CN117624530A - 聚氨酯树脂及其制造方法 - Google Patents
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Abstract
本发明公开一种聚氨酯树脂及其制造方法,其包括下列步骤:混合一聚酯多元醇、一聚醚多元醇、一第一链延长剂、二异氰酸酯与一混合溶剂,进行聚合反应以获得一预聚物。将一第二链延长剂加入预聚物中,进行扩链反应,以获得聚氨酯树脂。混合溶剂包括二乙基甲酰胺与丁酮,混合溶剂中二乙基甲酰胺与丁酮的质量比值为0.45至1.80。以聚氨酯树脂的总重为100重量百分比,第一链延长剂与第二链延长剂的总添加量为0.9重量百分比至2.5重量百分比。本发明的聚氨酯树脂具有良好的加工性、耐曲折性以及剥离强度。
Description
技术领域
本发明涉及一种聚氨酯树脂及其制造方法,特别是涉及一种可作为鞋材的聚氨酯树脂及其制造方法。
背景技术
聚氨酯是一种多功能用途的高分子材料,通常作为人造皮革的主要原料。通过调整原料的种类及组成,可合成不同软硬度的聚氨酯树脂。
传统的聚氨酯树脂是以湿式制造过程制得,在固化之前,聚氨酯树脂含有有机溶剂,例如:二甲基甲酰胺(dimethylformamide,DMF)。含有二甲基甲酰胺的聚氨酯树脂虽然具有良好的稳定性,然而,二甲基甲酰胺的沸点高(153℃),在固化时需以较高的温度蒸散溶剂,而具有耗能较高的缺点。并且,二甲基甲酰胺是列管的毒性物质,一旦被人体吸收便不易排出,故容易对人体造成永久的危害。
据此,传统的聚氨酯树脂具有固化温度较高的缺点,以及聚氨酯产品存有安全疑虑而无法完全安心的应用于所有产品中的问题。因此,如何通过制造方法的改良,在不使用二甲基甲酰胺的前提合成聚氨酯树脂,以克服上述的缺陷,已成为该项事业所欲解决的重要课题之一。
发明内容
本发明所要解决的技术问题在于,针对现有技术的不足提供一种聚氨酯树脂及其制造方法。
为了解决上述的技术问题,本发明所采用的其中一技术方案是提供一种聚氨酯树脂的制造方法。聚氨酯树脂的制造方法包括下列步骤:混合一聚酯多元醇、一聚醚多元醇、一第一链延长剂、二异氰酸酯与一混合溶剂,进行聚合反应以获得一预聚物。将一第二链延长剂加入预聚物中,进行扩链反应,以获得聚氨酯树脂。混合溶剂包括二乙基甲酰胺与丁酮,混合溶剂中二乙基甲酰胺与丁酮的质量比值为0.45至1.80。以聚氨酯树脂的总重为100重量百分比,第一链延长剂与第二链延长剂的总添加量为0.9重量百分比至2.5重量百分比。
更进一步地,聚氨酯树脂中的溶剂在80℃至110℃之间的加工温度下被去除。
更进一步地,第二链延长剂的添加量是第一链延长剂添加量的3.5至4.8倍。
更进一步地,以聚氨酯树脂的总重为100重量百分比,聚酯多元醇的含量为18重量百分比至28重量百分比,聚醚多元醇的含量为8重量百分比至15重量百分比,二异氰酸酯的含量为3重量百分比至10重量百分比。
更进一步地,聚氨酯树脂的制造方法进一步包括:在扩链反应后,于聚氨酯树脂中加入丁酮,以使聚氨酯树脂中二乙基甲酰胺与丁酮的质量比值为0.09至0.35。
更进一步地,聚氨酯树脂的固含量为38%至45%。
为了解决上述的技术问题,本发明所采用的另外一技术方案是提供一种聚氨酯树脂,聚氨酯树脂是由前述制造方法所制得。
更进一步地,聚酯多元醇是由己二酸与丁二醇聚合而成,聚醚多元醇是分子链两端具有一级羟基的直链聚醚多元醇。
更进一步地,聚氨酯树脂包括一软链段与一硬链段,软链段的比例为75重量百分比至85重量百分比,硬链段的比例为15重量百分比至25重量百分比。
更进一步地,聚氨酯树脂的黏度为20000cps至30000cps。
