CN1184490A - 用受控自由基聚合制备窄分子量分布的乙烯基单体聚合物的方法 - Google Patents
用受控自由基聚合制备窄分子量分布的乙烯基单体聚合物的方法 Download PDFInfo
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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Abstract
乙烯基单体聚合物的制备方法,其聚合是在自由基引发剂和电子给体存在下进行的。
Description
本发明涉及制备乙烯基单体聚合物的方法。本发明也涉及将这种方法得到的聚合物用于制备模塑制件的用途。
自由基聚合是聚合乙烯基单体最广泛应用的技术,它可使结构、官能团和极性各不相同的多种单体聚合,不同单体相互共聚也是可能的。但是由于不可避免的副反应,诸如链转移、歧化作用、重组或消除作用,分子量的分布是很难控制的。在正常情况下,得到的聚合物的多分散指数PDI为2.0或更大。PDI定义为式中Mw为重均分子量,Mn为数均分子量。
早已知道的一种制备窄分子量分布聚合物的方法是阴离子聚合,但这种方法只能用于数目有限的单体。非极性单体(诸如苯乙烯或丁二烯)可用阴离子聚合法聚合;如果是极性单体(诸如丙烯酸正烷基酯),阴离子聚合就很困难。阴离子聚合还要求有高纯度单体和溶剂,并需完全排除大气湿度。
制备窄分子量分布聚合物的另一方法是所谓的“受控自由基聚合”,有时也称“活自由基聚合”,叙述于例如下述文献中:M.K.Georges等人,聚合物科学动向(Trends in Polymer Science)Vol.2,No.2(1994),pp.66-72。该方法的基本策略包括暂时的封闭然后再有目的地活化生长的聚合物链的活性自由基链端。活化和休止形式之间的动态平衡导致自由聚合物残基的低稳定态浓度。
封闭和稳定自由基链端有许多技术,它们采用稳定的自由基和/或金属盐。
例如,已知的是使用“iniferter”,即能用自由基引发聚合又能以结合终止链端的自由基发生剂。光化学活化的iniferter的实例,诸如二硫代氨基甲酸酯,叙述于下述文献中:T·Otsu等人,欧洲聚合物杂志(Eur.Polym.J.),vol.25,No.718(1989),pp643-650。但是这些光化学iniferter都是非常贵的化合物,而且用光化学引发聚合在工业实践中是非常不经济的。再者,在某些情况下聚合物多分散指数是很高的。也有热iniferter,诸如二硫化四亚甲基,它叙述于例如下述文献中:K·Endo等人,大分子(Macromolecules),Vol.25(1992),pp.5554-5556。此例的PDI值在3-4之间,该值太高而不能令人满意。
EP-A135280叙述了稳定的N-氧基的使用,它能可逆地与反应性链端结合。但此方法生产的不是高分子量的聚合物而仅仅是低聚物。
US-A5322912公开了环状空间屏蔽的N-氧基,是与常规引发剂结合使用的。但这些体系不会使丙烯酸烷基酯聚合。
EP-A487370叙述了在烷基碘存在下用自由基引发的聚合,其分子量之低也是不能令人满意的。
EP-A222619中叙述的产物显示了同样的缺点,这种产物是借助于含环戊二烯基配位体的双金属催化剂制备的。
至今所知的各种方法均有这样的缺点,即用以控制反应的添加剂是非常贵的,因而这些方法都是不经济的。
因此,本发明的目的是提供制备乙烯基单体聚合物的新方法,该方法没有上述缺点,能适用于极性和非极性单体,可控制分子量和分子量分布,并且对少量的湿气不敏感。
现发现此目的的达到是用这样的制备乙烯基单体聚合物的方法,其中聚合是在自由基引发剂和电子给体存在下进行的。
我们也发现了用这样的方法得到的聚合物可用来制备模塑制件的用途。
