CN104204090A - 生产pet泡沫体的方法和采用所述方法获得的pet泡沫体 - Google Patents
生产pet泡沫体的方法和采用所述方法获得的pet泡沫体 Download PDFInfo
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Abstract
生产PET泡沫体的方法,其特征在于它包括挤出PET,环氧树脂,由咪唑,咪唑衍生物或其混合物组成的催化剂,和发泡剂这些的混合物,其中在引入发泡剂的上游,在挤出机内进行环氧相的均聚反应。与已知的现有技术的方法相比,本发明的方法提供稳定的PET泡沫体的优点,其中聚合物链的结构保持不变。该体系因此具有允许PET/环氧均聚物接受发泡剂的发泡作用远至还具有显著厚度的泡沫体的最内部和最深层的粘弹性特征。
Description
本发明涉及生产PET泡沫体的增强的方法。
本发明还延伸到采用这一方法获得的PET泡沫体和由这些泡沫体获得的发泡材料的物体。
本发明的领域是生产PET(聚对苯二甲酸乙二酯)泡沫体,所述泡沫体通常用于采用许多类型的加工来生产面板,使得它们适合于作为用于各类夹层结构且还具有绝热功能的“芯材”。
为了给予PET接收发泡剂的所需的一致性,用均苯四酸酐和其他交联剂使PET链扩链是已知的,从而获得发泡且稳定的泡沫体。结果,在泡沫体的随后的挤出段期间,可出现或多或少严重的聚合物降解现象,在任何情况下,这代表最终产品质量的问题。
在环氧化物存在下制备通过光敏催化剂交联的热塑性聚合物泡沫体也是已知的(US 6,323,251),其中在注入发泡剂的下游,尤其在挤出的外部进行环氧化物的交联反应。该已知方法因此不适合于提供形成具有最终产品所需的一致性的泡沫体。另外,光敏催化剂仅仅在泡沫体的表面层上起作用,这不允许交联反应还在发泡物料内部发生。
本发明的主要目的是提供适合于获得PET泡沫体的方法,与已知方法不同的是,它具有在挤出机出口处稳定的特性,然而PET链的结构没有改变。
通过分别根据权利要求1,10和11的本发明的方法,PET泡沫体和发泡材料,来实现这些和其他目的。在其余权利要求中列出了本发明的优选实施方案。
与已知技术的方法相反,本发明提供了提供稳定PET泡沫体的优点,其中该聚合物链的结构保持不变。该体系还具有粘弹性特征,这允许PET/环氧均聚物的混合物接收发泡剂的发泡作用,只要泡沫体的最内部和最深层也具有显著的厚度即可。
根据在附图中的图内阐述的本发明的优选实施方案的下述说明作为非限制性实施例,本发明的这些和其他目的,优点和特征似乎是显而易见的。
在这些中:
-图1阐述了进行本发明方法所使用的挤出机的流程图;
-图2和3阐述了与其中使用不同催化剂或者不使用催化剂的那些相比,当在咪唑及其衍生物存在下活化时,环氧树脂的放热均聚反应;
-图4阐述了评价在图2中加工的样品中环氧树脂交联的DSC(差示扫描量热法)的图表;和
-图5代表在PET热塑性基体内环氧均聚物的纳米分散体采用原子力显微术(AFM)获得的图像。
图1中图示且进行本发明方法所使用的挤出机基本上分成用于熔融和混合经料斗2喂入的PET物料10、催化剂和其他可能的添加剂的步骤1,反应性挤出步骤3(环氧相的均聚),发泡剂的注入步骤6和冷却步骤7。
所使用的PET尤其是适合于通过挤出加工的PET,其具有下述化学式(I):
然后添加催化剂到PET中,根据本发明,所述催化剂由用下式(II)表示的咪唑,咪唑衍生物及其混合物组成:
其中R1,R2,R3是芳族或脂族类型的无机或有机基团。
在本发明的方法中所使用的催化剂的一些非限制性实例是2-甲基咪唑,2-乙基-4-甲基咪唑,1-苄基-2-甲基咪唑,1-甲基咪唑,1,2–二甲基咪唑及其混合物。
可在适合于改进PET泡沫体的可加工性,外观和性能的本发明方法中使用的添加剂当中,可单独或彼此结合提及下述:
·增塑剂
·颜料
·阻燃剂
·填料
·稳定剂
·表面活性剂
·成核剂
·纳米添加剂
本发明中使用的催化剂在液相内,和在挤出机的步骤1中,它在PET物料内壁紧密地混合。如此获得的混合物然后从挤出机的螺杆(未示出)朝随后的步骤3输送以供PET物料与催化剂接触并混合它们与同样液态的环氧树脂的注入物4。
对于本发明来说,优选的环氧树脂是具有下式(III)的那些:
其中:
m和n是整数(0,1,2,3,..)
