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CN106574045A - 共聚碳酸酯和包含该共聚碳酸酯的组合物 - Google Patents

共聚碳酸酯和包含该共聚碳酸酯的组合物 Download PDF

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Publication number
CN106574045A
CN106574045A CN201580040574.4A CN201580040574A CN106574045A CN 106574045 A CN106574045 A CN 106574045A CN 201580040574 A CN201580040574 A CN 201580040574A CN 106574045 A CN106574045 A CN 106574045A
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CN
China
Prior art keywords
chemical formula
copolycarbonate
bis
repeating unit
hydroxyphenyl
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CN201580040574.4A
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Inventor
田炳圭
潘亨旼
黄英荣
朴正濬
洪武镐
李琪载
高雲
孙永旭
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from PCT/KR2015/013082 external-priority patent/WO2016089118A2/ko
Publication of CN106574045A publication Critical patent/CN106574045A/zh
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Abstract

本发明涉及一种共聚碳酸酯和包含该共聚碳酸酯的模制品。根据本发明的共聚碳酸酯具有在聚碳酸酯的主链中引入特定的硅氧烷化合物的结构,因此具有提供优异的驻留热稳定性的特性。

Description

共聚碳酸酯和包含该共聚碳酸酯的组合物
[相关申请的交叉引用]
本申请要求在韩国知识产权局于2014年12月04日提交的韩国专利申请号10-2014-0173005和于2015年12月01日提交的韩国专利申请号10-2015-0169804的权益,这两项申请的全部公开内容通过引用并入本文。
技术领域
本发明涉及一种共聚碳酸酯和包含该共聚碳酸酯的组合物,更具体地涉及一种被经济地生产并具有优异的驻留热稳定性的共聚碳酸酯以及包含该共聚碳酸酯的组合物。
背景技术
聚碳酸酯树脂通过芳香族二元醇如双酚A与碳酸酯前体如光气的缩聚反应制备并且具有优异的冲击强度、尺寸稳定性、耐热性和透明度。因此,聚碳酸酯树脂广泛地应用于例如电子电气产品的外部材料、汽车零部件、建筑材料和光学元件的用途中。
近来,为了将这些聚碳酸酯树脂应用于更多样的领域中,已经进行了许多研究以通过将两种以上彼此具有不同结构的芳香族二元醇化合物共聚并在聚碳酸酯的主链中引入具有不同结构的单元而获得所需的物理性能。
特别是,已进行了在聚碳酸酯的主链中引入聚硅氧烷结构的研究,但是这些技术大部分具有生产成本高且热稳定性低的缺点。
考虑到上述情况,本发明人已进行了深入的研究以解决现有技术遇到的上述缺点,并开发一种具有提高的热稳定性的共聚碳酸酯。结果,本发明人发现,下文描述的在聚碳酸酯的主链中引入特定的硅氧烷化合物的共聚碳酸酯满足上述性质,从而完成了本发明。
发明内容
技术问题
本发明的一个目的是提供一种具有优异的驻留热稳定性的共聚碳酸酯。
本发明的另一目的是提供一种包含上述共聚碳酸酯的组合物。
技术方案
为了达到这些目的,本发明提供了一种共聚碳酸酯,包含:芳香族聚碳酸酯类第一重复单元;以及一种或多种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元,并且根据下式1测定的ΔYI为0.5至5:
[式1]
ΔYI=YI(320℃,15分钟)-YI(320℃,0分钟)
在式1中,
