CN101580583A - 采用四元共聚技术制备聚芳醚酮类共聚物的方法 - Google Patents
采用四元共聚技术制备聚芳醚酮类共聚物的方法 Download PDFInfo
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- 238000007334 copolymerization reaction Methods 0.000 title claims description 10
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 15
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001643 poly(ether ketone) Polymers 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 4
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims abstract 7
- 229920001657 poly(etheretherketoneketone) Polymers 0.000 claims abstract 4
- 229920001660 poly(etherketone-etherketoneketone) Polymers 0.000 claims abstract 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 50
- 125000005594 diketone group Chemical group 0.000 claims description 23
- 229920006029 tetra-polymer Polymers 0.000 claims description 20
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 12
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 claims description 10
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
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- 239000012153 distilled water Substances 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 4
- 229920001577 copolymer Polymers 0.000 abstract 2
- 239000002904 solvent Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 3
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 2
- 238000013475 authorization Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- -1 PEEKK Polymers 0.000 description 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
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- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
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- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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Abstract
本发明属于高分子材料领域，具体涉及一种利用四元共缩聚技术制备不同品种聚芳醚酮共聚物的方法。本发明可以根据需要通过对苯二酚、4，4′－二羟基二苯酮、4，4′－二氟二苯酮、4，4′－二氟三苯二酮四种单体配料比的调控，制备出宏观物性与四种二元均聚物，即聚醚醚酮(PEEK)、聚醚酮(PEK)、聚醚醚酮酮(PEEKK)、聚醚酮醚酮酮(PEKEKK)性能当的共聚物产品。如当对苯二酚与4，4′－二羟基二苯酮的摩尔数比大于99∶1，4，4′－二氟二苯酮与4，4′－二氟三苯二酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以PEEK链段为主，其宏观物性与PEEK相当。
