TW202337931A - 一種共軛二烯系聚合物的製造方法及其得到之聚合物、橡膠及輪胎 - Google Patents
一種共軛二烯系聚合物的製造方法及其得到之聚合物、橡膠及輪胎 Download PDFInfo
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- TW202337931A TW202337931A TW111147382A TW111147382A TW202337931A TW 202337931 A TW202337931 A TW 202337931A TW 111147382 A TW111147382 A TW 111147382A TW 111147382 A TW111147382 A TW 111147382A TW 202337931 A TW202337931 A TW 202337931A
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- Prior art keywords
- conjugated diene
- diene polymer
- compound
- grams
- rubber
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- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- SGAOTOMUHFNBAR-UHFFFAOYSA-N strontium;2-methylpropan-2-olate Chemical compound [Sr+2].CC(C)(C)[O-].CC(C)(C)[O-] SGAOTOMUHFNBAR-UHFFFAOYSA-N 0.000 description 1
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- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
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- VTWDHPGFWOGSGR-UHFFFAOYSA-N trimethyl-(1-trimethylsilyl-2,4-dihydro-1,3,5-triazin-3-yl)silane Chemical compound C[Si](N1CN(CN=C1)[Si](C)(C)C)(C)C VTWDHPGFWOGSGR-UHFFFAOYSA-N 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
本發明為有關一種共軛二烯系聚合物的製造方法,共軛二烯系聚合物為經由起始劑與共軛二烯單體或共軛二烯單體與乙烯基芳香烴單體進行聚合反應得到,其中起始劑為式(1)表示之類二乙烯基芳香烴化合物與有機鹼金屬反應得到;A與B為C
nH
2n+1或芳香環,n為0~5,A與B可相同或不相同,Q為芳香環;其中類二乙烯基芳香烴化合物與有效活性之有機鹼金屬的莫耳比例為1.3~5.0。本發明進一步為有關於一種包含該共軛二烯系聚合物的橡膠,以及一種包含該橡膠之輪胎。
Description
本發明為有關於一種共軛二烯系聚合物的製造方法及其得到之聚合物、包含該共軛二烯系聚合物的橡膠、以及包含該橡膠之輪胎。
溶聚丁苯橡膠(solution styrene butadiene rubber, SSBR)為丁二烯單體與苯乙烯單體所組成共軛二烯聚合物。溶聚丁苯橡膠首先由美國Phillips公司提出批次式製程及Firestone公司提出連續式製程,並率先實現工業化生產。由於溶聚丁苯橡膠具有比乳聚丁苯橡膠(emulsion styrene butadiene rubber,ESBR)更優異的機械性能和滾動阻力,因而更能廣泛應用於汽車工業及其他橡膠製品。為使橡膠材料能有更好的性能,業界持續努力改善共軛二烯聚合物的特性。
美國專利US 8946339 B2及歐洲專利EP 2338919 B1提供一種改性共軛二烯系聚合物,其在共軛二烯系聚合物的末端部上具有經一或多個烷氧基取代的矽烷基及一或多個氮原子。改性共軛二烯系聚合物為藉由使共軛二烯系聚合物的聚合活性末端與具有經二或多個烷氧基取代的矽烷基及一或多個氮原子的化合物發生反應得到;共軛二烯系聚合物為藉由使用多官能陰離子聚合起始劑,使共軛二烯化合物聚合或者使共軛二烯化合物與芳香族乙烯基化合物共聚得到;多官能陰離子聚合起始劑為在聚乙烯基芳香族化合物與有機鋰化合物(指聚乙烯基芳香族化合物/有機鋰化合物)的莫耳比例(molar ratio)為0.05~1.0範圍的條件下製備。
美國專利US 6221975 B1提供一種雙末端官能化無序共聚物的製備方法,其包含:在非極性烴溶劑存在下,基於雙官能有機鋰起始劑的兩個陰離子末端之一,由芳香族乙烯基單體及共軛二烯單體形成無序共聚物;隨後將極性材料及親電子材料添加到此活性聚合物中,如此可獲得在聚合物兩個末端具有官能基的共聚物。
美國專利US 6455651提供一種陰離子聚合單體的方法,其包含使單體與官能陰離子聚合起始劑(經有機取代的鹼金屬化合物)接觸,其改良包含每當量的鹼金屬化合物添加0.1至1.0當量的金屬烷基化合物,其中金屬烷基化合物的烷基為選自其不會與鹼金屬化合物的有機取代基進行交換者,其中鹼金屬化合物的有機取代基為脂肪族、脂環族、芳香族或經烷基取代的芳香族。
美國專利US 6562923提供一種製備可用於陰離子聚合中二鋰化起始劑的方法,其包含:在二胺存在下,在脂肪族或脂環族烴溶劑中使帶有兩個雙鍵的二烯基苯與第二丁基鋰反應,使得二烯基苯對第二丁基鋰的莫耳比例基本上等於0.5以形成二鋰化起始劑,其中該起始劑為二結合物(bi-adduct),即二烯基苯的兩個雙鍵的每一者上分別加成有第二丁基鋰的分子。