YI(320℃,0分钟)是通过将所述共聚碳酸酯在320℃下注射成型而得到的试样(宽度/长度/厚度=60mm/40mm/3mm)根据ASTM D1925测定的YI(黄色指数),以及
YI(320℃,15分钟)是通过将所述共聚碳酸酯在320℃下保持15分钟然后进行注射成型而获得的试样(宽度/长度/厚度=60mm/40mm/3mm)根据ASTM D1925测定的YI(黄色指数)。
当使用共聚碳酸酯制备产品时,产品通常通过注射成型法形成。在注射成型期间,对共聚碳酸酯施加有一定时间的高温,因此在该过程中可能产生诸如热分解的变形。因此,为了提高共聚碳酸酯的适用性,应当使由注射工艺引起的变形最小化,为了评价这一点,在本发明中评价“驻留热稳定性”。
如此处所使用,术语“驻留热稳定性”是指将共聚碳酸酯在一定的高温下驻留一定时间然后注射以制备试样,测量该试样的YI(黄色指数)然后与未驻留的注射试样的YI进行比较。具体地,在本发明中,施加的条件为将试样在320℃下驻留15分钟(如式1所示)。
当驻留热稳定性优异时,即使在较高温下驻留一定时间也几乎不产生诸如热分解的变形,因此与未驻留的注射试样的YI(黄色指数)相比没有大的差异。
特别是,根据本发明的共聚碳酸酯根据式1测定的ΔYI为0.5至5。优选地,根据式1测定的ΔYI不大于4.5、不大于4.0、不大于3.5、不大于3.0、不大于2.5、不大于2.0、不大于1.9、不大于1.8、不大于1.7、不大于1.6或不大于1.5。
另外,ΔYI的值越小则驻留热稳定性越优异,并且不限于任何下限值。然而,作为一个实例,该值优选不小于0.5、不小于0.6、不小于0.7、不小于0.8、不小于0.9或不小于1.0。
另外,优选地,根据本发明的共聚碳酸酯的YI(320℃,15分钟)大于0、不大于9、不大于8、不大于7、不大于6或不大于5。此外,优选地,根据本发明的共聚碳酸酯的YI(320℃,0分钟)大于0、不大于5或不大于4。
另外,优选地,根据本发明的共聚碳酸酯在-30℃下根据ASTM D256(1/8英寸,缺口悬臂梁式)测定的低温冲击强度为600J/m至1000J/m。
另外,优选地,根据本发明的共聚碳酸酯的重均分子量为1,000g/mol至100,000g/mol,更优选地为15,000g/mol至35,000g/mol。在该重均分子量的范围内,所述共聚碳酸酯具有提供优异的驻留热稳定性的效果。
更优选地,上述重均分子量不小于20,000g/mol、不小于21,000g/mol、不小于22,000g/mol、不小于23,000g/mol、不小于24,000g/mol、不小于25,000g/mol、不小于26,000g/mol、不小于27,000g/mol或不小于28,000g/mol。此外,上述重均分子量不大于34,000g/mol、不大于33,000g/mol或不大于32,000g/mol。
另外,优选地,根据本发明的共聚碳酸酯根据ASTM D1238(300℃和1.2kg的条件下)测定的熔体指数为3至20g/10min。
更优选地,所述熔体指数不小于5g/10min、不小于6g/10min、不小于7g/10min或不小于8g/10min;且不大于15g/10min、不大于14g/10min、不大于13g/10min或不大于12g/10min。
另外,优选地,根据本发明的共聚碳酸酯包含两种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元。
另外,优选地,在根据本发明的共聚碳酸酯中,相对于芳香族聚碳酸酯类第一重复单元和一种或多种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元的总重量,芳香族聚碳酸酯类第一重复单元的含量为90至99%。在该含量范围内,共聚碳酸酯具有提供优异的驻留热稳定性的效果。
更优选地,相对于芳香族聚碳酸酯类第一重复单元和一种或多种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元的总重量,芳香族聚碳酸酯类第一重复单元的含量不小于91%、不小于92%、不小于93%或不小于94%;且不大于98%、不大于97%或不大于96%。此外,上述含量可以基于下面将描述的芳香族二醇化合物和硅氧烷化合物的重量比来确定。
另外,在根据本发明的共聚碳酸酯中,芳香族聚碳酸酯类第一重复单元优选通过使芳香族二元醇化合物与碳酸酯前体反应形成,并且更优选地由下面化学式1表示:
[化学式1]
在化学式1中,
