CN1662600A - 共轭二烯/单乙烯基芳烃嵌段共聚物的共混物 - Google Patents
共轭二烯/单乙烯基芳烃嵌段共聚物的共混物 Download PDFInfo
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- CN1662600A CN1662600A CN03814130.2A CN03814130A CN1662600A CN 1662600 A CN1662600 A CN 1662600A CN 03814130 A CN03814130 A CN 03814130A CN 1662600 A CN1662600 A CN 1662600A
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- Prior art keywords
- vinyl
- monomer
- conjugated
- diolefin
- uni
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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Abstract
本发明涉及聚合物共混物,它包括至少一种递变的共轭二烯烃-单乙烯基芳烃嵌段共聚物和至少一种苯乙烯类聚合物。该聚合物共混物具有良好的光学和机械性能。
Description
本申请是现已受权的09/576879(它是08/521335,即现在的US6096828的分案申请)和现已受权的申请09/576408的部分继续申请。
发明领域
本发明涉及聚合物共混物,它包括至少一种递变的共轭二烯烃/单乙烯基芳烃的嵌段共聚物和至少一种苯乙烯聚合物。
发明背景
共轭二烯烃/单乙烯基芳烃的共聚物是已知的且可用于各种目的。特别感兴趣的是可形成具有良好物理性能,如抗冲击性的无色、透明制品的聚合物。这种制品可用于玩具、窗户坯料、饮料容器和包装如起泡包装。
聚合物应当还显示出充足的热稳定性以适合于与常规的注模设备一起使用。对于许多应用来说,要求含有大量苯乙烯的共聚物的共混物。通常通过共混某些单乙烯基芳烃-共轭二烯烃共聚物与苯乙烯聚合物来制备这种聚合物。然而,这种共混物通常含有非所需的雾度且变蓝。因此希望开发具有低蓝色、良好透明度、硬度、刚度和韧度的聚合物和聚合物共混物。
发明概述
本发明的目的是提供可用于制备具有良好光学透明度的聚合物。
本发明另一目的是提供制备具有良好光学和机械性能的这种聚合物的方法。
根据本发明,提供含至少三种连续共轭二烯烃/单乙烯基芳烃的递变嵌段的嵌段共聚物。此处所使用的连续是指没有插入均聚物嵌段的三个连续的递变嵌段。递变嵌段含有单乙烯基芳烃和共轭二烯烃的混合物。
根据本发明另一方面,聚合物共混物包括至少一种偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物和至少一种苯乙烯属聚合物,其中采用这样一种方法,即:包括在聚合条件下,按序接触至少一种单乙烯基芳烃单体、有机碱金属引发剂、至少一种共轭二烯烃单体,和之后用多官能团偶联剂偶联,形成嵌段共聚物的方法,来生产偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物;提供含有单乙烯基芳烃单体和共轭二烯烃单体的至少三种连续的单体混合物原料,在嵌段共聚物内产生至少三种连续共轭二烯烃/单乙烯基芳烃的递变嵌段;在进料开始时刻添加包含在每一原料内的所有单乙烯基芳烃单体和共轭二烯烃单体,从而允许过量单体存在于反应器中;至少一种单乙烯基芳烃单体含有8-18个碳原子,和至少一种共轭二烯烃单体含有4-12个碳原子,和苯乙烯类聚合物选自通过共聚至少一种苯乙烯属共聚单体和至少一种不饱和的含氧或氮共聚单体而生产的至少一种共聚物。
在本发明又一方面中,苯乙烯类聚合物(不包括苯乙烯均聚物)选自通过共聚至少一种苯乙烯属共聚单体和至少一种不饱和的含氧或氮共聚单体而生产的至少一种共聚物;其中聚合物共混物包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物;单乙烯基芳烃单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;共轭二烯烃单体选自丁二烯、异戊二烯、2,3-二甲基丁二烯;苯乙烯共聚单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和不饱和的含氧或氮共聚单体选自丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、丙烯腈及其混合物。
发明详述
在美国专利Nos.4091053、4584346、4704434、4704435和5227419中披露了制备共轭二烯烃/单乙烯基芳烃嵌段共聚物的基本起始材料和聚合条件。
可在嵌段共聚物中使用的合适共轭二烯烃包括每一分子具有4-12个碳原子的那些,其中优选具有4-8个碳原子的那些。这种合适的化合物的实例包括1,3-丁二烯、2-甲基-1,3-丁二烯、2-乙基-1,3-丁二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、3-丁基-1,3-辛二烯及其混合物。优选的二烯烃是1,3-丁二烯和异戊二烯,更优选1,3-丁二烯。