特别适合的乙烯基单体是乙烯基芳族化合物,诸如苯乙烯,2-乙烯基萘和9-乙烯基蒽;取代的乙烯基芳族化合物,诸如对甲基苯乙烯,α-甲基苯乙烯,对氯苯乙烯,2,4-二甲基苯乙烯和4-乙烯基联苯;丙烯酸或甲基丙烯酸C1-8烷基酯,特别是丙烯酸和甲基丙烯酸C1-4烷基酯;不饱和二元羧酸,例如脂族不饱和二元羧酸,诸如马来酸或富马酸或它们的衍生物,诸如酐、酯和酰胺,特别是酐,诸如马来酐;或是乙烯基氰,特别是丙烯腈。不同单体的混合物同样能使用。
优选的单体是苯乙烯、取代苯乙烯、丙烯酸和甲基丙烯酸C1-4烷基酯,特别是甲基丙烯酸甲酯,以及丙烯腈。
在新方法中采用的自由基引发剂是已知的并叙述于例如下述文献中:乌尔曼技术化学大全(Ullmanns Encyclopadie der technischenChemie),4thed,Vol.15,p.187。特别适合的引发剂是过氧化物,诸如过氧化二苯甲酰和氢过氧化枯烯,并特别是偶氮化合物,诸如偶氮二异丁腈(AIBN)。不同自由基引发剂的混合物也是可以采用的。
自由基引发剂的摩尔量可以是10-6-1摩尔/升,优选10-4-10-1摩尔/升。
新方法也在电子给体存在下进行。
电子给体是由于内消旋和/或诱导效应而具有过剩兀电子的分子。
氧基)或C6-18芳基(优选苯基),A为双键、
优选的式I或式II化合物是其中的R1与R2含义相同、R3与R4也相同的化合物,或是其中的R1与R3相同、R2与R4也相同的化合物,即对称的化合物。优选的X为硫,优选的R1-R4为氢或甲基。特别优选的化合物是四硫富瓦烯(TTF)电子给体的其它实例是 式中:X为硫或硒,R1-R4为氢、C1-20烷基(优选C1-6烷基)、C1-20烷氧基(优选C1-6烷
氧基)或C6-18芳基(优选苯基)。
在此,优选的也是对称化合物,即R1与R2相同以及R3与R4相同的化合物或是R1与R3相同以及R2与R4相同的化合物。同样,优选的X为硫,优选的R1-R4为氢或甲基。
其它可以使用的电子给体是式III或式IV的化合物式中:Y为氧或硫,R5为C1-20烷基(优选C1-6烷基)、C1-20烷氧基(优选C1-6烷氧基)或
C6-18芳基(优选苯基),n为2-6的整数。
-SRa、-ORa或-NRaRb;Ra为C1-25烷基,优选C1-22烷基,特别是C1-10烷基,例如甲基、乙
基、正丙基、异丙基、正丁基、异丁基或叔丁基或C6-18芳基,优
选苯基,Rb为氢、C1-25烷基,优选C1-22烷基,特别是C1-10烷基,例如甲基、
乙基、正丙基、异丙基、正丁基、异丁基或叔丁基、C6-18芳基,优
选苯基,R7为氢或TZ;T为支化或非支化的C1-25亚烷基,优选C1-25亚烷基,特别优选C1-10亚烷基,例如亚甲基、亚乙基、2-甲基亚乙基、亚正丙基
或亚正丁基,Z为-OH、-OR8、-SR8、-NR9R10或Q,其中优选的是-NR9R10
或Q;R8为C1-25烷基,优选C1-22烷基,特别是C1-10烷基,例如甲基、乙
基、正丙基、异丙基、正丁基、异丁基或叔丁基或C6-18芳基,优
选苯基;R9为氢或C1-25烷基,优选C1-22烷基,特别是C1-10烷基,例如甲基、
乙基、正丙基、异丙基、正丁基、异丁基或叔丁基或C6-18芳基,
优选苯基;R10为C1-25烷基,优选C1-22烷基,特别是C1-10烷基,例如甲基、乙
基、正丙基、异丙基、正丁基、异丁基或叔丁基或C6-18芳基,优
选苯基;其中:R9和R10相互并与氮一起能形成C4-7环-N-脂肪环,优选C5环-
N-脂肪环或C6环-N-脂肪环,该环可以是未取代的或被一
个或多个C1-5烷基所取代,优选甲基、乙基、正丙基或异丙基取
代的,并可含一个或多个(优选一个)-O-、-S-或-N(R11)-
,优选后者;其中-O-、-S-和-N(R11)-互相间不直接
相连;Q为C4-7环脂族基(优选C5或C6环脂族环),它们可含一个或多个
-O-、-S-或-N(R11)-,后者是优选的;在每种情况中Q
通过一碳原子与T相连;其中-O-、-S-或-N(R11)-互相
