CN114685722A - 共聚物与混掺物 - Google Patents
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Abstract
一种共聚物包括对应聚醚砜的重复单元与对应乙烯基单体的重复单元,其中对应聚醚砜的重复单元的重复数目为200至450,且对应乙烯基单体的重复单元的重复数目为20至100。上述共聚物可与其他高分子如聚苯硫醚混掺形成混掺物。
Description
技术领域
本发明涉及含对应聚醚砜的重复单元与对应乙烯基单体的重复单元的共聚物,更特别涉及聚苯硫醚与共聚物的混掺物。
背景技术
高分子复合材料、高分子合金及高分子胶可结合不同特性的高分子材料,以改善单一高分子物性。芳香族聚醚砜为具有优异耐化性、热稳定性及机械强度的非晶相工程塑胶,可作为高分子复材、合金、及胶的配方之一,以提升其耐化性、耐热性、韧性等等。
然而,由于极性差异及芳香族结构,造成芳香族聚醚砜不易与常见塑胶均匀混掺分散。必须加入相容剂以利提升分散性,达到性能强化的效果。然而相容剂可能会劣化混掺物的部分性质。综上所述,目前需开发一改质聚醚砜树脂,以直接作为其他高分子材料的改性剂而不需额外添加相容剂。
发明内容
本发明一实施例提供的共聚物,包括:对应聚醚砜的重复单元与对应乙烯基单体的重复单元,其中对应聚醚砜的重复单元的重复数目为200至450,且对应乙烯基单体的重复单元的重复数目为20至100。
本发明一实施例提供的混掺物,包括:聚苯硫醚与共聚物彼此混掺,其中聚苯硫醚与共聚物的重量比为98∶2至92∶8,其中共聚物,包括:对应聚醚砜的重复单元与对应乙烯基单体的重复单元,其中对应聚醚砜的重复单元的重复数目为200至450,且对应乙烯基单体的重复单元的重复数目为20至100。
附图说明
图1为本发明一实施例中,聚苯硫醚(PPS)与混掺物(PPS+PES-GMA)的流变分析比较图。
具体实施方式
本发明一实施例提供的共聚物的形成方法,包括:以紫外线照射聚醚砜的溶液,以形成聚醚砜的自由基。在一些实施例中,溶解聚醚砜的溶剂可为N-甲基吡咯烷酮、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜或上述的组合,且溶液中聚醚砜的浓度可为5wt%至30wt%。若聚醚砜的浓度过低,则产率不佳。若聚醚砜的浓度过高,则溶解不完全。
聚醚砜的自由基可与乙烯基单体共聚形成共聚物,因此共聚物包括对应聚醚砜的重复单元与对应乙烯基单体的重复单元。在一些实施例中,乙烯基单体可在照射紫外线之前即溶解于聚醚砜的溶液中。在其他实施例中,可在聚醚砜的溶液照射紫外线之后,再添加乙烯基单体至含聚醚砜的自由基的溶液中。在共聚物中,对应聚醚砜的重复单元的重复数目为200至450,而对应乙烯基单体的重复单元的重复数目为20至100。若对应聚醚砜的重复单元的重复数目过低,则共聚物的耐热性下降。若对应乙烯基单体的重复单元的重复数目过低,则无法有效改变共聚物的特性。若对应乙烯基单体的重复单元的重复数目过高,则溶解度不佳。
上述共聚物可用于与其他高分子混掺。举例来说,共聚物可与聚苯硫醚彼此混掺以形成混掺物,其中聚苯硫醚与共聚物的重量比为98∶2至92∶8。若共聚物的比例过低,则特性改善程度有限。若共聚物的比例过高,则相容性下降。在一些实施例中,聚苯硫醚的重复单元为且聚苯硫醚的熔融指数为100至200g/10min(测量标准为ISO1133)。若聚苯硫醚的熔融指数过低,则无法成型。若聚苯硫醚的熔融指数过高,则加工性不佳。
为让本发明的上述内容和其他目的、特征和优点能更明显易懂,下文特列举出较佳实施例,并配合所附附图,作详细说明如下:
[实施例]
实施例1(PES-GMA共聚物)
将聚醚砜(PES,E6020P,10g)及甲基丙烯酸缩水甘油酯(Glycidylmethacrylate,GMA,20g)加入N-甲基吡咯烷酮(NMP,100mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-GMA。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应GMA的重复单元的重复数目为96,而对应PES的重复单元的重复数目为288,且PES/GMA的比例为75∶25。
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160g/10min,参照ISO1133标准测试法)与3重量份的PES-GMA导入双螺杆挤出机,并在310℃混掺形成混掺物。将PPS与混掺物分别置入差示扫描量热计(DSC TA-100)中,在氮气下由室温以10℃/min的速率升温至310℃,在310℃恒温2分钟,再由310℃以40℃/min的速率降温至室温,以测量PPS与混掺物的熔点、结晶点及结晶度如表1。加入PES-GMA后,PPS的结晶点由236℃降至227℃。在热塑性聚合物加工过程中,熔点至结晶点的温度区间为可加工视窗,增加可加工视窗可以提升热塑性聚合物的可加工性,有利于纤维及薄膜加工。
表1
熔点(℃) | 结晶点(℃) | 结晶度(%) | |
PPS | 279 | 236 | 43 |
PPS+PES-GMA | 281 | 227 | 54 |
分别取30克PPS与混掺物(PPS+PES-GMA)填充于流变仪料管中并压实。在310℃下,挤出并记录不同剪切速率下的粘度值。混掺物的粘度与原PPS接近,合理推测两者具有接近的熔融流动性,如图1所示。