R1、R2、R3和R4各自独立地是氢、C1-10烷基、C1-10烷氧基或卤素,
Z是未被取代或被苯基取代的C1-10亚烷基、未被取代或被C1-10烷基取代的C3-15亚环烷基、O、S、SO、SO2或CO。
优选地,在化学式1中,R1、R2、R3和R4各自独立地是氢、甲基、氯或溴。
另外,Z优选为未被取代或被苯基取代的直链或支链C1-10亚烷基,更优选为亚甲基、乙烷-1,1-二基、丙烷-2,2-二基、丁烷-2,2-二基、1-苯乙烷-1,1-二基或二苯亚甲基。此外,优选地,Z是环己烷-1,1-二基、O、S、SO、SO2或CO。
优选地,由化学式1表示的重复单元可以来自于选自双(4-羟苯基)甲烷、双(4-羟苯基)醚、双(4-羟苯基)砜、双(4-羟苯基)亚砜、双(4-羟苯基)硫醚、双(4-羟苯基)甲酮、1,1-双(4-羟苯基)乙烷、双酚A、2,2-双(4-羟苯基)丁烷、1,1-双(4-羟苯基)环己烷、2,2-双(4-羟基-3,5-二溴苯基)丙烷、2,2-双(4-羟基-3,5-二氯苯基)丙烷、2,2-双(4-羟基-3-溴苯基)丙烷、2,2-双(4-羟基-3-氯苯基)丙烷、2,2-双(4-羟基-3-甲基苯基)丙烷、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、1,1-双(4-羟苯基)-1-苯乙烷、双(4-羟苯基)二苯基甲烷和α,ω-双[3-(邻羟苯基)丙基]聚二甲基硅氧烷中的一种或多种芳香族二元醇化合物。
如此处所使用,“来自于芳香族二元醇化合物”是指芳香族二元醇化合物的羟基与碳酸酯前体反应形成由化学式1表示的重复单元。
例如,当使芳香族二元醇化合物双酚A与碳酸酯前体三光气聚合时,由化学式1表示的重复单元由下面化学式1-1表示:
[化学式1-1]
此处所使用的碳酸酯前体可以包括选自碳酸二甲酯、碳酸二乙酯、碳酸二丁酯、碳酸二环己酯、碳酸二苯酯、碳酸二甲苯酯、碳酸双(氯苯基)酯、碳酸二间甲酚酯、碳酸二萘酯、碳酸双(联苯)酯、光气、三光气、双光气、溴光气以及双卤代甲酸酯中的一种或多种。优选地,可以使用三光气或光气。
另外,优选地,在根据本发明的共聚碳酸酯中,一种或多种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元通过使一种或多种硅氧烷化合物与碳酸酯前体反应形成,并且更优选地包含由下面化学式2表示的重复单元和由下面化学式3表示的重复单元:
[化学式2]
在化学式2中,
X1各自独立地是C1-10亚烷基,
R5各自独立地是氢;未被取代或被环氧乙烷基、被环氧乙烷基取代的C1-10烷氧基或C6-20芳基取代的C1-15烷基;卤素;C1-10烷氧基;烯丙基;C1-10卤代烷基;或C6-20芳基,
n是10至200的整数,
[化学式3]
在化学式3中,
X2各自独立地是C1-10亚烷基,
Y1各自独立地是氢、C1-6烷基、卤素、羟基、C1-6烷氧基或C6-20芳基,
R6各自独立地是氢;未被取代或被环氧乙烷基、被环氧乙烷基取代的C1-10烷氧基或C6-20芳基取代的C1-15烷基;卤素;C1-10烷氧基;烯丙基;C1-10卤代烷基;或C6-20芳基,
m是10至200的整数。
在化学式2中,X1各自独立地优选为C2-10亚烷基,更优选为C2-4亚烷基且最优选为丙烷-1,3-二基。
另外,优选地,R5各自独立地是氢、甲基、乙基、丙基、3-苯丙基、2-苯丙基、3-(环氧乙烷基甲氧基)丙基、氟、氯、溴、碘、甲氧基、乙氧基、丙氧基、烯丙基、2,2,2-三氟乙基、3,3,3-三氟丙基、苯基或萘基。此外,R5各自独立地优选为C1-10烷基,更优选为C1-6烷基,还更优选为C1-3烷基且最优选为甲基。
另外,优选地,n是不小于10、不小于15、不小于20、不小于25、不小于30、不小于31或不小于32;且不大于50、不大于45、不大于40、不大于39、不大于38或不大于37的整数。
在化学式3中,X2各自独立地优选为C2-10亚烷基,更优选为C2-6亚烷基且最优选为亚异丁基。
另外,优选地,Y1是氢。
另外,优选地,R6各自独立地是氢、甲基、乙基、丙基、3-苯丙基、2-苯丙基、3-(环氧乙烷基甲氧基)丙基、氟、氯、溴、碘、甲氧基、乙氧基、丙氧基、烯丙基、2,2,2-三氟乙基、3,3,3-三氟丙基、苯基或萘基。此外,优选地,R6各自独立地是C1-10烷基,更优选为C1-6烷基,还更优选为C1-3烷基且最优选为甲基。
优选地,m是不小于40、不小于45、不小于50、不小于55、不小于56、不小于57或不小于58;且不大于80、不大于75、不大于70、不大于65、不大于64、不大于63或不大于62的整数。
