CN115103869A - 断链以制备用于3d打印的改进聚合物 - Google Patents
断链以制备用于3d打印的改进聚合物 Download PDFInfo
- Publication number
- CN115103869A CN115103869A CN202180015011.5A CN202180015011A CN115103869A CN 115103869 A CN115103869 A CN 115103869A CN 202180015011 A CN202180015011 A CN 202180015011A CN 115103869 A CN115103869 A CN 115103869A
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- Prior art keywords
- condensation polymer
- polymer
- capped
- anhydride
- polyamide
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- 229920000642 polymer Polymers 0.000 title claims abstract description 100
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- 238000009833 condensation Methods 0.000 claims abstract description 64
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- 150000001875 compounds Chemical class 0.000 claims abstract description 35
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- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 46
- 239000004952 Polyamide Substances 0.000 claims description 32
- 229920002647 polyamide Polymers 0.000 claims description 32
- 229920000728 polyester Polymers 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 16
- 150000008064 anhydrides Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
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- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 4
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- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- IAZFBDCXIGRJLS-UHFFFAOYSA-N 1,3-dioxo-2-benzofuran-4-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=C1C(=O)OC2=O IAZFBDCXIGRJLS-UHFFFAOYSA-N 0.000 claims description 3
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 3
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims 3
- 229930182556 Polyacetal Natural products 0.000 claims 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229920003695 Grilamid® L 16 nat Polymers 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 235000013339 cereals Nutrition 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 239000002734 clay mineral Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract
封端的缩聚物可以通过以下方法形成：在封端化合物的存在下加热缩聚物以形成裂解的缩聚物，使裂解的缩聚物的至少一部分与封端化合物反应以形成封端的缩聚物。封端的缩聚物可用于形成具有高固体负荷和由于改进的流变性能带来的改进的加工的增材制造制品。
Description
技术领域
本发明涉及用于3D打印的聚合物和制备它们的方法。具体而言，本发明涉及缩聚物(例如，聚酰胺和聚酯)的裂解，裂解聚合物的封端以实现可用于3D打印的所期望的稳定流变性能。
背景技术
缩聚物已用于通过诸如挤出、薄膜吹塑、注塑等的传统方法形成成型制品。在这些工艺中，聚合物被熔化并基本上被剪切，导致聚合物的裂解和不受控制的分子量损失，从而在形状(例如，吹塑瓶和挤出管)形成期间引起变形。通常，添加扩链剂以复原分子量损失，从而实现足够高的熔体强度和熔体粘度，如在第4,246,378号和7,544,387号美国专利中分别针对聚酯和聚对苯二甲酸乙二醇酯所描述的。
热塑性聚合物的增材制造通常需要以分层模式进行局部熔化，然后熔合并支撑后续层。熔丝制造(FFF)，通常也称为塑料喷射打印，已被用于通过使用热塑性长丝形成3d部件，这些热塑性长丝被抽吸加热的喷嘴中，被熔化然后挤出，其中挤出的长丝在冷却时熔合在一起(例如，参见第5,121,329和5,503,785号美国专利)。
同样，选择性激光烧结或熔化(SLS或SLM)已用于通过在粉末床中选择性地烧结粉末来制造3d部件(例如，参见第5,597,589号美国专利)。在这种方法中，使用CO2激光或其他电磁辐射源选择性地烧结保持在升高温度下的粉末床。一旦第一层被烧结，另外的粉末层被计量并重复选择性烧结直到制造出所期望的3d部件。由于粉末必须烧结或熔化，SLS受到需要复杂设备和使用具有非常特殊特性的热塑性聚合物的限制，以允许烧结而不会翘曲、塌陷并实现所期望的熔合，特别是在层之间。这通常限制其主要适用于聚酰胺(即尼龙)或含有尼龙的复合粉末。
然而，由于局部加热和熔合到后续层和层内的需求，标准类型的热塑性聚合物(诸如，聚酰胺)由于低熔体流动而限制了打印速度，例如，以实现层内和层间的充分粘合而不会变形或塌陷。由于流变特性(例如，低熔体流动)，向SLS热塑性颗粒或FFF长丝加载其他成分(例如，无机填料)以实现特定特性(诸如硬度和刚度)的能力可能会受到限制。并且，由于典型的3D制造(FFF和SLS)不涉及诸如在注塑中遇到的显著剪切，因此所期望的流变特性在加工期间可能不会因裂解及冷却和缺少剪切时的重组而发生。
因此，期望提供一种缩聚物，该缩聚物在用于3D打印部件时独特地适应此类聚合物的问题。
发明内容
已经发现，可以形成诸如聚酰胺和聚酯的缩聚物，其具有理想的熔体流变特性，从而允许改进聚合物在层内和层间的熔合。例如，该工艺允许降低重均分子量，同时仍保留所需量的高分子量部分，从而实现所期望的增强熔体流变行为，同时还保留较高分子量部分的所期望性质。
本发明的第一方面是一种形成可用于增材制造的封端的缩聚物的方法，包括：