更进一步地,聚氨酯树脂的重量平均分子量为90000克/摩尔至110000克/摩尔。
更进一步地,聚氨酯树脂固化相对于一聚氨酯基材的剥离强度为12.0kg/3cm至18.0kg/3cm。
本发明的其中一有益效果在于,本发明所提供的聚氨酯树脂及其制造方法,其能通过“混合溶剂中二乙基甲酰胺与丁酮的质量比值为0.45至1.80”以及“第一链延长剂与第二链延长剂的总添加量为0.9重量百分比至2.5重量百分比”的技术方案,以提升聚氨酯树脂的加工性、耐曲折性以及剥离强度。
为使能更进一步了解本发明的特征及技术内容,请参阅以下有关本发明的详细说明与附图,然而所提供的附图仅用于提供参考与说明,并非用来对本发明加以限制。
附图说明
图1为本发明聚氨酯树脂的制造方法的流程步骤图。
具体实施方式
以下是通过特定的具体实例来说明本发明所公开有关“聚氨酯树脂及其制造方法”的实施方式,本领域技术人员可由本说明书所公开的内容了解本发明的优点与效果。本发明可通过其他不同的具体实施例加以施行或应用,本说明书中的各项细节也可基于不同观点与应用,在不背离本发明的构思下进行各种修改与变更。另外,本发明的附图仅为简单示意说明,并非依实际尺寸的描绘,事先声明。以下的实施方式将进一步详细说明本发明的相关技术内容,但所公开的内容并非用以限制本发明的保护范围。另外,本文中所使用的术语“或”,应视实际情况可能包括相关联的列出项目中的任一个或者多个的组合。
为了解决上述问题,本发明提供一种聚氨酯树脂的制造方法,在制造过程中不需使用二甲基甲酰胺,而可降低产品对人体的毒性威胁。并且,制成的聚氨酯树脂具有加工性良好、耐曲折性佳且剥离强度高的优点,可符合目前市面上将聚氨酯树脂应用于鞋材上的特性需求。
请参阅图1所示,本发明的聚氨酯树脂的制造方法包括以下步骤:混合聚酯多元醇、聚醚多元醇、第一链延长剂、二异氰酸酯与混合溶剂,进行聚合反应以获得预聚物(步骤S1);将第二链延长剂加入预聚物中,进行扩链反应,以获得聚氨酯树脂(步骤S2);于聚氨酯树脂中加入丁酮,以使聚氨酯树脂的固含量为38%至45%(步骤S3)。
形成聚氨酯树脂的固态成分包括:聚酯多元醇、聚醚多元醇、链延长剂(第一链延长剂及第二链延长剂)与二异氰酸酯。若以聚氨酯树脂中固态成分的总重为100重量百分比,聚酯多元醇的含量为48重量百分比至63重量百分比,聚醚多元醇的含量为20重量百分比至30重量百分比,链延长剂的含量为1.5重量百分比至8重量百分比,二异氰酸酯的含量为10重量百分比至20重量百分比。
本发明的聚氨酯树脂包括一软链段与一硬链段,软链段是由聚酯多元醇及聚醚多元醇所构成,硬链段是由二异氰酸酯及链延长剂所构成,软链段与硬链段的掺混可使聚氨酯树脂具有较佳的耐曲折性。
于一较佳实施例中,软链段的重量比例高于硬链段的重量比例。具体来说,以聚氨酯树脂中固态成分的总重为100重量百分比,聚氨酯树脂包括75重量百分比至85重量百分比的软链段以及15重量百分比至25重量百分比的硬链段。如此一来,聚氨酯树脂在聚合后可具有良好的物理特性,可应用于鞋材。
于一较佳实施例中,聚酯多元醇是己二酸系聚酯多元醇。举例来说,合成聚酯多元醇的单体可以包括己二酸与丁二醇,聚酯多元醇的数均分子量为1000克/摩尔至3000克/摩尔,聚酯多元醇的羟值为35至39,聚酯多元醇的酸值为0.4至0.6。然而,本发明不以此为限。
于一较佳实施例中,聚醚多元醇是直链聚醚多元醇,且分子末端具有一级羟基。举例来说,聚醚多元醇可以是四氢呋喃均聚醚(数均分子量为1000克/摩尔至3000克/摩尔)或聚丙二醇(数均分子量为1000克/摩尔至4000克/摩尔),聚醚多元醇的数均分子量为1000克/摩尔至4000克/摩尔。然而,本发明不以此为限。