由化学式2表示的重复单元和由化学式3表示的重复单元分别来自于由下面化学式2-1表示的硅氧烷化合物和由下面化学式3-1表示的硅氧烷化合物:
[化学式2-1]
在化学式2-1中,X1、R5和n与此前定义相同。
[化学式3-1]
在化学式3-1中,X2、Y1、R6和m与此前定义相同。
如此处所使用,“来自于硅氧烷化合物”是指各个硅氧烷化合物的羟基与碳酸酯前体反应形成由化学式2表示的重复单元和由化学式3表示的重复单元。此外,可以用于形成由化学式2和3表示的重复单元的碳酸酯前体与上述可以用于形成由化学式1表示的重复单元的碳酸酯前体相同。
用于制备由化学式2-1表示的硅氧烷化合物和由化学式3-1表示的硅氧烷化合物的方法分别由下面反应图解1和2表示:
[反应图解1]
在反应图解1中,
X1'是C2-10烯基,
X1、R5和n与此前定义相同。
[反应图解2]
在反应图解2中,
X2'是C2-10烯基,
X2、Y1、R6和m与此前定义相同。
在反应图解1和反应图解2中,反应优选在金属催化剂的存在下进行。作为所述金属催化剂,优选使用铂催化剂。此处所使用的铂催化剂可以包括选自Ashby催化剂、Karstedt催化剂、Lamoreaux催化剂、Speier催化剂、PtCl2(COD)、PtCl2(苄腈)2和H2PtBr6中的一种或多种。基于100重量份的由化学式7或9表示的化合物,金属催化剂的用量可以不小于0.001重量份、不小于0.005重量份或不小于0.01重量份;且不大于1重量份、不大于0.1重量份或不大于0.05重量份。
另外,上述反应温度优选为80℃至100℃。此外,上述反应时间优选为1小时至5小时。
另外,由化学式7或9表示的化合物可以通过使有机二硅氧烷和有机环硅氧烷在酸性催化剂的存在下反应来制备,n和m可以通过调节所使用的反应物的量来调节。反应温度优选为50℃至70℃。此外,反应时间优选为1小时至6小时。
上述有机二硅氧烷可以包括选自四甲基二硅氧烷、四苯基二硅氧烷、六甲基二硅氧烷和六苯基二硅氧烷中的一种或多种。此外,上述有机环硅氧烷可以包括,例如,有机环四硅氧烷。作为其中的一个实例,可以包括八甲基环四硅氧烷和八苯基环四硅氧烷等。
基于100重量份的有机环硅氧烷,上述有机二硅氧烷的用量可以不小于0.1重量份或不小于2重量份;且不大于10重量份或不大于8重量份。
可以在此处使用的上述酸性催化剂包括选自H2SO4、HClO4、AlCl3、SbCl5、SnCl4和酸性粘土(漂白土)中的一种或多种。此外,基于100重量份的有机环硅氧烷,酸性催化剂的用量可以不小于0.1重量份、不小于0.5重量份或不小于1重量份;且不大于10重量份、不大于5重量份或不大于3重量份。
特别是,通过调节由化学式2表示的重复单元和由化学式3表示的重复单元的含量,可以同时提高共聚碳酸酯的低温冲击强度和YI(黄色指数)。优选地,上述重复单元之间的重量比可以是从1:99至99:1。优选地,所述重量比是从3:97至97:3、从5:95至95:5、从10:90至90:10或从15:85至85:15,并且更优选从20:80至80:20。上述重复单元的重量比对应于硅氧烷化合物例如由化学式2-1表示的硅氧烷化合物与由化学式3-1表示的硅氧烷化合物的重量比。
优选地,由化学式2表示的重复单元由下面化学式2-2表示:
[化学式2-2]
在化学式2-2中。R5和n与此前定义相同。优选地,R5是甲基。
另外,优选地,由化学式3表示的重复单元由下面化学式3-2表示:
[化学式3-2]
在化学式3-2中,R6和m与此前定义相同。优选地,R6是甲基。
另外,根据本发明的共聚碳酸酯包含由化学式1-1表示的重复单元、由化学式2-2表示的重复单元和由化学式3-2表示的重复单元全部。
另外,本发明提供了一种制备共聚碳酸酯的方法,该方法包括使芳香族二元醇化合物、碳酸酯前体以及一种或多种硅氧烷化合物聚合的步骤。
所述芳香族二元醇化合物、碳酸酯前体以及一种或多种硅氧烷化合物与此前描述相同。
在聚合的过程中,基于共计100wt%的芳香族二元醇化合物、碳酸酯前体和一种或多种硅氧烷化合物,所述一种或多种硅氧烷化合物的用量可以不小于0.1wt%、不小于0.5wt%、不小于1wt%或不小于1.5wt%;且不大于20wt%、不大于10wt%、不大于7wt%、不大于5wt%、不大于4wt%、不大于3wt%或不大于2wt%。此外,基于共计100wt%的芳香族二元醇化合物、碳酸酯前体和一种或多种硅氧烷化合物,上述芳香族二元醇化合物的用量可以不小于40wt%、不小于50wt%或不小于55wt%;且不大于80wt%、不大于70wt%或不大于65wt%。基于共计100wt%的芳香族二元醇化合物、碳酸酯前体和一种或多种硅氧烷化合物,上述碳酸酯前体的用量可以不小于10wt%、不小于20wt%或不小于30wt%;且不大于60wt%、不大于50wt%或不大于40wt%。