R1,R2和R3表示脂族或芳族基团,或无机链。
可在本发明的方法中使用的环氧树脂当中,可引证下述:
·来自苯酚或甲酚的环氧化酚醛清漆(novolacquer)(多苯基-缩水甘油基醚-共-甲醛,聚-间甲酚基-缩水甘油基醚-共-甲醛);
·单-或多-缩水甘油基醚或酯,脂族或芳族(聚双酚A-共-表氯醇-缩水甘油基封端的;2-乙基己基缩水甘油基醚;缩水甘油基醚的1,4-丁二醇;四缩水甘油基-甲基双苯胺;丁基苯基-缩水甘油基醚),
·有机或无机环氧化链(环氧丙氧丙基三甲氧基硅烷;环氧丙氧丙基三乙氧基硅烷;丁基二甲基硅烷-缩水甘油基醚;双-环氧丙氧丙基四-甲基二硅氧烷);
基于硅-硅酮的多面体缩水甘油基低聚物(POSS)(实例:CAS:445379-56-6;CAS:307496-38-4)。
在本发明方法的这一步骤中,环氧树脂经历均聚工艺,这在挤出机自身内发生(所谓的反应性挤出)。此外,由于使用液态(或事先没有交联)的环氧树脂,因此可在连续的PET物料内部获得均聚物颗粒的纳米分散体(参见图5)。
在PET物料内存在纳米分散的环氧均聚物的结果是,后者提供有引入发泡剂所需的粘弹性,以允许随后发生发泡段。
咪唑及其衍生物对环氧树脂均聚反应的高催化活性也允许这一均聚反应在以上提及的步骤3内完成,因此不牵涉在反应环境内存在PET链,从而使得它们的化学结构保持不变。
图2-4中的图表示出了在没有牵涉PET聚合物分子的情况下,在本发明方法中使用的催化剂对环氧树脂的选择行为。特别地,图2比较了具有下式的1,2-二甲基咪唑的选择行为与已知的现有技术的催化剂,尤其六氟三苯基锍锑酸盐,二甲基苄基胺,2-庚基哌嗪或者在不存在催化剂的情况下提供的选择行为。
其中R1=H;R2=CH3;R3=CH3。
根据模拟DSC分析的图2的图表,单独的环氧树脂的混合物(100份)与催化剂(2份)的挤出工艺的操作条件,可观察到本发明的催化剂具有放热部分(a),所述放热部分(a)的峰值与涉及根据现有技术已知的催化剂的曲线的相应曲线(b)的平坦趋势相比或者与在不存在催化剂情况下曲线的趋势相比表明环氧相的均聚反应完全,且没有牵涉PET分子,从而留下它们未反应。
可由检验图3中表示的放热部分,得出相同的结论,此刻它涉及可在本发明的方法中使用的咪唑家族。
图4示出了在模拟挤出工艺之后,与图2一样测试的样品的DSC分析。根据该图表,可观察到已经经历了均聚反应的样品是对应于催化剂2-乙基-4-甲基咪唑的样品(图4的曲线c)。事实上,它的玻璃化转变温度(Tg)为99.3℃。涉及用不同于根据本发明的方法的催化剂处理的环氧树脂样品或者不具有催化剂的样品的其余曲线的平坦趋势表明没有发生均聚反应。
在PET物料内,在挤出机的步骤3中,形成纳米分散的环氧均聚物的结果是,后者提供有足以在挤出步骤6中引入5发泡剂的粘弹性,从而使得它适合于随后的挤出机的出口8处的发泡段。所述发泡段之前进行挤出产物9的冷却步骤7,后者由连续流动的发泡材料组成,其冷却工艺在室温下完成。随后由这一挤出产物9获得由发泡材料主体组成的终产物。
下文提供了在本发明方法中使用的PET泡沫体的配方的一些实例,其中百分比是指混合物的重量。
挤出机
如图1概述的且采用下述温度曲线,通过使用LeistritzZSE40MAXX-44D挤出机获得的挤出进行的发泡工艺:
设置℃ | 1区 | 3区 | 6区 | 7区 | 8区 |
B | 295 | 280-260 | 255 | 255-230 | 260 |
实施例1-不存在催化剂和环氧树脂
通过料斗2,将下述试剂引入到挤出机内:
·PET:Invista的Polyclear 1011(IV=0.83)
·在PET内分散的滑石(相对于PET,1.3-3%)。
通过注入点(5),添加发泡剂:
·在液相内的环己烷
在挤出机内部的压力值(混合物粘弹性的指示)没有使得发泡剂保持在均匀分散的超临界流体相内。因此尝试发泡PET失败,因为在挤出机出口处的聚合物物料不具有充足的粘弹性用以保持气相密闭在泡孔内。
实施例2-不存在催化剂和存在环氧树脂
通过料斗2,将下述试剂引入到挤出机内:
·PET:Invista的Polyclear 1011(IV=0.83)
·在PET内分散的滑石(相对于PET,1.3-3%)。
通过注入点(4),添加下述在液相内的环氧树脂:
·Poly-epoxy:Lindoxy 290(在液相内)
通过注入点(5),添加发泡剂:
·在液相内的环己烷
同样在这一情形中,在挤出机内部的压力值(它表示混合物的粘弹性)没有使得发泡剂保持在均匀分散的超临界流体相内。因此尝试发泡PET失败,因为在挤出机出口处具有低粘弹性的聚合物物料不能保持气相密闭在泡孔内。
实施例3-存在环氧树脂和催化剂-二甲基苄基胺
通过料斗2,将下述试剂引入到挤出机内:
·PET:Invista的Polyclear 1011(IV=0.83)
·在PET内分散的滑石(相对于PET,1.3-3%)。
·二甲基苄基胺(相对于环氧树脂,百分比最多2.3%)
通过注入点(4),添加下述在液相内的环氧树脂:
·Poly-epoxy:Lindoxy 290(在液相内),1.3-5%
通过注入点(5),添加发泡剂:
·在液相内的环己烷
同样在这一情形中,在挤出机内部的压力值(它表示混合物的粘弹性)没有使得发泡剂保持在均匀分散的超临界流体相内。因此尝试发泡PET失败,因为在挤出机出口处具有低粘弹性的聚合物物料不能保持气相密闭在泡孔内。
实施例4-存在环氧树脂和催化剂-2-乙基哌啶
通过料斗2,将下述试剂引入到挤出机内:
·PET:Invista的Polyclear 1011(IV=0.83)
·在PET内分散的滑石(相对于PET,1.3-3%)。
·2–乙基哌啶(相对于环氧树脂,百分比最多2%)
通过注入点(4),添加下述在液相内的环氧树脂:
·Poly-epoxy:Lindoxy 290(在液相内),1.3-5%
通过注入点(5),添加发泡剂:
·在液相内的环己烷
同样在这一情形中,在挤出机内部的压力值(它表示混合物的粘弹性)没有使得发泡剂保持在均匀分散的超临界流体相内。因此尝试发泡PET失败,因为在挤出机出口处具有低粘弹性的聚合物物料不能保持气相密闭在泡孔内。
实施例5-存在环氧树脂和基于咪唑的催化剂
通过料斗2,将下述试剂引入到挤出机内:
·PET:Invista的Polyclear 1011(IV=0.83)或M&G的CLEARTUFP76(IV=0.74)
·在PET内分散的滑石(相对于PET,1.3-3%)。
·基于咪唑的催化剂(分别采用2-甲基咪唑,2-乙基-4-甲基咪唑和1,2–二甲基咪唑进行的试验,相对于环氧树脂,百分比为最多2%)。
通过注入点(4),添加下述在液相内的环氧树脂:
·Poly-epoxy:Lindoxy 290(在液相内,相对于PET,1.3-5%)
·单-或二-环氧树脂:2-乙基己基缩水甘油基醚或1,6-己二醇二缩水甘油基醚(相对于PET,0-0.5%)
通过注入点(5),添加发泡剂:
·在液相内的环己烷
在挤出机内部的压力值(它表示混合物的粘弹性)使得发泡剂保持在均匀分散的超临界流体相内。对于合适地剂量的各种百分比的环氧树脂和催化剂来说,尝试发泡PET因此是成功的,因为在挤出机出口处聚合物物料的粘弹性足以保持气相在具有减少的尺寸(小于0.7mm)的闭孔内,从而产生密度范围为60-140 Kg/m3的稳定泡沫体。
Claims (11)