上述先前技術所揭示帶有陰離子末端的雙官能有機鋰起始劑,其二乙烯基芳香烴與有機鹼金屬的莫耳比例在0.05~1.0的範圍內,使用聚合反應所得到共軛二烯系聚合物於製備橡膠,橡膠有滾動阻力較小致抓地性較差、拉伸強度及撕裂強度較低致抗變形性較差、剛度較低及耐磨耗較差等諸多缺點,對於汽車工業及其他橡膠製品所需的機械性質明顯不足,此為業界所亟欲改善的問題。
有鑑於上述,本發明提供一種共軛二烯系聚合物的製造方法,其加入類二乙烯基芳香烴化合物與有機鹼金屬反應得到起始劑,當類二乙烯基芳香烴化合物與有效活性之有機鹼金屬的莫耳比例為1.3~5.0時,本發明驚訝地發現,相較於未添加類二乙烯基芳香烴化合物或添加量不足的情形,可得到在滾動阻力、斷裂拉伸強度與斷裂延伸率的乘積、撕裂強度及剛度各機械性質均明顯優異的橡膠。
於一方面,本發明提供一種共軛二烯系聚合物的製造方法,包含:步驟(a):將式(1)表示之類二乙烯基芳香烴化合物與有機鹼金屬反應得到起始劑,其中A與B為C
nH
2n+1或芳香環,n為0~5,A與B可相同或不相同,Q為芳香環,其中類二乙烯基芳香烴化合物與有效活性之有機鹼金屬的莫耳比例為1.3~5.0;及
(1)
步驟(b):將起始劑與共軛二烯單體或共軛二烯單體與乙烯芳香族單體進行聚合反應。
於另一方面,本發明提供一種共軛二烯系聚合物,其為以前述之製造方法得到。
又於另一方面,本發明提供一種橡膠,包含前述之共軛二烯系聚合物。
再於另一方面,本發明提供一種輪胎,其含有前述之橡膠。
為使本發明及其所要主張的申請專利範圍能被充分地理解,以下將示範本發明之較佳實施例。為避免模糊本發明之內容,以下說明可能會省略習知的元件、相關材料、及其相關處理技術。以下所述僅為本發明之較佳實施例而已,並非用以限定本發明之申請專利範圍;凡其它未脫離本發明所揭示之精神下所完成之等效改變或修飾,均應包含在下述之申請專利範圍內。
共軛二烯系聚合物的製造方法
本發明提供一種共軛二烯系聚合物的製造方法,係利用陰離子聚合法得到共軛二烯系聚合物。所謂陰離子聚合法係指利用起始劑形成活性碳陰離子,在加入單體後與活性碳陰離子行加成聚合反應,形成分子鏈末端帶有負電荷的聚合物,再加入終止劑終止反應,以獲得聚合物,較佳採用批次式絕熱製程。前述製造方法包含:
步驟(a):將式(1)表示之類二乙烯基芳香烴化合物與有機鹼金屬反應得到一起始劑,其中A與B為C
nH
2n+1或芳香環,n為0~5,A與B可相同或不相同,Q為芳香環;其中類二乙烯基芳香烴化合物與有效活性之有機鹼金屬的莫耳比例為1.3~5.0;及
(1)
步驟(b):將起始劑與共軛二烯單體或共軛二烯單體與乙烯芳香族單體進行聚合反應得到共軛二烯系聚合物。共軛二烯系聚合物可為嵌段共聚物或無序共聚物。
類二乙烯基芳香烴化合物中,取代基A、B及/或Q可為芳香環,包括取代或未經取代的單環、多環或稠合多環,舉例而言,可獨立地選自以下項目所組成的群組:經取代或未經取代的苯、萘、蒽、菲、芴、并四苯、芘、聯苯、三聯苯、四聯苯、䓛、三伸苯、苝、茚及上述各項之任何組合或組合稠環。其中,較佳為苯。類二乙烯基芳香烴化合物,舉例而言,可獨立地選自以下項目所組成的群組:間-二乙烯基苯、對-二乙烯基苯、1,2-二異丙烯基苯、1,3-二異丙烯基苯、1,4-二異丙烯基苯、1,3-二乙烯基萘、1,8-二乙烯基萘、1,4-二乙烯基萘、1,5-二乙烯基萘、2,3-二乙烯基萘、2,7-二乙烯基萘、2,6-乙烯基萘、4,4'-二乙烯基聯苯、4,3'-二乙烯基聯苯、4,2'-二乙烯基聯苯、3,2'-二乙烯聯苯、3,3'-二乙烯基聯苯、2,2'-二乙烯基聯苯、2,4-二乙烯基聯苯、1,2-二乙烯基-3,4-二甲基苯、1,3-二乙烯基-4,5,8-三丁基萘、2,2'-二乙烯基-4-乙基-4'-丙基聯苯及上述各項之任何組合。其中,較佳為1,3-二異丙烯基苯或對-二乙烯基苯。
有效活性之有機鹼金屬的莫耳數,係指參與反應之有機鹼金屬的莫耳數,而非添加至反應器之有機鹼金屬的莫耳數,可通過凝膠滲透層析儀(Gel Permeation Chromatography, GPC)得到。
有機鹼金屬,可舉出甲基鋰、乙基鋰、正丙基鋰、異丙基鋰、正丁基鋰、仲丁基鋰、叔丁基鋰、異丁基鋰、正戊基鋰、正己基鋰、苄基鋰、苯基鋰、甲苯基鋰及其所有異構物、萘基鋰、二苯乙烯鋰(stilbenelithium)等一元有機鋰化合物(monoorganic lithium compound);1,4-二鋰丁烷、1,5-二鋰戊烷、1,2-二鋰二苯基乙烷、1,4-二鋰-1,1,4,4-四苯基丁烷、1,3-或1,4-二(1-鋰-3-甲基戊基)苯、萘二鋰、二鋰己基苯、1,4-二鋰代-2-乙基環己烷、1,3,5-三鋰代苯、1,3,5-三(鋰代甲基)苯;萘基鈉等有機鈉化合物;萘基鉀、乙氧基鉀等有機鉀化合物;二甲基氨基鋰、二己基氨基鋰、二異丙基氨基鋰和六亞甲基亞氨基鋰等具有氮-鋰鍵的化合物(金屬醯胺化合物 metal amide compound)。該金屬醯胺化合物,優選為烷基鋰、芳香族鋰等鋰化合物與仲胺化合物的反應產物。作為該仲胺化合物,可舉出二甲胺、二乙胺、二丙胺、二丁胺、二己胺、二苄胺、十二亞甲基亞胺、N,N'-二甲基-N'-三甲基甲矽烷基-1,6-二氨基己烷、呱啶、吡咯烷、六亞甲基亞胺、七亞甲基亞胺、二環己胺、N-甲基苄胺、二-(2-乙基己基)胺、二烯丙基胺、嗎啉、N-(三甲基甲矽烷基)呱嗪、N-(叔丁基二甲基甲矽烷基)呱嗪、1,3-雙三甲基甲矽烷基-1,3, 5-三嗪烷等。作為有機鹼土金屬化合物,可以舉出二正丁基鎂、二正己基鎂、二乙氧基鈣、硬脂酸鈣、二硬脂酸鈣、二叔丁氧基鍶、二乙氧基鋇、二異丙氧基鋇、二乙基巰基鋇(diethyl mercapto barium)、二叔丁氧基鋇、二苯氧基鋇、二硬脂酸鋇和二羰游離基鋇(diketyl barium)等。該等聚合起始劑可單獨使用或組合二種以上使用,其中鋰化合物是較佳的選擇。其中,較佳為正丁基鋰及仲丁基鋰。
