CN101072834A - 由聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺而制成的嵌段共聚物 - Google Patents
由聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺而制成的嵌段共聚物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
本发明涉及一种制备由对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺而制成的嵌段共聚物的方法。
Description
本发明涉及聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段共聚物，以及它们的制备方法。
EP-A-1 200 522公开了一种制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的完全缩合聚酰胺的聚合物混合物(共混物)的方法。这些混合物在生产容器中并不完全令人满意。
因此，本发明的目的是消除上述缺点。
因此已经发现聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段共聚物。还发现了制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段共聚物的新型改进方法，其包括在0.1-20巴的压力和245-300℃的温度下在1.5-2.2的相对溶液粘度下加入聚对苯二甲酸乙二醇酯。
本发明方法可以按如下进行：
可以使用常规方法进行间苯二甲胺[3-(氨基甲基)苄基胺]与己二酸的缩合，其实例公开于Ullmanns Encyklopdie der Technischen Chemie[乌尔曼工业化学百科全书]，第4版，第19卷，39-54页，Verlag Chemie，Weinheim1980和乌尔曼工业化学百科全书，第A21卷，179-206页，VCH Verlag，Weinheim 1992，以及Stoeckhert，Kunststofflexikon[塑料百科全书]，第8版，425-428页，Hanser Verlag Munich 1992(关键词“Polyamide”[聚酰胺]以及随后部分等等)中。可以优选使间苯二甲胺、己二酸和水组分以单独组分形式或以任何所需混合物形式，优选以所有三个组分的混合物形式，在2-20巴、优选5-15巴、特别优选7-12巴的压力和170-280℃、优选180-270℃、特别优选190-260℃、尤其是200-250℃的温度下分批或优选连续地进行反应。优选的起始混合物是浓度为30-80重量％、尤其为45-70重量％的由间苯二甲胺和己二酸组成的盐化合物的溶液。一旦已将该混合物加热至目标压力和温度，通过蒸馏来除去水。
然后可以进行后缩合或直接熔融聚酰胺，优选的是，在惰性气体气氛如氮气或氩气下，在0.1-3巴、优选0.5-2巴、特别优选0.7-1.5巴的压力、尤其大气压下，在240-300℃、优选250-290℃、特别优选260-280℃的温度下进行后缩合。
聚对苯二甲酸乙二醇酯向聚酰胺中的添加通常可以在0.1-20巴的压力和240-300℃、优选245-300℃的温度下进行。在一个优选实施方案中，聚对苯二甲酸乙二醇酯的添加在制备聚酰胺的过程中进行。
在反应之后，嵌段共聚物可以经由本身已知的方法完成，例如经由水下珠粒造粒、水下线料切粒或其它形式的线料切粒方法。所得粒料可以进行抽提工序，该抽提可以连续或者分批进行。合适的提取剂尤其是水和C1-C8链烷醇，例如乙醇和甲醇，优选水。抽提过的嵌段共聚物可以在另外的步骤中进行固相缩合。这或者可以在真空中或者可以在惰性气体如氮气或氩气，优选氮气下进行。此处的温度可以宽范围变动，但是通常为120-230℃，优选130-210℃，特别优选140-190℃。
聚对苯二甲酸乙二醇酯与聚酰胺的重量比可以宽范围变动，但是通常为0.001∶1-1000∶1，优选0.005∶1-500∶1，特别优选0.001∶1-100∶1。在一个优选实施方案中，聚对苯二甲酸乙二醇酯与聚酰胺的重量比通常为0.002∶1-0.1∶1，优选0.002∶1-0.08∶1，特别优选0.003∶1-0.07∶1。