Description
技术领域
本发明属于高分子材料领域，具体涉及一种利用四元共缩聚技术制备不同品种聚芳醚酮共聚物的方法。
技术背景
聚芳醚酮类树脂国际上是从七十年代以来由英国ICI公司最早研发，并于1981年投产商品化的。目前国际上已经商品化的主要有聚醚醚酮(PEEK)、聚醚酮(PEK、PEEK-HT)两个品种，主要由英国Victrex公司生产。
这类产品早期的专利从高分子缩聚反应原理来讲都属于二元均聚，即两种双官能团的单体进行缩聚反应。这在已故唐敖庆教授所著《高分子反应统计理论》一书中，被称为A2、B2型均聚，它是缩聚反应最简单的一类也是最常采用的一类。我们的前期研究也从这里开始并取得过相关专利(如中国专利ZL 85105138.3等)。不过后来的深入研究发现具有相同基本特性的缩聚物也可以通过A2、A2′、B2这类三元共缩聚反应得到。我们已申请并获得授权的中国专利(专利号为：ZL200510017239.8)等即属于这类型。这种三元共缩聚的合成方法取得成功后，我们近些年已相继申请了一系列相关专利并有六项已获得授权，其余还在实审中。
在完成上述二元均聚、三元共聚研发的基础上，我们近年来又开展了四元共聚的研发并完成了本发明。
发明内容
本发明的目的在于提供一种有别于前人所采取的二元均聚、三元共聚方法，而采取四元共聚的方法合成聚芳醚酮类树脂。其要旨是在高温有机溶剂存在下，同时向反应体系中加入：
(1)、对苯二酚：
(2)、4，4′-二羟基二苯酮：
(3)、4，4′-二氟二苯酮：
(4)、4，4′-二氟三苯二酮：
四种单体和成盐剂碱金属碳酸盐M2CO3在一定温度和时间控制下就可以得到分子链中含有下述重复单元结构的四元共聚物：
其缩聚反应的步骤是：在装有温度计、通氮气管和搅拌器的三口瓶中，先加入高温有机溶剂(如二苯砜或环丁砜)后开始搅拌加热。待熔融后依次加入4，4′-二氟二苯酮、4，4′-二氟三苯二酮、对苯二酚和4，4′-二羟基二苯酮，并搅拌至全部溶解后，再向体系中加入比对苯二酚和4，4′-二羟基二苯酮摩尔数之和过量1％～5％的碱金属碳酸盐搅拌下继续升温至220～230℃，恒温20～40分钟完成第一步成盐反应，再继续升温至250～260℃恒温20～40分钟完成第二步成盐反应，再升温至300～320℃开始缩聚反应，在此阶段恒温3～4小时完成聚合反应。将上述聚合物溶液倒入室温蒸馏水中冷却成条状固体。经粉碎后分别用乙醇抽提去聚合物中的溶剂二苯砜，再用无离子水抽提去副产物盐后，进行真空干燥即得到分子链中含有PEEK、PEEKK、PEK和PEKEKK重复单元结构的四元共聚物。
在特定条件下，当上述四种单体中，对苯二酚与4，4′-二羟基二苯酮的摩尔数比大于99∶1，4，4′-二氟二苯酮与4，4′-二氟三苯二酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以结构I链段为主，其宏观物性与PEEK相当；其中，对苯二酚与4，4′-二氟二苯酮的摩尔数相同，4，4′-二羟基二苯酮与4，4′-二氟三苯二酮的摩尔数相同；
当上述四种单体中，对苯二酚与4，4′-二羟基二苯酮的摩尔数比大于99∶1，4，4′-二氟三苯二酮与4，4′-二氟二苯酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以结构II链段为主，其宏观物性与PEEKK相当；其中，对苯二酚与4，4′-二氟三苯二酮的摩尔数相同，4，4′-二羟基二苯酮与4，4′-二氟二苯酮的摩尔数相同；
当上述四种单体中，4，4′-二羟基二苯酮与对苯二酚的摩尔数比大于99∶1，4，4′-二氟二苯酮与4，4′-二氟三苯二酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以结构III链段为主，其宏观物性与PEK相当；其中，4，4′-二羟基二苯酮与4，4′-二氟二苯酮的摩尔数相同，对苯二酚与4，4′-二氟三苯二酮的摩尔数相同；
当上述四种单体中，4，4′-二羟基二苯酮与对苯二酚的摩尔数比大于99∶1，4，4′-二氟三苯二酮与4，4′-二氟二苯酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以结构IV链段为主，其宏观物性与PEKEKK相当；其中，4，4′-二羟基二苯酮与4，4′-二氟三苯二酮的摩尔数相同；对苯二酚与4，4′-二氟二苯酮的摩尔数相同。
本发明的核心思想在于，根据已故唐敖庆教授的《高分子反应统计理论》一书的基本原理，在A2、A2′、B2、B2′型四元共聚反应中，只要控制投料时的单体摩尔比，就可以在同一套反应设备中，分别制备出上述四种结构(I～IV)中以任何一种为主要成份的四元共聚物，从而使这种共聚物的宏观物性与这种结构的均聚物的宏观物性相当。