另外,作为所述聚合方法,可以使用界面聚合法作为一个实例。在这种情况下,具有聚合反应可以在低温和大气压力下进行的效果,而且分子量容易控制。上述界面聚合优选在酸结合剂和有机溶剂的存在下进行。此外,上述界面聚合可以包括,例如,进行预聚合然后加入偶联剂以及再进行聚合的步骤。在这种情况下,可以获得具有较高的分子量的共聚碳酸酯。
对在界面聚合中使用的材料没有特别地限制,只要它们可以在聚碳酸酯的聚合中使用即可。其用量可以根据需要控制。
所述酸结合剂可以包括,例如,碱金属氢氧化物如氢氧化钠或氢氧化钾,或胺类化合物如吡啶。
对所述有机溶剂没有特别地限制,只要它是在聚碳酸酯的聚合中通常可以使用的溶剂即可。作为一个实例,可以使用卤代烃,如二氯甲烷或氯苯。
另外,在界面聚合的过程中,还可以使用用于加速反应的反应加速剂,例如,叔胺化合物如三乙胺、四正丁基溴化铵和四正丁基溴化鏻;或者季铵化合物或季鏻化合物。
在界面聚合中,反应温度优选为0℃至40℃且反应时间优选为10分钟至5小时。此外,在界面聚合反应中,pH优选地保持在9以上或11以上。
另外,界面聚合可以通过进一步包含分子量调节剂来进行。所述分子量调节剂可以在聚合开始之前、聚合开始的过程中或聚合开始之后加入。
作为上述分子量调节剂,可以使用单烷基苯酚。作为一个实例,所述单烷基苯酚是选自对叔丁基苯酚、对枯基苯酚、癸基苯酚、十二烷基苯酚、十四烷基苯酚、十六烷基苯酚、十八烷基苯酚、二十烷基苯酚、二十二烷基苯酚和三十烷基苯酚中的一种或多种,而且优选为对叔丁基苯酚。在这种情况下,调节分子量的效果优异。
基于100重量份的芳香族二元醇化合物,上述分子量调节剂的含量为,例如,不小于0.01重量份、不小于0.1重量份或不小于1重量份,且不大于10重量份、不大于6重量份或不大于5重量份。在该范围内,可以获得所需的分子量。
另外,本发明提供了一种包含上述共聚碳酸酯和聚碳酸酯的聚碳酸酯组合物。共聚碳酸酯可以单独使用,但需要控制共聚碳酸酯的物理性能时,它可以与聚碳酸酯一起使用。
上述聚碳酸酯与根据本发明的共聚碳酸酯的区别在于,在该聚碳酸酯的主链中未引入聚硅氧烷结构。
优选地,上述聚碳酸酯包含由下面化学式4表示的重复单元:
[化学式4]
在化学式4中,
R'1、R'2、R'3和R'4各自独立地是氢、C1-10烷基、C1-10烷氧基或卤素,
Z'是未被取代或被苯基取代的C1-10亚烷基、未被取代或被C1-10烷基取代的C3-15亚环烷基、O、S、SO、SO2或CO。
另外,优选地,上述聚碳酸酯的重均分子量为15,000g/mol至35,000g/mol。更优选地,所述重均分子量(g/mol)不小于20,000、不小于21,000、不小于22,000、不小于23,000、不小于24,000、不小于25,000、不小于26,000、不小于27,000或不小于28,000。此外,上述重均分子量(g/mol)不大于34,000、不大于33,000或不大于32,000。
由化学式4表示的重复单元通过使芳香族二元醇化合物与碳酸酯前体反应形成。此处可以使用的芳香族二元醇化合物和碳酸酯前体与此前描述的用于由化学式1表示的重复单元相同。
优选地,化学式4中的R'1、R'2、R'3、R'4和Z'分别与此前描述的化学式1中的R1、R2、R3、R4和Z相同。
另外,优选地,由化学式4表示的重复单元由下面化学式4-1表示:
[化学式4-1]
在聚碳酸酯组合物中,共聚碳酸酯与聚碳酸酯的重量比优选为99:1至1:99,更优选为90:10至50:50,最优选为80:20至60:40。
另外,本发明提供了一种包含上述共聚碳酸酯或聚碳酸酯组合物的制品。
优选地,上述制品是注塑制品。此外,所述制品还可以包含,例如,选自抗氧化剂、热稳定剂、光稳定剂、增塑剂、抗静电剂、成核剂、阻燃剂、润滑剂、抗冲击增强剂、荧光增白剂、紫外吸收剂、颜料和染料中的一种或多种。
如上所述,根据本发明的共聚碳酸酯具有优异的驻留热稳定性,因此即使在用于注塑的高温下也难以产生变形(如热分解)。因此,在注塑制品的制造过程中可以保持共聚碳酸酯的固有特性,并且几乎不产生诸如颜色变化的变化。