可在嵌段共聚物中使用的合适单乙烯基芳烃包括每一分子具有8-18个碳原子,优选8-12个碳原子的那些。这种合适的化合物的实例包括苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、2-乙基苯乙烯、3-乙基苯乙烯、4-乙基苯乙烯、4-正丙基苯乙烯、4-叔丁基苯乙烯、2,4-二甲基苯乙烯、4-环己基苯乙烯、4-癸基苯乙烯、2-乙基-4-苄基苯乙烯、4-(4-苯基正丁基)苯乙烯、1-乙烯基萘、2-乙烯基萘及其混合物。苯乙烯是优选的单乙烯基芳烃化合物。
取决于所需的特定特征,共轭二烯烃和单乙烯基芳烃在嵌段共聚物内的相对含量可在宽的范围内变化。一般地,基于最终的嵌段共聚物的总重量,共轭二烯烃/单乙烯基芳烃嵌段共聚物含有用量在约55wt%-约95wt%范围内的单乙烯基芳烃单体,优选在约60wt%-约95wt%范围内,和更优选在65wt%-90wt%范围内。
一般地,基于最终的嵌段共聚物的总重量,共轭二烯烃单体以约45wt%-约5wt%的用量范围存在于最终的嵌段共聚物内,优选在约40wt%-约5wt%范围内,和更优选在35wt%-10wt%范围内。
制备本发明的聚合物共混物所使用的至少一种递变嵌段共聚物含有至少三种连续的共轭二烯烃/单乙烯基芳烃递变嵌段,所述递变嵌段按序掺入嵌段共聚物内,且没有插入均聚物嵌段。
取决于所需的特定特征,各单体在递变嵌段内的含量可在宽的范围内变化。一般地,基于最终的嵌段共聚物的总重量,单乙烯基芳烃以约1wt%-约20wt%的用量范围存在于每一递变嵌段内,优选约2wt%-约15wt%。
一般地,基于最终的嵌段共聚物的总重量,共轭二烯烃以约1wt%-约15wt%的用量范围存在于每一递变嵌段内,优选约2wt%-约12wt%。特别优选的是,存在于最终的嵌段共聚物内的所有共轭二烯烃单体被掺入到递变嵌段内。
取决于所需的特定特征,各单体在递变嵌段内的相对含量也可在宽的范围内变化。一般地,共轭二烯烃存在于每一递变嵌段内,其用量范围为约0.1份-约10份/份在递变嵌段内的单乙烯基芳烃,优选约0.2份-约5份/份单乙烯基芳烃。
在引发剂存在下,单体和单体混合物按序共聚。引发剂可以是已知用于该目的的任何有机单碱金属化合物。优选使用分子式RM的化合物,其中R是含有4-8个碳原子的烷基、环烷基或芳基,更优选R是烷基。M是碱金属,优选锂。优选的引发剂是正丁基锂。
所使用的引发剂用量取决于所需的聚合物或递增的嵌段分子量,这是本领域已知的,且在对原料流内的痕量毒物进行修正的情况下,可容易确定。一般地,引发剂的存在量范围为约0.01phm(相对于每100重量份全部单体的重量份数)-约1.0phm,优选约0.01phm-约0.5phm,和更优选0.01phm-0.2phm。
可在烃稀释剂内使用小量极性有机化合物,如醚、硫醚和叔胺,以改进引发剂的有效性和使至少一部分单乙烯基芳烃单体随机分布在混合单体原料内。优选四氢呋喃。当使用时,有机溶剂化合物的存在量足以改进引发剂的有效性。例如,当使用四氢呋喃改进引发剂的有效性时,四氢呋喃的存在量通常在约0.01-约1.0phm范围内,优选约0.02-约1.0phm。
在约-100℃到约150℃,优选约0℃到约150℃的合适温度范围内,在足以维持反应混合物基本上处于液相的压力下,在烃稀释剂中进行聚合工艺。优选的烃稀释剂包括线性或环状烷属烃或其混合物。典型的实例包括戊烷、己烷、辛烷、环戊烷、环己烷及其混合物。目前优选环己烷。在基本上不存在氧气和水,优选在惰性气体氛围下进行聚合。
在溶液聚合条件下聚合每一单体原料或单体混合物原料,使得在引入随后的原料之前,每一单体原料或单体混合物原料的聚合基本上完全。
典型的引发剂、单体和单体混合物原料顺序包括,但不限于下述:
模式A
(a)单乙烯基芳烃单体和引发剂,
(b)单乙烯基芳烃单体和引发剂,
(c)共轭二烯烃/单乙烯基芳烃单体混合物,
(d)共轭二烯烃/单乙烯基芳烃单体混合物,
(e)共轭二烯烃/单乙烯基芳烃单体混合物,和
(f)偶联剂;
模式B
(a)单乙烯基芳烃单体和引发剂,
(b)单乙烯基芳烃单体和引发剂,
(c)共轭二烯烃/单乙烯基芳烃单体混合物,
(d)共轭二烯烃/单乙烯基芳烃单体混合物,
(e)共轭二烯烃/单乙烯基芳烃单体混合物,
(f)共轭二烯烃/单乙烯基芳烃单体混合物,和
(g)偶联剂;
模式C
(a)单乙烯基芳烃单体和引发剂,
(b)单乙烯基芳烃单体和引发剂,
(c)共轭二烯烃/单乙烯基芳烃单体混合物,
(d)共轭二烯烃/单乙烯基芳烃单体混合物,
(e)共轭二烯烃/单乙烯基芳烃单体混合物,
(f)共轭二烯烃/单乙烯基芳烃单体混合物,
(g)共轭二烯烃/单乙烯基芳烃单体混合物,和
(h)偶联剂;
模式D
(a)单乙烯基芳烃单体和引发剂,
(b)共轭二烯烃/单乙烯基芳烃单体混合物和引发剂,
(c)共轭二烯烃/单乙烯基芳烃单体混合物,
(d)共轭二烯烃/单乙烯基芳烃单体混合物,和
(e)偶联剂;
模式E
(a)单乙烯基芳烃单体和引发剂,
(b)共轭二烯烃/单乙烯基芳烃单体混合物和引发剂,
(c)共轭二烯烃/单乙烯基芳烃单体混合物,
(d)共轭二烯烃/单乙烯基芳烃单体混合物,
(e)共轭二烯烃/单乙烯基芳烃单体混合物,和
(f)偶联剂;
模式F
(a)单乙烯基芳烃单体和引发剂,
(b)共轭二烯烃/单乙烯基芳烃单体混合物和引发剂,
(c)共轭二烯烃/单乙烯基芳烃单体混合物,
(d)共轭二烯烃/单乙烯基芳烃单体混合物,
(e)共轭二烯烃/单乙烯基芳烃单体混合物,
(f)共轭二烯烃/单乙烯基芳烃单体混合物,和
(g)偶联剂。