间苯二甲胺与己二酸的摩尔比可以宽范围变动，但是通常为1.5∶1-0.75∶1，优选1.2∶1-0.8∶1，特别优选1.1∶1-0.9∶1或等摩尔(1∶1)，尤其是1.05∶1-0.95∶1。
在意欲改进浊度的情况下，间苯二甲胺与己二酸的摩尔比通常为1.5∶1-1∶1，优选1.2∶1-1.01∶1，特别优选1.1∶1-1.02∶1，尤其是1.05∶1-1.01∶1。
在意欲改进色数的情况下，己二酸与间苯二甲胺的摩尔比通常为1.5∶1-1∶1，优选1.2∶1-1.01∶1，特别优选1.1∶1-1.02∶1，尤其是1.05∶1-1.01∶1。
在间苯二甲胺与己二酸缩合的一个实施方案中，缩聚过程可以在1-20巴的压力下在钢质高压釜中分批进行。此处可以使用的原料为浓度为30-80重量％的水溶液。
在另一个实施方案中，缩聚过程可以在1-20巴的压力下连续进行。此处缩聚系统可以由补给容器、锅炉反应器、分离器和造粒机组成。可以使用的原料为浓度为30-80重量％的水溶液。
本发明嵌段共聚物中的残留单体含量通常不超过500ppm，例如0.1-500ppm，优选0.5-50ppm，特别优选1-15ppm的间苯二甲胺。残留己二酸单体的含量通常低于10ppm。本发明嵌段共聚物中环状二聚体(MXDA+己二酸)的含量通常不超过1500ppm，例如10-1500ppm，优选50-1000ppm，特别优选100-250ppm。
通常合适的聚酰胺为任何聚酰胺，并且通常为由50-100重量％、优选70-100重量％、特别优选85-100重量％的间苯二甲胺和50-100重量％、优选70-100重量％、特别优选85-100重量％的己二酸以及0-50重量％、优选0-30重量％、特别优选0-15重量％的合适共聚单体和/或合适的话，链长调节剂和/或合适的话，稳定剂组成的那些，并且分子量Mn为10000-50000，优选分子量Mn为30000-40000的高分子量聚酰胺或分子量Mn为11000-22000的低分子量聚酰胺，特别优选分子量Mn为13000-20000的低分子量聚酰胺，尤其是分子量Mn为15000-19000的低分子量聚酰胺。
摩尔质量通过使用由Kontron Instruments 420 HPLC泵、GilsonAbimed自动进样器、Gamma Analysentechnik LCD UV光度计(230/D)和Agilent G1362A差示折光仪组成的装置用与DIN 55672-1类似的方法经由GPC而测定。所用的洗脱液包含六氟异丙醇和0.05％三氟乙酸钾的混合物。所用聚合物实验室柱分别为HFIP凝胶预备柱(内径：7.5mm，长度：5cm)和HFIP凝胶线性柱(内径：7.5mm，长度：5cm)。柱温为40℃且流速为0.5ml/min。将密度为1.5g/l的样品通过Millipore Millex FG(孔宽度为0.2[μm])预过滤。将得自PSS的PMMA标准样用于校准。
相对溶液粘度通常为1.5-2.2，优选1.55-2.1，特别优选1.6-2，尤其是1.65-1.8。
聚酰胺的相对溶液粘度使用1g聚酰胺在100ml的96重量％浓度的硫酸中的样品进行测定，测量依据DIN EN ISO 1628-1借助50120(Schott)Ubbelohde粘度计2进行。
间苯二甲胺的合适共聚单体的实例为脂族、芳族或芳脂族二胺，例如乙二胺、丁二胺、五亚甲基二胺、六亚甲基二胺、环己二胺、八亚甲基二胺、二(4，4-氨基环己基)甲烷、二(4，4-氨基-3，3-甲基环己基)甲烷、二(氨基)环己烷、对苯二胺、邻苯二甲胺和对苯二甲胺。
己二酸的合适共聚单体的实例为脂族、芳族或芳脂族二羧酸，例如对苯二甲酸、间苯二甲酸、磺基间苯二甲酸、萘-2，6-二甲酸、环己烷二甲酸、丁二酸、戊二酸、壬二酸和癸二酸。
合适的链长调节剂的实例为单官能调节剂，例如三丙酮二胺化合物(参见WO-A 95/28443)，单羧酸如乙酸、丙酸和苯甲酸，以及碱如(单)胺类，例如己胺或苯甲胺，二胺如六亚甲基二胺或1，4-环己二胺，C4-C10二羧酸如己二酸、壬二酸、癸二酸、十二烷二酸，C5-C8环烷二羧酸如环己烷-1，4-二甲酸，苯二羧酸和萘二羧酸如间苯二甲酸、对苯二甲酸和萘-2，6-二甲酸。