制备所述制品的方法可以包括以下步骤:利用混合器混合根据本发明的共聚碳酸酯和添加剂(如抗氧化剂),用挤出机将所得混合物挤出成型以制备颗粒,干燥颗粒然后用注塑机注射干燥后的颗粒。
有益效果
如前文所述,根据本发明,在聚碳酸酯的主链中引入特定的硅氧烷化合物的共聚碳酸酯具有提供优异的驻留热稳定性的效果。
具体实施方式
下面,为了帮助理解本公开的内容,将提供优选实施方案。然而,提供这些实施例只是为了说明本发明,而不应被解释为本发明局限于这些实施例。
制备实施例1:AP-PDMS(n=34)
混合47.60g(160mmol)的八甲基环四硅氧烷和2.40g(17.8mmol)的四甲基二硅氧烷。然后将混合物与1重量份的酸性粘土(DC-A3)(相对于100重量份的八甲基环四硅氧烷)一同放入3L的烧瓶中,并在60℃下反应4小时。反应完成后,用乙酸乙酯稀释反应产物并用赛力特硅藻土快速过滤。通过1H NMR确定由此制备的末端未改性的聚有机硅氧烷的重复单元(n)为34。
向所得的末端未改性的聚有机硅氧烷中加入4.81g(35.9mmol)的2-烯丙基苯酚和0.01g(50ppm)的Karstedt铂催化剂并在90℃下反应3小时。反应完成后,通过在120℃和1托的条件下进行蒸发去除未反应的硅氧烷。将由此制备的末端改性的聚有机硅氧烷称为AP-PDMS(n=34)。AP-PDMS是淡黄色油,利用Varian 500MHz通过1H NMR确定重复单元为(n)为34,并且不需要进一步的纯化。
制备实施例2:MBHB-PDMS(m=58)
混合47.60g(160mmol)的八甲基环四硅氧烷和1.5g(11mmol)的四甲基二硅氧烷。然后将混合物与1重量份的酸性粘土(DC-A3)(相对于100重量份的八甲基环四硅氧烷)一同引入3L的烧瓶中,并在60℃下反应4小时。反应完成后,用乙酸乙酯稀释反应产物并用赛力特硅藻土快速过滤。通过1H NMR确定由此制备的末端未改性的聚有机硅氧烷的重复单元(m)为58。
向所得的末端未改性的聚有机硅氧烷中加入6.13g(29.7mmol)的3-甲基-3-丁烯基4-羟基苯甲酸酯和0.01g(50ppm)的Karstedt铂催化剂并在90℃下反应3小时。反应完成后,通过在120℃和1托的条件下进行蒸发去除未反应的硅氧烷。将由此制备的末端改性的聚有机硅氧烷称为MBHB-PDMS(m=58)。MBHB-PDMS是淡黄色油,利用Varian 500MHz通过1HNMR确定重复单元为(m)为58,并且不需要进一步的纯化。
制备实施例3:丁香酚-PDMS
混合47.60g(160mmol)的八甲基环四硅氧烷和1.7g(13mmol)的四甲基二硅氧烷。然后将混合物与1重量份的酸性粘土(DC-A3)(相对于100重量份的八甲基环四硅氧烷)一同放入3L的烧瓶中,并在60℃下反应4小时。反应完成后,用乙酸乙酯稀释反应产物并用赛力特硅藻土快速过滤。通过1H NMR确定由此制备的末端未改性的聚有机硅氧烷的重复单元(n)为50。
向所得的末端未改性的聚有机硅氧烷中加入6.13g(29.7mmol)的丁香酚和0.01g(50ppm)的Karstedt铂催化剂并在90℃下反应3小时。反应完成后,通过在120℃和1托的条件下进行蒸发去除未反应的硅氧烷。将由此制备的末端改性的聚有机硅氧烷称为丁香酚-PDMS。丁香酚-PDMS是淡黄色油,利用Varian 500MHz通过1H NMR确定重复单元为(n)为50,并且不需要进一步的纯化。
实施例1
向聚合反应器中加入1784g的水、385g的NaOH和232g的BPA(双酚A),并在N2气氛下混合溶解。将4.3g的PTBP(对叔丁基苯酚)和5.91g的在制备实施例1中制得的AP-PDMS(n=34)与0.66g的在制备实施例2中制得的MBHB-PDMS(m=58)的混合溶液溶解在MC(二氯甲烷)中,然后加入至其中。接着,将128g的TPG(三光气)溶解在MC中,并将溶解的TPG溶液加入至其中,在将TPG溶液的pH保持在11以上的同时反应1小时。10分钟后,向其中加入46g的TEA(三乙胺)以进行偶联反应。在总反应时间1小时20分钟后,将pH降至4以去除TEA,然后通过用蒸馏水清洗三次将所制备的聚合物的pH调节至6至7的中性pH。将由此获得的聚合物在甲醇和己烷的混合溶液中再沉淀,然后在120℃下干燥,获得最终的共聚碳酸酯。
比较例1