可预混单体混合物并作为混合物进料,或者可同时引入单体。在步骤(a)中,可在单乙烯基芳烃单体进料之前或之后添加引发剂。在大规模操作中,希望在步骤(a)中,在添加引发剂之前,可添加单乙烯基芳烃单体。在随后含有引发剂的步骤中,应当在单体或单体混合物之前添加引发剂。
在偶联之前,通过以上所述的序列聚合制备的典型聚合物链包括下述:
模式A
S1-S2-B1/S3-B2/S4-B3/S5-Li
S2-B1/S3-B2/S4-B3/S5-Li
模式B
S1-S2-B1/S3-B2/S4-B3/S5-B4/S6-Li
S2-B1/S3-B2/S4-B3/S5-B4/S6-Li
模式C
S1-S2-B1/S3-B2/S4-B3/S5-B4/S6-B5/S7-Li
S2-B1/S3-B2/S4-B3/S5-B4/S6-B5/S7-Li
模式D
S1-B1/S2-B2/S3-B3/S4-Li
B1/S2-B2/S3-B3/S4-Li
模式E
S1-B1/S2-B2/S3-B3/S4-B4/S5-Li
B1/S2-B2/S3-B3/S4-B4/S5-Li
模式F
S1-B1/S2-B2/S3-B3/S4-B4/S5-B5/S6-Li
B1/S2-B2/S3-B3/S4-B4/S5-B5/S6-Li
其中“S”是单乙烯基嵌段,“B/S”是含有单乙烯基芳烃和共轭二烯烃“B”的混合物的递变嵌段,和“Li”是来自碱金属引发剂的阳离子残基。
在聚合完成之后添加偶联剂。合适的偶联剂包括二-或多乙烯基芳烃化合物,二-或多环氧化物,二-或多异氰酸酯,二-或多亚胺,二-或多醛,二-或多酮,烷氧基锡化合物,二-或多卤化物,特别地卤化硅和卤代硅烷,单-、二/或多酸酐,二-或多酯,优选一元醇与多羧酸的酯,二酯(它是一元醇与二羧酸的酯),二酯(它是一元酸与多元醇如甘油等的酯),和两种或多种这些化合物的混合物。
有用的多官能团偶联剂包括环氧化植物油如环氧化豆油、环氧化亚麻子油等或其混合物。目前优选的偶联剂是环氧化植物油,优选环氧化豆油。
可使用任何有效量的偶联剂。尽管认为用量不关键,但一般地相对于活性聚合物,化学计量用量的碱金属倾向于促进最大的偶联。然而,对于特定的产品,对于不同的偶联效率来说,可视需要使用多于或小于化学计量的用量。典型地,聚合中使用的偶联剂的总量在约0.1phm-约20phm范围内,优选约0.1phm-约5phm,和更优选0.1phm-2phm。
在完成偶联反应之后,可用终止剂如水、醇、酚或线性饱和脂族单-二羧酸处理聚合反应混合物,从嵌段共聚物中除去碱金属并控制颜色。优选的终止剂为水和二氧化碳。
聚合物胶泥(cement)(在聚合溶剂内的聚合物)通常含有约10-40wt%的固体,更通常20-35wt%的固体。可闪蒸聚合物胶泥蒸发一部分溶剂,以便增加固体含量到约50-约99wt%固体的浓度,接着通过真空烘箱或脱挥发挤出机干燥处理剩余溶剂。
可回收嵌段共聚物和例如通过研磨、挤塑或注塑加工成所需形状。递变嵌段共聚物也可含有添加剂如抗氧剂、防粘连剂、脱模剂、填料、增量剂和染料等,只要用量和类型没有干扰本发明的目的即可。
在本发明另一实施方案中,共混嵌段共聚物与其它苯乙烯类聚合物如聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物和苯乙烯-丙烯腈共聚物。
苯乙烯类聚合物通常是(a)苯乙烯的均聚物,或(b)苯乙烯作为主要组分与小量除苯乙烯之外的任何其它可共聚单乙烯基芳烃化合物如α-甲基苯乙烯、乙烯基甲苯或对叔丁基苯乙烯的共聚物。小量其它单体如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯腈等可与苯乙烯共聚。含本发明嵌段共聚物和聚苯乙烯的共混物显示出所需特征的结合和它们是优选的。
本发明优选的苯乙烯类聚合物包括具有至少一个苯乙烯属共聚单体和至少一个不饱和的含氧或氮(杂原子)的共聚单体的共聚物。
优选的苯乙烯属共聚单体选自每一分子具有8-18个碳原子,优选8-12个碳原子的那些。这种合适的共聚单体的实例包括苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、2-乙基苯乙烯、3-乙基苯乙烯、4-乙基苯乙烯、4-正丙基苯乙烯、4-叔丁基苯乙烯、2,4-二甲基苯乙烯、4-环己基苯乙烯、4-癸基苯乙烯、2-乙基-4-苄基苯乙烯、4-(4-苯基正丁基)苯乙烯、1-乙烯基萘、2-乙烯基萘及其混合物。苯乙烯是更优选的共聚单体。
含氧或氮的共聚单体包括含有羧基的不饱和单体,如丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、马来酸、富马酸等(优选甲基丙烯酸),(甲基)丙烯酸(优选甲基丙烯酸)的C2-8羟烷酯,如(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸3-羟丙酯、(甲基)丙烯酸羟丁酯等,聚醚多元醇(例如聚乙二醇、聚丙二醇或聚丁二醇)与不饱和羧酸(优选甲基丙烯酸)的单酯;聚醚多元醇(例如聚乙二醇、聚丙二醇或聚丁二醇)与含羟基的不饱和单体(例如甲基丙烯酸2-羟乙酯)的单醚;不饱和羧酸与单环氧化合物的加合物;(甲基)丙烯酸(优选甲基丙烯酸)缩水甘油酯与一元酸(例如乙酸、丙酸、对丁基苯甲酸或脂肪酸)的加合物;含酸酐的不饱和化合物(例如马来酸酐或衣康酸酐)与二元醇(例如乙二醇、1,6-己二醇或新戊二醇)的单酯或二酯;含氯-、溴-、氟和羟基的单体如(甲基)丙烯酸(优选甲基丙烯酸)3-氯-2-羟丙酯等;或(甲基)丙烯酸(优选甲基丙烯酸)的C1-24烷酯或环烷酯,如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基正丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸辛酯、甲基丙烯酸癸酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂醇酯、甲基丙烯酸环己酯等,(甲基)丙烯酸(优选甲基丙烯酸)的C2-8烷氧基烷酯,如甲基丙烯酸甲氧基丁酯、甲基丙烯酸甲氧基乙酯、甲基丙烯酸乙氧基乙酯、甲基丙烯酸乙氧基丁酯等;可聚合酰胺如(甲基)丙烯酰胺、N-甲基(甲基)丙烯酰胺、(甲基)丙烯腈等;含缩水甘油基的乙烯基单体如(甲基)丙烯酸缩水甘油酯。可单独或以两种或大于两种的混合物的形式使用所有这些单体。
