CN114380993A - 共聚物与其形成方法 - Google Patents
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Abstract
一种共聚物的形成方法包括:在螺杆的第一区混合反应聚酯、脂肪族多元醇或脂肪族多元醇的寡聚物、与第一催化剂,以形成聚酯多元醇;以及侧进料内酯或内酰胺至螺杆的第二区,使内酯或内酰胺与聚酯多元醇共聚反应形成共聚物,其中第一区与第二区为连续相连的区域。
Description
技术领域
本发明涉及共聚物与其形成方法。
背景技术
聚酯如聚对苯二甲酸乙二酯(PET)的熔点为255℃。依熔点高低划分,一般将熔点低于230℃的聚酯称为低熔点聚酯。在纺织领域,低熔点聚酯是热熔粘合工艺生产非织造布所需的重要原料,可用于鞋面消失线及热熔胶粘合。目前市售的低熔点聚酯大多采用逐步聚合的方式,以对苯二甲酸与乙二醇为基础原料,添加间苯二甲酸、脂肪族二元酸、新戊二醇等多种酸、醇成分,在反应槽中以批次方式进行聚合反应。此作法缺点在于聚合反应时间长、成本高、且需添加大量软链段分子,会导致聚缩合反应效率低、分子量低及机械性质不佳。综上所述,目前亟需新的方式克服上述低熔点聚酯的缺点,以符合经济、快速与低成本的需求。
发明内容
本发明一实施例提供的共聚物的形成方法,包括:在螺杆的第一区混合反应聚酯、脂肪族多元醇或脂肪族多元醇的寡聚物与第一催化剂,以形成聚酯多元醇;以及侧进料内酯或内酰胺至螺杆的第二区,使内酯或内酰胺与聚酯多元醇共聚反应形成共聚物,其中第一区与第二区为连续相连的区域。
本发明一实施例提供的共聚物,为由:内酯或内酰胺与聚酯多元醇共聚反应而成,其中聚酯多元醇为由聚酯与脂肪族多元醇或脂肪族多元醇的寡聚物在第一催化剂存在下反应而成。
具体实施方式
本发明一实施例提供的共聚物的形成方法,包括提供螺杆。螺杆可为螺杆挤出机或双螺杆挤出机的螺杆,其两端分别为主进料口与出料口,内部可粗分为连续相连的第一区与第二区。第一区可位于进料口与第二区之间。举例来说,可在螺杆的第一区混合反应聚酯、脂肪族多元醇或脂肪族多元醇的寡聚物、与第一催化剂,以形成聚酯多元醇。
举例来说,若聚酯为聚对苯二甲酸乙二酯(PET),脂肪族多元醇为脂肪族二醇,在催化剂的存在下,PET与脂肪族二醇的反应如下:
上述反应属于降解反应,因此m>n。
接着,可侧进料内酯或内酰胺至螺杆的第二区,使内酯或内酰胺与聚酯二醇共聚反应形成共聚物。举例来说,内酯可为C2-7的内酯,而内酰胺可为C2-7的内酰胺。举例来说,若内酯为R(例如H或烷基)取代的己内酯,在催化剂的存在下,上述反应如下:
举例来说,若内酰胺为己内酰胺,在催化剂的存在下,上述反应如下:
经上述反应所形成的共聚物,其熔点将大幅下降(与一般聚酯相较)。以PET为例,其熔点为约250℃,而经上述方法所形成的共聚物的熔点可大幅下降至低于220℃,例如低于200℃,低于约180℃或更低,甚至降低至约150℃,将有利于共聚物后续与其他树脂共加工,扩大应用范围。在一些实施例中,共聚物的熔点为120℃至220℃。在一些实施例中,共聚物的熔点为120℃至200℃。在一些实施例中,共聚物的熔点为120℃至180℃。
在一些实施例中,聚酯可包括聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚碳酸酯、聚对萘二甲酸乙二酯、聚对萘二甲酸丁二酯、聚乳酸酯、聚丁酸酯-己二酸酯-对苯二甲酸酯、聚氨酯或上述的组合。