分别测量PPS与混掺物(PPS+PES-GMA)的物理特性如表2。抗拉强度及应变的测量标准为ASTM-D638,冲击强度的测量标准为ASTM-D256。
表2
实施例2(PES-GMA共聚物)
将PES(E6020P,10g)及GMA(25g)加入NMP(100mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-GMA。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应GMA的重复单元的重复数目为99,而对应PES的重复单元的重复数目为242,且PES/GMA的比例为71∶29。
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法)与3重量份的PES-GMA导入双螺杆挤出机,并在310℃混掺形成混掺物。
实施例3(PES-GMA共聚物)
将PES(E6020P,30g)及GMA(50g)加入NMP(100mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-GMA。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应GMA的重复单元的重复数目为64,而对应PES的重复单元的重复数目为396,且PES/GMA的比例为86∶14。
将93重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法。)与7重量份的PES-GMA导入双螺杆挤出机,并在310℃混掺形成混掺物。
实施例4(PES-HEAA共聚物)
将PES(E6020P,10g)及N-羟乙基丙烯酰胺(N-(Hydroxyethyl)acrylamide,HEAA,13g)加入NMP(100mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-HEAA。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应HEAA的重复单元的重复数目为26,而对应PES的重复单元的重复数目为298,且PES/HEAA的比例为92∶8。上述HEAA的化学结构为
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法。)与3重量份的PES-HEAA导入双螺杆挤出机,并在310℃混掺形成混掺物。
实施例5(PES-MMA共聚物)
将PES(E6020P,15g)及甲基丙烯酸甲酯(methyl methacrylate,MMA,16g)加入NMP(150mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-MMA。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应MMA的重复单元的重复数目为29,而对应PES的重复单元的重复数目为388,且PES/MMA的比例为93∶7。上述MMA的结构为
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法。)与3重量份的PES-MMA导入双螺杆挤出机,并在310℃混掺形成混掺物。
实施例6(PES-BMA共聚物)
将PES(E6020P,15g)及丁基丙烯酸甲酯(Butyl methacrylate,BMA,23g)加入NMP(150mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-BMA。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应BMA的重复单元的重复数目为21,而对应PES的重复单元的重复数目为391,且PES/BMA的比例为95∶5。上述BMA的化学结构为
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法。)与3重量份的PES-BMA导入双螺杆挤出机,并在310℃混掺形成混掺物。
实施例7(PES-VBC共聚物)
将PES(E6020P,15g)及4-乙烯基苄基氯(4-Vinylbenzyl chloride,VBC,24g)加入NMP(150mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-VBC。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应VBC的重复单元的重复数目21,而对应PES的重复单元的重复数目为397,且PES/VBC的比例为95∶5。上述VBC的化学结构为
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法。)与3重量份的PES-VBC导入双螺杆挤出机,并在310℃混掺形成混掺物。
实施例8(PES-DAEA共聚物)
将PES(E6020P,15g)及丙烯酸二甲胺基乙酯(2-(Dimethyl amino)ethyl acrylate,DAEA,25g)加入NMP(150mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-DAEA。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应DAEA的重复单元的重复数目为73,而对应PES的重复单元的重复数目为384,且PES/DAEA的比例为84∶16。上述DAEA的化学结构为