于一较佳实施例中,第一链延长剂及第二链延长剂各自独立选自由下列所构成的群组:乙二醇、1,4-丁二醇及1,6-己二醇。第一链延长剂及第二链延长剂可以相同或不同,于一较佳实施例中,第一链延长剂与第二链延长剂相同。
于一较佳实施例中,二异氰酸酯可以是选自由下列所构成的群组:二苯基甲烷二异氰酸酯(methylenediphenyl diisocyanate,MDI)、甲苯二异氰酸酯(toluenediisocyanate,TDI)及异佛尔酮二异氰酸酯(isophorone diisocyanate,IPDI)。然而,本发明不以此为限。
在本发明中,分别于步骤S1及步骤S2中添加链延长剂,并控制第二链延长剂的添加量大于第一链延长剂的添加量,如此一来,聚氨酯树脂的耐曲折性可被提升。于一较佳实施例中,第二链延长剂的添加量是第一链延长剂添加量的3.5至4.8倍,具体来说,第二链延长剂的添加量可以是第一链延长剂添加量的3.6、3.8、4.0、4.2、4.4或4.6倍。
在本发明中,阶段性的添加链延长剂,可使聚氨酯树脂具备较佳的加工性、剥离强度与耐曲折性。第一链延长剂的添加,可先适当延长聚氨酯树脂的分子链长。第二链延长剂的添加,再使聚氨酯树脂具备理想的分子链长,并提升聚氨酯树脂的加工性、剥离强度与耐曲折性。
值得注意的是,第二链延长剂的添加量过低时,聚氨酯树脂的结构强度不足,会负面影响聚氨酯树脂的加工性、剥离强度与耐曲折性。具体来说,以聚氨酯树脂的总重(包含固态成分及液态成分)为100重量百分比,第一链延长剂的添加量可以为0.2重量百分比至0.6重量百分比,第二链延长剂的添加量可以为0.9重量百分比至2.5重量百分比。
为了聚合出理想的聚氨酯树脂,添加第二链延长剂的时机也会影响聚氨酯树脂的特性。于一较佳实施例中,当预聚物的异氰酸基(-NCO)的含量为1.0重量百分比至2.0重量百分比时,于预聚物中添加第二链延长剂,以进行步骤S2。
另一方面,为了使固态成分(聚酯多元醇、聚醚多元醇、链延长剂及二异氰酸酯)具有良好的兼容性与反应性,本发明选用二乙基甲酰胺与丁酮作为溶剂(液态成分),以取代具毒性的二甲基甲酰胺。
在聚合反应的过程中(步骤S1及S2),二乙基甲酰胺的添加可提升聚氨酯树脂的兼容性与反应性,但过多或过少的二乙基甲酰胺会负面影响聚氨酯树脂的兼容性与物性。因此,本发明控制二乙基甲酰胺的添加量,并混合适量的丁酮来调整聚氨酯树脂的固含量,以利于聚合反应的进行。
于一较佳实施例中,混合溶剂中二乙基甲酰胺与丁酮的质量比值为0.45至1.80,具体来说,混合溶剂中二乙基甲酰胺与丁酮的质量比值可以为0.45至1.80之间公差为0.05的等差数列中的数值(例如,0.45、0.50、0.55...1.70、1.75、1.80)。
具体来说,以聚氨酯树脂的总重(包含固态成分及液态成分)为100重量百分比,二乙基甲酰胺的添加量为5重量百分比至16重量百分比。例如,二乙基甲酰胺的添加量可以为6重量百分比、8重量百分比、10重量百分比、12重量百分比或14重量百分比。
值得说明的是,在步骤S1中添加的丁酮,可使聚氨酯树脂的固含量维持在利于反应进行的浓度。在步骤S3中添加的丁酮,可调整聚氨酯树脂的固含量为38%至45%。并且,丁酮的添加可降低聚氨酯树脂中溶剂的蒸散温度,以降低固化聚氨酯树脂所需的能耗。具体来说,聚氨酯树脂中的溶剂(丁酮与二乙基甲酰胺)可在80℃至110℃的加工温度下被去除。