间不直接相连;R11为C1-10烷基,优选C1-5烷基,例如甲基、乙基、正丙基、异丙基、
正丁基、异丁基或叔丁基;R12为氢、C1-20烷基(优选C1-6烷基)或C6-18芳基(优选苯基)。
其它适合的电子给体是下列的化合物: 式中:X为硫或硒,优选硫;Y为氧或硫;R1-R4为氢、C1-20烷基(优选C1-6烷基)或C6-18芳基(优选苯基);m为0-4的整数;q为0-2的整数;p为2-100的整数。
使用不同电子给体的混合物也是可能的。
用作电子给体的化合物本身是已知的,或是可用实质上已知的方法来制备,它们叙述于例如下列文献中:J.H.Perlstein,应用化学(Angew.Chem.)国际版,英文,16(1977),pp.519-534;和M.R.Bryce,Aldrichimica Acta,Vol.18(1985)pp.73-77。
电子给体与自由基引发剂的摩尔比可在1∶1至3∶1的范围,优选1.6∶1至2.4∶1。
反应的条件不是关键问题。反应可在0-220℃的温度下进行。优选20-150℃;虽然也可在达30巴的压力下进行,但通常在大气压下进行,反应时间的选择最好是使聚合的进行直到达到了所要求的分子量,例如1小时至6天。
新方法也可在有机溶剂存在下进行。适合的溶剂的实例是四氢呋喃(THF)、甲苯、乙苯或它们的混合物。
新方法最好是先向反应器中加自由基引发剂和电子给体,然后加入一种单体或多种单体和溶剂(如果使用的话)。但也可以相反的顺序加入。可以用沉淀法处理聚合物,例如从甲醇或己烷中沉淀。
所得聚合物的分子量Mn可在较宽的范围内变化,例如5,000-500,000。
新方法的特征是其经济性:可使用极性和非极性单体,对少量湿气不敏感以及反应单体混合物以得到无规共聚物的可能性。所得的聚合物的PDI小于2,可以有高的分子量并呈现较高的热稳定性。
实施例
实施例1-6
聚甲基丙烯酸甲酯(PMMA)的制备
甲基丙烯酸甲酯(MMA)经氢化钙蒸馏。THF和甲苯分别经钾和钠蒸馏。从甲醇中重结晶AIBN。使用市售TTF不需再纯化。
单体浓度为4.8摩尔/升溶剂。所用的自由基引发剂量为2.4×10-2摩尔/升,电子给体量为4.8×10-2摩尔/升。聚合反应是在50ml的Schlenk管中于氩气下进行的。用针管经隔片将单体和溶剂注入在氩气吹扫的Schlenk管中先加入的自由基引发剂和电子给体中。
聚合物溶液用THF稀释,从10倍体积的甲醇中沉淀聚合物进行处理。在甲苯中制备的聚合物从正己烷中沉淀。
分子量用GPC(凝胶渗透色谱法)测定,用PMMA标准物质校准。
对比实施例V1-V4
PMMA的制备
重复实施例1-6,但不加TTF。
反应条件和聚甲基丙烯酸甲酯的性质总结于表1中。
热稳定性可用热重分析法(TGA)测定。发现在用新方法制备的PMMA情况下,其质量损失开始时的温度波动到了明显的较高温度。
图1所示为实施例2的PMMA的TGA曲线和对比实施例V2的PMMA的TGA曲线;图2所示为实施例5和对比实施例V4(N2气氛,加热速率为10°K/分钟)的PMMA的TGA曲线。
表1
实施例7-10聚苯乙烯的制备重复实施例1-6,但以苯乙烯代替MMA作为单体。对比实施例V5-V8聚苯乙烯的制备重复实施例7-10,但不加TTF。反应条件和聚苯乙烯的性质总结于表2中。
试验号 | 单体 | 自由基引发剂 | 电子给体 | 溶剂 | 温度[℃] | 反应时间 | Mn | Mw | PDI |
1 | MMA | AIBN | TTF | THF | 60 | 72h | 21 500 | 31 800 | 1,48 |
2 | MMA | AIBN | TTF | THF | 60 | 72h | 31 500 | 46 000 | 1,46 |
3 | MMA | AIBN | TTF | THF | 60 | 72h | 32 300 | 50 100 | 1,54 |
