TW201534652A - 嵌段共聚物 - Google Patents

嵌段共聚物 Download PDF

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Publication number
TW201534652A
TW201534652A TW103142956A TW103142956A TW201534652A TW 201534652 A TW201534652 A TW 201534652A TW 103142956 A TW103142956 A TW 103142956A TW 103142956 A TW103142956 A TW 103142956A TW 201534652 A TW201534652 A TW 201534652A
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Taiwan
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block copolymer
block
chain
group
forming
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TW103142956A
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TWI557173B (zh
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No-Jin Park
Jung-Keun Kim
Je-Gwon Lee
Sung-Soo Yoon
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Lg Chemical Ltd
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    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
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    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Abstract

本申請案提供嵌段共聚物和其應用。該嵌段共聚物具有極佳的自組裝性和相分離，且必需時，可自由地施加各種要求的功能。

Description

嵌段共聚物
本申請案係關於嵌段共聚物。
嵌段共聚物具有化學結構彼此不同的聚合物次單元藉共價鍵彼此連接之分子結構。嵌段共聚物能夠經由相分離而形成週期性排列的結構，如球、圓筒或積層。藉嵌段共聚物之自組裝而形成之結構的區域尺寸可調整於寬範圍內，並可製成各種結構形狀。因此，彼等可用於藉蝕刻而形成圖案的方法、各種磁性記錄介質或新一代奈米裝置(如金屬點、量子點或奈米線)、高密度磁性儲存介質等。
本申請案提供嵌段共聚物和其應用。
除非另外界定，否則文中所用“烷基”是指具1至20，1至16，1至12，1至8，或1至4個碳原子的烷基。烷基可具有直鏈、支鏈或環狀結構，且可任意地經至少一個取代基取代。
除非另外界定，否則文中所用“烷氧基”是指具1至20，1至16，1至12，1至8，或1至4個碳原子的烷基。烷氧基可具有直鏈、支鏈或環狀結構，且可任意地經至少一個取代基取代。
除非另外界定，否則文中所用“烯基或炔基”是指具2至20，2至16，2至12，2至8，或2至4個碳原子的烷基。烯基或炔基可具有直鏈、支鏈或環狀結構，且可任意地經至少一個取代基取代。