众所周知，在用缩聚反应原理制备均聚物时，只能采用二元均聚技术，每种反应只能得到一种聚合物，而采用三元共聚技术时，则通过三种单体配料比的调控，就可以得到两种在宏观物性上与对应的均聚物相当的共聚物。而通过我们在本专利中完成的四元共聚技术，只要在投料时通过对四种单体的配料比的调控，就分别可以得到四种在宏观物性上与相应的均聚物相同的共聚物。四种均聚物，即聚醚醚酮(PEEK)、聚醚酮(PEK)、聚醚醚酮酮(PEEKK)和聚醚酮醚酮酮(PEKEKK)。
这里所用的溶剂可以是二苯砜、环丁砜。所用的碱金属碳酸盐为K2CO3、Na2CO3、或两者不同比例的混合物。
具体实施方式
实施例1：
在装有温度计、通氮气管、搅拌器的三口瓶中，先加入677.53g溶剂二苯砜，加热待其全部熔化后顺次加入109.00g(0.99mol)对苯二酚、2.14g(0.01mol)4，4′-二羟基二苯酮、216.01g(0.99mol)4，4′-二氟二苯酮、3.22g(0.01mol)4，4′-二氟三苯二酮，待全部溶解成均一液相后再加入114.00g(1.075mol)Na2CO3。在搅拌下开始升温至230℃恒温30分钟，再升温至250℃恒温30分钟，最后升温至310℃恒温3小时完成反应，得到四元共聚物。
停止搅拌后，将四元共聚物立即注入室温蒸馏水中，冷却后用粉碎器粉碎。离心后将固体粉末先用10倍于四元共聚物重量的乙醇回流抽提溶剂二苯砜1小时，过滤后用新乙醇再抽提，反复多次直到经熔融指数仪检测，二苯砜含量合格(＜0.5％)后，再用蒸馏水同样抽提到副产物NaF，同样经多次反复直到经氟离子检测仪检测，产物中NaF含量(＜1ppm)合格为止，得到固体粒状四元共聚物(＞95％)。
将固体粒状聚合物真空干燥至水份含量＜0.5％时，即得到宏观物性与PEEK相当的四元共聚物。
用DSC测其热性能得：
Tg＝143℃，
Tm＝334℃，
测其力学性能得：
拉伸强度＞94Mpa，
弯曲强度＞140Mpa，
结果表明，所得共聚物的宏观物性确与均聚物PEEK相当。
实施例2：
在与实施例1相同的反应仪器中按相同顺序和操作分别加入915.64g溶剂二苯砜，109.00g(0.99mol)对苯二酚、2.14g(0.01mol)4，4′-二羟基二苯酮、2.18g(0.01mol)4，4′-二氟二苯酮、319.10g(0.99mol)4，4′-二氟三苯二酮和114.00g(1.075mol)Na2CO3。其他步骤完全同实施例1操作，即可得到宏观物性与PEEKK相当的四元共聚物。
用DSC测其热性能得：
Tg＝156℃
Tm＝367℃
测其力学性能得：
拉伸强度＞98MPa
弯曲强度＞150MPa
结果表明共聚物的宏观物性确与均聚物PEEKK相当。
实施例3：
在与实施例1相同的反应仪器中按相同顺序和操作分别加入915.62g溶剂二苯砜，1.10g(0.01mol)对苯二酚、212.07g(0.99mol)4，4′-二羟基二苯酮、216.02g(0.99mol)4，4′-二氟二苯酮、3.22g(0.01mol)4，4′-二氟三苯二酮和114.00g(1.075mol)Na2CO3。其他步骤完全同实施例1操作，即可得到宏观物性与PEK相当的四元共聚物。
用DSC测其热性能得：
Tg＝157℃
Tm＝373℃
测其力学性能得：
拉伸强度＞100MPa
弯曲强度＞160MPa
结果表明共聚物的宏观物性确与均聚物PEK相当。
实施例4：
在与实施例1相同的反应仪器中按相同顺序和操作分别加入1146.32g溶剂二苯砜，1.10g(0.01mol)对苯二酚、109.00g(0.99mol)4，4′-二羟基二苯酮、2.18g(0.01mol)4，4′-二氟二苯酮、319.10g(0.99mol)4，4′-二氟三苯二酮和95.40g，103.35g(0.975mol)Na2CO3，13.82g(0.1mol)K2CO3，其他步骤完全同实施例1操作，即可得到宏观物性与PEKEKK相当的四元共聚物。
用DSC测其热性能得：
Tg＝171℃
Tm＝381℃
测其力学性能得：
拉伸强度＞102MPa
弯曲强度＞165MPa
结果表明共聚物的宏观物性确与均聚物PEKEKK相当。
Claims (7)
1、采用四元共聚技术制备聚芳醚酮类共聚物的方法，其步骤为：在装有温度计、通氮气管和搅拌器的三口瓶中，先加入高温有机溶剂后开始搅拌加热，待熔融后依次加入4，4′-二氟二苯酮、4，4′-二氟三苯二酮、对苯二酚和4，4′-二羟基二苯酮，并搅拌至全部溶解后，再向体系中加入比对苯二酚和4，4′-二羟基二苯酮摩尔数之和过量1％～5％的碱金属碳酸盐，搅拌下继续升温至220～230℃，恒温20～40分钟完成第一步成盐反应；再继续升温至250～260℃恒温20～40分钟完成第二步成盐反应；再升温至300～320℃开始缩聚反应，在此阶段恒温3～4小时完成聚合反应；最后将上述聚合物溶液倒入室温蒸馏水中冷却成条状固体，经粉碎后分别用乙醇抽提除去聚合物中的有机溶剂，再用无离子水抽提除去副产物盐后，进行真空干燥即得到分子链中含有PEEK、PEEKK、PEK和PEKEKK重复单元结构的四元共聚物。