可通过本领域已知的任何方法制备苯乙烯类聚合物和共聚物。通常通过在约100℃-约200℃的温度范围内和在足以聚合单体的压力下,加热苯乙烯和任何共聚单体,来制备苯乙烯类聚合物。也可在较低的温度下,通过添加生成自由基的过氧化物催化剂,如过氧化苯甲酰、过氧化乙酰、过氧化二叔丁基等进行聚合。或者,可在悬浮液中进行聚合,得到干燥粉末,或在乳液中进行聚合,从而导致可凝聚的聚苯乙烯胶乳,得到固体粉状聚苯乙烯。也可在溶液中进行聚合并沉淀产品。可通过标准技术如蒸汽汽提或溶剂蒸发除去溶剂。
也可在含有本发明嵌段共聚物的共混物内使用高抗冲聚苯乙烯。可通过在弹性体,典型地聚丁二烯橡胶存在下聚合苯乙烯制备高抗冲聚苯乙烯。
取决于最终的聚合物共混物所需的特征,在制备聚合物共混物中使用的递变嵌段共聚物和苯乙烯类聚合物的相对量可在宽的范围内变化。基于最终的聚合物共混物的总重量,典型的聚合物共混物含有用量范围为约5wt%-约95wt%的嵌段共聚物,优选约10wt%-约90wt%,和基于最终的聚合物共混物的总重量,更优选约20wt%-约80wt%。
基于最终的聚合物共混物的总重量,苯乙烯类聚合物的存在量范围为约5wt%-约95wt%,优选约10wt%-约90wt%,和基于最终的聚合物共混物的总重量,更优选约20wt%-约80wt%。
当使用至少一种优选的苯乙烯类聚合物,即通过共聚至少一种苯乙烯属共聚单体和至少一种不饱和含杂原子(如氧或氮)的共聚单体而生产的那些时,优选在聚合物共混物内具有50wt%(基于最终的聚合物共混物的总重量)或更低的这种苯乙烯类聚合物。因此优选在共混物内具有50wt%或更高,更优选60wt%或更高,最优选70wt%或更高的至少一种三元(三种连续的)递变嵌段共聚物。在聚合物共混物内具有其它单、二元、三元或更高程度的递变嵌段共聚物也在本发明范围内。也可在成品内共混非递变嵌段共聚物。
以上所述的聚合物共混物显示出所需特征的结合。聚合物共混物显示出小于约15%,优选小于约10%的雾度值,这是使用厚度为50mil的样品和诸如Gardner Hazemeter之类的仪器,根据ASTM 1003测量的。当使用厚度为15mil的样品和诸如HunterLab ColorQuest之类的仪器时,优选雾度值小于5%。
聚合物共混物优选显示出大于约0.2ft-lb/in,优选大于0.3ft-lb/in,更优选大于约0.4ft-lb/in的缺口悬臂梁式冲击强度,这根据ASTM D-256来测量。
聚合物共混物还显示出低的蓝色,优选具有小于20的绝对蓝色值,这是使用以校正的黑色背景为背景测量厚度为50mil的三组注塑(350°F/30吨/2粉状)树脂盘,采用HunterLab D25M Optical Sensor测量的。正数表示黄色和负数表示蓝色。当使用厚度为15mil的挤塑片材(400°F/20mil标称模隙)时,蓝色绝对值优选小于15,更优选小于5。
可通过本领域已知的任何方法,其中包括熔体共混和溶液共混,来实现共混。优选使用任何所需的设备如本伯里氏密炼机、热辊或挤塑机,熔体共混聚合物。更优选使用挤塑机共混技术,熔体共混聚合物。可使用单或双螺杆挤塑机。可在熔体共混之前,干混聚合物和任何其它成分或添加剂。
共混条件取决于所使用的共混技术和聚合物。若使用聚合物的起始干混,则干混条件可包括从室温到正好低于聚合物的熔融温度的温度,和共混时间在数秒到数小时范围内,例如2秒到30分钟。
在熔体共混过程中,聚合物在掺混机内混合的温度通常在所使用的聚合物的最高熔点到高于这一熔点100IC的范围内。
熔体共混所要求的时间可在宽的范围内变化和取决于所使用的共混方法。所要求的时间是足以彻底混合各组分的时间。一般地,共混单独的聚合物约10秒到约15分钟的时间。
聚合物共混物可含有添加剂如稳定剂、抗氧剂、防粘连剂、脱模剂、染料、颜料和阻燃剂,以及填料和增强剂,如玻璃纤维,只要用量和类型没有干扰本发明的目的即可。
根据本发明制备的嵌段共聚物和聚合物共混物可用于生产通过研磨、挤塑、吹塑或注塑制备的制品。
列出下述实施例进一步阐述本发明和不意味着辛酯本发明。
实施例1
下述实施例说明了嵌段共聚物的制备和各种聚合物共混物的透明度与机械性能的结合。
在氮气下,使用按序的溶液聚合制备苯乙烯/丁二烯嵌段共聚物(SB)。使用基本上无水的反应物和条件,在具有内部冷却蛇管的搅拌的100加仑碳钢反应器内进行聚合试验。
在每次进料之后,用0.5kg环己烷冲洗管线。在每一单体或单体混合物的进料之后,使聚合继续完成。聚合温度范围为约38℃-约120℃,和压力范围为约2psig-约60psig。全部单体重量为约90kg。四氢呋喃(THF)、苯乙烯(S)、正丁基锂引发剂(i)、丁二烯/苯乙烯混合物(B/S)和偶联剂(CA)的进料顺序如下所述。
嵌段共聚物A1