除非另外界定，否則文中所用“伸烷基”是指具1至20，1至16，1至12，1至8，或1至4個碳原子的伸烷基。伸烷基可具有直鏈、支鏈或環狀結構，且可任意地經至少一個取代基取代。
除非另外界定，否則文中所用“伸烯基或伸炔基”是指具2至20，2至16，2至12，2至8，或2至4個碳原子的伸烯基或伸炔基。伸烯基或伸炔基可具有直鏈、支鏈或環狀結構，且可任意地經至少一個取代基取代。
除非另外界定，否則文中所用“芳基或伸芳基”是指自包括一個苯環結構的化合物，或包括其中至少兩個苯環以共享的一或兩個碳原子或藉任意的連接基連接 之結構的化合物，或此化合物之衍生物，衍生之單價或二價取代基。除非另外界定，否則芳基或伸芳基可為具6至30，6至25，6至21，6至18，或6至13個碳原子的芳基。
文中所用“芳族結構”是指芳基或伸芳基。
除非另外界定，否則文中所用“脂環族結構”是指非芳環結構的環狀烴結構。除非另外界定，否則脂環族結構可為具3至30，3至25，3至21，3至18，或3至13個碳原子的結構。
文中所用“單鍵”是指在相關位置沒有原子的情況。例如，“A-B-C”所示結構中的“B”是單鍵的情況，意謂“B”位置沒有原子並因此而使得“A-C”所示結構係由“A”直接連接至“C”而形成。
可任意地取代烷基、烯基、炔基、伸烷基、伸烯基、伸炔基、烷氧基、芳基、伸芳基、鏈、芳族結構等之取代基可為羥基、鹵原子、羧基、環氧丙基、丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、巰基、烷基、烯基、炔基、伸烷基、伸烯基、伸炔基、烷氧基或芳基，但不限於此。
本申請案之例示嵌段共聚物可包括下式1所示嵌段。
式1中，X2是單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基，R1至R5各自獨立地為氫、具1至8個碳原子的烷基、或具9或更多個成鏈原子的直鏈，且R1至R5中之至少一者係具9或更多個成鏈原子的直鏈。
一個具體實施例中，式1的X2可為單鍵或氧原子；或可為單鍵，但不限於此。
式1中，R1至R5可以各自獨立地為氫、具1至8個碳原子的烷基、或包含9或更多個成鏈原子的直鏈。R1至R5中之至少一者可為包含9或更多個成鏈原子的直鏈。
一個具體實施例中，R1至R5中，R1、R2、R4和R5可以各自獨立地為氫或具1至8個碳原子的烷基；或可各自獨立地為氫或具1至4個碳原子的烷基；或可為氫；而R3可為具9或更多個成鏈原子的直鏈。
文中所用“成鏈原子”是指形成某些鏈的直鏈 結構之原子。此鏈可具有直鏈或支鏈結構；但是，成鏈原子的數目僅以形成最長直鏈的原子數計算。因此，其他原子如，在成鏈原子是碳原子的情況中，連接至碳原子的氫原子等未計入成鏈原子數。此外，在支鏈的情況中，成鏈原子數是形成最長鏈的原子數。例如，鏈為正戊基，所有的成鏈原子是碳原子且其數目為5。若鏈是2-甲基戊基，所有的成鏈原子亦為碳原子且其數目是5。成鏈原子可為碳、氧、硫或氮等且適當的成鏈原子可為碳、氧或氮；或碳或氧。成鏈原子的數目可為8或更高，9或更高，10或更高，11或更高，或12或更高。成鏈原子數可為30或更低，25或更低，20或更低，或16或更低。
式1的單元使得嵌段共聚物得以展現極佳的自組裝性。
一個具體實施例中，該鏈可為直鏈烴原子，如直鏈烷基。此情況中，烷基可為包括9或更高，9至30，9至25，9至20或9至16個碳原子的烷基。烷基的碳原子中之至少一個碳原子可任意地經氧原子取代；且烷基的至少一個氫原子可任意地經另一取代基取代。
任意地，直鏈烴基可包括至少一個雜原子。此雜原子可為氧原子或氮原子。
此鏈可為，例如，烷基、烷氧基或烷氧烷基。此情況中，烷基、烷氧基或烷氧烷基中之碳原子和氧原子的數目可為9或更高，9至30，9至25，9至20或9至16。
未特別限制可與第一嵌段一起含括於嵌段共聚物中的另一嵌段(下文中可稱為“第二嵌段”)。