为了改进本发明嵌段共聚物的性质，可以使用用于改性的任何已知添加剂，例如成核剂、染料、颜料、流动改进剂、紫外吸收物质、消光剂、氧清除剂、无机或有机填料或抗冲改性填料。
合适的稳定剂为由文献中已知的如下化合物：空间位阻酚、磷化合物如次磷酸盐以及这两类稳定剂的混合物。
聚酰胺通常包含0-1重量％、优选0.05-0.8重量％、特别优选0.1-0.7重量％、尤其是0.3-0.6重量％的稳定剂。
通常合适的聚对苯二甲酸乙二醇酯为任何聚对苯二甲酸乙二醇酯，并且通常为由50-100重量％、优选70-100重量％、特别优选85-100重量％的乙二醇和50-100重量％、优选70-100重量％、特别优选85-100重量％的对苯二甲酸以及0-50重量％、优选0-30重量％、特别优选0-15重量％的合适共聚单体组成的那些，并且分子量Mn为10 000-50 000，优选分子量Mn为35 000-50 000的高分子量聚对苯二甲酸乙二醇酯或分子量Mn为10 000-25 000的低分子量聚对苯二甲酸乙二醇酯，特别优选分子量Mn为12 000-22 000的低分子量聚对苯二甲酸乙二醇酯。
分子量Mn为3000-12 000、优选5000-12 000、特别优选10 000-12 000的聚对苯二甲酸乙二醇酯低聚物也是合适的。摩尔质量的测定方法类似于上述嵌段共聚物的测定方法。
乙二醇的合适共聚单体为三甘醇、1，4-环己烷二甲醇、1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、3-甲基-1，4-戊二醇、2-甲基-1，4-戊二醇、2，2，4-三甲基-1，3-戊二醇、2-乙基-1，3-己二醇、2，2-二乙基-1，3-丙二醇、1，3-己二醇、1，4-二羟基苯、2，2-二(4-羟基环己基)丙烷、2，4-二羟基-1，1，3，3-四甲基环丁烷、2，2-二(3-羟基乙氧基苯基)丙烷和2，2-二(4-羟基乙氧基苯基)丙烷。
对苯二甲酸的合适共聚单体为己二酸、间苯二甲酸、邻苯二甲酸、2，6-萘二甲酸、环己烷二甲酸、丁二酸、戊二酸、癸二酸和壬二酸。
可以以0.1-5重量％、优选0.1-3重量％、特别优选0.1-2重量％的极少量而存在于聚对苯二甲酸乙二醇酯中的其它成分为三官能或四官能的共聚单体，例如偏苯三酸或1，2，4，5-苯四酸或这些的混合物。
本发明的聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段共聚物适于例如经由挤出、注塑、压延、吹塑、压模、烧结或其它热塑性塑料加工的常用方法而生产或作为原料而生产模制品、管、型材、塑坯预塑、容器、盘、纤维、箔、薄膜、瓶以及任何类型的泡沫体。
本发明的嵌段共聚物(聚对苯二甲酸乙二醇酯和聚酰胺的嵌段共聚物)的优选用途为制备与聚对苯二甲酸乙二醇酯的共混物.它们尤其适于生产透明、无色的容器和注塑品，尤其是生产用于饮料工业的塑坯预塑和瓶。在该优选应用中，嵌段共聚物在聚对苯二甲酸乙二醇酯中的存在量为0.01-15重量％，优选0.02-10重量％，特别优选0.03-7重量％。
为了可能应用于食品包装中，将嵌段聚合物的粒料进行挤出抽提。这有效地降低了残余聚合物的含量。
在将所制得的嵌段聚合物和聚对苯二甲酸乙二醇酯混合时，结果使聚酰胺与聚对苯二甲酸乙二醇酯基质之间具有改进的相相容性，因此实现了这些共混物在随后用于容器、模制品和箔中的高透明性。同时，显著改进了不希望的发黄。
实施例
发明实施例1
由间苯二甲胺和己二酸制成的聚酰胺与2重量％低分子量聚对苯二甲酸乙二醇酯的嵌段共聚物的制备
在10升的罐中将2070.4g己二酸(14.17mol)用作起始加料，在搅拌下加入1714.1g水(95.12mol)和1977.1g间苯二甲胺(14.52mol)，将该混合物在氮气下加热至220℃的温度，并且在10巴的压力下通过蒸馏除去水。在减压至大气压力后，在氮气下在260℃的温度下进行后缩合1小时，在相对粘度为1.65[45分钟后]和提高转速(由80rpm提高至120rpm)下加入80g低分子量聚对苯二甲酸乙二醇酯(IV＝0.6，Mn＝18 500，由2mol％间苯二甲酸改性)，并且在5分钟之后，将体系抽空至400毫巴并保持10分钟，然后减压。在下一步中，将聚合物熔体通过水浴排出并造粒。