1.生产PET泡沫体的方法,其特征在于它包括PET,环氧树脂,由咪唑、咪唑衍生物或其混合物组成的催化剂和发泡剂的混合物的挤出物,其中在引入发泡剂的上游,在挤出机内进行环氧相的均聚反应。
2.权利要求1的方法,其特征在于所述PET是能通过挤出来加工的类型,其化学式为:
3.权利要求1的方法,其特征在于所述催化剂由具有下式(II)的咪唑、咪唑衍生物或其混合物组成:
其中R1,R2,R3是芳族或脂族类型的无机或有机基团。
4.权利要求1和3的方法,其特征在于在熔融和混合步骤(1)中,混合所述催化剂与PET和液态的催化剂。
5.权利要求1的方法,其特征在于所述环氧树脂处于液态且具有下式:
其中:
m和n是整数(0,1,2,3,..)
R1,R2和R3是有机的脂族或芳族基团,或无机链。
6.权利要求1的方法,其特征在于它包括步骤(3),其中环氧树脂经历均聚工艺,所述均聚工艺在挤出机内部进行(反应性挤出)。
7.权利要求6的方法,其特征在于在所述步骤(3)中,在连续的PET物料内部进行环氧均聚物颗粒的纳米分散,PET链的化学结构在反应环境中保持不变。
8.前述一项或多项权利要求的方法,其特征在于它还包括引入发泡剂(5)到所述分散体内的步骤(6)、冷却步骤(7)和发泡步骤(8)。
9.权利要求1-7一项或多项的方法,其特征在于所述混合物还包括单独的或彼此结合的以下物质:
*增塑剂
*颜料
*阻燃剂
*填料
*稳定剂
*表面活性剂
*成核剂
*纳米添加剂。
10.一种PET泡沫体,其特征在于它通过前述一项或多项权利要求的方法获得。
11.一种挤出材料的物体,其特征在于它由权利要求10的泡沫体组成。
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IT000135A ITMI20120135A1 (it) | 2012-02-02 | 2012-02-02 | Procedimento per la produzione di schiume di pet e schiume di pet ottenute con questo procedimento |
ITMI2012A000135 | 2012-02-02 | ||
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NL2006236C2 (en) * | 2011-02-17 | 2012-08-20 | Af X Systems B V | Fire-extinguishing composition. |
TWI637976B (zh) | 2017-07-07 | 2018-10-11 | 財團法人工業技術研究院 | 分枝聚合物、其製備方法以及發泡體的製備方法 |
KR102608315B1 (ko) | 2021-08-05 | 2023-12-01 | 이승민 | Pet 발포폼을 포함하는 벽지 |
KR102595158B1 (ko) | 2021-08-05 | 2023-10-27 | 이승아 | Pet 발포폼을 포함하는 가구용 판재 |
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CA2861004C (en) | 2019-08-27 |
KR101958513B1 (ko) | 2019-07-04 |
EA201491192A1 (ru) | 2015-01-30 |
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BR112014017887A8 (pt) | 2017-07-11 |
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