例如，第二嵌段可為聚乙烯基吡咯烷酮嵌段、聚乳酸嵌段、聚乙烯基吡啶嵌段、聚苯乙烯嵌段(如聚苯乙烯嵌段或聚三甲基甲矽基苯乙烯)、聚伸烷化氧嵌段(如聚伸乙化氧嵌段)、或聚烯烴嵌段(如聚乙烯嵌段或聚異戊烯嵌段或聚丁二烯嵌段)。
一個具體實施例中，此第二嵌段可藉下式2表示。
此嵌段共聚物可進一步包含藉下式2表示的第二嵌段。
式2中，R1可為氫或烷基而R2可為烷基。
一個具體實施例中，式2的R1可為氫或具1至4個碳原子的烷基；或可為氫或甲基；或可為甲基。
一個具體實施例中，式2的R2可為包含1至20，1至16，1至12，1至8或1至4個碳原子的烷基。
未特別限制製造嵌段共聚物之明確方法，只要其包含藉由使用能夠形成嵌段的單體以形成嵌段共聚物 的至少一個嵌段的步驟即可。
例如，可藉活性自由基聚合反應(LPR)使用單體製造嵌段共聚物。例如，下列方法：陰離子聚合反應，其中，在無機酸鹽(如鹼金屬或鹼土金屬鹽)存在下，合成嵌段共聚物，此使用有機稀土金屬錯合物或有機鹼金屬化合物作為聚合反應引發劑；陰離子聚合反應，其中，在有機鋁化合物存在下，合成嵌段共聚物，此使用有機鹼金屬化合物作為聚合反應引發劑；原子轉移自由基聚合反應(ATRP)，此使用原子轉移自由基聚合劑作為聚合反應控制劑；藉電子轉移(ATGET)ATRP產生的活化劑進行聚合反應，此在生成電子的有機或無機還原劑存在下，使用原子轉移自由基聚合反應劑作為聚合反應控制劑；用於連續活化劑再生(ICAR)ATRP之引發劑；可逆加成-開環鏈轉移(RAFT)聚合反應，其使用無機還原劑可逆加成-開環鏈轉移劑；及使用有機鉈化合物作為引發劑之方法，而適當的方法可選自以上的方法。
一個具體實施例中，製造嵌段共聚物的方法可包括在自由基引發劑和活性自由基聚合反應劑存在下，藉活性自由基聚合反應，將包含能夠形成嵌段的單體之材料加以聚合。
在嵌段共聚物之製造中，未特別限制用於形成嵌段共聚物中所含括之其他嵌段及藉以上單體形成嵌段的方法，此其他嵌段可藉由考慮待形成的嵌段種類，選擇適當的單體而形成。
製造嵌段共聚物之方法可進一步包括令藉前述方法製得的聚合產物沉澱於非溶劑中。
可以考慮聚合效能，無特別限制地適當地選擇自由基引發劑的種類，且可以使用偶氮化合物(如偶氮基雙異丁腈(AIBN)或2,2’-偶氮基雙-(2,4-二甲基戊腈))或過氧化物化合物(如苄醯基過氧化物(BPO)或二-三級丁基過氧化物(DTBP))。
LPR可在例如下列溶劑中進行：二氯甲烷、1,2-二氯乙烷、氯苯、二氯苯、苯、甲苯、丙酮、氯仿、四氫呋喃、二噁烷、乙醇二甲醚(monoglyme)、二乙二醇二甲醚(diglyme)、二甲基甲醯胺、二甲亞碸或二甲基乙醯胺。
作為非溶劑，例如，可以無限制地使用醇化合物(如甲醇、乙醇、正丙醇或異丙醇)、二醇化合物(如乙二醇)、或醚化合物(如正己烷、環己烷、正庚烷或石油醚)。
由於嵌段共聚物包含經由共價鍵彼此連接的二或更多個聚合物鏈，所以其可以相分離。本申請案之嵌段共聚物展現極佳的相分離性質，需要時，可藉微相分離形成奈米尺寸結構。奈米尺寸結構的形狀或尺寸可藉嵌段共聚物的尺寸(分子量等)或嵌段的相對比控制。藉相分離形成的結構可包括球、圓柱、螺旋二十四面體、和層合物及相反結構，並將形成前述結構的能力稱為自組裝性。
