CN107189043B - 高分子量弱结晶性的聚酯及其制备方法和应用 - Google Patents
高分子量弱结晶性的聚酯及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了高分子量弱结晶性的聚酯及其制备方法。所述聚酯由生物基1,5‑戊二醇和二元酸、选择性的加入支化单体经过酯化‑熔融缩聚过程制得。所述高分子量弱结晶性的聚酯中的二元醇链段的碳原子数为奇数,并且结晶性能弱,因而具有优异的力学性能,具有广阔的应用前景。本发明提供的制备方法工艺简单;无需采用溶剂,过程环境友好;催化剂活性高、反应时间短、产物色泽好,有利于实现工业化生产。
Description
技术领域
本发明属于高分子材料及其制备技术领域,涉及聚酯及其制备方法,尤其涉及高分子量弱结晶性的聚酯及其制备方法和应用。
背景技术
弱结晶性聚酯具有透明、柔性好的特点,适用于对材料的透明性、韧性要求较高的应用领域。传统的聚酯通常使用偶数个碳的二元醇,如乙二醇和1,4-丁二醇,相比于这些二元醇,1,5-戊二醇中含有奇数个碳原子且分子链长更长,使得1,5-戊二醇聚酯分子链段柔性更好,对于含有脂肪或芳香族环状分子结构的1,5-戊二醇聚酯来说,其结晶性也会弱于基于偶数碳链的二元醇的聚酯,故1,5-戊二醇聚酯将具有不同于基于偶数碳链的二元醇的聚酯的物理和力学性能。
传统的弱结晶性聚合物如聚氯乙烯大多来源于化石原料。1,5-戊二醇由糠醛催化加氢、氢解制得,糠醛是半纤维素水解、脱水环化的产物,随着糠醛一锅法合成1,5-戊二醇高效催化剂研究的深入,将以更低廉的价格获得足够高纯度的生物基1,5-戊二醇。生物基单体的使用不仅有益于减少对化石资源的依赖,而且可以合成具有新颖结构和独特性能的生物基聚酯新材料。
目前文献(Materials Letters.,2016,178:64-67)报道了采用2,5-呋喃二甲酸和1,5-戊二醇通过酯化-熔融缩聚的方法制备的聚2,5-呋喃二甲酸戊二醇酯,特性粘数为0.53dL/g,由于分子量不高,故差示扫描量热仪(DSC)测试结果显示,其具有较尖锐的熔融峰;低结晶性的戊二醇共聚酯也有报道,文献(Macromolecular Bioscience.,2015,16:207-213)报道了采用1,5-戊二醇、1,6-己二酸和含有侧链的单体2-丁基-2-乙基-1,3-丙二醇,通过酯化-缩聚的方法合成了数均分子量最高达59 000g/mol的共聚酯,但是合成过程中缩聚反应需要进行40个小时,时间长,能耗大,难以工业化生产,并且由于含有侧链单体的引入,降低了共聚酯的熔点,使得这种聚酯材料难以在常温下使用。
综上所述,为了开发弱结晶性、熔点高于室温、并且具有优良物理-力学性能的基于1,5-戊二醇的聚酯新材料,有必要研究开发基于1,5-戊二醇的高分子弱结晶性聚酯及其制备技术。
发明内容
针对现有技术中基于1,5-戊二醇的均聚酯分子量较低、力学性能较差的不足,本发明的目的是提供一种高分子量弱结晶性的聚酯及其制备方法,所得聚酯的分子量高,具有柔性好、强度高等优良的力学性能,热稳定性好因而具有优异的加工性能。
一种高分子量弱结晶性的聚酯,由99~100mol%的式(1)所示的线性重复单元和0~1mol%的式(2)所示的支化单元组成;
式(1)和(2)中,n为3~6的整数,R为支化单体残基,A选自式(3)~(7)任一项所示的结构:
1,5-戊二醇中含有奇数个碳原子且分子链较长,使得本发明基于1,5-戊二醇的聚酯分子链段柔性更好,结晶性也会弱于基于偶数碳链的二元醇的聚酯,具有不同于基于偶数碳链的二元醇的聚酯的物理和力学性能。具体来说,基于1,5-戊二醇的聚酯具有更高的断裂伸长率和更低的熔点。同时,刚性的芳香族二元酸或环己烷二甲酸分子链段与柔性的1,5-戊二醇分子链段使得整体分子的规整性下降,结晶性减弱,使得聚酯的透明性增强、断裂伸长率增加、模量降低,但仍具有一定断裂强度(>4MPa),能够直接应用于日用品的生产,特别是用作具有透明性的柔性材料。