0.5THF,0.05i1,30S1,0.05i2,20S2,(5B1/10S3),(10B2/10S4),(10B3/55S5),CA(用量份数/100份单体)
嵌段共聚物A2
0.1THF,0.05i1,30S1,0.05i2,20S2,(5B1/10S3),(10B2/10S4),(10B3/55S5),CA(用量份数/100份单体)
在完成序列聚合之后,向反应器中引入Vikoflex7170(一种由Viking Chemical Co.销售的含环氧化豆油的偶联剂)。在完成偶联反应之后,通过添加二氧化碳和0.2phm的水终止反应。用0.25phr(每100份树脂的份数)Irganox1076和1.0phr三(壬基苯基)亚磷酸酯稳定苯乙烯/丁二烯嵌段共聚物。Vikoflex是Viking Chemical Company的注册商标。Irganox是Ciba Geigy Corporation的注册商标。
嵌段共聚物A1和A2分别显示出7.2和6.5g/10min的熔体流动,这根据ASTMD-1238,条件D来测量。
实施例II
通过混合与共混至少一种由苯乙烯和丁二烯制造的递变嵌段共聚物,和至少一种由苯乙烯和甲基丙烯酸甲酯制造的苯乙烯类聚合物,形成聚合物共混物。以各种重量比共混Nova 9203和NAS 90(二者均是获自Novacor Plastics Division的苯乙烯和甲基丙烯酸甲酯的共聚物)与至少一种三元递变的苯乙烯-丁二烯嵌段共聚物。
结果概述于表1。使用15mil的挤塑片材(400°F/20mil标称模隙),采用HunterLab D25M Optical Sensor,测量蓝色、三色值“b”,一种蓝色和黄色的量度。以校正的黑色背景为背景测量。正数表示黄色和负数表示蓝色。根据ASTM 1003,在15mil的片材上,使用HunterLabColorQuest仪,测量以百分数表示的雾度值。如上所述测量蓝色。通过公知和已接受的ASTM或标准方法测量其它性能(缺口悬臂梁式冲击强度,挠曲屈服强度等)。
所使用的共聚物是苯乙烯/丁二烯三元递变嵌段共聚物。所使用的苯乙烯类聚合物是苯乙烯与甲基丙烯酸甲酯的共聚物。
表1三元递变嵌段共聚物和苯乙烯-甲基丙烯酸甲酯共聚物的聚合物共混物的物理性能
三元递变嵌段共聚物(wt%) | 100% | 80% | 60% | 50% | 40% | 30% | 20% | 10% | ||||
苯乙烯/MMA#共聚物(wt%) | 20% | 40% | 50% | 60% | 70% | 80% | 90% | |||||
熔体流动(g/10min) | 10.9 | 9.1 | 6.8 | 5.1 | 4.8 | 4.2 | 3.0 | 2.4 | ||||
ASTM D1238,条件G | ||||||||||||
密度(g/cc) | 1.0182 | 1.0279 | 1.038 | 1.0431 | 1.0482 | 1.0533 | 1.0581 | 1.067 | ||||
ASTM D792 | ||||||||||||
断裂拉伸@伸长率(%) | 343 | 238 | 145 | 113 | 76 | 50 | 39 | 8 | ||||
ASTM D638,2”/min | ||||||||||||
拉伸屈服强度(psi) | 2203 | 2111 | 3025 | 3651 | 4266 | 5066 | 6620 | 7661 | ||||
ASTM D638,2”/min | ||||||||||||
挠曲模量(Tan)(psi) | 104991 | 129401 | 182426 | 221981 | 261879 | 332010 | 387423 | 450820 | ||||
ASTM D790 | ||||||||||||
HDT,66psi(℃) | 54 | 55 | 62 | 70 | 71 | 79 | 81 | 81 | ||||
ASTM D648 | ||||||||||||
HDT,264psi(℃) | 46 | 48 | 51 | 56 | 63 | 68 | 71 | 72 | ||||
ASTM D648 | ||||||||||||
维卡(℃) | 60 | 62 | 74 | 80 | 87 | 92 | 93 | 93 | ||||
ASTM D1545 | ||||||||||||
肖氏D硬度 | 61 | 65 | 69 | 72 | 75 | 78 | 81 | 85 | ||||
ASTM D2240 | ||||||||||||
缺口悬臂梁式冲击强度(ft-lb/in) | 15.4 | 17.2 | 14.3 | 3.7 | 0.39 | 0.27 | 0.25 | 0.36 | ||||
ASTM D256,1/8”厚度 | 部分 | 部分 | 部分 | 完全2部分 | 完全 | 完全 | 完全 | 完全 | ||||
无缺口悬臂梁式冲击强度(ft-lb/in) | 27.1 | 4.7 | 3.1 | 5.4 | ||||||||
ASTM D256,1/8”厚度 | 未断裂 | 未断裂 | 完全4未断裂 | 未断裂 | 未断裂 | 完全 | 完全 | 完全 | ||||
Dynatup Tot.Enrgy(in-lb) | 296 | 338 | 371 | 395 | 39.2 | 31.0 | 23.8 | 20.4 | ||||
直径0.5”dia,Tup,15lbs,30” | ||||||||||||