此嵌段共聚物可具有，例如，在約3,000至 300,000範圍內的數量平均分子量(Mn)。文中所用“數量平均分子量”是指藉GPC(凝膠穿透層析法)測定，相對於聚苯乙烯標準品之轉化值。除非另外指出，否則文中所用“分子量”是指數量平均分子量。另一具體實施例中，分子量(Mn)可為，例如，3000或更高，5000或更高，7000或更高，9000或更高，11000或更高，13000或更高，或15000或更高。另一具體實施例中，此分子量(Mn)可為，例如，250000或更低，200000或更低，180000或更低，160000或更低，140000或更低，120000或更低，100000或更低，90000或更低，80000或更低，70000或更低，60000或更低，50000或更低，40000或更低，30000或更低，或25000或更低。此嵌段共聚物可具有在1.01至1.60之範圍內的多分散性(Mw/Mn)。另一具體實施例中，多分散性可為約1.1或更高，約1.2或更高，約1.3或更高，或約1.4或更高。
在以上範圍中，嵌段共聚物展現適當的自組裝性。可以考慮標的自組裝結構，控制嵌段共聚物的數量平均分子量等。
若嵌段共聚物至少包括第一和第二嵌段，則第一嵌段(例如，嵌段共聚物中之包括該鏈的嵌段)之比可在10莫耳%至90莫耳%範圍內。
本申請案係關於包括嵌段共聚物之聚合物層。此聚合物層可用於各種應用。例如，其可用於生物感知器、記錄介質(如快閃記憶體)、磁性記憶介質或圖案 形成方法或電力裝置或電子裝置等。
一個具體實施例中，聚合物層中之嵌段共聚物可藉自組裝物製成周期性結構，包括球、圓筒、螺旋二十四面體、或層合物。
例如，在嵌段共聚物中經由共價鍵連接至上述嵌段之第一嵌段或第二嵌段或其他嵌段的一個鏈段中，其他鏈段可形成規則結構，如層合形式、圓筒形式等。
本申請案亦係關於使用嵌段共聚物形成聚合物層之方法。此方法包括在基板上形成包括自組裝狀態之嵌段共聚物之聚合物層。例如，此方法包括藉由塗覆等方法在基板上形成嵌段共聚物層或塗覆液的層(其中，嵌段共聚物稀釋於適當溶劑，和需要時，接著老化或熱處理該層。
此老化或熱處理可基於，例如，嵌段共聚物的相轉變溫度或玻璃轉變溫度，進行，且例如，可於高於玻璃轉變溫度或相轉變溫度的溫度進行。未特別限制熱處理的時間，且熱處理可進行約1分鐘至72小時，但可因需要而改變。此外，聚合物層的熱處理溫度可為，例如，100℃至250℃，但可考慮此處所用嵌段共聚物而改變。
形成的層可在非極性溶劑和/或極性溶劑中於室溫下老化約1分鐘至72小時。
本申請案亦係關於形成圖案的方法。該方法包括從包括基板和形成於該基板上之包含自組裝的嵌段共聚物之聚合物層的層合物，選擇性地移除該嵌段共聚物中 的第一或第二嵌段。此方法可為在上述基板上形成圖案之方法。例如，此方法可包括在基板上形成聚合物層，選擇性地移除嵌段共聚物(其為聚合物層)中的一個嵌段或二或更多個嵌段；及之後蝕刻此基板。藉上述方法，例如，可形成奈米尺寸的微圖案。此外，根據聚合物層中之嵌段共聚物的形狀，可藉上述方法形成各種形狀的圖案(如奈米棍或奈米孔)。需要時，為形成圖案，嵌段共聚物可與另一共聚物或均聚物混合。可以無特別限制地選擇施用於此方法之基板的種類，且，例如，可施用氧化矽等。
例如，根據此方法，可形成具有高縱橫比之氧化矽的奈米尺寸圖案。例如，藉由在氧化矽上形成聚合物層，在聚合物層中的嵌段共聚物以預定結構形成的狀態下，選擇性地移除嵌段共聚物的任一嵌段，並以各種方法(例如，反應性離子蝕刻)蝕刻氧化矽，可形成各種類型的圖案(如奈米棍或奈米孔圖案)。此外，根據上述方法，可形成具有高縱橫比的奈米圖案。
例如，形成的圖案尺寸可為數十奈米，且此圖案可用於各種用途，包括下一代資訊電子磁記錄介質。
例如，藉上述方法，可形成以約6至80奈米的間隔配置之具有約3至40的寬度之奈米結構圖案(例如，奈米線)。另一具體實施例中，可得到例如，約3至40奈米直徑以約6至80奈米間隔排列的奈米孔結構。
此外，此結構中，可形成具有高縱橫比的奈米線或奈米孔。
此方法中，未特別限制選擇性地移除嵌段共聚物中之任何嵌段的方法，例如，可以使用藉照射適當的電磁波(例如，超紫外射線)於聚合物層以移除相對軟嵌段之方法。此情況中，用於超紫外射線的條件可以根據嵌段共聚物的嵌段類型而決定，且具有約254奈米的波長之超紫外射線可照射1至60分鐘。
