s，C(12)H)1.40-1.07(m，10H，-CH2-)，0.83(t，3H，-C(10)H3)。13C NMR(125MHz，CDCl3)：δ=134.78(C2)，130.39(C1)，44.67(C3)，35.33(C4)，32.77(C8)，29.90(C6)，29.40(C5)，28.31(C9)，27.26(C7)，11.89(C10)。
然後，二胺基甲酸酯遙爪不飽和聚烯烴預聚合物，P(3ECOE)係如下之流程3所示般，使用對-甲苯磺醯肼作為一氫化催化劑氫化：
P(3ECOE)(1.5克，10毫莫耳之烯烴)、對-甲苯磺醯肼(3.74克，20毫莫耳)、三丁胺(4.75mL g，20毫莫耳)、小量之BHT(約5毫克)，及二甲苯(80毫升)之混合物迴流9小
時，然後，冷卻至室溫。反應混合物倒至甲醇內，且預聚合物沉澱。沉澱之預聚合物藉由傾析隔離，且藉由使用甲醇系統重複沉澱而純化。然後，預聚合物於50℃高度真空下乾燥，提供呈黏稠液體之PH(3ECOE)。
1H NMR(500MHz，CDCl3)：δ=δ 4.5(b，NH)，3.10(m，C(11)H)，1.45(s，C(12)H)，1.43-1.07(b，17H，-CH2-，-C(3)H-)，0.85(t，3H，-C(10)H3)。13C NMR(125MHz，CDCl3)：δ=38.98(C3)，33.34(C2，C4)，30.32(C6，C8)，29.91(C7)，26.88(C1，C5)，26.00(C9)，10.99(C10)。
氫化反應9小時後，達成95莫耳%轉化成飽和二胺基甲酸酯遙爪聚烯烴預聚合物，PH(3ECOE)。
依據如下之流程4進行飽和二胺基甲酸酯遙爪聚烯烴預聚合物，PH(3ECOE)之酸性去保護，形成官能性/反應性聚烯烴預聚合物，A-PH(3ECOE)：
PH(3ECOE)與二氯甲烷(0.5M)混合，且於室溫劇烈攪拌。三氯乙酸以每一第三丁氧基羰基保護基為5當量一
次地添加至溶液，且溶液於室溫攪拌5小時。此後，三乙胺(每一boc基團為5當量，即，1：1之三乙胺：三氟乙酸)一次地添加，且反應另外攪拌5分鐘。溶液於真空下濃縮至原始體積之1/3，然後，於甲醇中沉澱。然後，預聚合物於50℃之高度真空下乾燥，提供呈黏稠液體之A-PH(3ECOE)。
1H NMR(500MHz，CDCl3)：δ=δ 2.73(m，C(11)H)，1.45(s，C(12)H)，1.43-1.07(b，17H，-CH2-，-C(3)H-)，0.85(t，3H，-C(10)H3)。13C NMR(125MHz，CDCl3)：δ=38.98(C3)，33.34(C2，C4)，30.32(C6，C8)，29.91(C7)，26.88(C1，C5)，26.00(C9)，10.99(C10)。
表1提供不飽和及飽和之預聚合物與反應性聚烯烴之分子特徵及玻璃轉移溫度。
如以下流程5所示般，使用反應性聚烯烴(A-PH(3ECOE))，進行三個不同交聯反應。首先，反應性聚烯烴使用1,4-丁二醇二縮水甘油醚交聯，製備一經交聯之聚合物xD-A-PH(3ECOE)。
表2提供經交聯之聚合物xD-A-PH(3ECOE)之分子特徵。
於第二及第三交聯反應，如以下流程6所示般，三甲基丙烷三縮水甘油醚及三(2,3-環氧丙基)異氰脲酸酯被個別作為一交聯劑：
交聯劑及胺基-遙爪聚烯烴預聚合物於一加速混合器(DAC 150.1 FVZ，FlackTek Inc.)中以1800rpm，20個區段，每一者45秒而混合。然後，混合物緩慢轉移至一鐵弗隆模具內。然後，模具置入於100℃預熱之一烘箱內，且材料被固化16小時。獲得淡黃色透明熱固彈性體。三官能性交聯劑以3：2之聚合物對交聯劑的莫耳比例混合。於使用三(2,3-環氧丙基)異氰脲酸酯之範例，交聯劑溶於最小量之CH2Cl2，然後，於加速混合器內與聚合物混合。然後，混合物置於高度真空下於室溫72小時，至溶劑被移除為止。此後，施用一般交聯程序。
三甲基丙烷三縮甘油醚可自Sigma-Aldrich以一試劑級購得，其以1H NMR測量具有92%純度。三(2,3-環氧丙基)異氰脲酸酯可購自Sigma-Aldrich，具有98%純度。三(2,3-環氧丙基)異氰脲酸酯溶於二氯甲烷，其後用於交聯反應。圖1提供經交聯之聚合物，XT-A-PH(3ECOE)-2之應力應變測試曲線。圖2例示經交聯之聚合物，XT-A-PH(3ECOE)-2之動態機械性熱分析。
測試方法包括如下：數平均分子量(Mn)係藉由1H NMR端基分析判定。
分散性(Ð)係於25℃(以一10-點校正曲線為基準，使用聚苯乙烯標準物)，使用尺寸排除層析術(SEC)儀器，以THF作為移動相，以1毫升/分鐘之流動判定。使用之SEC儀器係裝設一RI Wyatt Optilab T-rEX檢測器。尺寸排除係以一個Waters Styragel保護管柱及三個連續Waters Styragel管柱(HR6，HR4及HR1)實施，其等係以剛性5μm苯乙烯二乙烯苯顆粒填充。此等管柱一起於100-10,000,000克/莫耳之分子量範圍提供有效之樣品分離。
示差掃瞄量熱術(DSC)係於以一銦標準物校正之一TA Instruments Discovery DSC上實施。具有4毫克最小質量之樣品於不透氣密封鋁盤中製備，且於N2下以10℃/分鐘之加熱速率分析。熱轉移溫度自第二加熱除去熱歷史而判定。
動態機械性溫度分析(DMTA)係以一8mm或25mm平行板幾何，使用ARES-G2流變計(TA Instruments)(ω=6.28rad/s，γ=0.05%)實施。實驗期間，溫度係以5℃/分鐘之速率增加。
固化彈性體之抗拉應變測試係於一Shimadzu AGS-X Instrument上進行。ASTM D1708微抗拉桿之抗拉性質係以127mm/分鐘之應變速率測試；所有數值係以至少四個樣品之平均值及標準偏差報導。
本發明可於未偏離其精神及基本特性下以其它型式實施，因此，於指示本發明範圍時，需參考所附申請專利範圍，而非前述說明書。