具体来说,以聚氨酯树脂的总重(包含固态成分及液态成分)为100重量百分比,步骤S1中丁酮的添加量为6重量百分比至12重量百分比,步骤S3中丁酮的添加量为32重量百分比至45重量百分比。聚氨酯树脂中丁酮的总添加量为40重量百分比至60重量百分比。
为了证实本发明的聚氨酯树脂加工性良好、耐曲折性佳且剥离强度高的优点,根据下列步骤配制了实施例1至4(E1至E4)与比较例1至3(C1至C3)的聚氨酯树脂,各成分的具体添加量如表1所示。
在步骤S1中,先将己二酸系聚酯多元醇(聚酯多元醇)、四氢呋喃均聚醚(聚醚多元醇)、1,6-己二醇(第一链延长剂)、二乙基甲酰胺(DEF)与丁酮(MEK)(混合溶剂)添加于一反应槽内,在持续搅拌的状态下升温至70℃。接着,于反应槽中添加二苯基甲烷二异氰酸酯(二异氰酸酯)与少量催化剂,再升温至78℃并反应两小时,以制成预聚物。
在步骤S2中,于预聚物中添加1,6-己二醇(第二链延长剂),于78℃的温度下反应一小时,便可获得聚氨酯树脂。
在步骤S3中,待聚氨酯树脂降温至45℃以下后,加入丁酮稀释聚氨酯树脂的固含量为38%至45%(较佳为39%至41%)。
配制完成后,将实施例1至4(E1至E4)与比较例1至3(C1至C3)的聚氨酯树脂分别进行黏度、重均分子量、加工性、剥离强度与耐曲折性的测试。
黏度是以黏度计(厂牌:BROOKFIELD,型号:DV-E)测量而得。重均分子量是以凝胶渗透分析仪(厂牌:SHIMADZU,型号:LC-40XR)测量而得。加工性是评估在80℃至110℃的加工温度下,涂布性是否异常,若无异常以「OK」表示,若有异常缺陷以「NG」表示。剥离强度以万能拉力试验机(厂牌:SHIMADZU,型号:AG-X)测量而得。常温耐曲折性的评估是使用耐曲折试验机(厂牌:GOTECH,型号:GT-7006-V50),以角度22.5°、频率100次/分钟及25℃×10万次进行曲折测试,若外观无异常缺陷及无破损以「OK」表示,若外观异常缺陷及破损以「NG」表示。低温耐曲折性的评估是使用耐曲折试验机(厂牌:GOTECH,型号:GT-7006-V50),以角度22.5°、频率100次/分钟及-10℃×1万次进行曲折测试,若观无异常缺陷及无破损以「OK」表示,若外观异常缺陷及破损以「NG」表示。
表1
由表1的结果可得知,本发明的聚氨酯树脂具有良好的加工性,可在80℃至110℃的加工温度下去除溶剂,且具有良好的涂布平整性。本发明的聚氨酯树脂在常温与低温的环境下具耐曲折性,在常温(25℃)下可耐受十万次的曲折测试,在低温(-10℃)下可耐受一万次的曲折测试。
本发明的聚氨酯树脂的剥离强度大于12kg/3cm。具体来说,聚氨酯树脂相对于一聚氨酯基材的剥离强度可以是12.0kg/3cm至18.0kg/3cm。也就是说,聚氨酯树脂相对于聚氨酯材料具有良好结合强度。
此外,本发明的聚氨酯树脂的黏度可以为20000cps至30000cps,较佳的,聚氨酯树脂的黏度为25000cps至30000cps。本发明的聚氨酯树脂的重均分子量可以为90000克/摩尔至110000克/摩尔,较佳的,聚氨酯树脂的重均分子量为92000克/摩尔至109000克/摩尔。然而,本发明不以此为限。
由比较例1的内容可得知,当链延长剂(第一链延长剂与第二链延长剂)的添加浓度不足(小于0.9重量百分比)时,无法获得本发明的聚氨酯树脂。第二链延长剂的添加浓度较佳为0.9重量百分比至2.5重量百分比。
由比较例2、3的内容可得知,混合溶剂中二乙基甲酰胺与丁酮的质量比值会影响聚氨酯树脂的特性,当二乙基甲酰胺与丁酮的质量比值小于0.9重量百分比(比较例2)或大于2.5重量百分比(比较例3)时,无法获得本发明的聚氨酯树脂。
[实施例的有益效果]