4 | MMA | AIBN | TTF | THF | 60 | 72h | 31 500 | 48 400 | 1,53 |
5 | MMA | AIBN | TTF | 甲苯 | 110 | 72h | 19 000 | 26 000 | 1,38 |
6 | MMA | AIBN | TTF | 甲苯 | 110 | 72h | 14 400 | 19 700 | 1,37 |
V1 | MMA | AIBN | - | THF | 60 | 24h | 51 300 | 103 100 | 2,01 |
V2 | MMA | AIBN | - | THF | 60 | 24h | 34 000 | 70 000 | 2,06 |
V3 | MMA | AIBN | - | 甲苯 | 110 | 24h | 7 700 | 35 800 | 4,65 |
V4 | MMA | AIBN | - | 甲苯 | 110 | 24h | 5 600 | 28 500 | 5,03 |
表2
实施例11MMA和苯乙烯共聚物的制备重复实施例1-6,但用MMA和苯乙烯作为单体(摩尔比1∶1)。反应条件和共聚物的性质总结于表3中。
试验号 | 单体 | 自由基引发剂 | 电子给体 | 溶剂 | 温度[℃] | 反应时间 | Mn | Mw | PDI |
7 | 苯乙烯 | AIBN | TTF | THF | 60 | 72h | 14 200 | 25 400 | 1,78 |
8 | 苯乙烯 | AIBN | TTF | THF | 60 | 72h | 16 300 | 29 000 | 1,77 |
9 | 苯乙烯 | AIBN | TTF | 甲苯 | 110 | 72h | 9 200 | 15 400 | 1,67 |
10 | 苯乙烯 | AIBN | TTF | 甲苯 | 110 | 72h | 13 800 | 25 600 | 1,85 |
V5 | 苯乙烯 | AIBN | - | THF | 60 | 24h | 10 600 | 28 400 | 2,68 |
V6 | 苯乙烯 | AIBN | - | THF | 60 | 24h | 10 800 | 28 000 | 2,59 |
V7 | 苯乙烯 | AIBN | - | 甲苯 | 110 | 24h | 16 700 | 63 500 | 3,78 |
V8 | 苯乙烯 | AIBN | - | 甲苯 | 110 | 24h | 15 500 | 55 500 | 3,56 |
表3
试验号 | 单体 | 自由基引发剂 | 电子给体 | 溶剂 | 温度[℃] | 反应时间 | Mn | Mw | PDI |
11 | 苯乙烯/MMA | AIBN | TTF | THF | 60 | 72h | 21 100 | 32 000 | 1,51 |
实施例12-14
用吩噻嗪作为电子给体制备聚苯乙烯和苯乙烯/丙烯腈共聚物
重复实施例1-6,但以市售吩噻嗪(V、R6、R7=H)(PTA)和二甲基氨丙基吩噻嗪(V、R6=H,R7=-CH2-CH(CH3)-N(CH3)2)(DMAPPTA)作为电子给体。所用的单体分别为苯乙烯和苯乙烯/丙烯腈(AN)混合物(重量比3∶1)。使用市售过氧化苯甲酰(不需另外纯化)作为自由基引发剂。过氧化苯甲酰和电子给体使用等摩尔量。过氧化苯甲酰相对于单体的浓度为0.1摩尔%。
反应条件和得到的聚合物和共聚物的性质给于表4中。
表4
试验员 | 单体 | 自由基引发剂 | 电子给体 | 溶剂 | 温度[℃] | 反应时间 | Mn | Mw | PDI |
12 | 苯乙烯 | BPO | PTA | THF | 130 | 2h | 178 600 | 300 000 | 1,68 |
13 | 苯乙烯 | BPO | DMAPPTA | THF | 130 | 25h | 76 500 | 193 600 | 2,53 |