所述聚酯的特性粘度≥0.7dL/g,熔体结晶焓为0~15J/g,本发明基于1,5-戊二醇的聚酯分子量高,结晶性能弱,色泽优良,聚酯产品色泽为白色或浅黄色。
所述支化单体残基为甘油、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇和甘露醇残基中的一种或几种。
作为优选,所述聚酯由99~99.9mol%的式(1)所示的线性重复单元和0.1~1mol%的式(2)所示的支化单元组成。通过多官能团支化剂引入支化单元,能有效提高聚酯的熔体强度,当其应用于薄膜生产时,较高的熔体强度可以在降低膜厚情况下降低产品成本,同时增强成膜稳定性。
作为优选,所述聚酯为聚对苯二甲酸1,5-戊二醇酯、聚间苯二甲酸1,5-戊二醇酯、聚邻苯二甲酸1,5-戊二醇酯、聚2,5-呋喃二甲酸1,5-戊二醇酯或聚1,4-环己烷二甲酸1,5-戊二醇酯,上述聚酯的透明性、力学性能,特别是断裂伸长率高。
本发明提供了一种上述高分子量弱结晶性的聚酯的制备方法,包括以下步骤:
(1)酯化反应:
摩尔比为110~300:100:0~1的1,5-戊二醇、二元酸和支化单体在氮气保护和催化剂存在下,在180~230℃下反应2~6小时,得到酯化产物;
所述的催化剂选自钛酸正丁酯、钛酸异丙酯、钛-硅-氮复合催化剂或钛-磷复合催化剂;
(2)缩聚反应:步骤(1)所得的酯化产物在压力≤200Pa,温度为200~260℃的条件下反应2~6小时,制得所述的聚酯。
本发明所用1,5-戊二醇为生物基1,5-戊二醇,由糠醛催化加氢、氢解制得,有利于减少对石油资源的依赖。
所述二元酸为对苯二甲酸、间苯二甲酸、邻苯二甲酸、2,5-呋喃二甲酸、联苯二甲酸、萘二甲酸或环己烷二甲酸。
所述支化单体为甘油、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇和甘露醇中的一种或几种。
所述催化剂的用量为二元酸物质的量的0.02~0.2%。所用催化剂活性高,选择性好,有利于缩短反应时间,提高分子量,获得较优色泽的聚酯产品。
作为优选,步骤(1)中,所述酯化反应分阶段进行,第一阶段在160~200℃下反应1小时,第二阶段在220℃下反应1小时,第三阶段在230℃下反应1~4小时。
作为优选,步骤(2)中,向步骤(1)所得的酯化产物中补加催化剂再进行缩聚反应,补加的催化剂为钛酸正丁酯、钛酸异丙酯、钛-硅-氮复合催化剂或钛-磷复合催化剂;补加量为步骤(1)中二元酸物质的量的0.02~0.2%。
作为优选,所述的催化剂为钛-硅-氮复合催化剂,该催化剂稳定性好,在酯化反应中一次添加即可,无需在缩聚反应中额外补加催化剂。
为了得到色泽良好的高特性粘数的聚酯产品,作为优选,步骤(2)中,所述缩聚反应分阶段进行,第一阶段在200~230℃下反应1小时,第二阶段在240℃下反应1小时,第三阶段在250℃下反应1~3小时,第四阶段在260℃下反应0.5~1小时。
本发明的另一目的是提供一种上述高分子量弱结晶性的聚酯在制备透明柔性材料中的应用。因为基于1,5-戊二醇的聚酯具有较高的断裂伸长率和较低的熔点,同时,刚性的芳香族二元酸或环己烷二甲酸分子链段与柔性的1,5-戊二醇分子链段使得整体分子的规整性下降,结晶性减弱,使得聚酯的透明性增强、断裂伸长率增加、模量降低,但仍具有一定断裂强度(>4MPa),能够直接应用于日用品的生产,特别是用作具有透明性的柔性材料。
与现有技术相比,本发明具有以下有益效果:
(1)本发明提供的基于1,5-戊二醇的弱结晶性聚酯分子量高,其特性粘数高于0.7dL/g;结晶性能弱,熔体结晶焓为0~15J/g;且因1,5-戊二醇为奇数碳的直链二元醇,因而具有柔性好,力学性能优异,透明度高等材料特点。
(2)本发明提供的基于1,5-戊二醇的聚酯色泽优良,聚酯产品在室温下为白色或浅黄色透明或半透明状固体。
(3)本发明提供的基于1,5-戊二醇的聚酯热稳定性好,加工温度窗口宽,加工性好。
(4)本发明提供的基于1,5-戊二醇的聚酯中的1,5-戊二醇单体为生物基单体,属于生物基聚酯,因而有利于减少对石油资源的依赖。
(5)本发明提供的高分子量弱结晶性的基于1,5-戊二醇的聚酯的合成方法,由于催化剂活性高,选择性好,有利于缩短反应时间,提高分子量,获得较优色泽的聚酯产品,同时工艺简单,无需采用溶剂,过程环境友好,有利于实现工业化生产。
附图说明
图1为本发明实施例1制备的聚间苯二甲酸戊二醇酯的核磁共振氢谱图。
具体实施方式
下面结合附图和实施例对本发明进行具体描述,但本发明不限于这些实施例。
下述实施例中所采用的测试分析方法如下:
特性粘数:称取0.125g左右的样品溶于25mL氯仿中,在25℃恒温水浴中定容,利用杭州中旺公司IVS300自动粘数仪,粘数管选用内径0.36mm,测定样品的特性粘数。
采用美国TA公司的TA Q200型差热扫描量热仪(DSC)测试样品的热转变行为。首先称取8~10mg样品放入铝制坩埚中,然后设定温度程序,先由-100℃以10℃/min的速率升温至200℃,保温3min,然后以10℃/min的速率降温至-100℃,保温5min,再以10℃/min的速率升温至200℃,参比为空的铝制坩埚,保护气体为氮气。
核磁共振氢谱:将20mg左右的样品溶于0.5mL氘代氯仿中,采用德国BRUKER公司的AC-80核磁共振谱仪(400M)进行测试,内标为四甲基硅烷。
拉伸强度:将热压成型制备得到的聚酯的2mm厚的板材,用标准裁刀裁得哑铃型样条(75×4×2mm),样条在25℃,50%湿度条件下放置至少48小时,以消除内应力。采用德国Zwick公司的Zwick/Roell Z020型SANS微机控制电子万能材料实验机,按GB/T 1040-2006《塑料拉伸性能的测定》标准在测试拉伸性能。拉伸速率为20mm/min,预载1N,每个样品至少测试5次,取其平均值。
实施例1
(1)在250mL四口烧瓶中加入间苯二甲酸(0.375mol,58.53g)、1,5-戊二醇(1.0mol,104.15g)和二氧化钛-二氧化硅-聚乙烯吡咯烷酮复合催化剂(1.5mmol,114mg),醇酸比为2.7,在200℃下反应1小时,220℃下反应1小时,230℃下反应1小时,得到酯化产物,酯化率达98.9%;
(2)步骤(1)所得酯化产物中不再补加催化剂,在约120Pa条件下,230℃下反应1小时,240℃下反应1小时,250℃下反应1小时,260℃下反应0.5小时,脱除过量的1,5-戊二醇及少量低聚物,制得聚间苯二甲酸戊二醇酯,缩写为PPeI,其核磁共振氢谱图如图1所示。
经测试,本实施例制备的PPeI的特性粘数为0.81dL/g,玻璃化转变温度为-13.5℃,无明显熔融结晶峰和熔点;拉伸模量9.5MPa,拉伸强度4.2MPa,断裂伸长率>1300%。
实施例2
(1)在250mL四口烧瓶中加入2,5-呋喃二甲酸(0.375mol,58.53g)、1,5-戊二醇(0.75mol,78.11g)和钛酸正丁酯(0.375mmol,128mg),醇酸比为2,在200℃下反应1小时,220℃下反应1小时,230℃下反应1.5小时,得到酯化产物,酯化率达98.9%;