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法。)与3重量份的PES-DAEA导入双螺杆挤出机,并在310℃混掺形成混掺物。
实施例9(PES-AGE共聚物)
将PES(E6020P,15g)及烯丙基缩水甘油基醚(Allyl glycidyl ether,AGE,24g)加入NMP(150mL)中搅拌至均匀溶解。以紫外光照射溶液后,在室温下搅拌反应数小时。将溶液倒入水中沉淀析出白色固体,以乙醇清洗白色固体,除去残余溶剂及单体。在80℃下干燥得共聚物PES-AGE。由NMR光谱(Bruker 400MHz,DMSO-d6)标定完成,计算对应AGE的重复单元的重复数目为25,而对应PES的重复单元的重复数目为393,且PES/AGE的比例为94∶6。上述AGE的化学结构为
将97重量份的聚苯硫醚(PPS,购自浙江新和成的3220,熔融指数为160/10min,参照ISO1133标准测试法。)与3重量份的PES-AGE导入双螺杆挤出机,并在310℃混掺形成混掺物。
虽然本发明已以数个较佳实施例公开如上,但其并非用以限定本发明,任何所属技术领域中普通技术人员,在不脱离本发明的精神和范围内,当可作任意的更动与润饰,因此本发明的保护范围当视权利要求书所界定者为准。
Claims (7)
1.一种共聚物,包括:
对应聚醚砜的重复单元与对应乙烯基单体的重复单元,
其中该对应聚醚砜的重复单元的重复数目为200至450,且该对应乙烯基单体的重复单元的重复数目为20至100。
4.一种混掺物,包括:
聚苯硫醚与共聚物彼此混掺,其中该聚苯硫醚与该共聚物的重量比为98∶2至92∶8,
其中该共聚物,包括:
对应聚醚砜的重复单元与对应乙烯基单体的重复单元,
其中该对应聚醚砜的重复单元的重复数目为200至450,且该对应乙烯基单体的重复单元的重复数目为20至100。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0485364A (ja) * | 1990-07-30 | 1992-03-18 | Tosoh Corp | ポリフェニレンスルフィド樹脂組成物 |
US5883150A (en) * | 1996-08-09 | 1999-03-16 | Millipore Corporation | Compositions of a copolymer including a sulfone polymer |
JP2009242760A (ja) * | 2008-04-01 | 2009-10-22 | Toray Ind Inc | ポリエーテルスルホン樹脂組成物、その製造方法および成形品 |
US20110240550A1 (en) * | 2010-03-31 | 2011-10-06 | General Electric Company | Block copolymer membranes and associated methods for making the same |
CN104837929A (zh) * | 2013-01-04 | 2015-08-12 | 沙特基础全球技术有限公司 | 聚醚砜和聚苯硫醚的共混物 |
-
2020
- 2020-12-28 US US17/135,294 patent/US20220204676A1/en not_active Abandoned
-
2021
- 2021-01-05 TW TW110100244A patent/TW202229458A/zh unknown
- 2021-02-25 CN CN202110209801.9A patent/CN114685722A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0485364A (ja) * | 1990-07-30 | 1992-03-18 | Tosoh Corp | ポリフェニレンスルフィド樹脂組成物 |
US5883150A (en) * | 1996-08-09 | 1999-03-16 | Millipore Corporation | Compositions of a copolymer including a sulfone polymer |
JP2009242760A (ja) * | 2008-04-01 | 2009-10-22 | Toray Ind Inc | ポリエーテルスルホン樹脂組成物、その製造方法および成形品 |
US20110240550A1 (en) * | 2010-03-31 | 2011-10-06 | General Electric Company | Block copolymer membranes and associated methods for making the same |
CN104837929A (zh) * | 2013-01-04 | 2015-08-12 | 沙特基础全球技术有限公司 | 聚醚砜和聚苯硫醚的共混物 |
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