共軛二烯單體,可為含4個至12個碳原子的共軛二烯,具體例子包括:1,3-丁二烯、1,3-戊二烯、1,3-己二烯、1,3-庚二烯、2-甲基-1,3-丁二烯(異戊二烯)、2-甲基-1,3-戊二烯、2-己基-1,3-丁二烯、2-苯基-1,3-丁二烯、2-苯基-1,3-戊二烯、2-對甲苯基-1,3-丁二烯、2-苄基-1,3-丁二烯(2-benzyl-1,3-butadiene)、3-甲基-1,3-戊二烯、3-甲基-1,3-己二烯、3-丁基-1,3-辛二烯、3-苯基-1,3-戊二烯、4-甲基-1,3-戊二烯、1,4-二苯基-1,3-丁二烯(1,4-diphenyl-1,3-butadiene)、2,3-二甲基-1,3-丁二烯、2,3-二甲基-1,3-戊二烯、2,3-二苄基-1,3-丁二烯(2,3-dibenzyl-1,3-butadiene)、4,5-二乙基-1,3-辛二烯、月桂烯(myrcene),及其上述各項之任何組合。其中1,3-丁二烯及異戊二烯是較佳的選擇。
適用於本發明之乙烯芳香族單體,具體例子包括:苯乙烯、甲基苯乙烯及其所有異構物、乙基苯乙烯及其所有異構物、叔丁基苯乙烯及其所有異構物、二甲基苯乙烯及其所有異構物、甲氧基苯乙烯及其所有異構物、環己基苯乙烯及其所有異構物、乙烯基聯苯、1-乙烯基-5-己基萘、乙烯基萘、乙烯基蒽、2, 4-二異丙基苯乙烯、5-叔丁基-2-甲基苯乙烯、二乙烯基苯、三乙烯基苯、二乙烯基萘、叔丁氧基苯乙烯、4-丙基苯乙烯、4-十二烷基苯乙烯、2-乙基-4-苄基苯乙烯(2-ethyl-4-benzylstyrene)、4-(苯基丁基)苯乙烯、N-4-乙烯基苯基-N,N-二甲胺、(4-乙烯基苯基)二甲基氨基乙基醚、N,N-二甲基氨基甲基苯乙烯、N,N-二甲基氨基乙基苯乙烯、N,N-二乙基氨基甲基苯乙烯、N,N-二乙基氨基乙基苯乙烯、乙烯基二甲苯、乙烯基吡啶、二苯基乙烯、2,4,6-三甲基苯乙烯、α-甲基-2,6-二甲基苯乙烯、α-甲基-2,4-二甲基苯乙烯、β-甲基-2,6-二甲基苯乙烯、β-甲基-2,4-二甲基苯乙烯、茚、含有叔氨基的二苯基乙烯,如l-(4-N,N-二甲基氨基苯基)-1-苯基乙烯,及其上述各項之任何組合。其中苯乙烯或甲基苯乙烯及其所有異構物是較佳的選擇。
關於步驟(a),在一具體實例中,類二乙烯基芳香烴化合物與有機鹼金屬為混合在溶劑中反應,聚合反應合適的溶劑如鈍性有機溶劑,該鈍性有機溶劑意為在聚合反應中不會參與反應的溶劑,此類溶劑包含正丁烷、異丁烷、正戊烷、異戊烷、2,2,4-三甲基戊烷、異己烷、正己烷、異庚烷、正庚烷、異辛烷、正辛烷、正癸烷等脂肪族碳氫化合物;或者像環己烷、甲基環己烷、乙基環己烷、環戊烷、環庚烷、甲基環戊烷、甲基環庚烷等環烷族化合物;或者苯、甲苯、二甲苯、乙苯、二乙苯及丙苯等芳香烴化合物。該等鈍性有機溶劑可單獨使用或組合二種以上使用。其中環己烷是較佳的選擇。在另一具體實例中,一部分之類二乙烯基芳香烴化合物與有機鹼金屬反應一段時間後,再加入剩餘部分之類二乙烯基芳香烴化合物繼續反應另一段時間。在另一具體實例中,類二乙烯基芳香烴化合物於溶劑中之濃度為0.001~20wt%。在另一具體實例中,反應於溫度為0~60℃下進行,較佳為提升溫度至55℃~60℃下進行,溫度操控方法可使用絕熱反應方式,也可採用恆溫控制,或者採用部分冷卻方式。
在一般情況下,若單純使用鈍性有機溶劑作為溶劑,乙烯基芳香族單體與共軛二烯單體的聚合速率差異相當大,可藉由在步驟(b)中加入極性溶劑的方式克服。在一具體實例中,可加入環醚化合物及/或二醚化合物,環醚化合物可為單環醚化合物或雙環醚化合物,舉例而言,單環醚化合物可獨立地選自以下項目所組成的群組:四氫呋喃、呋喃、四氫吡喃、2-甲基-四氫吡喃、3-甲基-四氫吡喃、冠醚(crown ethers)(如12-冠-4醚(12-crown-4 ether)、15-冠-5醚(15-crown-5 ether)或18-冠-6醚(18-crown-6 ether))、1,4-二噁烷及上述各項之任何組合;雙環醚化合物可為2,2-二(2-四氫呋喃基)丙烷;二醚化合物可獨立地選自以下項目所組成的群組:二乙基醚、二正丙基醚、二正丁基醚、乙二醇二丁醚、乙二醇二乙醚、乙二醇二甲醚、二乙二醇二丁醚、二乙二醇二乙醚、二乙二醇二甲醚、甲基正丙基醚、二異丙基醚、三級戊基乙基醚、甲基三級丁基醚或乙基三級丁基醚及上述各項之任何組合。其中,四氫呋喃、二乙基醚、乙二醇二甲醚及乙二醇二乙醚是較佳的選擇。在另一具體實例中,可在步驟(a)中加入有機鹼金屬之前,加入環醚化合物及/或二醚化合物與類二乙烯基芳香烴化合物進行混合。
在一具體實例中,本發明之共軛二烯系聚合物的製造方法更包含步驟(c):於步驟(b)之後加入含矽改性劑。加入矽改性劑的目的在於透過共價鍵、氫鍵等鍵結或凡得瓦力等作用力,增加共軛二烯系聚合物與各種添加劑之間的作用力。含矽改性劑具有甲矽烷的結構,可藉由其上4個共價鍵位置中一或多個與有機鹼金屬反應並結合於共軛二烯系聚合物上。含矽改性劑與有效活性之有機鹼金屬之莫耳比例為1.3~5.0,較佳為1.4~3.5,更佳為1.5~2.5。
含矽改性劑結構如式(2)所示:
(2),
其中A
1、A
2及A
3為烷類、烷氧類或是鹵素,烷類或烷氧類的碳數為C1-C5,A
1、A
2及A
3中至少二者是烷氧類或鹵素,X基團為含有氮、氧、硫或磷原子中之一種或多種的基團,n為1~10。較佳為4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉(4-{3-[dimethoxy(methyl)silyl]propyl}morpholine) 或3-(三甲氧基甲矽烷基)-N,N-二甲基丙-1-胺(3-(trimethoxysilyl)-N,N-dimethylpropan-1-amine)。
共軛二烯系聚合物
本發明亦提供一種共軛二烯系聚合物,係利用本發明之共軛二烯系聚合物的製造方法得到。依據本發明之各實施例,共軛二烯系聚合物的門尼黏度之範圍為20~100,較佳為30~75,更佳為30~65。共軛二烯系聚合物的玻璃轉移溫度之範圍為-15~ -70℃,較佳為-20~ -65℃。
依據本發明之各實施例,共軛二烯系聚合物以凝膠滲透層析儀(GPC)量測具有m個波峰之特徵(m為大於或等於1),第一波峰(Mi)表示最低的重均分子量為5×10
4至150×10
4g/mole,較佳為10×10
4至150×10
4g/mole,更佳為15×10
4至150×10
4g/mole。
依據本發明之各實施例,共軛二烯系聚合物之重均分子量為15×10
4至200×10
4g/mole,較佳為20×10