(2)向步骤(1)所得酯化产物中加入钛酸异丙酯(0.375mmol,106mg),在约140Pa条件下,230℃下反应1小时,240℃下反应1小时,250℃下反应1小时,260℃下反应1小时,脱除过量的1,5-戊二醇及少量低聚物,制得聚2,5-呋喃二甲酸戊二醇酯,缩写为PPeF。
经测试,本实施例制备的PPeF的特性粘数为0.84dL/g,玻璃化转变温度为21.9℃,无明显熔融结晶峰和熔点;拉伸模量4.2MPa,拉伸强度11.2MPa,断裂伸长率680%。
实施例3
(1)在250mL四口烧瓶中加入对苯二甲酸(0.5mol,78.04g)、木糖醇(5mmol,0.761g)、1,5-戊二醇(0.75mol,78.11g)、和钛-磷复合催化剂(306mg,南京能德新材料技术公司,TCAIA10),醇酸比为1.5,在200℃下反应1小时,220℃下反应1小时,230℃下反应3小时,得到酯化产物,酯化率达97.0%;
(2)步骤(1)所得酯化产物中不再补加催化剂,在约120Pa条件下,230℃下反应1小时,240℃下反应1小时,250℃下反应1.5小时,260℃下反应1小时,脱除过量的1,5-戊二醇及少量低聚物,制得木糖醇支化的聚对苯二甲酸戊二醇酯,缩写为PPeT-b。
经测试,本实施例制备的PPeT-b的特性粘数为0.78dL/g,玻璃化转变温度为13.5℃,熔融结晶峰温为61.3℃,结晶焓为4.1J/g;熔点为131.5℃,熔融焓为38.7J/g;拉伸模量647MPa,拉伸强度22.8MPa,断裂伸长率448%。
实施例4
(1)在250mL四口烧瓶中加入间苯二甲酸(0.375mol,58.53g)、1,5-戊二醇(1.0mol,104.15g)和二氧化钛-二氧化硅-聚乙烯吡咯烷酮复合催化剂(1.5mmol,114mg),醇酸比为2.7,在200℃下反应3小时,得到酯化产物,酯化率达89.9%;
(2)步骤(1)所得酯化产物中不再补加催化剂,在约120Pa条件下,260℃下反应3小时,脱除过量的1,5-戊二醇及少量低聚物,制得聚间苯二甲酸戊二醇酯,缩写为PPeI。
经测试,本实施例制备的PPeI的特性粘数为0.66dL/g,色泽较黄。由于反应过程没有分阶段进行,所得聚酯的特性粘数较低,且色泽较黄。
实施例5
(1)在250mL四口烧瓶中加入1,4-环己烷二甲酸(0.375mol,64.57g)、1,5-戊二醇(0.75mol,78.11g)、甘油(1mmol,0.092g)和钛酸正丁酯(0.5mmol,170mg),醇酸比为2,在230℃下反应4小时,得到酯化产物,酯化率达93.4%;
(2)向步骤(1)所得酯化产物中加入钛酸正丁酯(0.5mmol,170mg),在约120Pa条件下,250℃下反应4.5小时,脱除过量的1,5-戊二醇及少量低聚物,制得甘油支化的聚环己烷二甲酸戊二醇酯。
经测试,本实施例制备的甘油支化的聚环己烷二甲酸戊二醇酯的特性粘数为0.58dL/g,色泽较黄。
Claims (1)
1.一种高分子量弱结晶性的聚酯在制备透明柔性材料中的应用,其特征在于,所述的高分子量弱结晶性的聚酯由以下步骤制得:
(1)在250mL四口烧瓶中加入0.375mol间苯二甲酸、1.0mol1,5-戊二醇和1.5mmol二氧化钛-二氧化硅-聚乙烯吡咯烷酮复合催化剂,醇酸比为2.7,在200℃下反应1小时,220℃下反应1小时,230℃下反应1小时,得到酯化产物;
(2)步骤(1)所得酯化产物中不再补加催化剂,在120Pa条件下,230℃下反应1小时,240℃下反应1小时,250℃下反应1小时,260℃下反应0.5小时,最后脱除过量的1,5-戊二醇及少量低聚物得到。
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