亨特色度,b | 3.5 | 4.7 | 4.2 | 3.9 | 3.3 | 1.9 | 1.5 | 2.7 | ||||
雾度值(%) | 14.90 | 9.20 | 4.80 | 1.60 | 1.20 | 3.80 | 11.70 | 26.50 | ||||
透光率(%) | 89.5 | 83.7 | 84.1 | 85.9 | 88.3 | 91.0 | 91.8 | 90.0 | ||||
*递变嵌段共聚物不含防粘连/沉积改性剂添加剂 |
#Nova NAS 90苯乙烯-甲基丙烯酸甲酯共聚物
表2三元递变嵌段共聚物和苯乙烯-甲基丙烯酸甲酯共聚物的聚合物共混物的注塑性能
三元递变嵌段共聚物(wt%) | 90 | 70% | 60% | 50% | 40% | 30% | 20% | 15%* |
苯乙烯/MMA#共聚物(wt%) | 10 | 30% | 40% | 50% | 60% | 70% | 80% | 80% |
挠曲屈服强度(psi) | 3394 | 3826 | 4538 | 5847 | 7610 | 9407 | 10466 | 11172 |
拉伸屈服强度 | 2086 | 2155 | - | 3575 | 4326 | 5243 | 6515 | 6910 |
拉伸断裂 | 2744 | 2730 | 2833 | 3195 | 3588 | 4161 | 4812 | 5108 |
缺口悬臂梁式冲击强度(ft-lb) | - | - | - | 2.19 | 0.46 | 0.38 | 0.37 | 0.35 |
无缺口悬臂梁式冲击强度(ft-lb) | - | - | - | - | 19.9 | 5.16 | 3.64 | 4.05 |
雾度值(%) | 19.2 | 21.0 | 15.6 | 11.23 | 5.7 | 2.37 | 0.78 | 0.93 |
光泽(%) | 129 | 126 | 126 | 137 | 142 | 143 | 154 | 154 |
亨特色度(b) | 4.54 | 4.70 | 4.49 | 4.12 | 3.44 | 2.69 | 1.79 | 1.48 |
黄色指数 | 8.23 | 8.95 | 8.51 | 7.53 | 5.75 | 3.98 | 2.00 | 1.32 |
透光率(%) | 86.5 | 84.3 | 84.0 | 85.5 | 87.9 | 90.2 | 91.9 | 92 |
肖氏D硬度 | 63 | 67 | 69 | 72 | 75 | 78 | 81 | 82 |
维卡°F | 143 | 150 | 159 | 175 | 190 | 196 | 199 | 201 |
*共混物含有5wt%KR03苯乙烯-丁二烯共聚物(Chevron PhillipsChemical Company LP的商业产品)
#使用Nova 9203 SMMA。
表1和2的结果证明当三元递变苯乙烯-丁二烯嵌段共聚物用量是聚合物共混物总重量的50wt%或更多,尤其60wt%或更多时,使用含三元递变嵌段的嵌段共聚物显示出良好透明度和良好冲击韧度的结合。
实施例仅用于说明目的。不打算用它们限制本发明的范围,本发明的范围由所披露的内容和权利要求来定义。
Claims (19)
1.一种聚合物共混物,它包括至少一种偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物和至少一种苯乙烯类聚合物,其中
通过包括在聚合条件下,按序接触至少一种单乙烯基芳烃单体、有机碱金属引发剂、至少一种共轭二烯烃单体,和之后用多官能团偶联剂偶联,形成嵌段共聚物的方法,来生产偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物;
提供含有单乙烯基芳烃单体和共轭二烯烃单体的至少三种连续的单体混合物原料,在嵌段共聚物内产生至少三种连续共轭二烯烃/单乙烯基芳烃的递变嵌段;
在进料开始时刻添加包含在每一原料内的所有单乙烯基芳烃单体和共轭二烯烃单体,从而允许过量单体存在于反应器中;
至少一种单乙烯基芳烃单体含有8-18个碳原子,和至少一种共轭二烯烃单体含有4-12个碳原子,和
苯乙烯类聚合物选自通过共聚至少一种苯乙烯属共聚单体和至少一种不饱和的含氧或氮共聚单体而生产的至少一种共聚物。
2.权利要求1的聚合物共混物,它包括:
(A)50wt%或更低的苯乙烯类聚合物;和
(B)50wt%或更多的偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
3.权利要求2的聚合物共混物,其中
单乙烯基芳烃单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
共轭二烯烃单体选自丁二烯、异戊二烯、2,3-二甲基丁二烯。
4.权利要求2的聚合物共混物,其中
苯乙烯属共聚单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
不饱和的含氧或氮共聚单体选自丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、丙烯腈及其混合物。
5.权利要求2的聚合物共混物,它包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
6.权利要求3的聚合物共混物,它包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