(i)在封端化合物的存在下，加热缩聚物以形成裂解的缩聚物，并且，
(ii)使裂解的缩聚物的至少一部分与封端化合物反应以形成封端的缩聚物。在一个实施方案中，可以通过向缩聚物施加足够量的机械能来实现充分加热，诸如由双螺杆混炼挤出机提供的。
本发明的第二方面是一种形成制品的方法，包括熔合由本发明第一方面制备的封端的缩聚物的层，该层通过增材制造方法依次沉积和通过直接施加加热而熔合。
本发明的第三方面是包括通过本发明第一或第二方面的方法制备的封端的缩聚物的制品。
本发明的第四方面是包括用封端化合物的残基封端的缩聚物的聚合物。
具体实施方式
本文提供的解释和说明旨在使本领域的其他技术人员熟悉本发明、其原理和实际应用。所阐述的本公开的具体实施方案并非旨在是穷举的或限制本公开的范围。
本发明的方法通过在封端化合物的存在下加热缩聚物以形成裂解的聚合缩聚物来形成可用于增材制造的封端聚合物。
缩聚物可以是任何合适的缩聚物，诸如本领域已知的和可商购的那些。有用的聚合物的示例包括聚酰胺、聚酯、聚碳酸酯、聚酰胺酰亚胺、聚酰亚胺、聚缩醛或它们的组合。较佳地，聚合物是聚酰胺、聚酯或聚碳酸酯。缩聚物可以是线性或支链的。较佳地，缩聚物是线性的。聚酰胺的示例包括可从宇部兴产株式会社(Ube Industries Ltd.)获得的那些，诸如聚酰胺6、共聚酰胺(6/66)、共聚酰胺(6/66/12)和共聚酰胺(6/12)类型。聚酯的示例包括聚对苯二甲酸乙二醇酯和其他商业聚酯，诸如可从Celanese以商标名CELANEX获得的那些。聚碳酸酯的示例包括可从Trinseo S.A.以商标名CALIBRE获得的那些。
封端化合物可以是任何可用于使裂解的缩聚物反应和封端的化合物，并且可以根据具体的缩聚物而不同。封端化合物的示例包括包含环氧化物、羧酸、醇、酸酐、胺、异氰酸酯、氮丙啶、噁唑啉或亚磷酸酯的那些。较佳地，封端化合物是酸酐或羧酸。特别可用于封端聚酰胺和聚酰亚胺的酸酐的示例包括邻苯二甲酸酐、四溴邻苯二甲酸酐、六氢邻苯二甲酸酐、磺基邻苯二甲酸酐、偏苯三酸酐、1，8-萘二甲酸酐。在一个实施方案中，封端剂可以引入有用的化学基团，这些化学基团赋予所期望的性质或特性，诸如阻燃性、紫外线抗性或其他功能性，诸如与不同聚合物或反应基团进行进一步反应的能力。例如，封端化合物(例如，酸酐)可以具有如下的可变官能度。封端化合物(例如，酸酐)只能与聚酰胺反应一次(官能度为1)，但与聚酯的官能度为2，因此封端聚酰胺的封端化合物可能具有剩余的官能度，使其能够与聚酯反应(如果需要)。
在一个实施方案中，封端化合物是液体或固体，其沸点高于用于加热和裂解缩聚物的温度。为了说明，沸点可较佳地为至少约250℃、275℃、300℃或更高。
取决于封端的缩聚物的所期望的特性，封端剂的量可以是任何有用的量。通常，该量可以是缩聚物和封端剂的重量的约0.001％、0.01％、0.1％至约5％、3％或1％。
加热可以是到任何有用的温度并且可以取决于将被封端的具体缩聚物。说明性地，温度可以低于或高于缩聚物的熔融温度约50℃。在一个实施方案中，加热可达到缩聚物的熔融温度的约40℃、30℃或25℃以内的温度。说明性地，温度通常可以是从约150℃或200℃至300℃或250℃。
可以使用任何可用于加热缩聚物和封端剂的方法，诸如那些已知的用于加热和混合聚合物的方法。当加热时，可能期望对聚合物和封端剂也施加剪切以混合并进一步促进缩聚物的裂解。在一个实施方案中，可以使用加热的单螺杆或双螺杆挤出机，例如本领域已知的那些。剪切量可以是可用于实现特定设备中所期望的裂解和封端的任何量。挤出机可保持在一个温度或沿挤出机长度具有梯度以促进所需的裂解和封端。
为了帮助形成封端的缩聚物，可以在该方法的至少一部分期间除去在封端反应期间形成的副产物，诸如水。可以使用任何方法来去除这样的副产物，包括例如，施加真空。
为了说明该方法，将聚酰胺与由偏苯三酸酐表示的封端剂一起加热，如下所示。从这些说明中，很明显，聚酰胺的封端可能导致产生水，如本文所述，可能期望将其除去。