在一些实施例中,前述的脂肪族多元醇为C-(R1-OH)x,其中x=2~42,C为核心,该核心可为一碳原子或一碳链,且R1为C2-20的亚烷基、聚酯基或环亚烷基。可以理解的是,当x=2时,上述脂肪族多元醇为脂肪族二元醇,可为寡聚物并与聚酯反应形成聚酯二醇;当x=3时,上述脂肪族多元醇为脂肪族三元醇,可为寡聚物并与聚酯反应形成聚酯三元醇;当x=4时,上述脂肪族多元醇为脂肪族四元醇,可为寡聚物并与聚酯反应形成聚酯四元醇;以此类推。在一些实施例中,脂肪族多元醇可为脂肪族二元醇、脂肪族三元醇、脂肪族四元醇、上述的寡聚物或上述的组合。举例来说,脂肪族多元醇可为(CAPA3050,500≥n≥1)、(CAPA2054,R为C2-20的亚烷基、聚酯基或环亚烷基,500≥n≥1)、(MPDO)或(CAPA500≥n≥1)。
在一些实施例中,前述的脂肪族二元醇为H(OCH2CH2)nOH或H(OCH2CH2CH2)nOH,其中500≥n≥2。
在一些实施例中,前述第一催化剂可为金属醇盐,举例来说,第一催化剂为M(OR2)x,x=3或4,M为Al、Ti、Zn、Sb、Ge、Sn或上述的组合,且R2为C1-6的直链或支链烷基。在一些实施例中,共聚物的形成方法还包括侧进料第二催化剂至螺杆的该第二区,且第二催化剂可为金属醇盐,举例来说,第二催化剂为M(OR2)x,x=3或4,M为Al、Ti、Zn、Sb、Ge、Sn或上述的组合,且R2为C1-6的直链或支链烷基。换言之,可将与第一催化剂相同或不同组成的第二催化剂侧进料至第二区中,以确保内酯或内酰胺与聚酯多元醇反应时,仍有足够的催化剂量催化反应。
在一些实施例中,前述螺杆的第一区与第二区的温度约为90℃至300℃。一般而言,第一区与第二区的温度略高于聚酯熔点。若第一区的温度过低,则聚酯尚未完全熔化导致反应性不佳。若第一区与第二区的温度过高,则会导致聚酯裂解。
在一些实施例中,前述螺杆第一区与第二区的反应时间总计约5分钟至15分钟。在一些实施例中,前述的聚酯与“脂肪族多元醇或脂肪族多元醇的寡聚物”的重量比为100∶1至100∶50。若脂肪族多元醇或脂肪族多元醇的寡聚物的比例过低,则产物熔点下降不显著。若脂肪族多元醇或脂肪族多元醇的寡聚物的比例过高,虽产物熔点有显著下降,但产物物性过低无法被加工利用且制作成本高,经济效益低。在一些实施例中,前述的聚酯与“内酯或内酰胺”的重量比为100∶1至100∶50。若内酯或内酰胺的比例过低,则产物熔点降低幅度不显著。若内酯或内酰胺的比例过高,则导致产物成本过高。
在一些实施例中,前述聚酯的本质粘度可为0.1dL/g至2.0dL/g。前述聚酯本质粘度的适当范围取决于最终应用目的,举例来说,当前述聚酯要应用于胶体材料,聚酯的本质粘度需大于0.1dL/g;然而,当前述聚酯要应用于纤维纺织,聚酯的本质粘度需于0.4dL/g至0.98dL/g;再然而,当前述聚酯要应用于瓶级材料,则聚酯的本质粘度需大于0.7dL/g,也就是前述聚酯的本质粘度范围为0.7dL/g至2.0dL/g。若聚酯的本质粘度过低,则聚酯缺乏所需物性无法被加工再利用。
本发明所提供的方法,可使所形成的共聚物的熔点降低的同时,仍维持共聚物的本质粘度在一合适的范围。在一些实施例中,聚酯(例如PET)的熔点约250℃,经上述方法所形成的共聚物的熔点可大幅下降至低于220℃或低于200℃,且共聚物的本质粘度可维持为0.1dL/g至2dL/g,甚至,可维持为0.4dL/g至1.2dL/g。本发明所提供的方法,可克服目前业界制造低熔点聚酯采用逐步聚合的方式,所遭遇到的聚合反应时间过长、成本高的问题。