本发明的其中一有益效果在于,本发明所提供的聚氨酯树脂及其制造方法,其能通过“混合溶剂中二乙基甲酰胺与丁酮的质量比值为0.45至1.80”以及“第一链延长剂与第二链延长剂的总添加量为0.9重量百分比至2.5重量百分比”的技术方案,以提升聚氨酯树脂的加工性、耐曲折性以及剥离强度。
更进一步来说,本发明通过“混合溶剂包括二乙基甲酰胺与丁酮”的技术方案,可达到提升聚氨酯树脂中固态成分之间的兼容性与反应性的效果,并可使聚氨酯树脂具有良好的加工性。
更进一步来说,本发明通过“第二链延长剂的添加量是第一链延长剂添加量的3.5至4.8倍”的技术方案,以提升聚氨酯树脂的加工性、耐曲折性以及剥离强度。
更进一步来说,本发明通过“在扩链反应后,于聚氨酯树脂中加入丁酮,以使聚氨酯树脂中二乙基甲酰胺与丁酮的质量比值为0.09至0.35”的技术方案,以提升聚氨酯树脂的加工性。
以上所公开的内容仅为本发明的优选可行实施例,并非因此局限本发明的权利要求书的保护范围,所以凡是运用本发明说明书及附图内容所做的等效技术变化,均包含于本发明的权利要求书的保护范围内。
Claims (12)
1.一种聚氨酯树脂的制造方法,其特征在于,所述聚氨酯树脂的制造方法包括:
混合一聚酯多元醇、一聚醚多元醇、一第一链延长剂、二异氰酸酯与一混合溶剂,进行聚合反应以获得一预聚物;其中,所述混合溶剂包括二乙基甲酰胺与丁酮,所述混合溶剂中二乙基甲酰胺与丁酮的质量比值为0.45至1.80;以及
将一第二链延长剂加入所述预聚物中,进行扩链反应,以获得聚氨酯树脂;
其中,以所述聚氨酯树脂的总重为100重量百分比,所述第一链延长剂与所述第二链延长剂的总添加量为0.9重量百分比至2.5重量百分比。
2.根据权利要求1所述的制造方法,其特征在于,所述聚氨酯树脂中的溶剂在80℃至110℃之间的加工温度下被去除。
3.根据权利要求1所述的制造方法,其特征在于,所述第二链延长剂的添加量是所述第一链延长剂添加量的3.5至4.8倍。
4.根据权利要求1所述的制造方法,其特征在于,以所述聚氨酯树脂的总重为100重量百分比,所述聚酯多元醇的含量为18重量百分比至28重量百分比,所述聚醚多元醇的含量为8重量百分比至15重量百分比,所述二异氰酸酯的含量为3重量百分比至10重量百分比。
5.根据权利要求1所述的制造方法,其特征在于,进一步包括:在扩链反应后,于所述聚氨酯树脂中加入丁酮,以使所述聚氨酯树脂中二乙基甲酰胺与丁酮的质量比值为0.09至0.35。
6.根据权利要求5所述的制造方法,其特征在于,所述聚氨酯树脂的固含量为38%至45%。
7.一种聚氨酯树脂,其特征在于,所述聚氨酯树脂是由根据权利要求1至6中任一项所述的制造方法所制得。
8.根据权利要求7所述的聚氨酯树脂,其特征在于,所述聚酯多元醇是由己二酸与丁二醇聚合而成,所述聚醚多元醇是分子链两端具有一级羟基的直链聚醚多元醇。
9.根据权利要求7所述的聚氨酯树脂,其特征在于,所述聚氨酯树脂包括一软链段与一硬链段,所述软链段的比例为75重量百分比至85重量百分比,所述硬链段的比例为15重量百分比至25重量百分比。
10.根据权利要求7所述的聚氨酯树脂,其特征在于,所述聚氨酯树脂的黏度为20000cps至30000cps。
11.根据权利要求7所述的聚氨酯树脂,其特征在于,所述聚氨酯树脂的重量平均分子量为90000克/摩尔至110000克/摩尔。
12.根据权利要求7所述的聚氨酯树脂,其特征在于,所述聚氨酯树脂固化相对于一聚氨酯基材的剥离强度为12.0kg/3cm至18.0kg/3cm。
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