Claims (10)
- 一種製備聚烯烴反應性遙爪預聚合物之方法，包含：使烷基-順-環辛烯及選擇性之順-環辛烯於擁有二或更多個胺基基團之一多官能性鏈轉移劑存在中且於開環移位聚合反應條件下反應，以形成一個二胺基甲酸酯遙爪不飽和聚烯烴預聚合物，其中，該等二或更多個胺基基團係以一或多個保護基團保護；使該二胺基甲酸酯遙爪不飽和聚烯烴預聚合物部份氫化以製備一飽和聚烯烴二胺基甲酸酯遙爪預聚合物；及自該飽和聚烯烴二胺基甲酸酯遙爪預聚合物移除該一或多個保護基團。
- 如請求項1之方法，其中，該烷基-順-環辛烯係3-己基-順-環辛烯。
- 如請求項1或2之方法，其中，該鏈轉移劑係二第三丁基丁-2-烯-1,4-二基(E)-二胺基甲酸酯。
- 如請求項1之方法，其中，該移除該一或多個保護基團之步驟係藉由使二胺基甲酸酯遙爪聚烯烴預聚合物與一酸接觸而達成。
- 一種用於製備經交聯聚合物之方法，包含選擇性於缺乏一催化劑中，使如請求項1之一個二胺基遙爪飽和聚烯烴預聚合物與一或多個與該遙爪預聚合物具反應性之多官能性化合物接觸，形成一經交聯且選擇性經鏈延長之聚合物。
- 一種用於製備高分子量聚合物之方法，包含選擇性於缺乏一催化劑中，使如請求項1之一個二胺基遙爪飽和聚烯烴預聚合物與一或多個與該預聚合物具反應性之二官能性化合物接觸，形成一高分子量聚合物。
- 如請求項5之方法，其中，該一或多個多官能性化合物包含一多官能性環氧化物。
- 如請求項7之方法，其中，該多官能性環氧化物係一個二官能性環氧化物。
- 如請求項5或6之方法，其中，該一或多個多官能性化合物係選自由多元異氰酸酯類、多元羧酸類、多元醯基氯化物類，及多元環氧化物類所組成之群組。
- 一種聚合物，其係藉由請求項5至9中任一項之方法製備。
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| TWI735442B (zh) * | 2015-05-28 | 2021-08-11 | 美商陶氏全球科技有限責任公司 | 聚烯烴反應性遙爪預聚合物 |
| JP7124702B2 (ja) * | 2016-10-31 | 2022-08-24 | 日本ゼオン株式会社 | 架橋性組成物および架橋体 |
| CN113004516B (zh) * | 2021-03-09 | 2023-01-13 | 贵州大学 | α,ω-多烯单体易位聚合制备聚氨酯的方法及聚氨酯 |
| US20250034290A1 (en) * | 2021-12-06 | 2025-01-30 | Exxonmobil Chemical Patents Inc. | Functional Cyclic Olefin Polymer, Process for Obtaining the Same and Compositions Containing the Same |
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| TW201702282A (zh) * | 2015-05-28 | 2017-01-16 | 陶氏全球科技有限責任公司 | 聚烯烴反應性遙爪預聚合物 |
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| JP5881693B2 (ja) | 2010-06-29 | 2016-03-09 | スリーエム イノベイティブ プロパティズ カンパニー | アジリジニル含有化合物から生成されるグラフト化化合物 |
| US20130172493A1 (en) | 2011-12-30 | 2013-07-04 | Exxonmobil Research And Engineering Company | Process for making dendritic polyolefins from telechelic polycyclic olefins |
| SG11201605672PA (en) | 2014-01-14 | 2016-08-30 | Dow Global Technologies Llc | A process to produce polyolefin ionomers and ionomers produced thereby |
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| TW201702282A (zh) * | 2015-05-28 | 2017-01-16 | 陶氏全球科技有限責任公司 | 聚烯烴反應性遙爪預聚合物 |
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| TW201704285A (zh) | 2017-02-01 |
| JP6810707B2 (ja) | 2021-01-06 |
| CN107922593A (zh) | 2018-04-17 |
| US10563009B2 (en) | 2020-02-18 |
| WO2016191688A1 (en) | 2016-12-01 |
| US20180134840A1 (en) | 2018-05-17 |
| EP3303443A1 (en) | 2018-04-11 |
| BR112017024414B1 (pt) | 2022-01-11 |
| JP2021050354A (ja) | 2021-04-01 |
| KR20180034323A (ko) | 2018-04-04 |
| JP2018517031A (ja) | 2018-06-28 |
| BR112017024414A2 (pt) | 2018-07-24 |
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