可以理解的是,本发明提供一共聚物,可由内酯(或内酰胺)与聚酯多元醇共聚反应而成,其中聚酯多元醇为由聚酯与脂肪族多元醇或脂肪族多元醇的寡聚物在第一催化剂存在下反应而成。上述反应可在螺杆中进行如前述,也可以批次式的方式进行。至于聚酯、脂肪族多元醇或脂肪族多元醇的寡聚物、第一催化剂、内酯(或内酰胺)、以及反应的温度与时间则与前述类似,在此不赘述。上述方式所形成的共聚物与聚酯相较,其熔点大幅降低。此外,共聚物具有一定程度的本质粘度,其机械性质不会因熔点大幅降低而劣化。
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,下文特别列举出较佳实施例,作详细说明如下:
[实施例]
实施例1
取100克的PET(IV=0.62dL/g,测量方法为ASTM D4603;熔点为250.0℃,购自新光)、0.5克的钛(IV)异丙醇盐(Titanium(IV)isopropoxide,购自Alfa Aesar,CAS 546-68-9)作为催化剂与10克的二醇MPDO(2-甲基-1,3-丙二醇,2-methyl-propan-1,3-diol)从主进料口直接进料至双螺杆挤出机的螺杆的第一区,在260℃下反应以形成聚酯二醇。螺杆主进料口的温度为20℃,挤出温度为260℃,且螺杆转速200rpm。挤出聚酯二醇后拉条过水造粒,并置入100℃的烘箱干燥4小时。所制得的聚酯二醇的本质粘度为0.11dL/g(测量方法为ASTM D4603),且熔点为207.8℃。
实施例2
取100g的PET(IV=0.62dL/g,测量方法为ASTM D4603;熔点为250.0℃,购自新光)从主进料口直接进料至双螺杆挤出机的螺杆。另外取0.5克的钛(IV)异丙醇盐作为催化剂,以及20克的CPL,ε-caprolactone,购自Alfa Aesar,CAS 502-44-3),以侧进料的方式进料至双螺杆挤出机的螺杆,在260℃下使PET与CPL反应以形成共聚酯。螺杆的主进料口温度为20℃,侧进料口温度为20℃,挤出温度为260℃,且螺杆转速200rpm。挤出共聚酯后拉条过水造粒,并置入100℃的烘箱干燥4小时。所制得的共聚酯的本质粘度为0.50dL/g(测量方法为ASTM D4603),且熔点为215.0℃。
实施例3
取100克的PET(IV=0.62dL/g,测量方法为ASTM D4603;熔点为250.0℃,购自新光)、0.5克的钛(IV)异丙醇盐作为催化剂与10克的MPDO从主进料口直接进料至双螺杆挤出机的螺杆的第一区,在260℃下,以形成聚酯二醇。另外取20克的CPL以侧进料的方式进料至双螺杆挤出机的螺杆的第二区(与主进料口隔有第一区),在260℃下使聚酯二醇与CPL反应,以形成共聚酯。螺杆主进料口的温度为20℃,侧进料口温度为20℃,挤出温度为260℃,且螺杆转速200rpm。挤出共聚酯后拉条过水造粒,并置入100℃的烘箱干燥4小时。所制得的共聚酯的本质粘度为0.16dL/g(测量方法为ASTM D4603),且熔点为154.3℃。由实施例1至3的比较可知,PET直接与CPL共聚形成的共聚酯,以及PET与MPDO反应形成的聚酯二醇,熔点的下降幅度小。不过,PET与MPDO反应形成聚酯二醇后,再与CPL反应形成的共聚酯的熔点大幅下降。
实施例4