向聚合反应器中加入1784g的水、385g的NaOH和232g的BPA(双酚A),并在N2气氛下混合溶解。将4.3g的PTBP(对叔丁基苯酚)和6.57g的AP-PDMS(n=34)溶解在MC(二氯甲烷)中并加入至其中。然后,将128g的TPG(三光气)溶解在MC中,并将溶解的TPG溶液加入至其中,在将TPG溶液的pH保持在11以上的同时反应1小时。10分钟后,向其中加入46g的TEA(三乙胺)以进行偶联反应。在总反应时间1小时20分钟后,将pH降至4以去除TEA,然后通过用蒸馏水清洗三次将所制备的聚合物的pH调节至6至7的中性pH。将由此获得的聚合物在甲醇和己烷的混合溶液中再沉淀,然后在120℃下干燥,获得最终的共聚碳酸酯。
比较例2
除了使用在制备实施例3中制备的丁香酚-PDMS(n=50)代替在制备实施例1中制备的AP-PDMS(n=34)之外,通过与比较例1中相同的方法制备共聚碳酸酯。
比较例3
除了不使用在制备实施例1中制备的AP-PDMS(n=34)之外,通过与比较例1中相同的方法制备共聚碳酸酯。
实施例2
将80重量份的实施例1中制备的共聚碳酸酯和20重量份的对比例3中制备的聚碳酸酯混合,制得聚碳酸酯组合物。
实施例3
除了使用6.24g的制备实施例1中制备的AP-PDMS(n=34)和0.33g的制备实施例2中制备的MBHB-PDMS(m=58)之外,通过与实施例1中相同的方法制备共聚碳酸酯。
试验例:性能的确定
在实施例和比较例中制备的共聚碳酸酯和聚碳酸酯组合物的重均分子量通过GPC利用Agilent 1200系列PC标准测定。此外,熔体指数(MI)根据ASTM D1238(300℃和1.2kg的条件下)测定。
另外,相对于1重量份的在实施例和比较例中制备的各个共聚碳酸酯和聚碳酸酯组合物,向其中加入0.050重量份的三(2,4-二叔丁基苯基)亚磷酸酯、0.010重量份的十八烷基-3-(3,5-二叔丁基-4-羟苯基)丙酸酯和0.030重量份的季戊四醇四硬脂酸酯,并使用设置有通气孔的Φ30mm双螺杆挤出机对所得混合物进行造粒,然后使用注塑机N-20C(JSWCo.,Ltd.制造)在300℃的料筒温度和80℃的模具温度下进行注塑以制备所需的试样。使用该试样根据ASTM D256(1/8英寸,缺口悬臂梁式)在-30℃下测定低温冲击强度。
驻留热稳定性如下测定。
使用设置有通气孔的Φ30mm双螺杆挤出机对实施例和比较例中制备的共聚碳酸酯和聚碳酸酯组合物进行造粒,并使用注塑机N-20C(JSW Co.,Ltd.制造)在没有驻留时间的情况下在320℃的料筒温度和90℃的模具温度下进行注塑,从而制备试样(宽度/长度/厚度=60mm/40mm/3mm)。根据ASTM D1925利用Color-Eye 7000A(由X-Rite Ltd.制造)测定YI(320℃,0分钟)。
另外,重复上述程序,但是将共聚碳酸酯和聚碳酸酯组合物装入料筒中并使它们在其中驻留15分钟。然后,通过注塑制备试样(宽度/长度/厚度=60mm/40mm/3mm)。根据ASTM D1925利用Color-Eye 7000A(由X-Rite Ltd.制造)测定YI(320℃,15分钟)。
将通过从YI(320℃,15分钟)中减去YI(320℃,0分钟)得到的值表示为ΔYI。
在这种情况下,YI(黄色指数)的测定条件如下。
-测定温度:室温(23℃)
-孔径尺寸:大孔径
-测定方法:在光谱范围(360nm至750nm)内测定透过率。
上述结果示于下表1中。
[表1]
实施例1 实施例2 实施例3 比较例1 比较例2 比较例3
重均分子量(g/mol) 30,000 28,000 30,200 30,000 30,000 30,000
YI(320℃,15分钟) 4.61 4.03 4.50 9.71 14.74 3.24
YI(320℃,0分钟) 3.11 2.43 3.10 3.71 6.74 1.24
ΔYI 1.5 1.6 1.4 6.0 8.0 2.0
MFR(g/10min) 3.5 10 4 8 7 10
低温冲击强度(J/m) 730 680 760 530 670 150
如上表1中所示,可以确定,与比较例相比,实施例1至3表现出显著较低的ΔYI,从而表现出显著较高的驻留热稳定性。

Claims (15)

1.一种共聚碳酸酯,包含:芳香族聚碳酸酯类第一重复单元;以及一种或多种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元,并且根据下式1测定的ΔYI为0.5至5:
[式1]
ΔYI=YI(320℃,15分钟)-YI(320℃,0分钟)
在式1中,
YI(320℃,0分钟)是通过将所述共聚碳酸酯在320℃下注射成型而得到的试样(宽度/长度/厚度=60mm/40mm/3mm)根据ASTM D1925测定的YI(黄色指数),以及