4至180×10
4g/mole,更佳為25×10
4至180×10
4g/mole。
共軛二烯系聚合物之應用
本發明亦提供一種橡膠,可藉由本發明之共軛二烯系聚合物與其他成分混合得到。其他成分的具體實例包含乳聚苯乙烯-丁二烯共聚物、聚丁二烯橡膠、丁二烯-異戊二烯共聚物及丁基橡膠。在一具體實例中,更包含天然橡膠、乙烯-丙烯共聚物及乙烯-辛烯共聚物。上述組成可以兩種或多種型式的混合應用。橡膠之組成可為,當全部成分的總量為100重量份時,共軛二烯系聚合物的含量較佳為至少10重量份,且更佳為至少20重量份。
再者,本發明之橡膠也可含有添加劑。添加劑之具體實例包含硫化劑,例如硫;硫化促進劑,例如噻唑基(thiazole-based)硫化促進劑、秋蘭姆基(thiuram-based)硫化促進劑或次磺醯胺基(sulfenamide-based)硫化促進劑;硫化活化劑,例如硬脂酸或氧化鋅;有機過氧化物;補強劑,例如白煙或碳黑;填充劑例如碳酸鈣或滑石;矽烷偶合劑;填充油;加工助劑;抗氧化劑;及潤滑劑等。在一具體實例中,添加劑更包含二氧化矽、填充油、抗氧化劑、硬脂酸、蠟、硫化促進劑、加工促進劑及碳黑中至少一個或及其組合。
本發明之橡膠可藉由將本發明之共軛二烯系聚合物與其他成分及/或添加劑混合得到,可使用習知的混合器,例如滾輪、萬馬力密閉式批量混合機(Banbury mixer)或密煉機(internal mixer)用以捏合(knead)各組成。關於捏合條件,除了硫化劑或硫化促進劑外,當混合其他添加劑時,捏和溫度通常為50℃至200℃,較佳為80℃至150℃,並且捏和時間通常為30秒至30分鐘,較佳為1分鐘至30分鐘。當硫化劑或硫化促進劑混合時,捏和溫度通常不超過100℃,較佳為25℃至90℃。由硫化劑或硫化促進劑混合的組成可使用例如壓力硫化(press vulcanization)的硫化處理方式加以實施,硫化處理溫度通常為120℃至200℃,較佳為140℃至180℃。
本發明之橡膠可使用於輪胎、鞋底、地板材料及震動阻絕材料等,並且特別適合用於輪胎,以增進輪胎胎面的低滾動阻力及促進抗濕滑,進而提升操縱穩定性及可靠度。
藉由以下實施例詳細說明本發明之共軛二烯系聚合物的製造方法及得到的共軛二烯系聚合物,尤其是一種苯乙烯-丁二烯共聚物的製造方法及得到的苯乙烯-丁二烯共聚物。
實施例1
實例1-1
預起始反應:於室溫(27℃)將1克1,3-二異丙烯基苯加入含有1克四氫呋喃與0.25克乙二醇二乙醚之20克環己烷溶液中,再加入15克正丁基鋰(5wt%環己烷溶液)反應30分鐘後,得到起始劑並冰存於4℃環境中。
聚合反應:將預起始反應得到的起始劑及0.2克1,3-二異丙烯基苯混和於5525克環己烷中,並加入10克四氫呋喃與2.5克乙二醇二乙醚反應15分鐘,再加入665克1,3-丁二烯與200克苯乙烯進行聚合。在聚合溫度到達60℃後15分鐘,加入35克1,3-丁二烯反應5分鐘,再加入1.4克4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉並反應30分鐘,最後加入0.5克甲醇使反應終了。
實例1-2、實例1-3以相同於實例1-1的步驟進行反應,差異僅在於1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量。更詳言之,在實例1-2中,1,3-二異丙烯基苯在預起始反應階段的添加量為1克,在聚合反應階段的添加量為0.7克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.5克;在實例1-3中,1,3-二異丙烯基苯在預起始反應階段的添加量為1克,在聚合反應階段的添加量為0.4克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.1克。
實施例1之優點在於:將起始劑預先冰存,等到進行聚合反應時再使用,可在聚合反應階段時,減少1,3-二異丙烯基苯混合於環己烷溶液中的反應時間,進而提升產量。
實施例2
實施例2與實施例1之不同點在於:在製備起始劑後,實施例2隨即進行聚合反應,而實施例1則將起始劑冰存。
實例2-1
於室溫(27℃)將0.8克1,3-二異丙烯基苯混合於含有10克四氫呋喃與2.5克乙二醇二乙醚之5525克環己烷溶液中,再加入20克正丁基鋰(5wt%環己烷溶液)混合反應60分鐘後,加入665克1,3-丁二烯與200克苯乙烯進行聚合。在聚合溫度到達60℃後15分鐘,加入35克1,3-丁二烯反應5分鐘,再加入1.6克4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉並反應30分鐘,最後加入0.5克甲醇使反應終了。
實例2-2至實例2-7以相同於實例2-1的步驟進行反應,差異僅在於1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量。更詳言之,在實例2-2中,1,3-二異丙烯基苯的添加量為1.2克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.5克;在實例2-3中,1,3-二異丙烯基苯的添加量為1.35克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.7克;在實例2-4中,1,3-二異丙烯基苯的添加量為1.8克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.6克;在實例2-5中,1,3-二異丙烯基苯的添加量為1.9克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.5克;在實例2-6中,1,3-二異丙烯基苯的添加量為1.8克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為3.5克;在實例2-7中,1,3-二異丙烯基苯的添加量為1克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為2.4克。
實施例3
實例3-1