在另一个说明中，聚酯可以使用如下所示的单官能醇封端剂封端。在该示例中，使用商标名为EXXAL 13的13碳支链醇在PET(聚对苯二甲酸乙二醇酯)中产生断链。因为缩合反应是可逆的，所以单官能醇能够裂解酯键，从而产生分子量降低的PET链和短链醇封端的PET链。由于EXXAL 13没有任何附加的官能团，因此当断链完成时，不会发生附加反应。
相反，如果封端剂邻苯二甲酸酐用于封端聚酯，则它充当扩链剂来构建分子量而不是降低分子量。
各种因素可以影响在该方法中发生的分子量降低的程度。例如，封端反应物的浓度、在挤出机中的停留时间(例如，取决于螺杆速度)、挤出机温度、聚合物的水分含量、压力(例如，在挤出机上抽真空)，和/或挤出机中的剪切速率可以影响分子量降低的程度。例如，减慢挤出机螺杆速度可以增加聚合物和封端反应物必须相互反应的停留时间，随着停留时间的增加，这可导致较低的平均分子量，直到所有封端反应物都反应为止。增加封端反应物的浓度还可以增加封端反应物在固定停留时间内附接于裂解聚合物的反应性位点的统计概率。增加的剪切和温度可以增加在挤出机内发生的断链速率，从而导致更多的裂解分子，当存在封端反应物时，这可导致更低的平均分子量。一种或多种封端反应物可以亚化学计量(使得该一种或多种封端反应物全部被反应消耗)、化学计量或化学计量过量加入。
当进行该方法时，封端的缩聚物具有小于起始缩聚物的平均分子量Mw以及增加的多分散性和更高的熔体流动。通常，Mw的降低和多分散性的增加导致缩聚物Mw/封端的缩聚物Mw大于1并且通常至少约1.2、1.5、2至高达10或5。同样，多分散性的增加导致封端的缩聚物与缩聚物的多分散性之比大于1，通常至少约1.2、1.5、2至最多10或5。
该方法特别适用于制备具有期望的熔体流动速率和流变特性的低熔体流动速率(MFR)缩聚物，以制备熔喷和增材制造制品。给定温度下的低熔体流动速率，诸如本文中通常测量的(例如，2.16Kg@235℃[g/10min.])小于约10或5(ASTM D1238)。该方法允许将MFR提高至少2、5、10、20或甚至50倍至任何实际有用的MFR(例如，～500倍)。在一个实施方案中，封端的缩聚物的MFR在上述条件下为至少约10、20、30、50或甚至75至200。
封端聚合物可以与任何有用的添加剂混合以制造诸如本领域已知的那些制品。说明性地，封端聚合物可以与在制造制品时可能有用的其他组分混合。其它组分可以是染料、颜料、增韧剂、流变改性剂、填料、增强剂、增稠剂、遮光剂、抑制剂、荧光标记物、热降解减少剂、耐热性赋予剂(thermal resistance conferring agents)、表面活性剂、润湿剂或稳定剂中的一种或多种。
在一个实施方案中，将封端的缩聚物与填料混合(例如，熔化并与填料混合)。填料可以是任何有用的填料，诸如本领域已知的那些。填料的示例包括陶瓷、金属、碳(例如，石墨、炭黑、石墨烯)、在打印温度下不熔化或分解的聚合物颗粒(例如，交联的聚合物颗粒、硫化的橡胶颗粒等)、植物基填料(例如，木材、果壳、谷物和稻壳粉或颗粒)。示例性填料包括碳酸钙、滑石、二氧化硅、硅灰石、粘土、硫酸钙、云母、无机玻璃(例如，二氧化硅、铝硅酸盐、硼硅酸盐、碱性铝硅酸盐等)、氧化物(例如，氧化铝、氧化锆、氧化镁、二氧化硅“石英”和氧化钙)、碳化物(例如，碳化硼和碳化硅)、氮化物(例如，氮化硅、氮化铝)、氧氮化物的组合、碳氧化物或它们的组合。在某些实施方案中，填料包括针状填料，诸如滑石、粘土矿物、短切无机玻璃、金属或碳纤维、莫来石、云母、硅灰石或它们的组合。在一个具体实施方案中，填料包括滑石粉。
填料的量可以是用于制造制品(诸如增材制造制品)的任何有用的量。例如，填料可以以封端的聚合物和填料的重量的从20％、30％、40％或50％至90％的量存在。已经发现，由于能够实现更高的MFR和期望的流变学，可以使用更高负载量的填料，同时仍然实现诸如聚酰胺的缩聚物的良好打印性能。