在60重量％苯酚与40重量％1，1，2，2-四氯乙烷的混合物中以0.5g/100ml溶剂的浓度测量固有粘度(IV)。
发明实施例2
由间苯二甲胺和己二酸制成的聚酰胺和5重量％低分子量聚对苯二甲酸乙二醇酯的嵌段共聚物的制备
该制备方法与发明实施例1相似，但是使用200g的低分子量聚对苯二甲酸乙二醇酯(IV＝0.6，Mn＝18 500，由2mol％间苯二甲酸改性)。
发明实施例3
由间苯二甲胺和己二酸制成的聚酰胺和1重量％低分子量聚对苯二甲酸乙二醇酯的嵌段共聚物的制备
该制备方法与发明实施例1相似，但是使用40g的低分子量聚对苯二甲酸乙二醇酯(IV＝0.6，Mn＝18 500，由2mol％间苯二甲酸改性)。
发明实施例4
由间苯二甲胺和己二酸制成的聚酰胺和0.5重量％低分子量聚对苯二甲酸乙二醇酯的嵌段共聚物的制备
该制备方法与发明实施例1相似，但是使用20g的低分子量聚对苯二甲酸乙二醇酯(IV＝0.6，Mn＝18 500，由2mol％间苯二甲酸改性)。
对比例A
本对比例涉及可由Mitsubishi Gas Chemical市购的聚酰胺MXD6007。结果在下表1中给出：
表1
| 实施例编号 | 相对粘度* | 端氨基含量 | 端羧基含量 |
| 1 | 1.856 | 137 | 54 |
| 2 | 1.736 | 141 | 42 |
| 3 | 1.815 | 148 | 38 |
| 4 | 1.765 | 154 | 30 |
| A | 2.671 | 20 | 65 |
*相对粘度＝1g聚酰胺在100ml的96重量％浓度硫酸中的样品；测量借助Sehott 50120 Ubbelohde粘度计2依据DIN EN ISO 1628-1进行
发明实施例I
塑坯预塑的生产
由购自Mossi&Ghisolfi的95重量％CleartufAqua D82聚对苯二甲酸乙二醇酯和每种情况下5重量％的表1所示的发明实施例和对比例嵌段共聚物而制备均匀的粒料混合物。然后将这些粒料混合物用于注塑瓶塑坯预塑。在275℃的温度下在单-模具Arburg 320注塑机上生产重49g的塑坯预塑。
发明实施例II
瓶的生产
将如发明实施例I中生产的塑坯预塑在110℃的温度和40巴的压力下在Sidel SB01制瓶机中的瓶模具中吹塑以形成1.5升的瓶。
结果在下表2中给出：
表2
| 来自如下实施例的聚合物 | 瓶的浊度*[％] |
| 1 | 3.7 |
| 2 | 3.5 |
| A | 12.5 |
*浊度：通过ASTM D100392方法借助Gardner双测量设备进行测量
Claims (8)
1.一种聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段聚合物。
2.一种制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段聚合物的方法，其包括在0.1-20巴的压力和240-300℃的温度下向相对溶液粘度为1.5-2.2的聚酰胺中加入聚对苯二甲酸乙二醇酯。
3.根据权利要求1的制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段聚合物的方法，其中在0.1-3巴的压力和260-300℃的温度下加入聚对苯二甲酸乙二醇酯。
4.根据权利要求1或2的制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段聚合物的方法，其中在制备所述聚酰胺的过程中加入所述聚对苯二甲酸乙二醇酯。
5.根据权利要求1或2的制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段聚合物的方法，其中在大气压力下加入所述聚对苯二甲酸乙二醇酯。
6.根据权利要求1-4中任一项的制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段聚合物的方法，其中所用聚对苯二甲酸乙二醇酯与聚酰胺的重量比为0.005∶1-1000∶1。