於室溫(27℃)將1克1,3-二異丙烯基苯混合於含有10克四氫呋喃與0.2克乙二醇二乙醚之5525克環己烷溶液中並升溫至55℃,再加入20克正丁基鋰(5wt%環己烷溶液)混合反應30分鐘後,加入780克1,3-丁二烯與90克苯乙烯進行聚合。在聚合溫度到達60℃後15分鐘,加入30克1,3-丁二烯反應5分鐘,再加入1.1克4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉並反應30分鐘,最後加入0.5克甲醇使反應終了。
實例3-2、實例3-3以相同於實例3-1的步驟進行反應,差異僅在於1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量。更詳言之,在實例3-2中,1,3-二異丙烯基苯的添加量仍為1克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.7克;在實例3-3中,1,3-二異丙烯基苯的添加量為1.2克,4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的添加量為1.3克。
實施例3之優點在於:在製備起始劑時,藉由升溫至55℃縮短正丁基鋰的反應時間,並透過減少乙二醇二乙醚的使用量,以得到低玻璃轉移溫度的共軛二烯系聚合物。
比較例1
比較例1與實施例2之不同點在於:關於製備起始劑,比較例1加入1,3-二異丙烯基苯的含量與實施例2相比較少;在聚合反應時,比較例1未加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,而實施例2則有加入。詳述如下:於室溫(27℃)將0.4克1,3-二異丙烯基苯混合於含有10克四氫呋喃與2.5克乙二醇二乙醚之5525克環己烷溶液中,再加入20克正丁基鋰(5wt%環己烷溶液)混合反應60分鐘後,加入665克1,3-丁二烯與200克苯乙烯進行聚合。在聚合溫度到達60℃後15分鐘,加入35克1,3-丁二烯反應5分鐘,最後加入0.5克甲醇使反應終了。
比較例2
比較例2與實施例2之不同點在於:關於製備起始劑,比較例2未加入1,3-二異丙烯基苯,而實施例2則有加入。詳述如下:於室溫(27℃)加入665克1,3-丁二烯與200克苯乙烯於含有10克四氫呋喃與2.5克乙二醇二乙醚之5525克環己烷溶液中,並加入20克正丁基鋰(5wt%環己烷溶液)進行聚合。在聚合溫度到達60℃後15分鐘,加入35克1,3-丁二烯反應5分鐘,再加入1.6克4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉並反應30分鐘,最後加入0.5克甲醇使反應終了。
比較例3
比較例3與實施例2之不同點在於:在聚合反應時,比較例3加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉的含量與實施例2相比較少。詳述如下:於室溫(27℃)將1.5克1,3-二異丙烯基苯混合於含有10克四氫呋喃與2.5克乙二醇二乙醚之5525克環己烷溶液中,再加入20克正丁基鋰(5wt%環己烷溶液)混合反應60分鐘後,加入665克1,3-丁二烯與200克苯乙烯進行聚合。在聚合溫度到達60℃後15分鐘,加入35克1,3-丁二烯反應5分鐘,再加入0.4克4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉並反應30分鐘,最後加入0.5克甲醇使反應終了。
比較例4
比較例4與實施例2之不同點在於:關於製備起始劑,比較例4加入1,3-二異丙烯基苯的含量與實施例2相比較少。詳述如下:於室溫(27℃)將0.4克1,3-二異丙烯基苯混合於含有10克四氫呋喃與2.5克乙二醇二乙醚之5525克環己烷溶液中,再加入20克正丁基鋰(5wt%環己烷溶液)混合反應60分鐘後,加入665克1,3-丁二烯與200克苯乙烯進行聚合。在聚合溫度到達60℃後15分鐘,加入35克1,3-丁二烯反應5分鐘,再加入1.6克4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉並反應30分鐘,最後加入0.5克甲醇使反應終了。
比較例5
比較例5與實施例3之不同點在於:關於製備起始劑,比較例5加入1,3-二異丙烯基苯的含量與實施例3相比較少。詳述如下:於室溫(27℃)將0.4克1,3-二異丙烯基苯混合於含有10克四氫呋喃與0.2克乙二醇二乙醚之5525克環己烷溶液中並升溫至55℃,再加入20克正丁基鋰(5wt%環己烷溶液)混合反應30分鐘後,加入780克1,3-丁二烯與90克苯乙烯進行聚合。在聚合溫度到達60℃後15分鐘,加入30克1,3-丁二烯反應5分鐘,再加入1.6克4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉並反應30分鐘,最後加入0.5克甲醇使反應終了。
以下說明將本發明之上述各實施例及比較例得到的共軛二烯系聚合物進一步製成橡膠試片以測試其機械性質的方法。
取70重量份之各實施例及比較例之共軛二烯系聚合物、30重量份的聚丁二烯橡膠(商品名TAIPOL BR0150,TSRC公司)、70重量份的二氧化矽、37.5重量份的填充油(TDAE,IRPC公司)、11.2重量份的矽烷(商品名Si69,EVONIK公司)、2重量份的硬脂酸、3重量份的氧化鋅、1重量份的抗氧化劑(商品名Antigene)、1.5重量份的硫、及3.3重量份硫化促進劑(包含N-環己基-2-苯並噻唑次磺醯胺(CBS) 1.8重量份及1,3-二苯胍(DPG) 1.5重量份)捏和以形成橡膠。該橡膠可藉由兩滾輪機模鑄成片板膜,將該片板膜進行硫化(加熱至160℃維持45分鐘)得到硫化片板膜。
各實施例及比較例之共軛二烯系聚合物的組成及物理性質、及其製備橡膠試片的機械性質,如表一至表三所示。
共軛二烯系聚合物的分析方法
類二乙烯基芳香烴化合物與有效活性之有機鹼金屬的莫耳比例:即類二乙烯基芳香烴化合物莫耳數(Q)與參與反應之有機鹼金屬的莫耳數(M)之比例(Q/M),其中Q=類二乙烯基芳香烴化合物重量/類二乙烯基芳香烴化合物分子量,M=加入反應的單體總重量/第一波峰(Mi)所表示最低的重均分子量,而第一波峰(Mi)是以凝膠滲透層析儀(GPC)對共軛二烯系聚合物或改性共軛二烯系聚合物分析而得。