7.权利要求4的聚合物共混物,它包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
8.权利要求7的聚合物共混物,其中
单乙烯基芳烃单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
共轭二烯烃单体选自丁二烯、异戊二烯、2,3-二甲基丁二烯及其混合物。
9.一种聚合物,它包括至少一种偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物和至少一种苯乙烯类聚合物,其中
通过包括在聚合条件下,按序接触至少一种单乙烯基芳烃单体、有机碱金属引发剂、至少一种共轭二烯烃单体,和之后用多官能团偶联剂偶联,形成嵌段共聚物的方法,来生产偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物;
提供含有单乙烯基芳烃单体和共轭二烯烃单体的至少三种连续的单体混合物原料,在嵌段共聚物内产生至少三种连续共轭二烯烃/单乙烯基芳烃的递变嵌段;
在进料开始时刻添加包含在每一原料内的所有单乙烯基芳烃单体和共轭二烯烃单体,从而允许过量单体存在于反应器中;
至少一种单乙烯基芳烃单体含有8-18个碳原子,和至少一种共轭二烯烃单体含有4-12个碳原子,
苯乙烯类聚合物选自通过共聚至少一种苯乙烯属共聚单体和至少一种不饱和的含氧或氮共聚单体而生产的至少一种共聚物;其中
单乙烯基芳烃单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
共轭二烯烃单体选自丁二烯、异戊二烯、2,3-二甲基丁二烯及其混合物;
苯乙烯属共聚单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
不饱和的含氧或氮共聚单体选自丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、丙烯腈及其混合物。
10.权利要求9的聚合物共混物,它包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
11.一种聚合物,它包括至少一种偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物和至少一种苯乙烯类聚合物,其中
通过包括在聚合条件下,按序接触至少一种单乙烯基芳烃单体、有机碱金属引发剂、至少一种共轭二烯烃单体,和之后用多官能团偶联剂偶联,形成嵌段共聚物的方法,来生产偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物;
提供含有单乙烯基芳烃单体和共轭二烯烃单体的至少三种连续的单体混合物原料,在嵌段共聚物内产生至少三种连续共轭二烯烃/单乙烯基芳烃的递变嵌段;
在进料开始时刻添加包含在每一原料内的所有单乙烯基芳烃单体和共轭二烯烃单体,从而允许过量单体存在于反应器中;
至少一种单乙烯基芳烃单体含有8-18个碳原子,和至少一种共轭二烯烃单体含有4-12个碳原子,
苯乙烯类聚合物选自通过共聚至少一种苯乙烯属共聚单体和至少一种不饱和的含氧或氮共聚单体而生产的至少一种共聚物;其中
聚合物共混物包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物;
单乙烯基芳烃单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯及其混合物;和
共轭二烯烃单体选自丁二烯、异戊二烯及其混合物;
苯乙烯属共聚单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯及其混合物;和
不饱和的含氧或氮共聚单体选自丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸乙酯及其混合物。
12.一种制造聚合物共混物的方法,该方法包括共混至少一种偶联的/单乙烯基芳烃嵌段共聚物和至少一种苯乙烯类聚合物,其中:
通过包括在聚合条件下,按序接触至少一种单乙烯基芳烃单体、有机碱金属引发剂、至少一种共轭二烯烃单体,和之后用多官能团偶联剂偶联,形成嵌段共聚物的方法,来生产偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物;
提供含有单乙烯基芳烃单体和共轭二烯烃单体的至少三种连续的单体混合物原料,在嵌段共聚物内产生至少三种连续共轭二烯烃/单乙烯基芳烃的递变嵌段;
在进料开始时刻添加包含在每一原料内的所有单乙烯基芳烃单体和共轭二烯烃单体,从而允许过量单体存在于反应器中;
至少一种单乙烯基芳烃单体含有8-18个碳原子,和至少一种共轭二烯烃单体含有4-12个碳原子,和
苯乙烯类聚合物选自通过共聚至少一种苯乙烯属共聚单体和至少一种不饱和的含氧或氮共聚单体而生产的至少一种共聚物。
13.权利要求12的方法,其中聚合物共混物包括:
(A)50wt%或更低的苯乙烯类聚合物;和
(B)50wt%或更多的偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
14.权利要求13的方法,其中:
单乙烯基芳烃单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
共轭二烯烃单体选自丁二烯、异戊二烯、2,3-二甲基丁二烯。
15.权利要求13的方法,其中:
苯乙烯属共聚单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
不饱和的含氧或氮共聚单体选自丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、丙烯腈及其混合物。
16.权利要求13的方法,其中聚合物共混物包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
17.权利要求14的方法,其中聚合物共混物包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
18.权利要求15的方法,其中聚合物共混物包括60wt%或更多偶联的共轭二烯烃/单乙烯基芳烃嵌段共聚物。
19.权利要求18的方法,其中
单乙烯基芳烃单体选自苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-叔丁基苯乙烯、α-甲基苯乙烯及其混合物;和
共轭二烯烃单体选自丁二烯、异戊二烯、2,3-二甲基丁二烯及其混合物。
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-
2002
- 2002-05-20 US US10/151,443 patent/US6835778B2/en not_active Expired - Lifetime
-
2003
- 2003-05-19 DE DE60315454T patent/DE60315454T2/de not_active Expired - Lifetime
- 2003-05-19 WO PCT/US2003/015654 patent/WO2003099925A1/en active IP Right Grant
- 2003-05-19 CA CA2486190A patent/CA2486190C/en not_active Expired - Fee Related
- 2003-05-19 JP JP2004508172A patent/JP2005529992A/ja active Pending
- 2003-05-19 MX MXPA04011501A patent/MXPA04011501A/es active IP Right Grant
- 2003-05-19 ES ES03755376T patent/ES2287515T3/es not_active Expired - Lifetime
- 2003-05-19 BR BRPI0311162-8A patent/BR0311162B1/pt not_active IP Right Cessation
- 2003-05-19 AT AT03755376T patent/ATE369397T1/de not_active IP Right Cessation
- 2003-05-19 CN CN03814130.2A patent/CN1662600A/zh active Pending
- 2003-05-19 EP EP03755376A patent/EP1513896B1/en not_active Expired - Lifetime
- 2003-05-19 AU AU2003247378A patent/AU2003247378A1/en not_active Abandoned
- 2003-05-19 TW TW092113476A patent/TWI322166B/zh not_active IP Right Cessation
- 2003-08-06 US US10/635,662 patent/US20040059057A1/en not_active Abandoned
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TW200404857A (en) | 2004-04-01 |
JP2005529992A (ja) | 2005-10-06 |
TWI322166B (en) | 2010-03-21 |
AU2003247378A1 (en) | 2003-12-12 |
US20030004267A1 (en) | 2003-01-02 |
DE60315454D1 (de) | 2007-09-20 |
MXPA04011501A (es) | 2005-02-17 |
CA2486190A1 (en) | 2003-12-04 |
CA2486190C (en) | 2011-04-19 |
US6835778B2 (en) | 2004-12-28 |
DE60315454T2 (de) | 2008-04-24 |
BR0311162B1 (pt) | 2013-03-05 |
ATE369397T1 (de) | 2007-08-15 |
BR0311162A (pt) | 2005-03-15 |
US20040059057A1 (en) | 2004-03-25 |
WO2003099925A1 (en) | 2003-12-04 |
ES2287515T3 (es) | 2007-12-16 |
EP1513896A1 (en) | 2005-03-16 |
EP1513896B1 (en) | 2007-08-08 |
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