取1.0公斤的PET(IV=0.62dL/g,测量方法为ASTM D4603;熔点为250℃,购自新光)、0.5克的钛(IV)异丙醇盐作为催化剂与100克的二元醇寡聚物2054(购自Perstorp,Mw=550)从主进料口直接进料至双螺杆挤出机的螺杆的第一区,在260℃下反应以形成聚酯二醇。另外取200克的CPL以侧进料的方式进料至双螺杆挤出机的螺杆的第二区(与主进料口隔有第一区),在260℃下使聚酯二醇与CPL反应,以形成共聚酯。螺杆主进料口的温度为20℃,侧进料口温度为20℃,挤出温度为260℃,且螺杆转速200rpm。挤出共聚酯后拉条过水造粒,并置入100℃的烘箱干燥4小时。所制得的共聚酯的本质粘度为0.58dL/g(测量方法为ASTM D4603),且熔点为194.8℃。由实施例3与实施例4可知,由二醇与PET先反应形成聚酯二醇,再与CPL共聚形成的共聚酯熔点较低。
实施例5
取100克的PET(IV=0.62dL/g,测量方法为ASTM D4603;熔点为250.0℃,购自新光)、0.5克的钛(IV)异丙醇盐作为催化剂与5g的三元醇3050(购自Perstorp,MW=500)从主进料口直接进料至双螺杆挤出机的螺杆的第一区,在260℃下反应,以形成聚酯三元醇。另外取20克的CPL以侧进料的方式进料至双螺杆挤出机的螺杆的第二区(与主进料口隔有第一区),在260℃下使聚酯三元醇与CPL反应以形成共聚酯。螺杆主进料口的温度为20℃,侧进料口温度为20℃,挤出温度为260℃,且螺杆转速200rpm。挤出共聚酯后拉条过水造粒,并置入100℃的烘箱干燥4小时。所制得的共聚酯的本质粘度为0.51dL/g(测量方法为ASTM D4603),且熔点为178℃。
实施例6
取100克的PET(IV=0.62dL/g,测量方法为ASTM D4603;熔点为250.0℃,购自新光)、0.5克的钛(IV)异丙醇盐作为催化剂、5克的聚乙二醇polyethylene glycol 8000(购自Alfa Aesar,MW=8,000)与0.05克的加工油从主进料口直接进料至双螺杆挤出机的螺杆的第一区,在260℃下反应,以形成聚酯二醇。另外取20克的CPL以侧进料的方式进料至双螺杆挤出机的螺杆的第二区(与主进料口隔有第一区),在260℃下使聚酯二醇与CPL反应以形成共聚酯。螺杆主进料口的温度为20℃,侧进料口温度为20℃,挤出温度为260℃,且螺杆转速200rpm。挤出共聚酯后拉条过水造粒,并置入100℃的烘箱干燥4小时。所制得的共聚酯的本质粘度为0.55dL/g(测量方法为ASTM D4603),且熔点为226℃。
实施例7
取100克的PET(IV=0.62dL/g,测量方法为ASTM D4603;熔点为250.0℃,购自新光)、0.5克的钛(IV)异丙醇盐作为催化剂、5克的二醇MPDO从主进料口直接进料至双螺杆挤出机的螺杆的第一区,在260℃下反应,以形成聚酯二醇。另外取40克的CPL以侧进料的方式进料至双螺杆挤出机的螺杆的第二区(与主进料口隔有第一区),在260℃下使聚酯二醇与CPL反应以形成共聚酯。螺杆主进料口的温度为20℃,侧进料口温度为20℃,挤出温度为260℃,且螺杆转速200rpm。挤出共聚酯后拉条过水造粒,并置入100℃的烘箱干燥4小时。所制得的共聚酯的本质粘度为0.16dL/g(测量方法为ASTM D4603),且熔点为137℃。
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 (20)
1.一种共聚物的形成方法,包括:
在一螺杆的一第一区混合反应一聚酯、一脂肪族多元醇或一脂肪族多元醇的寡聚物、与一第一催化剂,以形成一聚酯多元醇;以及侧进料一内酯或一内酰胺至该螺杆的一第二区,使该内酯或该内酰胺与该聚酯多元醇共聚反应形成一共聚物,
其中该第一区与该第二区为连续相连的区域。