含矽改性劑與有效活性之有機鹼金屬之莫耳比例:即含矽改性劑的莫耳數(Si)與參與反應之有機鹼金屬的莫耳數(M)之比例(Si/M),其中Si=含矽改性劑重量/含矽改性劑分子量,M=加入反應的單體總重量/第一波峰(Mi)所表示最低的重均分子量,而第一波峰(Mi)是以凝膠滲透層析儀(GPC)對改性共軛二烯系聚合物分析而得。
偶合率(Coupling Ratio, CR%):改性共軛二烯系聚合物以凝膠滲透層析儀(GPC)量測具有m個波峰之特徵,偶合率=[(m個波峰的總積分面積-第一波峰的積分面積)/m個波峰的總積分面積] × 100%。於量測時以四氫呋喃作為移動相(mobile phase)。
重均分子量(Mw)及分子量分佈(Molecular Weight Distribution, MWD):以凝膠滲透層析儀(GPC)分析,利用Waters 1525 Binary HPLC Pump,偵測器為Waters 2414 Refractive Index Detector,洗提液(Eluent)為四氫呋喃,洗提液流速為1 ml/min。
門尼黏度(Mooney Viscosity, ML
1+4100℃):使用ALPHA Mooney MV 2000型,測試方法為ASTM D-1646。
玻璃轉移溫度(Tg,℃):使用TA Instrument Q200的微掃描卡計差式掃描量熱計(Differential Scanning Calorimeter, DSC)測定,於氮氣環境下,掃描速度為20℃/min,掃描範圍為-90℃至100℃。
橡膠試片的分析方法
損失正切(loss tangent, tan δ):此指標用來判斷共軛二烯系聚合物製成胎面膠(tread rubber stock)的滾動阻力(Rolling Resistance, R.R.)。使用TA instrument ARES-G2機型在應變掃描(Strain sweep)下,量測試片的儲存模量(G’)與損耗模量(G”)的變化,tan δ = G”/G’求得該數值,掃描時樣品溫度為60℃,應變掃描範圍為0.1%~10%,取5.0%應變數值。
斷裂拉伸強度(Tensile Strength at Break, Tb, Mpa):使用INSTRON 33R4464機型,依據ASTM D412標準量測。
斷裂延伸率(Elongation Strength at Break, Eb, %):使用INSTRON 33R4464機型,依據ASTM D412標準量測。
撕裂強度(Tear, N/mm):使用INSTRON 33R4464機型,依據ASTM D412標準量測。
剛度(stiffness, Mpa):使用TA instrument ARES-G2機型在應變掃描(Strain sweep)下,量測試片的儲存模量(G’),掃描時樣品溫度為60℃,應變掃描範圍為0.1%~10%,取5.0%應變數值。
磨耗測試(DIN):使用GT-7012-DN機型,依據ASTM D5963標準量測。
需說明的是,以下所示各橡膠試片的機械性質並非實際值,而是以任一比較例為基準(基準值100)進行比較,顯示本發明之各實施例及其他比較例的參考值。
表一
11,3-二異丙烯基苯與有效活性之正丁基鋰的莫耳比例
24-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉與有效活性之正丁基鋰的莫耳比例
共軛二烯系聚合物的組成及物理性質 | |||||||
比較例1 | 比較例2 | 比較例3 | 比較例4 | 實例1-1 | 實例1-2 | 實例1-3 | |
丁二烯含量(%) | 78 | ||||||
苯乙烯含量(%) | 22 | ||||||
乙烯基含量(%) | 64 | 65 | 64 | 66 | 65 | 64 | 64 |
Q/M 1 | 0.5 | - | 2.3 | 0.4 | 1.9 | 2.6 | 2.2 |
Si/M 2 | - | 2.3 | 0.5 | 2.3 | 2.0 | 2.2 | 1.6 |
門尼黏度(ML 1+4100℃) | 54 | 64 | 55 | 66 | 47 | 46 | 30 |
玻璃轉移溫度(℃) | -24 | -23 | -25 | -21 | -24 | -25 | -25 |
橡膠試片的機械性質 | |||||||
滾動阻力 | 63 | 88 | 90 | 100 | 103 | 116 | 117 |
斷裂拉伸強度 × 斷裂延伸率 | 92 | 100 | 98 | 100 | 109 | 108 | 111 |
撕裂強度 | 100 | 100 | 99 | 100 | 102 | 105 | 102 |
剛度 | 82 | 95 | 105 | 100 | 103 | 104 | 106 |
表一顯示實例1-1至實例1-3之各共軛二烯系聚合物及其所製成之橡膠試片的各種特性。實例1-1至實例1-3均加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,且Q/M值及Si/M值均在本發明的範圍(即1.3~5.0)。比較例1加入1,3-二異丙烯基苯但未加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值及Si/M值均不符本發明的範圍。比較例2未加入1,3-二異丙烯基苯但加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值不符本發明的範圍但Si/M值則符合。比較例3加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值符合本發明的範圍但Si/M值則不符。比較例4加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值不符本發明的範圍但Si/M值則符合。相較於比較例1至比較例4,實例1-1至實例1-3均顯示在不影響聚合物的玻璃轉移溫度的情況下,本發明可得到在滾動阻力、斷裂拉伸強度與斷裂延伸率的乘積、撕裂強度及剛度各機械性質均明顯優異的橡膠。