YI(320℃,15分钟)是通过将所述共聚碳酸酯在320℃下保持15分钟然后进行注射成型而得到的试样(宽度/长度/厚度=60mm/40mm/3mm)根据ASTM D1925测定的YI(黄色指数)。
2.根据权利要求1所述的共聚碳酸酯,其中,
所述共聚碳酸酯根据ASTM D1238(300℃和1.2kg的条件下)测定的熔体指数为3至20g/10min。
3.根据权利要求1所述的共聚碳酸酯,其中,
所述共聚碳酸酯的重均分子量为1,000g/mol至100,000g/mol。
4.根据权利要求1所述的共聚碳酸酯,其中,
相对于芳香族聚碳酸酯类第一重复单元和一种或多种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元的总重量,所述芳香族聚碳酸酯类第一重复单元的含量为90至99%。
5.根据权利要求1所述的共聚碳酸酯,其中,
所述共聚碳酸酯包含两种具有硅氧烷键的芳香族聚碳酸酯类第二重复单元。
6.根据权利要求1所述的共聚碳酸酯,其中,
所述第一重复单元由下面化学式1表示:
[化学式1]
在化学式1中,
R1、R2、R3和R4各自独立地是氢、C1-10烷基或卤素,
Z是未被取代或被苯基取代的C1-10亚烷基、未被取代或被C1-10烷基取代的C3-15亚环烷基、O、S、SO、SO2或CO。
7.根据权利要求6所述的共聚碳酸酯,其中,
所述由化学式1表示的重复单元来自于选自双(4-羟苯基)甲烷、双(4-羟苯基)醚、双(4-羟苯基)砜、双(4-羟苯基)亚砜、双(4-羟苯基)硫醚、双(4-羟苯基)甲酮、1,1-双(4-羟苯基)乙烷、双酚A、2,2-双(4-羟苯基)丁烷、1,1-双(4-羟苯基)环己烷、2,2-双(4-羟基-3,5-二溴苯基)丙烷、2,2-双(4-羟基-3,5-二氯苯基)丙烷、2,2-双(4-羟基-3-溴苯基)丙烷、2,2-双(4-羟基-3-氯苯基)丙烷、2,2-双(4-羟基-3-甲基苯基)丙烷、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、1,1-双(4-羟苯基)-1-苯乙烷、双(4-羟苯基)二苯基甲烷和α,ω-双[3-(邻羟苯基)丙基]聚二甲基硅氧烷中的一种或多种芳香族二元醇化合物。
8.根据权利要求6所述的共聚碳酸酯,其中,
所述化学式1由下面化学式1-1表示:
[化学式1-1]
9.根据权利要求1所述的共聚碳酸酯,其中,
所述第二重复单元包含由下面化学式2表示的重复单元和由下面化学式3表示的重复单元:
[化学式2]
在化学式2中,
X1各自独立地是C1-10亚烷基,
R5各自独立地是氢;未被取代或被环氧乙烷基、被环氧乙烷基取代的C1-10烷氧基或C6-20芳基取代的C1-15烷基;卤素;C1-10烷氧基;烯丙基;C1-10卤代烷基;或C6-20芳基,
n是10至200的整数,
[化学式3]
在化学式3中,
X2各自独立地是C1-10亚烷基,
Y1各自独立地是氢、C1-6烷基、卤素、羟基、C1-6烷氧基或C6-20芳基,
R6各自独立地是氢;或未被取代或被环氧乙烷基、被环氧乙烷基取代的C1-10烷氧基或C6-20芳基取代的C1-15烷基;卤素;C1-10烷氧基;烯丙基;C1-10卤代烷基;或C6-20芳基,
m是10至200的整数。
10.根据权利要求9所述的共聚碳酸酯,其中,
所述由化学式2表示的重复单元与由化学式3表示的重复单元的的重量比为1:99至99:1。
11.根据权利要求9所述的共聚碳酸酯,其中,
所述由化学式2表示的重复单元由下面化学式2-2表示:
[化学式2-2]
12.根据权利要求9所述的共聚碳酸酯,其中,
所述由化学式3表示的重复单元由下面化学式3-2表示:
[化学式3-2]
13.一种聚碳酸酯组合物,包含权利要求1至12中的任一项所述的共聚碳酸酯,及聚碳酸酯。
14.根据权利要求13所述的聚碳酸酯组合物,其中,
在所述聚碳酸酯的主链中未引入聚硅氧烷结构。
15.根据权利要求13所述的聚碳酸酯组合物,其中,
所述聚碳酸酯包含由下面化学式4表示的重复单元:
[化学式4]
在化学式4中,
R'1、R'2、R'3和R'4各自独立地是氢、C1-10烷基、C1-10烷氧基或卤素,
Z'是未被取代或被苯基取代的C1-10亚烷基、未被取代或被C1-10烷基取代的C3-15亚环烷基、O、S、SO、SO2或CO。
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