2.如权利要求1所述的共聚物的形成方法,其中该聚酯包括聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚碳酸酯、聚对萘二甲酸乙二酯、聚对萘二甲酸丁二酯、聚乳酸酯、聚丁酸酯-己二酸酯-对苯二甲酸酯、聚氨酯或上述的组合。
3.如权利要求1所述的共聚物的形成方法,其中该脂肪族多元醇为C-(R1-OH)x,x=2~42,其中C为核心,该核心为一碳原子或一碳链,且R1为C2-20的亚烷基、聚酯基或环亚烷基。
5.如权利要求1所述的共聚物的形成方法,其中该第一催化剂为金属醇盐。
6.如权利要求1所述的共聚物的形成方法,其中所述形成方法还包括侧进料一第二催化剂至该螺杆的该第二区,且该第二催化剂为金属醇盐。
7.如权利要求1所述的共聚物的形成方法,其中该聚酯与该脂肪族多元醇或该脂肪族多元醇的寡聚物的重量比为100∶1至100∶50。
8.如权利要求1所述的共聚物的形成方法,其中该聚酯与该内酯或该内酰胺的重量比为100∶1至100∶50。
9.如权利要求1所述的共聚物的形成方法,其中该共聚物的熔点为120℃至220℃。
10.如权利要求1所述的共聚物的形成方法,其中该聚酯的本质粘度为0.1dL/g至2dL/g,且该共聚物的本质粘度为0.1dL/g至2dL/g。
11.一种共聚物,为由:
一内酯或一内酰胺与一聚酯多元醇共聚反应而成,
其中该聚酯多元醇为由一聚酯与一脂肪族多元醇或一脂肪族多元醇的寡聚物在一第一催化剂的存在下反应而成。
12.如权利要求11所述的共聚物,其中该聚酯包括聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚碳酸酯、聚对萘二甲酸乙二酯、聚对萘二甲酸丁二酯、聚乳酸酯、聚丁酸酯-己二酸酯-对苯二甲酸酯、聚氨酯或上述的组合。
13.如权利要求11所述的共聚物,其中该脂肪族多元醇为C-(R1-OH)x,其中x=2~42,C为核心,该核心为一碳原子或一碳链,且R1为C2-20的亚烷基、聚酯基或环亚烷基。
15.如权利要求11所述的共聚物,其中该脂肪族多元醇为H(OCH2CH2)nOH或H(OCH2CH2CH2)nOH,其中500≥n≥2。
16.如权利要求11所述的共聚物,其中该第一催化剂为金属醇盐。
17.如权利要求11所述的共聚物,其中该聚酯与该脂肪族多元醇或该脂肪族多元醇的寡聚物的重量比为100∶1至100∶50。
18.如权利要求11所述的共聚物,其中该聚酯与该内酯或该内酰胺的重量比为100∶1至100∶50。
19.如权利要求11所述的共聚物,其中该共聚物的熔点为120℃至220℃。
20.如权利要求11所述的共聚物,其中该聚酯的本质粘度为0.1dL/g至2dL/g,且该共聚物的本质粘度为0.1dL/g至2dL/g。
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CN101367914A (zh) * | 2008-10-10 | 2009-02-18 | 东华大学 | 一种用酯交换法制造低熔点聚酯的方法 |
CN103102646A (zh) * | 2011-11-09 | 2013-05-15 | 金发科技股份有限公司 | 一种低熔点、高结晶温度pet共聚酯及其制备方法和应用 |
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US20220106439A1 (en) | 2022-04-07 |
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