由比較例2、比較例4及實例1-2可知,僅加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉至其Si/M值符合本發明的範圍(比較例2)時,橡膠的滾動阻力及剛度較差;當再加入1,3-二異丙烯基苯(比較例4)時,橡膠的滾動阻力及剛度逐漸提升;當更進一步加入1,3-二異丙烯基苯至其Q/M值符合本發明的範圍(實例1-2)時,可得到在滾動阻力、斷裂拉伸強度與斷裂延伸率的乘積、撕裂強度及剛度各機械性質均明顯優異的橡膠。
由比較例1、比較例3及實例1-3可知,僅加入1,3-二異丙烯基苯(比較例1)時,橡膠的滾動阻力及剛度較差;當再加入1,3-二異丙烯基苯至其Q/M值符合本發明的範圍(比較例3)時,橡膠的滾動阻力及剛度已提升;當更進一步加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉至其Si/M值符合本發明的範圍(實例1-3)時,所得到的橡膠在滾動阻力、斷裂拉伸強度與斷裂延伸率的乘積、撕裂強度及剛度各機械性質均明顯優異。
表二
11,3-二異丙烯基苯與有效活性之正丁基鋰的莫耳比例
24-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉與有效活性之正丁基鋰的莫耳比例
共軛二烯系聚合物的組成及物理性質 | |||||||
比較例1 | 比較例2 | 比較例3 | 比較例4 | 實例2-1 | 實例2-2 | 實例2-3 | |
丁二烯含量(%) | 78 | ||||||
苯乙烯含量(%) | 22 | ||||||
乙烯基含量(%) | 64 | 65 | 64 | 66 | 64 | 64 | 63 |
Q/M 1 | 0.5 | - | 2.3 | 0.4 | 1.3 | 1.8 | 2.1 |
Si/M 2 | - | 2.3 | 0.5 | 2.3 | 2.3 | 2.1 | 2.4 |
門尼黏度(ML 1+4100℃) | 54 | 64 | 55 | 66 | 47 | 47 | 58 |
玻璃轉移溫度(℃) | -24 | -23 | -25 | -21 | -24 | -24 | -26 |
橡膠試片的機械性質 | |||||||
滾動阻力 | 63 | 88 | 90 | 100 | 110 | 119 | 117 |
斷裂拉伸強度 × 斷裂延伸率 | 92 | 100 | 98 | 100 | 105 | 101 | 111 |
撕裂強度 | 100 | 100 | 99 | 100 | 105 | 105 | 105 |
剛度 | 82 | 95 | 105 | 100 | 106 | 108 | 106 |
共軛二烯系聚合物的組成及物理性質 | ||||
實例2-4 | 實例2-5 | 實例2-6 | 實例2-7 | |
丁二烯含量(%) | 78 | |||
苯乙烯含量(%) | 22 | |||
乙烯基含量(%) | 64 | 65 | 64 | 63 |
Q/M 1 | 2.8 | 2.9 | 2.8 | 1.5 |
Si/M 2 | 2.3 | 2.2 | 5.0 | 3.5 |
門尼黏度(ML 1+4100℃) | 58 | 44 | 45 | 43 |
玻璃轉移溫度 (℃) | -24 | -22 | -22 | -22 |
橡膠試片的機械性質 | ||||
滾動阻力 | 113 | 109 | 108 | 108 |
斷裂拉伸強度 × 斷裂延伸率 | 109 | 108 | 104 | 103 |
撕裂強度 | 107 | 102 | 103 | 101 |
剛度 | 106 | 109 | 107 | 106 |
表二顯示實例2-1至實例2-7之各共軛二烯系聚合物及其所製成之橡膠試片的各種特性。實例2-1至實例2-7均加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,且Q/M值及Si/M值均在本發明的範圍(即1.3~5.0)。比較例1加入1,3-二異丙烯基苯但未加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值及Si/M值均不符本發明的範圍。比較例2未加入1,3-二異丙烯基苯但加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值不符本發明的範圍但Si/M值則符合。比較例3加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值符合本發明的範圍但Si/M值則不符。比較例4加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值不符本發明的範圍但Si/M值則符合。相較於比較例1至比較例4,實例2-1至實例2-7均顯示在不影響聚合物的玻璃轉移溫度的情況下,本發明可得到在滾動阻力、斷裂拉伸強度與斷裂延伸率的乘積、撕裂強度及剛度各機械性質均明顯優異的橡膠。
由比較例2、比較例4及實例2-1至實例2-5可知,僅加入4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉至其Si/M值符合本發明的範圍(比較例2)時,橡膠的滾動阻力及剛度較差;當再加入1,3-二異丙烯基苯(比較例4)時,橡膠的滾動阻力及剛度逐漸提升;當更進一步加入1,3-二異丙烯基苯至其Q/M值符合本發明的範圍(實例2-1至實例2-5)時,可得到在滾動阻力、斷裂拉伸強度與斷裂延伸率的乘積、撕裂強度及剛度各機械性質均明顯優異的橡膠。
由實例1-1及實例2-2可知,實例1-1為將起始劑冰存,等到進行聚合反應時再使用,而實例2-2為製備起始劑後,隨即進行聚合反應。實例1-1及實例2-2得到共軛二烯系聚合物的組成及物理性質幾乎完全相同,且得到橡膠在各機械性質均明顯優異於比較例1至比較例4。相較於實例2-2,在製備起始劑時,實例1-1可減少1,3-二異丙烯基苯的反應時間,具有提升產量之優點。