2、如权利要求1所述的采用四元共聚技术制备聚芳醚酮类共聚物的方法，其特征在于：高温有机溶剂为二苯砜或环丁砜。
3、如权利要求1所述的采用四元共聚技术制备聚芳醚酮类共聚物的方法，其特征在于：碱金属碳酸盐为K2CO3、Na2CO3、或两者不同比例的混合物。
4、如权利要求1所述的采用四元共聚技术制备聚芳醚酮类共聚物的方法，其特征在于：四种单体中，对苯二酚与4，4′-二羟基二苯酮的摩尔数比大于99∶1，4，4′-二氟二苯酮与4，4′-二氟三苯二酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以PEEK链段为主，其宏观物性与PEEK相当；其中，对苯二酚与4，4′-二氟二苯酮的摩尔数相同，4，4′-二羟基二苯酮与4，4′-二氟三苯二酮的摩尔数相同。
5、如权利要求1所述的采用四元共聚技术制备聚芳醚酮类共聚物的方法，其特征在于：四种单体中，对苯二酚与4，4′-二羟基二苯酮的摩尔数比大于99∶1，4，4′-二氟三苯二酮与4，4′-二氟二苯酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以PEEKK链段为主，其宏观物性与PEEKK相当；其中，对苯二酚与4，4′-二氟三苯二酮的摩尔数相同，4，4′-二羟基二苯酮与4，4′-二氟二苯酮的摩尔数相同。
6、如权利要求1所述的采用四元共聚技术制备聚芳醚酮类共聚物的方法，其特征在于：四种单体中，4，4′-二羟基二苯酮与对苯二酚的摩尔数比大于99∶1，4，4′-二氟二苯酮与4，4′-二氟三苯二酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以PEK链段为主，其宏观物性与PEK相当；其中，4，4′-二羟基二苯酮与4，4′-二氟二苯酮的摩尔数相同，对苯二酚与4，4′-二氟三苯二酮的摩尔数相同。
7、如权利要求1所述的采用四元共聚技术制备聚芳醚酮类共聚物的方法，其特征在于：四种单体中，4，4′-二羟基二苯酮与对苯二酚的摩尔数比大于99∶1，4，4′-二氟三苯二酮与4，4′-二氟二苯酮的摩尔数比大于99∶1时，得到的四元共聚物的分子链中，以PEKEKK链段为主，其宏观物性与PEKEKK相当；其中，4，4′-二羟基二苯酮与4，4′-二氟三苯二酮的摩尔数相同；对苯二酚与4，4′-二氟二苯酮的摩尔数相同。
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| US13/318,195 US8981034B2 (en) | 2009-06-26 | 2010-06-23 | Method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology |
| EP10791546.4A EP2447300B9 (en) | 2009-06-26 | 2010-06-23 | Method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology |
| PCT/CN2010/074303 WO2010149040A1 (zh) | 2009-06-26 | 2010-06-23 | 采用四元共聚技术制备聚芳醚酮类共聚物的方法 |
| KR1020117024432A KR20120027152A (ko) | 2009-06-26 | 2010-06-23 | 사원 공중합 기술을 이용한 폴리아릴에테르케톤계 공중합체의 제조방법 |
| JP2012507600A JP5480367B2 (ja) | 2009-06-26 | 2010-06-23 | ４成分共重合技術でポリアリールエーテルケトン類共重合物を調製する方法 |
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| WO2010149040A1 (zh) * | 2009-06-26 | 2010-12-29 | 金发科技股份有限公司 | 采用四元共聚技术制备聚芳醚酮类共聚物的方法 |
| CN102167811A (zh) * | 2011-01-18 | 2011-08-31 | 长春博文特塑技术咨询服务有限责任公司 | 采用四元共缩聚技术制备聚醚联苯酮共聚物的方法 |
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-
2009
- 2009-06-26 CN CN2009100671787A patent/CN101580583B/zh not_active Expired - Fee Related
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2010
- 2010-06-23 JP JP2012507600A patent/JP5480367B2/ja not_active Expired - Fee Related