7.根据权利要求1-4中任一项的制备聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺的嵌段聚合物的方法，其中所用聚对苯二甲酸乙二醇酯与聚酰胺的重量比为0.005∶1-0.1∶1。
8.一种由聚对苯二甲酸乙二醇酯和由间苯二甲胺与己二酸制成的聚酰胺通过在0.1-20巴的压力和120-300℃的温度下向相对溶液粘度为1.55-2.1的聚酰胺中加入聚对苯二甲酸乙二醇酯而制备的嵌段聚合物。
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2005
- 2005-12-03 WO PCT/EP2005/012983 patent/WO2006061160A2/de active Application Filing
- 2005-12-03 JP JP2007544790A patent/JP2008523180A/ja not_active Withdrawn
- 2005-12-03 CA CA002587631A patent/CA2587631A1/en not_active Abandoned
- 2005-12-03 AU AU2005313606A patent/AU2005313606A1/en not_active Abandoned
- 2005-12-03 NZ NZ555393A patent/NZ555393A/en not_active IP Right Cessation
- 2005-12-03 US US11/721,073 patent/US20100240839A1/en not_active Abandoned
- 2005-12-03 KR KR1020077015502A patent/KR20070098848A/ko not_active Application Discontinuation
- 2005-12-03 CN CNA200580042213XA patent/CN101072834A/zh active Pending
- 2005-12-03 RU RU2007125569/04A patent/RU2007125569A/ru not_active Application Discontinuation
- 2005-12-03 EP EP05825926A patent/EP1828311A2/de not_active Withdrawn
- 2005-12-03 BR BRPI0518515-7A patent/BRPI0518515A2/pt not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316532A (zh) * | 2022-01-04 | 2022-04-12 | 海信（山东）冰箱有限公司 | Pet注塑级厚材、其制备方法及冰箱 |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0518515A2 (pt) | 2008-11-25 |
| EP1828311A2 (de) | 2007-09-05 |
| WO2006061160A3 (de) | 2006-08-24 |
| RU2007125569A (ru) | 2009-01-20 |
| WO2006061160A2 (de) | 2006-06-15 |
| KR20070098848A (ko) | 2007-10-05 |
| US20100240839A1 (en) | 2010-09-23 |
| NZ555393A (en) | 2009-08-28 |
| AU2005313606A1 (en) | 2006-06-15 |
| DE102004059597A1 (de) | 2006-06-22 |
| JP2008523180A (ja) | 2008-07-03 |
| CA2587631A1 (en) | 2006-06-15 |
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Open date: 20071114 |