表三
11,3-二異丙烯基苯與有效活性之正丁基鋰的莫耳比例
24-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉與有效活性之正丁基鋰的莫耳比例
共軛二烯系聚合物的組成及物理性質 | ||||
比較例5 | 實例3-1 | 實例3-2 | 實例3-3 | |
丁二烯含量(%) | 90 | |||
苯乙烯含量(%) | 10 | |||
乙烯基含量(%) | 41 | 41 | 42 | 41 |
Q/M 1 | 0.5 | 1.3 | 1.3 | 1.5 |
Si/M 2 | 2.7 | 1.6 | 2.5 | 2.0 |
門尼黏度 (ML 1+4100℃) | 66 | 48 | 42 | 71 |
玻璃轉移溫度(℃) | -60 | -62 | -61 | -57 |
橡膠試片的機械性質 | ||||
滾動阻力 | 100 | 117 | 118 | 119 |
磨耗測試 | 100 | 109 | 112 | 111 |
表三顯示實例3-1至實例3-3之各共軛二烯系聚合物及其所製成之橡膠試片的各種特性。實例3-1至實例3-3均加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,且Q/M值及Si/M值均在本發明的範圍(即1.3~5.0)。比較例5加入1,3-二異丙烯基苯及4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉,其Q/M值不符本發明的範圍但Si/M值則符合。相較於比較例5,實例3-1至實例3-3均顯示在不影響聚合物的玻璃轉移溫度的情況下,加入1,3-二異丙烯基苯至其Q/M值為本發明的最低範圍(即1.3),可得到在滾動阻力及磨耗測試各機械性質均明顯優異的橡膠。
由實例2-1及實例3-2可知,兩者的Q/M值及Si/M值相當接近,均在本發明的範圍,但實例2-1使用的苯乙烯含量較多(丁二烯與苯乙烯的重量比例為78/22),故聚合物的玻璃轉移溫度較高(-24℃),得到的橡膠適合在夏季使用,而實例3-2使用的1,3-丁二烯含量較多(丁二烯與苯乙烯的重量比例為90/10),故聚合物的玻璃轉移溫度較低(-61℃),得到的橡膠適合在冬季使用。實例2-1得到橡膠在各機械性質均明顯優異於比較例1至比較例4,而實例3-2得到橡膠在各機械性質均明顯優異於比較例5。相較於實例2-1,在製備起始劑時,實例3-2藉由升溫可減少正丁基鋰的反應時間,具有提升產量之優點。
雖然本發明已以較佳實施例揭露如上,然其並非用以限制本發明,任何熟習此項技藝者,在不脫離本發明之精神和範圍內,當可做更動與潤飾,因此本發明之保護範圍當以後附之申請專利範圍所界定者為準。
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Claims (17)
- 一種共軛二烯系聚合物的製造方法,包含: 步驟(a):將式(1)表示之一類二乙烯基芳香烴化合物與一有機鹼金屬反應得到一起始劑,其中A與B為C nH 2n+1或芳香環,n為0~5,A與B可相同或不相同,Q為芳香環;其中該類二乙烯基芳香烴化合物與有效活性之該有機鹼金屬的莫耳比例為1.3~5.0;及 (1) 步驟(b):將該起始劑與一共軛二烯單體或一共軛二烯單體與一乙烯芳香族單體進行聚合反應得到該共軛二烯系聚合物。
- 如請求項1之共軛二烯系聚合物的製造方法,其中該類二乙烯基芳香烴化合物為1,3-二異丙烯基苯或對-二乙烯基苯。
- 如請求項1之共軛二烯系聚合物的製造方法,其中該步驟(a)更包含:將一部分之該類二乙烯基芳香烴化合物與該有機鹼金屬反應一第一段時間後,再加入剩餘部分之該類二乙烯基芳香烴化合物繼續反應一第二段時間。
- 如請求項1之共軛二烯系聚合物的製造方法,其中該步驟(a)更包含:使該類二乙烯基芳香烴化合物於溶劑中之濃度為0.001~20wt%。
- 如請求項1之共軛二烯系聚合物的製造方法,其中該步驟(a)更包含:提升溫度至55℃~60℃下進行。
- 如請求項1之共軛二烯系聚合物的製造方法,更包含:於該步驟(b)加入一環醚化合物及/或二醚化合物。
- 如請求項6之共軛二烯系聚合物的製造方法,其中該環醚化合物為四氫呋喃,該二醚化合物為乙二醇二乙醚。
- 如請求項1之共軛二烯系聚合物的製造方法,其中該步驟(a)更包含:於加入該有機鹼金屬之前加入一環醚化合物及/或二醚化合物與該類二乙烯基芳香烴化合物混合。
- 如請求項1之共軛二烯系聚合物的製造方法,更包含步驟(c):於該步驟(b)之後加入一含矽改性劑,該含矽改性劑如式(2)表示: (2), 其中A 1、A 2及A 3為烷類、烷氧類或是鹵素,烷類或烷氧類的碳數為C1-C5,A 1、A 2及A 3中至少二者是烷氧類或鹵素,X基團為含有氮、氧、硫或磷原子中之一種或多種的基團,n為1~10。
- 如請求項9之共軛二烯系聚合物的製造方法,其中該含矽改性劑為4-{3-[二甲氧基(甲基)甲矽烷基]丙基}嗎啉或3-(三甲氧基甲矽烷基)-N,N-二甲基丙-1-胺。
- 如請求項9之共軛二烯系聚合物的製造方法,其中該步驟(c)更包含:該含矽改性劑與有效活性之該有機鹼金屬之莫耳比例為1.3~5.0。
- 如請求項9之共軛二烯系聚合物的製造方法,其中該步驟(c)更包含:該含矽改性劑與有效活性之該有機鹼金屬之莫耳比例為1.4~3.5。
- 如請求項9之共軛二烯系聚合物的製造方法,其中該步驟(c)更包含:該含矽改性劑與有效活性之該有機鹼金屬之莫耳比例為1.5~2.5。
- 一種共軛二烯系聚合物,其為以如請求項1至13中任一項之製造方法得到。
- 一種橡膠,包含如請求項14之共軛二烯系聚合物。
- 如請求項15之橡膠,更包含獨立地選自以下項目所組成的群組:二氧化矽、填充油、抗氧化劑、硬脂酸、蠟、硫化促進劑、加工促進劑、碳黑及上述各項之任何組合。
- 一種輪胎,其含有如請求項15至16中任一項之橡膠。
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