在一个实施方案中，将封端的聚合物形成为可用于诸如SLS或FFF的增材制造的粉末或长丝，然后将其用于制造包含封端的缩聚物的增材制造制品。
说明性实施方案
提供以下实施例以说明该方法和由它们形成的聚合物，但不旨在限制其范围。除非另有说明，所有份数和百分比均按重量计。
每个实施例和对比例在27mm双螺杆挤出机/混料机中以400转/分钟以60磅/小时的速度加载所述的聚酰胺、封端化合物及对于实施例详述的封端化合物浓度进行，如下所示。挤出机的长度/直径比为40，且沿挤出机长度从入口到出口通过模头的温度在240℃和280℃之间(即，从开始到结束的某种线性梯度)。压力(真空)保持在约800毫巴。
实施例1(A至D)和对比例1：
在这些实施例和对比例中，使用的聚酰胺是UBE 6434类型6/66/12。封端化合物是如表1所示的邻苯二甲酸酐，各实施例和对比例的MFR也在表1中示出。
表1
实施例2(A至D)和对比例2：
在这些实施例和对比例中，使用的聚酰胺是UBE 6434类型6/66/12。封端化合物是如表1中所示的六氢邻苯二甲酸酐，各实施例和对比例的MFR也在表中示出。
表2
实施例3(A至D)和对比例3：
在这些实施例和对比例中，使用的聚酰胺是UBE 6434类型6/66/12。封端化合物是如表3所示的偏苯三酸酐，各实施例和对比例的MFR也在表3中示出。即使当聚酰胺如本实施例那样支化时，该方法在实现期望的MFR方面也是有效的。
表3
实施例4(A至D)和对比例4：
在这些实施例和对比例中，使用的聚酰胺是RILSAN聚酰胺11(Arkema)。如表4所示，封端化合物是六氢邻苯二甲酸酐，各实施例和对比例的MFR也在表4中示出。用于实施例的MFR太高而无法测量。不完全理解MFR增加如此迅速的原因，但可能是因为(不在于以任何方式进行限制)残留单体的存在充当了进一步的增塑剂。
表4
实施例5(A至C)和对比例1：
在这些实施例和对比例中，使用的聚酰胺是NYLENE 615NP PA6(Nylene PolymerSolution)。如表5所示，封端化合物是六氢邻苯二甲酸酐，各实施例和对比例的MFR也在表5中示出。
表5
实施例6(A至C)和对比例6：
在这些实施例和对比例中，使用的聚酰胺是Shadong Guangyin型PA 1012。封端化合物是如表6所示的六氢邻苯二甲酸酐，各实施例和对比例的MFR也在表6中示出。
表6
实施例6(A至C)和对比例6：
在该实施例和对比例中，使用的聚酰胺是EMS Grilamid L16 nat PA12(EMS-Grivory)。封端化合物是如表1中所示的邻苯二甲酸酐，测得的封端聚酰胺的MFR也在表中示出。
表7
Claims (39)
1.一种形成封端的缩聚物的方法，包括：
(i)在封端化合物的存在下，加热缩聚物以形成裂解的缩聚物，以及
(ii)使所述裂解的缩聚物的至少一部分与所述封端化合物反应以形成封端的缩聚物。
2.根据权利要求1所述的方法，其中所述封端化合物由环氧化物、羧酸、醇、酸酐、胺、异氰酸酯、氮丙啶、噁唑啉或亚磷酸酯组成。
3.根据权利要求1或2所述的方法，其中所述封端化合物是酸酐或羧酸。
4.根据权利要求3所述的方法，其中所述封端化合物是酸酐。
5.根据前述权利要求中任一项所述的方法，其中所述缩聚物是聚酰胺、聚酯、聚碳酸酯、聚酰胺酰亚胺、聚酰亚胺、聚缩醛或它们的组合。
6.根据权利要求5所述的方法，其中所述缩聚物是聚酰胺、聚酯、聚碳酸酯或它们的组合。
7.根据前述权利要求中任一项所述的方法，其中所述封端的缩聚物和所述缩聚物各自具有重均分子量(Mw)和多分散性，使得所述封端的缩聚物的Mw小于所述缩聚物的Mw并且所述封端的缩聚物的多分散性大于所述缩聚物的多分散性。
8.根据权利要求7所述的方法，其中所述缩聚物的Mw与所述封端的缩聚物的Mw之比大于1，并且所述封端的缩聚物的多分散性与所述缩聚物的多分散性之比大于1。
9.根据前述权利要求中任一项所述的方法，其中所述封端的缩聚物具有至少20克/10分钟(2.16kg@235℃)的熔体流动速率。