- 2010-06-23 EP EP10791546.4A patent/EP2447300B9/en not_active Not-in-force
- 2010-06-23 KR KR1020117024432A patent/KR20120027152A/ko not_active Application Discontinuation
- 2010-06-23 US US13/318,195 patent/US8981034B2/en not_active Expired - Fee Related
- 2010-06-23 WO PCT/CN2010/074303 patent/WO2010149040A1/zh active Application Filing
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| WO2010149040A1 (zh) * | 2009-06-26 | 2010-12-29 | 金发科技股份有限公司 | 采用四元共聚技术制备聚芳醚酮类共聚物的方法 |
| US8981034B2 (en) | 2009-06-26 | 2015-03-17 | Kingfa Science & Technology Co., Ltd. | Method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology |
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| CN102167811B (zh) * | 2011-01-18 | 2012-09-05 | 长春博文特塑技术咨询服务有限责任公司 | 采用四元共缩聚技术制备聚醚联苯酮共聚物的方法 |
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| CN102532441B (zh) * | 2012-02-22 | 2013-09-25 | 苏州乐华新材料有限公司 | 一种含半柔性结构的聚醚醚酮树脂的合成方法 |
| CN102924719B (zh) * | 2012-11-07 | 2015-02-18 | 金发科技股份有限公司 | 采用四元共聚技术制备聚芳醚砜类共聚物的方法 |
| CN102924719A (zh) * | 2012-11-07 | 2013-02-13 | 金发科技股份有限公司 | 采用四元共聚技术制备聚芳醚砜类共聚物的方法 |
| CN110845837A (zh) * | 2013-06-26 | 2020-02-28 | 威格斯制造有限公司 | 聚合物材料 |
| CN110845837B (zh) * | 2013-06-26 | 2022-08-30 | 威格斯制造有限公司 | 聚合物材料 |
| CN108137797A (zh) * | 2015-10-14 | 2018-06-08 | 沙特基础工业全球技术有限公司 | 热塑性聚合物的制造方法 |
| CN115335432A (zh) * | 2020-06-09 | 2022-11-11 | 奥瑞隆新材料(山东)有限公司 | 半结晶聚(芳醚酮)共聚物 |
| CN115335432B (zh) * | 2020-06-09 | 2024-03-08 | 奥瑞隆新材料(山东)有限公司 | 半结晶聚(芳醚酮)共聚物 |
| CN112961340A (zh) * | 2021-03-17 | 2021-06-15 | 吉林大学 | 一种四元共聚聚芳醚酮及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
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| JP2012525449A (ja) | 2012-10-22 |
| CN101580583B (zh) | 2011-03-30 |
| EP2447300A1 (en) | 2012-05-02 |
| EP2447300B1 (en) | 2014-04-30 |
| WO2010149040A1 (zh) | 2010-12-29 |
| US8981034B2 (en) | 2015-03-17 |
| EP2447300A4 (en) | 2013-01-09 |
| JP5480367B2 (ja) | 2014-04-23 |
| KR20120027152A (ko) | 2012-03-21 |
| US20120095182A1 (en) | 2012-04-19 |
| EP2447300B9 (en) | 2014-09-10 |
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