此外，超紫外射線照射之後，聚合物層可經酸處理以進一步移除被超紫外射線破壞的鏈段。
此外，對使用自彼選擇性地移除嵌段之聚合物層之基板進行蝕刻處理，此可藉由使用CF4/Ar離子藉反應性離子蝕刻進行，且在上述方法之後，可進一步藉氧電漿處理而自基板移除聚合物層。
本申請案提供嵌段共聚物和其應用。該嵌段共聚物具有極佳的自組裝性和相分離，且必需時，可自由地施加各種要求的功能。
圖1出示藉AFM觀察實例1之共聚物之結構。
圖2出示藉AFM觀察實例2之共聚物之結構。
下文中，將參考實例和比較例，詳細描述本申請案，但本申請案之範圍未限於以下實例。
1. NMR分析
藉由使用包括具有三重共振5mm探頭的Varian Unity Inova(500MHz)光譜儀之NMR光譜儀，於室溫進行NMR分析。待分析的樣品稀釋於用於NMR分析的溶劑(CDCl3)中至約10mg/ml的濃度之後，進行分析，化學位移(δ)以ppm表示。
<縮寫>
br=寬訊號，s=單峰，d=二重峰，dd=兩個二重峰，t=三重峰，dt=兩個三重峰，q=四重峰，p=五重峰，m=多重峰
2. GPC(凝膠穿透層析)
藉GPC(凝膠穿透層析)測定數量平均分子量和多分散性。
<GPC測定條件>
裝置：Agilent technologies,Co.的1200系列
管柱：使用Polymer laboratories,Co.，的PLgel mixed B中之二者
溶劑：THF
管柱溫度：35℃
樣品濃度：1mg/mL，注射200L
標準樣品：聚苯乙烯(Mp：3900000， 723000，316500，52200，31400，7200，3940，485)
實例或比較例之待測定的嵌段共聚物或巨分子引發劑置於5mL小瓶中，之後稀釋至約1mg/mL的濃度。之後，用於校正的標準樣品和待分析的樣品藉注射濾器(孔尺寸：0.45微米)過濾並於之後分析。使用得自Agilent technologies,Co.，的ChemStation作為分析程式。藉由比較樣品的沖提時間和校正曲線，得到數量平均分子量(Mn)和重量平均分子量(Mw)，之後自其比值(Mw/Mn)得到多分散性(PDI)。
製備例1. 對-十二碳烷基苯乙烯(A)之合成
對-十二碳烷基苯乙烯之合成如下。藉由將4-溴苯乙烯(5.0g，27.3mmole)和Mg屑(0.064g，27.31mmole)置於100mL瓶中；將其溶於已除水的30mL四氫呋喃中；添加少量碘作為觸媒；之後在室溫於氮下攪拌約6小時以使其反應，製得格林納試劑。1-溴十二碳烷置於另一100mL瓶中，之後，緩慢添加上述合成的格林納試劑於0℃。之後，將四氯銅酸(II)二鋰溶液(8.2mL，0.92mmole)加至其中，此瓶受熱至室溫且混合物藉攪拌3小時而反應。反應之後，移除四氫呋喃，標的化合物在管柱層析法中，使用己烷作為流動相而加以純化，並藉此得到透明的液態標的化合物(2.54g，9.32mmole)。
<NMR分析結果>
1H-NMR(CDCl3)：δ7.33(dd,2H)；δ7.14(dd, 2H)；δ6.70(dd,1H)；δ5.71(d,1H)；δ5.18(d,1H)；δ2.59(t,2H)；δ1.60(p,2H)；δ1.31-1.26(m,18H)；δ0.89(t,3H)
製備例2. 對-十二碳烷氧基甲基苯乙烯(B)之合成
對-十二碳烷氧基甲基苯乙烯(B)之合成如下。將4-氯甲基苯乙烯(22.1g，144.8mmole)和1-十二碳醇(30.0g，160.1mmole)溶於300mL四氫呋喃中，之後冷卻至0℃。將氫化鈉(NaH)(7.7g，320.8mmole)加至其中；藉由攪拌1小時，使此混合物反應；此混合物加熱至70℃並於之後反應24小時。反應之後，反應產物冷卻至室溫，藉由與小量水在冰水中反應而移除剩餘的氫化鈉，並藉過濾移除固體。移除作為反應溶劑的四氫呋喃；使用二氯甲烷/二度純化的水，藉分步萃取收集有機層，藉管柱層析法，使用己烷/二氯甲烷作為流動相，得到透明液態標的化合物(23.9g，79.0mmole)。