14 | 苯乙烯/AN | BPO | PTA | THF | 130 | 1h | 28 600 | 83 000 | 2,9 |
V9 | 苯乙烯 | BPO | - | THF | 130 | 2h | 71 200 | 192 300 | 2,7 |
V10 | 苯乙烯/AN | BPO | - | THF | 130 | 1h | 2 900 | 40 000 | 14 |
实施例15
分子量随时间的改变
除选择相对于苯乙烯的较小比例的BPO和PTA(0.29克BPO,0.18克PTA,104.15克苯乙烯)外,重复实施例12。在下表所示的时间间隔取样,产物从甲醇中沉淀,并收集沉淀,在80℃下减压干燥,分析。结果示于表5。
表5
表5显示,反应时间延长,则分子量增加。
时间 | Mn | Mw | PDI |
30min | 57 600 | 144 000 | 2,5 |
60min | 69 000 | 173 000 | 2,5 |
3h | 90 200 | 198 000 | 2,2 |
5h | 88 800 | 213 000 | 2,4 |
Claims (10)
1.一种制备乙烯基单体聚合物的方法,该方法包括在自由基引发剂和电子给体存在下进行聚合反应。
2.权利要求1所述的方法,其中所用的乙烯基单体为乙烯基芳族化合物、取代的乙烯基芳族化合物、丙烯酸或甲基丙烯酸C1-8烷基酯、不饱和二元羧酸或其衍生物、乙烯基氰或它们的混合物。
3.权利要求1或2所述的方法,其中所用的乙烯基单体为苯乙烯、取代的苯乙烯、丙烯酸或甲基丙烯酸C1-4烷基酯、丙烯腈或它们的混合物。
4.权利要求1-3任一项所述的方法,其中所用的电子给体是电中性化合物。
7.权利要求1-4任一项所述的方法,其中所用的电子给体为式V的化合物,式中:X为-O-、-S-或-Se-,R6为-H、C1-5烷基、-CF3、卤素、-CN、-SRa、-ORa、-NRaRb,Ra为C1-25烷基或C6-18芳基,Rb为-H、C1-25烷基或C6-18芳基,R7为-H或TZ,T为支化或非支化的C1-25亚烷基,Z为-OH、-OR8、-SR8、-NR9R10或Q,R8为C1-25烷基或C6-18芳基,R9为-H、C1-25烷基或C6-18芳基,R10为C1-25烷基或C6-18芳基;其中:R9和R10互相和氮一起也能形成C4-7环-N-脂肪环,可以是未取
代的或被一个或多个C1-5烷基所取代并可含一个或多个-O-
、-S-或-N(R11)-,Q为C4-7环脂基,可含一个或多个-O-、-S-或-N(R11)-,R11为C1-10烷基。
8.权利要求1-6任一项所述的方法,该方法是在有机溶剂中进行的。
9.权利要求1-7任一项所述的方法,其中电子给体和自由基引发剂的摩尔比在1∶1-3∶1的范围。
10.用权利要求1-8任一项所述方法制备的聚合物制造模塑制件的用途。
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DE19516967.0 | 1995-05-12 | ||
DE19516967A DE19516967A1 (de) | 1995-05-12 | 1995-05-12 | Verfahren zur Herstellung von Polymerisaten von vinylischen Monomeren mit enger Molekulargewichtsverteilung durch kontrollierte radikalische Polymerisation |
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EP0824552A1 (de) | 1998-02-25 |
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