10.根据权利要求9所述的方法，其中所述封端的缩聚物是聚酰胺、聚酯、聚碳酸酯、聚酰胺酰亚胺、聚酰亚胺、聚缩醛或它们的组合。
11.根据权利要求10所述的方法，其中所述封端的缩聚物是聚酰胺、聚酯或它们的组合。
12.根据权利要求9至11中任一项所述的方法，其中封端的缩聚物具有至少20克/10分钟(2.16kg@235℃)的MFR。
13.根据前述权利要求中任一项所述的方法，还包括在加热期间剪切所述缩聚物。
14.根据前述权利要求中任一项所述的方法，其中所述加热高于所述缩聚物的熔融温度并且低于所述缩聚物的分解温度。
15.根据前述权利要求中任一项所述的方法，其中所述加热在螺杆挤出机中进行。
16.根据前述权利要求中任一项所述的方法，还包括在所述方法的至少一部分期间去除水。
17.根据权利要求16所述的方法，其中通过在减压下实施所述方法来去除水。
18.根据前述权利要求中任一项所述的方法，其中所述封端化合物由四溴邻苯二甲酸酐、六氢邻苯二甲酸酐、偏苯三酸酐、1，8-萘二甲酸酐、邻苯二甲酸酐或磺基邻苯二甲酸酐中的一种或多种组成。
19.根据前述权利要求中任一项所述的方法，其中所述封端的缩聚物形成为粉末或长丝。
20.根据前述权利要求中任一项所述的方法，其中封端化合物的量为所述缩聚物和封端化合物的重量的0.01％至5％。
21.一种形成制品的方法，包括熔合由前述权利要求中任一项所述的方法制成的封端的缩聚物的层，所述层通过增材制造方法依次沉积和通过直接施加热而熔合。
22.根据权利要求21所述的方法，其中所述增材制造方法是SLS或FFF。
23.根据权利要求21或22所述的方法，其中所述封端的缩聚物具有填料，其量为所述聚合物和填料的重量的至少约25％至90％。
24.一种制品，包括根据权利要求1至20中任一项所述的封端的缩聚物。
25.一种聚合物，包括权利要求1至20中任一项所述的封端的缩聚物。
26.一种制品，由权利要求21至23中任一项所述的方法制成。
27.根据权利要求24所述的聚合物，其中所述封端的缩聚物的MFR至少为10。
28.根据权利要求27所述的制品，其中所述封端的缩聚物用环氧化物、羧酸、醇、酸酐、胺、异氰酸酯、氮丙啶、噁唑啉或亚磷酸酯的反应产物封端。
29.根据权利要求28所述的制品，其中所述封端的缩聚物用所述羧酸或酸酐的反应产物封端。
30.根据权利要求29所述的制品，其中所述封端的缩聚物是用酸酐封端的聚酰胺。
31.一种聚合物，包括用封端化合物的残基封端的缩聚物。
32.根据权利要求31所述的聚合物，其中所述缩聚物是聚酰胺、聚酯、聚碳酸酯、聚酰胺酰亚胺、聚酰亚胺、聚缩醛或它们的组合。
33.根据权利要求32所述的聚合物，其中所述缩聚物是聚酰胺、聚酯或聚碳酸酯。
34.根据权利要求33所述的聚合物，其中所述缩聚物是聚酰胺。
35.根据权利要求31至34中任一项所述的聚合物，其中所述封端化合物是环氧化物、羧酸、醇、酸酐、胺、异氰酸酯、氮丙啶、噁唑啉或亚磷酸酯。
36.根据权利要求35所述的聚合物，其中所述封端化合物是酸酐，并且所述缩聚物是聚酰胺。
37.根据权利要求36所述的聚合物，其中所述酸酐是四溴邻苯二甲酸酐、六氢邻苯二甲酸酐、偏苯三酸酐、1,8-萘二甲酸酐、邻苯二甲酸酐或磺基邻苯二甲酸酐。
38.根据权利要求36或37所述的聚合物，其中所述聚合物具有至少约10克/10分钟(2.16Kg@235℃)的熔体流动速率。
39.根据权利要求1所述的方法，其中所述封端化合物具有可变官能度。
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| CN117186388B (zh) * | 2023-08-01 | 2024-04-19 | 中山海明中科新材料有限公司 | 一种尼龙复合材料及其制备方法与应用 |
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