<NMR分析結果>
1H-NMR(CDCl3)：δ7.39(dd,2H)；δ7.30(dd,2H)；δ 6.71(dd,1H)；δ5.74(d,1H)；δ5.23(d,1H)；δ4.49(s,2H)；δ3.46(t,2H)；δ1.61(p,2H)；δ1.37-1.26(m,16H)；δ0.89(t,3H)
實例1
藉由令甲基丙烯酸甲酯與RAFT(可逆式加成-裂片鏈轉移劑)試劑和作為熱引發劑的AIBN(偶氮基 雙異丁腈)反應，合成巨分子引發劑(數量平均分子量(Mn)：7000，多分散性(PDI)：1.16)。合成的巨分子引發劑、製備例1中製備的化合物(A)和偶氮基雙異丁腈(AIBN)以重量比1：70：0.5(巨分子引發劑：化合物(A)：AIBN)溶於甲苯中(溶劑：20重量%)，之後在氮氣下於80℃反應16小時，藉此製得嵌段共聚物。此嵌段共聚物的數量平均分子量為19200，且多分散性為1.17。
實例2
藉與實例1中所述之相同的方法合成巨分子引發劑(數量平均分子量(Mn)：8400，多分散性(PDI)：1.15)，及之後藉與實例1中所述之相同的方法製備嵌段共聚物，但使用製備例2中的化合物(B)代替製備例1中的化合物(A)。此嵌段共聚物的數量平均分子量為21900，且多分散性為1.19。
試驗例1
使用旋轉塗覆機，於3000rpm，60秒鐘，將實例1或2的嵌段共聚物以約1.0重量%溶於甲苯中所製得的塗覆液塗覆於矽晶圓上，形成聚合物層。此聚合物層於160℃進行1小時的熱處理，藉此於其表面實現奈米結構。藉AFM(原子力顯微鏡)觀察所實現的奈米結構。圖1為實例1的結果而圖2為實例2的結果。

Claims (14)

  1. 一種嵌段共聚物，其包含下式1所示的第一嵌段： 其中X2是單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基，R1至R5各自獨立地為氫、具1至8個碳原子的烷基或具9或更多個成鏈原子的直鏈，且R1至R5中之至少一者係具9或更多個成鏈原子的直鏈。
  2. 如申請專利範圍第1項之嵌段共聚物，其中X2是單鍵或氧原子。
  3. 如申請專利範圍第1項之嵌段共聚物，其中該直鏈包含9至20個成鏈原子。
  4. 如申請專利範圍第1項之嵌段共聚物，其中該成鏈原子係碳、氧、氮或硫。
  5. 如申請專利範圍第1項之嵌段共聚物，其中該成鏈原子是碳或氧。
  6. 如申請專利範圍第1項之嵌段共聚物，其中該直鏈包含至少一個雜原子。
  7. 如申請專利範圍第6項之嵌段共聚物，其中該雜原子是氧原子。
  8. 如申請專利範圍第1項之嵌段共聚物，其中該直鏈是烷基、烷氧基或烷氧烷基。
  9. 如申請專利範圍第1項之嵌段共聚物，其進一步包含下式2所示的第二嵌段： 其中R1是氫或烷基且R2是烷基。
  10. 如申請專利範圍第9項之嵌段共聚物，其中式2的R1是具1至4個碳原子的烷基。
  11. 如申請專利範圍第9項之嵌段共聚物，其中式2的R2是具1至4個碳原子的烷基。
  12. 一種聚合物層，其包含如申請專利範圍第1項之嵌段共聚物的自組裝產物。
  13. 一種形成聚合物層之方法，其包括形成包含如申請專利範圍第1項之嵌段共聚物的自組裝產物之聚合物層。
  14. 一種形成圖案之方法，其包含從包括基板和形成於該基板上之包含如申請專利範圍第1項之嵌段共聚物的自組裝產物之聚合物層的層合物，選擇性地移除該嵌段共 聚物中的第一嵌段或不同於該第一嵌段的第二嵌段。
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